TW201334866A - Hydrocarbon transformations using carbocatalysts - Google Patents

Abstract

The disclosure relates to catalytically active carbocatalysts, e.g., a graphene oxide or graphite oxide catalyst suitable for use in a variety of high value chemical transformations.

Description

Hydrocarbon conversion using a carbon catalyst Cross reference

This application claims the benefit of US Provisional Application Serial No. 61/564,126, filed on Nov. 28, 2011, which is incorporated by reference in its entirety.

Federally sponsored research and funding statement

At least a portion of the invention is accomplished using funding from the Robert A. Welch Foundation under contract number F-1621.

The cost of the goods and services needed to make certain high value organic chemicals is prohibitively high and/or dependent on starting materials that are by-products of the petroleum industry.

This paper describes methods and processes with extensive synthetic utility that can be applied to the synthesis of high value and large quantities of chemicals that are utilized in a wide range of manufacturing processes. The chemical hydrocarbon conversions provided herein can be used inexpensively and efficiently in the synthesis of certain hydrocarbon starting materials used to produce a range of chemical products. Provided herein are methods for the synthesis of low molecular weight saturated or partially saturated organic compounds. In some instances, the compounds are gases and/or are volatile compounds.

Processes for hydrocarbon dehydrogenation, hydrocarbon cracking, hydrocarbon coupling (e.g., C-C alkane coupling), and/or hydrocarbon replacement are provided herein to provide a hydrocarbon product. Process package for hydrocarbon dehydrogenation, hydrocarbon cracking, hydrocarbon coupling (eg, C-C alkane coupling), and/or hydrocarbon replacement as described herein Containing, contacting a hydrocarbon with a catalytically active carbon-based material. In other words, the synthetic methods described herein comprise the use of a catalytically active carbon catalyst. In some embodiments, the catalytically active carbon catalyst is a graphene oxide-derived or graphite oxide-derived catalyst.

In one aspect, this article provides a method for conversion

(a) the alkane starting material becomes an olefin product (dehydrogenation); (b) the alkane starting material becomes one or more higher molecular weight alkane products (coupling); (c) the alkane starting material becomes one or more replacement products ( Substituting); (d) a higher alkane starting material to be one or more lower alkane products (cracking); (e) a cycloalkane starting material to be an alkane product or an olefin product or a combination thereof (cracking); or any combination thereof, It comprises contacting any of the starting materials in (a)-(e) with graphene oxide or graphite oxide having a catalytically active surface modification to provide a corresponding product of (a)-(e).

In one embodiment, provided herein is a process for converting an alkane starting material to an olefin product (dehydrogenation) comprising contacting an alkane starting material with graphene oxide or graphite oxide having a catalytically active surface modification to provide Corresponding olefin product. In one embodiment, a process for converting an alkane starting material to one or more higher molecular weight alkane products (coupling) comprising an alkane starting material and a catalytically active surface modified graphene oxide or The graphite oxide is contacted to provide a corresponding higher molecular weight product. In one embodiment, a process for converting an alkane starting material to one or more displacement products comprising contacting an alkane starting material with graphene oxide or graphite oxide having a catalytically active surface modification to provide a phase is provided. Corresponding to one or more replacement products. In one embodiment, a process for converting a higher alkane starting material to one or more lower alkane products (cracking) comprising a higher alkane starting material and a catalytically active surface modified graphene oxide or oxidation is provided herein. The graphite is contacted to provide a corresponding lower alkane product. In one embodiment, provided herein is a process for converting a naphthenic starting material to an alkane or olefin product or a combination thereof (cracking) comprising reacting a naphthenic starting material with The catalytically active surface-modified graphene oxide or graphite oxide is contacted to provide a corresponding alkane or olefin product or a combination thereof. In one embodiment, a process comprising cracking and coupling. In one embodiment, a process comprising cracking and dehydrogenation. In one embodiment, a process comprising displacement and dehydrogenation.

In a specific example of the above process, the catalytically active surface-modified graphene oxide or graphite oxide is a graphene oxide having a catalytically active surface modification.

In a specific example of the above process, the catalytically active surface-modified graphene oxide or graphite oxide is a catalytically active surface-modified graphite oxide.

In a specific example of the above process, the catalytically active surface-modified graphene oxide or graphite oxide is characterized by having one or at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 Multiple Fourier Transform Infrared (FT-IR) features.

In some embodiments, the catalytically active surface-modified graphene oxide or graphite oxide has a surface modification comprising one or more hydrogen peroxide capping surfaces, an epoxide capping surface, a ketone capping surface, a diketone capping Surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface, alcohol end surface, ether end surface, dioxopane end surface, ruthenium end surface, peroxy acid end surface, ester end Surface, anhydride capping surface or peroxyacid ester capping surface.

In some embodiments, the catalytically active surface-modified graphene oxide or graphite oxide has a surface modification comprising one or more hydrogen peroxide capping surfaces, an epoxide capping surface, a ketone capping surface, an aldehyde capping end Surface, carboxyl terminated surface, hydroxyl terminated surface, alcohol terminated surface or ether terminated surface.

In some embodiments, the catalytically active surface-modified graphene oxide or graphite oxide has a surface modification comprising one or more epoxide capping surfaces, a ketone-terminated surface, an aldehyde-terminated surface, a carboxyl-terminated surface, A hydroxyl terminated surface or an alcohol terminated surface.

In a further embodiment of the process, the catalytically active surface-modified graphene oxide or graphite oxide has at least about at least about as measured by X-ray photoelectron spectroscopy (XPS). 25% carbon and at least about 0.01% oxygen.

In some embodiments, the catalytically active surface-modified graphene oxide or graphite oxide has a carbon to oxygen ratio of between about 1.5:1 and about 1:1.5, as measured by X-ray photoelectron spectroscopy (XPS).

In some embodiments, the catalytically active surface-modified graphene oxide or graphite oxide has a carbon to oxygen ratio of between about 1:1 and about 5:1 as measured by X-ray photoelectron spectroscopy (XPS).

In some embodiments, the catalytically active surface modified graphene oxide or graphite oxide has a carbon to oxygen ratio of between about 1:1 and about 4:1 as measured by X-ray photoelectron spectroscopy (XPS).

In some embodiments, the catalytically active carbon catalyst has a carbon to oxygen ratio of between about 1:1 and about 3:1 as measured by X-ray photoelectron spectroscopy (XPS).

In some embodiments, the catalytically active surface modified graphene oxide or graphite oxide has a carbon to oxygen ratio of between about 2:1 and about 3:1 as measured by X-ray photoelectron spectroscopy (XPS).

Also provided herein is a process for converting an alkane to an olefin under power control, comprising, at a temperature for converting an alkane to an olefin in the presence of a catalyst other than a carbon catalyst (eg, a transition metal based catalyst) At low temperatures, the alkane is contacted with the catalytically active surface-modified graphene oxide or graphite oxide described above and herein.

Also provided herein is a process for converting an alkane to an olefin under motive control, comprising: converting an alkane to an olefin in the presence of a catalyst other than a catalytically active surface-modified graphene oxide or graphite oxide. At a low temperature, the alkane is contacted with the catalytically active surface-modified graphene oxide or graphite oxide described above and herein.

In a specific example of the power process, the catalytically active surface-modified graphene oxide or graphite oxide is a graphene oxide having a catalytically active surface modification.

In a specific example of the power process, the catalytically active surface-modified graphene oxide or graphite oxide is a catalytically active surface-modified graphite oxide.

Provided herein is a process for converting propane to propylene (an exemplary dehydrogenation) comprising contacting propane with graphene oxide or graphite oxide having catalytically active surface modification as described above and herein. Provided herein is a process for the conversion of ethane to ethylene comprising contacting a graphene oxide or graphite oxide having a catalytically active surface modification as described above and described herein.

Also provided herein is a process for converting methane to ethane (exemplary coupling) comprising contacting methane with a catalytically active surface modified graphene oxide or graphite oxide as described above and herein. Also provided herein is a process for converting methane to propane comprising contacting methane with a catalytically active surface modified graphene oxide or graphite oxide as described above and herein.

Further provided herein is a process for converting ethane to propane (exemplary substitution) comprising contacting ethane with a graphene oxide or graphite oxide having a catalytically active surface modification as described above and herein. Also provided herein is a process for converting methane to butane comprising contacting methane with a catalytically active surface modified graphene oxide or graphite oxide as described above and herein. Further provided herein is a process for converting ethane to butane comprising contacting ethane with a catalytically active surface-modified graphene oxide or graphite oxide as described above and herein.

Processes for the alkane and/or naphthenic cracking are also provided herein. Provided herein is a process for converting hexane to methane comprising contacting hexane with a catalytically active surface modified graphene oxide or graphite oxide as described above and herein. Further provided herein is a process for converting hexane to ethane comprising contacting hexane with graphene oxide or graphite oxide having catalytically active surface modification as described above and herein. Also provided herein is a process for converting hexane to propane comprising contacting hexane with graphene oxide or graphite oxide having catalytically active surface modification as described above and herein. This article further provides a Process for the conversion of hexane to propylene (exemplary cleavage and dehydrogenation) comprising contacting hexane with graphene oxide or graphite oxide having catalytically active surface modification as described above and herein. Also provided herein is a process for converting hexane to butane comprising contacting hexane with a catalytically active surface-modified graphene oxide or graphite oxide as described above and herein. Further provided herein is a process for converting hexane to butene or butadiene comprising contacting hexane with a graphene oxide or graphite oxide having a catalytically active surface modification as described above and herein. Also provided herein is a process for converting butane to 1-butene comprising contacting butane with graphene oxide or graphite oxide having catalytically active surface modification as described above and herein. Further provided herein is a process for converting butane to 2-butene comprising contacting butane with graphene oxide or graphite oxide having catalytically active surface modification as described above and herein. Also provided herein is a process for converting butane to butadiene comprising contacting butane with graphene oxide or graphite oxide having catalytically active surface modifications as described above and herein.

Further provided herein is a method for alkane displacement comprising contacting the alkane with a graphene oxide or graphite oxide having a catalytically active surface modification as described above and herein. In some embodiments, the alkane is a C ₁ -C ₆ alkane, and the product obtained by contacting the C ₁ -C ₆ alkane with a catalytically active surface-modified graphene oxide or graphite oxide is advanced and/or low-grade. A mixture of C ₁ -C ₁₂ alkanes.

Also provided herein is a process for the dehydrogenation of an alkane comprising contacting the alkane with a graphene oxide or graphite oxide having a catalytically active surface modification as described above and herein. In some embodiments, the alkane is a C ₂ -C ₆ alkane, and the product derived from contacting the C ₂ -C ₆ alkane with the catalytically active surface-modified graphene oxide or graphite oxide is one or more C A mixture of _2- C ₆ olefins. In some embodiments, the alkane is a C ₄ -C ₆ alkane, and the product derived from contacting the C ₄ -C ₆ alkane with the catalytically active surface-modified graphene oxide or graphite oxide is one or more C ₄ a mixture of -C ₆ diene.

Provided herein is a reaction vessel comprising the starting materials described above and herein, The product and graphene oxide or graphite oxide with catalytically active surface modification. In some such embodiments, the reaction vessel further comprises a heat source for heating the reaction vessel to a desired temperature, a means for controlling the temperature of the reaction vessel, and a means for determining the temperature within the reaction vessel.

In some embodiments, the reaction vessel is in the form of a fluidized bed reactor. In some embodiments, the reaction vessel is in the form of a fixed bed reactor.

In some of the foregoing specific examples, the reaction vessel further comprises a solid acid catalyst.

Further provided herein is a catalytically active surface-modified graphene oxide or graphite oxide in contact with propane and propylene.

Also provided herein is a reaction vessel comprising propane, propylene, and graphene oxide or graphite oxide having a catalytically active surface modification.

In a different aspect, provided herein is a process for converting propane to propylene comprising contacting propane with catalytically active surface modified graphene oxide or graphite oxide to provide propylene.

In one embodiment of the process, the catalytically active surface-modified graphene oxide or graphite oxide is a graphene oxide having a catalytically active surface modification.

In one specific example of the process, the catalytically active surface-modified graphene oxide or graphite oxide is a catalytically active surface-modified graphite oxide.

In one embodiment, the catalytically active surface-modified graphene oxide or graphite oxide is characterized by having one or more at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 FT-IR features.

In one embodiment, the catalytically active surface-modified graphene oxide or graphite oxide has a surface modification comprising one or more hydrogen peroxide capping surfaces, an epoxide capping surface, a ketone capping surface, a diketone seal End surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface, alcohol end surface, ether end surface, dioxopane end surface, tantalum end surface, peroxy acid end surface, ester seal End surface, anhydride capping surface or peroxyacid ester capping surface.

In one embodiment, the catalytically active surface-modified graphene oxide or graphite oxide has a surface modification comprising one or more hydrogen peroxide capping surfaces, an epoxide capping surface, a ketone capping surface, an aldehyde capping end Surface, carboxyl terminated surface, hydroxyl terminated surface, alcohol terminated surface or ether terminated surface.

In one embodiment, the catalytically active surface-modified graphene oxide or graphite oxide has a surface modification comprising one or more epoxide capping surfaces, a ketone-terminated surface, an aldehyde-terminated surface, a carboxyl-terminated surface, A hydroxyl terminated surface or an alcohol terminated surface.

In one embodiment, the catalytically active surface modified graphene oxide or graphite oxide has at least about 25% carbon and at least about 0.01% oxygen as measured by X-ray photoelectron spectroscopy (XPS).

In one embodiment, the catalytically active surface-modified graphene oxide or graphite oxide has a carbon to oxygen ratio of between about 1.5:1 and about 1:1.5 as measured by X-ray photoelectron spectroscopy (XPS).

In one embodiment, the catalytically active surface-modified graphene oxide or graphite oxide has a carbon to oxygen ratio of between about 1:1 and about 5:1 as measured by X-ray photoelectron spectroscopy (XPS).

In one embodiment, the catalytically active surface-modified graphene oxide or graphite oxide has a carbon to oxygen ratio of between about 2:1 and about 3:1 as measured by X-ray photoelectron spectroscopy (XPS).

Also provided herein is a process for converting propane to propylene under power control, comprising contacting a graphene oxide or graphite oxide having a catalytically active surface modification as described above with a less catalytically active surface-modified graphite oxide. The temperature at which the temperature at which propane is converted to propylene is low in the presence of a catalyst of olefin or graphite oxide.

Provided herein are propylene prepared according to the processes described above.

On the other hand, this article provides for conversion (a) the saturated hydrocarbon group on the hydrocarbon starting material becomes an unsaturated hydrocarbon group (dehydrogenation) on the hydrocarbon product; (b) the hydrocarbon starting material becomes one or more higher molecular weight hydrocarbon products (coupling) (c) the hydrocarbon starting material becomes one or more replacement products (displacement); (d) the higher hydrocarbon starting material becomes one or more lower hydrocarbon products (cracking); or any combination thereof, including any (a) - (d) The starting material is contacted with a catalytically active carbon catalyst to provide the corresponding product in (a)-(d).

In one embodiment, a process for converting a saturated hydrocarbon group on a hydrocarbon starting material to an unsaturated hydrocarbon group (dehydrogenation) on a hydrocarbon product, comprising a position in a hydrocarbon starting material, is provided herein. The saturated hydrocarbon group is contacted with a catalytically active carbon catalyst to provide a corresponding product having an unsaturated hydrocarbon group on the hydrocarbon product.

In one embodiment, provided herein is a process for converting a hydrocarbon starting material to one or more higher molecular weight hydrocarbon products (coupling) comprising contacting a hydrocarbon starting material with a catalytically active carbon catalyst to provide Corresponding to one or more higher molecular weight products.

In one embodiment, provided herein is a process for converting a hydrocarbon starting material to one or more replacement products (replacement) comprising contacting a hydrocarbon starting material with a catalytically active carbon catalyst to provide a corresponding one Or a variety of replacement products.

In one embodiment, provided herein is a process for converting a higher hydrocarbon starting material to one or more lower hydrocarbon products (cracking) comprising contacting a hydrocarbon starting material with a catalytically active carbon catalyst to provide a corresponding One or more lower hydrocarbon products.

In one embodiment, a process comprising cracking and coupling. In one embodiment, a process comprising cracking and dehydrogenation. In one embodiment, it is a process comprising replacement and dehydrogenation.

In some embodiments, the carbon catalyst is selected from the group consisting of fullerene-related materials and amorphous Carbon, crystalline carbon, mesoporous carbon, graphene oxide or graphite oxide derived material or activated carbon.

In some embodiments, the carbon catalyst is selected from the group consisting of fullerene-related materials, amorphous carbon, crystalline carbon, graphene oxide or graphite oxide-derived materials or activated carbon.

In some embodiments, the starting materials in (a)-(d) are materials that do not contain active C-H bonds.

In some embodiments, the catalytically active carbon catalyst is a modified form of graphene oxide or graphite oxide.

In some embodiments, the catalytically active carbon catalyst is characterized by having one or more FT-IR characteristics at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^{-1 ,} or 1140 cm ^-1 .

In some embodiments, the catalytically active carbon catalyst is a modified form of graphene oxide or graphite oxide (eg, a further oxidized form of graphene oxide or graphite oxide).

In some embodiments, the catalytically active carbon catalyst is graphene oxide or graphite oxide having a catalytically active surface modification.

In one embodiment of the process, the catalytically active surface-modified graphene oxide or graphite oxide is a graphene oxide having a catalytically active surface modification.

In one specific example of the process, the catalytically active surface-modified graphene oxide or graphite oxide is a catalytically active surface-modified graphite oxide.

In some embodiments, the catalytically active carbon catalyst has a surface modification comprising one or more hydrogen peroxide capping surfaces, an epoxide capping surface, a ketone capping surface, a diketone capping surface, an aldehyde capping end Surface, carboxyl terminated surface, hydroxyl terminated surface, alcohol terminated surface, ether terminated surface, dioxopane terminated surface, ruthenium capped surface, peroxyacid terminated surface, ester terminated surface, anhydride terminated Surface or peroxyacid ester capping surface.

In some embodiments, the catalytically active carbon catalyst has a surface modification comprising one or more hydrogen peroxide capping surfaces, an epoxide capping surface, a ketone capping surface, an aldehyde capping surface, a carboxyl capping surface , hydroxyl terminated surface, alcohol terminated surface or ether terminated table surface.

In some embodiments, the catalytically active carbon catalyst has a surface modification comprising one or more epoxide capping surfaces, a ketone capping surface, an aldehyde capping surface, a carboxyl terminated surface, a hydroxyl terminated surface, or an alcohol End surface.

In some embodiments, the catalytically active carbon catalyst has at least about 25% carbon and at least about 0.01% oxygen as measured by X-ray photoelectron spectroscopy (XPS). In an alternative embodiment, the catalytically active carbon catalyst has at least about 25% carbon and at least about 0.01% oxygen as measured by elemental combustion analysis.

In some embodiments, the catalytically active carbon catalyst has a carbon to oxygen ratio of between about 1.5:1 and about 1:1.5 as measured by X-ray photoelectron spectroscopy (XPS).

In some embodiments, the catalytically active carbon catalyst has a carbon to oxygen ratio of between about 1:1 and about 5:1 as measured by X-ray photoelectron spectroscopy (XPS).

In some embodiments, the catalytically active carbon catalyst has a carbon to oxygen ratio of between about 1:1 and about 4:1, as measured by X-ray photoelectron spectroscopy (XPS).

In some embodiments, the catalytically active carbon catalyst has a carbon to oxygen ratio of between about 1:1 and about 3:1 as measured by X-ray photoelectron spectroscopy (XPS).

In some embodiments, the catalytically active carbon catalyst has a carbon to oxygen ratio of between about 2:1 and about 3:1 as measured by X-ray photoelectron spectroscopy (XPS).

For any of the specific examples described above, in some examples, provided herein is a saturated hydrocarbon group for converting (a) a position on a hydrocarbon starting material to an unsaturated hydrocarbon group located on a hydrocarbon product. Hydrogen); (b) the hydrocarbon starting material becomes one or more higher molecular weight hydrocarbon products (coupling); (c) the hydrocarbon starting material becomes one or more replacement products (substitution); (d) the higher hydrocarbon starting material becomes One or more lower hydrocarbon products (cracking); or any combination thereof, Under dynamic control, any starting material in (a)-(d) is contacted with a catalytically active carbon catalyst to provide the corresponding product in (a)-(d).

In another aspect, provided herein is a process for converting propane to propylene comprising contacting propane with a catalytically active carbon catalyst to provide propylene.

In one embodiment, the carbon catalyst for converting propane to propylene is selected from the group consisting of fullerene-related materials, amorphous carbon, crystalline carbon, mesoporous carbon, graphene oxide or graphite oxide-derived materials or activated carbon.

In another embodiment, the carbon catalyst for converting propane to propylene is selected from the group consisting of fullerene-related materials, amorphous carbon, crystalline carbon, graphene oxide or graphite oxide-derived materials or activated carbon.

In some of the specific examples described above, the catalytically active carbon catalyst for converting propane to propylene is graphene oxide or graphite oxide derived material.

In some specific examples described above, the catalytically active carbon catalyst for converting propane to propylene is characterized by being at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^{- One} has one or more FT-IR features.

In some of the specific examples described above, the catalytically active carbon catalyst for converting propane to propylene is a catalytically active surface-modified graphene oxide or graphite oxide.

In one embodiment of the process, the catalytically active surface-modified graphene oxide or graphite oxide is a graphene oxide having a catalytically active surface modification.

In one specific example of the process, the catalytically active surface-modified graphene oxide or graphite oxide is a catalytically active surface-modified graphite oxide.

In some embodiments described above, the catalytically active carbon catalyst for converting propane to propylene has a surface modification comprising one or more hydrogen peroxide capping surfaces, an epoxide capping surface, a ketone End surface, diketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface, alcohol end surface, ether end surface, dioxane An alkyl terminated surface, a ruthenium terminated surface, a peroxyacid terminated surface, an ester terminated surface, an anhydride terminated surface, or a peroxyacid ester capped surface.

In some embodiments described above, the catalytically active carbon catalyst for converting propane to propylene has a surface modification comprising one or more hydrogen peroxide capping surfaces, an epoxide capping surface, a ketone The capping surface, the aldehyde capping surface, the carboxyl capping surface, the hydroxyl terminated surface, the alcohol capping surface or the ether capping surface.

In some embodiments described above, the catalytically active carbon catalyst for converting propane to propylene has a surface modification comprising one or more epoxide end capping surfaces, a ketone capping surface, an aldehyde capping end Surface, carboxyl terminated surface, hydroxyl terminated surface or alcohol terminated surface.

In some embodiments described above, the catalytically active carbon catalyst for converting propane to propylene has at least about 25% carbon and at least about 0.01% oxygen as measured by X-ray photoelectron spectroscopy (XPS).

In some of the specific examples described above for converting propane to propylene, the catalytically active carbon catalyst has a carbon to oxygen ratio of about 1.5:1 and about 1: as measured by X-ray photoelectron spectroscopy (XPS). Between 1.5.

In some of the specific examples described above for converting propane to propylene, the catalytically active carbon catalyst has a carbon to oxygen ratio of about 1:1 and about as measured by X-ray photoelectron spectroscopy (XPS). Between 5:1.

In some of the specific examples described above for converting propane to propylene, the carbon-to-oxygen ratio of the catalytically active carbon catalyst is between about 2:1 and about as measured by X-ray photoelectron spectroscopy (XPS). Between 3:1.

For any of the specific examples described above, in one example, provided herein is a process for the conversion of propane to propylene under power control comprising contacting propane with a catalytically active carbon catalyst to provide propylene.

For any specific example described above or below, this article provides a reminder An activated carbon catalyst, wherein the catalytically active carbon catalyst is an oxidized graphite. For any of the specific examples described above or below, a catalytically active carbon catalyst is provided herein, wherein the catalytically active carbon catalyst is an oxidized graphene. In some embodiments, the catalytically active carbon catalyst is modified graphene oxide or graphite oxide. In some embodiments, the catalytically active carbon catalyst is an oxidized carbonaceous material.

In some embodiments, the catalytically active carbon catalyst is a heterogeneous catalyst. In some embodiments, the catalytically active carbon catalyst provides a pH of the reaction solution which is neutral when dispersed in a reaction mixture. In some embodiments, the catalytically active carbon catalyst provides a pH of the reaction solution which is acidic when dispersed in a reaction mixture. In other embodiments, the catalytically active carbon catalyst provides a pH of the reaction solution which is basic when dispersed in a reaction mixture. In some embodiments, the catalytically active carbon catalyst is present on a solid support. In some embodiments, the catalytically active carbon catalyst is present in a solid support.

For any of the specific examples described above or below, various processes are provided herein, wherein the process further comprises contacting the reactant with a cocatalyst. In some embodiments, the cocatalyst is an oxidation catalyst. In some embodiments, the cocatalyst is a zeolite.

For any of the specific examples described above or below, various processes are provided herein, wherein the process further comprises an additional oxidant. In some specific examples of methods and/or processes described above or below, the method comprises a solventless reaction. In certain embodiments of the methods described above or below, the method comprises contacting one or more gaseous reactants with a carbon catalyst.

Incorporated reference

All publications, patents and patent applications mentioned in this specification are incorporated by reference as if individually and individually The same degree of incorporation by reference is indicated herein incorporated by reference.

The novel features of the invention are set forth with particularity in the appended claims. The features and advantages of the present invention can be better understood by referring to the following description of the embodiments and the accompanying drawings in which Illustrative examples of modified graphene oxide or graphite oxide (MG) in the examples.

Figure 2 shows an illustrative X-ray photoelectron spectroscopy (XPS) of a sample of the prepared graphene oxide or graphite oxide.

Figure 3 shows the original <^1> H NMR spectrum of the reaction of Example 4, i.e., the reaction mixture of propane to propylene after heating at 400 °C for 168 hours.

Figure 4 shows the conversion of propane to propylene as a function of reaction time in the reaction of Example 4.

Figure 5 shows an illustrative diagram of a generalized flow reactor coupled to an internal circulator that allows unreacted hydrocarbons to be recovered and recycled, thereby achieving in multiple passes Maximum yield.

The manufacture of raw materials such as low molecular weight alkanes or alkenes relies on the cracking of naphtha. Naphtha is a component of natural gas condensate or distillation products from petroleum, coal gangue or peat. Naphtha is a mixture of hydrocarbons boiling over a range of temperatures, covering certain low molecular weight and volatile parts of liquid hydrocarbons in petroleum. For example, 95% of the currently produced propylene is produced as a by-product of cracked naphtha. However, the supply of propylene is decreasing and the ethane cracker is unable to produce propylene as a by-product of recyclability. Therefore, while the industry avoids relying on petroleum (a decreasing natural resource), there is a need for a process that can produce high value commodities such as low molecular weight hydrocarbons.

This article provides the purpose of manufacturing high-value chemicals using low-cost starting materials. The method and process. Provided herein are practical techniques for the synthesis of low molecular weight saturated, partially saturated or unsaturated organic compounds using certain catalytically active carbon catalysts such as surface modified graphene oxide and/or graphite oxide. In some instances, the compounds are gases and/or are volatile compounds. In some examples, the compounds contain from one to six carbons. In some examples, the compounds contain from one to five carbons. In some examples, the compounds contain from one to four carbons. In some examples, the compounds contain one to three carbons. In some examples, the compounds contain from two to six carbons. In some examples, the compounds contain two to five carbons. In some examples, the compounds contain two to four carbons. In some examples, the compounds contain two to three carbons. In some examples, the compounds contain three carbons.

There is a need for broad-spectrum catalysts that overcome the absence of one or more existing catalysts and are capable of catalyzing the use of a wide variety of initial reactants or starting materials for various chemical reactions, such as hydrocarbon conversion.

Various limitations associated with currently commercially available methods for catalyzing hydrocarbon reactions are recognized herein. For example, while transition metal based catalysts can provide a commercially viable reaction rate, the use of metal catalysts has various deficiencies, such as metal contamination of the resulting product. This is especially problematic for industries that want to use the product for health or biological purposes or other applications that are sensitive to metals. The carbon catalysts (e.g., graphene oxide and/or graphite oxide) described herein for hydrocarbon conversion (e.g., conversion of propane to propylene) are substantially free of transition metals and can produce pure hydrocarbons free of metal contaminants.

Another disadvantage of metal catalysts is that metal catalysts are generally not selective in hydrocarbon reactions. Dehydrogenation of hydrocarbons based on transition metals is typically oxidative dehydrogenation (ODH) and requires a high proportion of oxygen/hydrocarbons, resulting in unwanted oxidation by-products. In some embodiments, the carbon catalysts provided herein (eg, graphene oxide or graphite oxide) may allow for the dynamics of certain hydrocarbon reactions (eg, dehydrogenation) to increase selectivity in hydrocarbon conversion.

As another example illustrating the absence of the metal-based catalysts recognized herein, Catalysts for transition metals can be quite expensive to manufacture, and processes using such catalysts can require significant initial and maintenance costs. Conversely, the techniques described herein for carbon-based catalysts, such as graphene oxide and/or graphite oxide, can improve existing manufacturing facilities, thereby reducing any of the new technologies associated with upgrading commercial hydrocarbons for mass production. Starting cost. Shale gas (including dry or wet shale gas) is very rich and can be easily transported to existing manufacturing facilities. Thus, the versatile techniques described herein are not impeded by the availability of starting materials and/or the cost of obtaining starting materials.

Described herein is a process for hydrocarbon conversion involving the use of a carbon catalyst that combines the benefits of metal-free synthesis with the convenience of heterogeneous processing. The methods provided herein are environmentally friendly as they reduce the need for metal based catalysts in production plants. Furthermore, the production steps are reduced, thereby reducing the cost of goods and manufacturing services.

Typical hydrocarbon starting materials for hydrocarbon conversion often have sulfur-containing impurities that contaminate metal-based catalysts. The catalytically active carbon catalysts described herein (e.g., graphene oxide and/or graphite oxide-derived catalysts) have the advantage that the catalyst is not contaminated with impurities (e.g., sulfur-containing impurities) that would normally contaminate other catalysts (e.g., transition metal-based catalysts). ) pollution.

Another advantage is that the catalytically active carbon catalysts described herein (e.g., modified graphene oxide and/or graphite oxide) can be regenerated to reduce industrial waste and reduce article and manufacturing costs. The carbon catalysts described herein and processes utilizing such carbon catalysts can activate relatively insensitive starting materials, such as hydrocarbons, and are suitable for activation of C-H bonds and/or C-C bonds.

Certain previously used catalysts, such as mesoporous carbon, produce coke during the course of the reaction, and the carbon catalysts described herein (e.g., graphene oxide and/or graphite oxide-derived catalysts) overcome this disadvantage. Furthermore, previously used catalysts have pores which retard the outward diffusion of the product from the mesoporous structure, and the carbon catalysts described herein (e.g., graphene oxide and/or graphite oxide-derived catalysts) overcome this disadvantage. In addition, catalysts based on mesoporous and/or amorphous carbon and/or activated carbon may block the reactor as a result of coking, the carbon catalysis described herein. Agents such as graphene oxide and/or graphite oxide derived catalysts overcome this disadvantage.

Some of the previously described catalysts, such as fullerene-related materials or crystalline carbon materials, have a deficiency. It is challenging to introduce catalytically active edge sites or defect sites in fullerene-related materials or crystalline carbon. Conversely, the catalytically active carbon catalysts provided herein (eg, modified graphene oxide and/or graphite oxide) overcome this potential disadvantage of fullerene-related materials; in some instances, compared to Fuller-based For olefinic materials, the catalysts provided herein (e.g., graphene oxide and/or graphite oxide) have significantly higher unit weights of edge or corner sites. The catalytically active carbon catalysts (e.g., modified graphene oxide and/or graphite oxide) provided herein comprise a higher percentage of edge sites for the powder material than fullerene-related and/or crystalline carbon-related materials.

Accordingly, the multifunctional carbon catalysts described herein and processes utilizing the carbon catalysts (eg, graphene oxide and/or graphite oxide) can be employed in a variety of organic reactions including, but not limited to, hydrocarbon-hydrocarbon (eg, CC) coupling. , alkane displacement, alkane and/or cycloalkane cracking and dehydrogenation of alkanes and/or naphthenes. The carbon catalysts described herein (e.g., graphene oxide and/or graphite oxide) comprise a relatively high concentration of reactive and/or selective sites on the surface and overcome the low overall activity and/or reaction of the previously described carbon-based catalysts. Sex.

The disclosed method can also be applied to the pharmaceutical industry. For example, chalcone is an important precursor to flavonoids and other pharmaceutically important materials and has many uses outside the pharmaceutical industry. In addition, the absence of metals in graphene oxide or graphite oxide may allow reactions that are concerned with metal contamination (such as the reaction of manufacturing pharmaceuticals or agricultural products), or that may be harmful to metal contamination (eg, products that undergo further reactions or These methods are used in further applications where the reaction or application is sensitive to metal contamination.

definition

The term "carbon catalyst" as used herein refers to a catalytically active carbonaceous material for use in various hydrocarbon conversions or synthesis as described herein. In one embodiment, the carbon catalysts described herein include graphite, graphite oxide, graphene, graphene oxide, and parts. Graphite oxide, partially graphene oxide or other related materials. In further embodiments, the carbon catalysts described herein include surface modified graphite, graphite oxide, graphene, graphene oxide, or other related materials. In further embodiments, the carbon catalysts described herein include graphite, graphite oxide, graphene, graphene oxide, partially graphite oxide, partially graphene oxide, fullerene-related materials, amorphous carbon, crystalline carbon, activated carbon, Carbon molecular sieve or related materials.

In other embodiments, the carbon catalyst comprises amorphous carbon, a nanotube, a carbon molecular sieve, a buckyball, a diamond, a graphite fluoride, a graphene fluoride, activated carbon, or other related materials, or a combination thereof. In some embodiments, the carbon catalyst comprises, amorphous carbon, crystalline carbon or fullerene related materials. In other embodiments, the carbon catalyst comprises amorphous carbon, crystalline carbon, nanotubes, buckyball, diamond, activated carbon, vitreous carbon, charcoal, activated charcoal, and intermediates or various combinations or mixtures thereof in the form of carbon. In a further embodiment, the carbon catalyst comprises porous carbon, mesoporous carbon, microporous carbon, partially oxidized porous carbon, partially oxidized mesoporous carbon or partially oxidized microporous carbon. In a further embodiment, the carbon catalyst comprises a carbon composite.

Fullerene-related materials as used herein include, for example, fullerenes, nanotubes, nanospheres, nanocones, nanofolders, nanobundles, onion-like carbons, and the like. material. Amorphous carbon as used herein refers to a carbon allotrope that does not have any crystalline structure. Amorphous carbon also includes glassy carbon. Crystalline carbon as used herein includes, for example, diamonds, nanodiamonds, and the like. Mesoporous carbon as used herein comprises a material having a pore diameter between 2 and 50 nm. The microporous carbon comprises a material having a pore diameter of less than 2 nm. Activated carbon refers to a highly porous material.

The term "catalytically active carbon catalyst" as used herein refers to a carbon catalyst material or species that promotes one or more chemical reactions. The term "catalytically active carbon catalyst" means a carbon catalyst which is catalytically active. Catalytically active carbon catalysts include one or more reactive sites for promoting chemical reactions, for example, For example, a surface group (eg, an OH group, an epoxide, an aldehyde, a carboxylic acid, or any other group described herein). The term catalytically active carbon catalyst includes surface modified graphene oxide, graphite oxide or other carbon and oxygen which promotes chemical reactions such as hydrocarbon-hydrocarbon CC coupling, hydrocarbon cracking and/or displacement and/or dehydrogenation reactions. material.

The term "used catalyst" or "used carbon catalyst" as used herein refers to a catalyst that has been exposed to a reactant to form a product. In some cases, the used catalyst does not promote the chemical reaction. The activity of the used catalyst has been reduced relative to the newly formed catalyst (also referred to herein as "new catalyst"). The used catalyst is partially or completely deactivated. In some instances, this reduced activity is due to a decrease in the number of reactive sites. The spent carbon catalyst can optionally be regenerated as described herein to provide a catalytically active carbon catalyst.

The term "heterogeneous catalyst" or "heterogeneous carbon catalyst" as used herein refers to a solid phase species configured to promote chemical conversion. In a heterogeneous catalytic reaction, the phase of the heterogeneous catalyst is typically different from the phase of the reactants. Heterogeneous catalysts include catalytically active materials on solid supports. In some instances, the support is catalytically active or non-active. In some cases, the catalytically active material and the solid support are collectively referred to as "heterogeneous catalysts" (or "catalysts").

The term "solid support" as used herein refers to a support structure for supporting or supporting a catalytically active material, such as a catalyst (eg, a carbon catalyst). In some instances, the solid support does not promote a chemical reaction. However, in other examples, solid support is involved in the chemical reaction.

The term "primary catalyst" or "primary carbon catalyst" as used herein refers to a substance or material used to form a catalyst. Primary catalysts are described as having a potential to become a catalyst, for example, after additional processing or chemical and/or physical (e.g., surface) modification or conversion.

As used herein, a catalytically active carbon catalyst as described herein (eg, surface modification) The "carbon to oxygen ratio" of graphene oxide or graphite oxide refers to the relative content of carbon and oxygen of the catalyst. Thus, by way of example, a 1 to 1 ratio of carbon to oxygen refers to a catalyst composition comprising equal amounts of carbon and oxygen. It will be understood that the catalyst also contains hydrogen.

Accordingly, in some embodiments, the catalytically active carbon catalyst (eg, surface modified graphene oxide or graphite oxide) described herein has a carbon to oxygen ratio of between about 1 and 1.5 to about 1.5 to 1. . In other embodiments, the catalytically active carbon catalysts (e.g., surface modified graphene oxide or graphite oxide) described herein have a carbon to oxygen ratio of between about 1 to 1 and about 9 to 1. In still other embodiments, the catalytically active carbon catalyst (eg, surface modified graphene oxide or graphite oxide) described herein has a ratio of from about 1 to 1 to about 5 to 1, about 1 to 1 to 4 ratio. 1. A ratio of carbon to oxygen between about 1 to 1 to 3 to 1 or about 1 to 1 to 2 to 1 or about 2 to 1 to about 3 to 1.

The term "surface" as used herein refers to liquids and solids, gases and solids, solids and solids, or interfaces between liquids and gases. The degree of freedom of species on the surface is reduced relative to species in the liquid, solid or gas phase.

"Surface-modified graphite oxide or graphene oxide" refers to graphite oxide or graphene oxide terminated with certain functional groups. By way of example only and with "hydrogen peroxide terminated surface" of the surface-modified graphite oxide or graphene oxide refers, -R-OOH or -ROO ^- group attached to the surface of the graphene oxide or graphite oxide, wherein R is a bond or any suitable divalent group such as an alkylene group, an arylene group, a cycloalkylene group, an alkenylene group, an alkynylene group, a heteroarylene group, a cycloalkenylene group, a hetero Cycloalkylene, heterocycloalkenylene and similar groups.

"Peroxide-terminated surface" means that the -R-OOR' group is attached to the surface of graphene oxide or graphite oxide, where R is a bond or any suitable divalent group, such as an alkylene group, an arylene group, or a ring. An alkylene group, an alkenylene group, an alkynylene group, a heteroarylene group, a cycloalkenylene group, a heterocyclic alkylene group, a heterocyclic alkenylene group, and the like, and R' is R attached to the surface or any Suitable single A valent group such as an alkyl group, an aryl group, a cycloalkyl group, an alkene, an alkyne, a heteroaryl group, a cyclic olefin, a heterocyclic ring, a heterocyclic olefin, and the like.

"Anhydride capping surface" means that the -RC(=O)OC(=O)-R' group is attached to the surface of graphene oxide or graphite oxide, where R is a bond or any suitable divalent group, such as an alkylene group. a aryl group, an arylene group, a cycloalkylene group, an alkenylene group, an alkynylene group, a heteroarylene group, a cycloalkenylene group, a heterocyclic alkylene group, a heterocyclic alkenylene group, and the like, and R' is attached thereto. R of the surface or any suitable monovalent group such as an alkyl group, an aryl group, a cycloalkyl group, an alkene, an alkyne, a heteroaryl group, a cyclic olefin, a heterocyclic ring, a heterocyclic olefin, and the like, or R and R' Together, a cyclic anhydride attached to the surface is formed.

"Carbonate-terminated surface" refers to -R-OC (= O) O -R ' , or -R-OC (= O) O - group is attached to graphene oxide or graphite oxide surface, or a bond wherein R Any suitable divalent group such as an alkylene group, an arylene group, a cycloalkylene group, an alkenylene group, an alkynylene group, a heteroarylene group, a cycloalkenylene group, a heterocyclic alkylene group, a heterocyclic alkenylene group And a similar group, and R' is R attached to the surface or any suitable monovalent group such as alkyl, aryl, cycloalkyl, alkene, alkyne, heteroaryl, cycloalkene, heterocyclic, heterocycloalkenyl And a similar group, or R and R' together form a cyclic carbonate attached to the surface.

"Formaldehyde-terminated surface" means that the -RC(=O)H group is attached to the surface of graphene oxide or graphite oxide, where R is a bond or any suitable divalent group such as an alkylene group, an arylene group, or a ring. An alkylene group, an alkenylene group, an alkynylene group, a heteroarylene group, a cycloalkenylene group, a heterocyclic alkylene group, a heterocyclic alkenylene group, and the like.

"Ket capping surface" means that the -RC(=O)-R' group is attached to the surface of graphene oxide or graphite oxide, where R is a bond or any suitable divalent group such as an alkylene group or an arylene group. a cycloalkylene, alkenylene, alkynylene, heteroarylene, cycloalkenylene, heterocycloalkylene, heterocycloalkenylene and similar group, and R' is R attached to the surface or Any suitable monovalent group, such as an alkyl group, an aryl group, a cycloalkyl group, an alkene, an alkyne, a heteroaryl group, a cycloalkene, a heterocyclic ring, a heterocyclic olefin, and the like, or a combination of R and R' Cyclic ketone on the surface.

"epoxide end surface" means a group attached to the surface of graphene oxide or graphite oxide, wherein R is a bond or any suitable divalent group, such as an alkylene group, an arylene group, a cycloalkylene group, an alkenylene group, an alkynylene group, a heteroarylene group a cycloalkenylene group, a heterocycloalkylene group, a heterocyclic alkenylene group, and the like, and R' is R, H or any suitable monovalent group attached to the surface, such as an alkyl group, an aryl group, or a cycloalkyl group. , olefins, alkynes, heteroaryls, cyclic olefins, heterocyclic rings, heterocyclic olefins, and the like.

"Carboxyl-terminated surface" refers to a -RC (= O) -OH, or -RC (= O) O ^- group is attached to graphene oxide or graphite oxide surface, where R is a bond or a divalent group of any suitable, For example, an alkylene group, an arylene group, a cycloalkylene group, an alkenylene group, an alkynylene group, a heteroarylene group, a cycloalkenylene group, a heterocyclic alkylene group, a heterocyclic alkenylene group, and the like.

"Ester-terminated surface" means that the -RC(=O)-OR' group is attached to the surface of graphene oxide or graphite oxide, where R is a bond or any suitable divalent group such as an alkylene group or an arylene group. a cycloalkylene, alkenylene, alkynylene, heteroarylene, cycloalkenylene, heterocycloalkylene, heterocycloalkenylene and similar group, and R' is R attached to the surface or Any suitable monovalent group, such as an alkyl group, an aryl group, a cycloalkyl group, an alkene, an alkyne, a heteroaryl group, a cycloalkene, a heterocyclic ring, a heterocyclic olefin, and the like, or a combination of R and R' Cyclic ester on the surface.

"Peroxyacid capping surface" means -RC(=O)-OOH or -RC(=O)OO ^- groups attached to the surface of graphene oxide or graphite oxide, where R is a bond or any suitable divalent A group such as an alkylene group, an arylene group, a cycloalkylene group, an alkenylene group, an alkynylene group, a heteroarylene group, a cycloalkenylene group, a heterocyclic alkylene group, a heterocyclic alkenylene group, and the like.

"Peroxyacidate capping surface" means that the -RC(=O)-OOR' group is attached to the surface of graphene oxide or graphite oxide, where R is a bond or any suitable divalent group, such as an alkylene group, Arylene, cycloalkylene, alkenylene, alkynylene, heteroarylene, cycloalkenylene, heterocycloalkylene, heterocycloalkenylene and the like, and R' is attached to the surface R or any suitable monovalent group such as alkyl, aryl, cycloalkyl, alkene, alkyne, heteroaryl, cycloalkene, hetero Rings, heterocyclic olefins and similar groups, or R and R' together form a cyclic peroxyacid ester attached to the surface.

"Diketone capping surface" means that the -RC(=O)-C(=O)-R' group is attached to the surface of graphene oxide or graphite oxide, where R is a bond or any suitable divalent group, such as An alkylene group, an arylene group, a cycloalkylene group, an alkenylene group, an alkynylene group, a heteroarylene group, a cycloalkenylene group, a heterocyclic alkylene group, a heterocyclic alkenylene group, and the like, and R' is R, H or any suitable monovalent group attached to the surface, such as an alkyl group, an aryl group, a cycloalkyl group, an alkene, an alkyne, a heteroaryl group, a cyclic olefin, a heterocyclic ring, a heterocyclic olefin, and the like, or R and R' together form a cyclic diketone attached to the surface.

"Alcohol-terminated surface" means that the -R-OH group is attached to the surface of graphene oxide or graphite oxide, where R is a bond or any suitable divalent group such as an alkylene group, an arylene group or a cycloalkylene group. An alkenylene group, an alkynylene group, a heteroarylene group, a cycloalkenylene group, a heterocyclic alkylene group, a heterocyclic alkenylene group, and the like. "Hydroxy-terminated surface" means that the -OH group is attached to the surface of graphene oxide or graphite oxide.

"ether terminated surface" means a group attached to the surface of graphene oxide or graphite oxide, wherein R is a bond or any suitable divalent group, such as an alkylene group, an arylene group, a cycloalkylene group, an alkenylene group, an alkynylene group, a heteroarylene group a cycloalkenylene group, a heterocycloalkylene group, a heterocyclic alkenylene group, and the like, and R' is R attached to the surface or any suitable monovalent group such as an alkyl group, an aryl group, a cycloalkyl group, an olefin An alkyne, a heteroaryl, a cyclic olefin, a heterocyclic ring, a heterocyclic olefin, and the like, or R and R' together form a cyclic ether attached to the surface.

"Dioxetane capping surface" means a group attached to the surface of graphene oxide or graphite oxide, wherein R is a bond or any suitable divalent group, such as an alkylene group, an arylene group, a cycloalkylene group, an alkenylene group, an alkynylene group, a heteroarylene group a cycloalkenylene group, a heterocycloalkylene group, a heterocyclic alkenylene group, and the like, and R' is R, H or any suitable monovalent group attached to the surface, such as an alkyl group, an aryl group, or a cycloalkyl group. An olefin, an alkyne, a heteroaryl, a cyclic olefin, a heterocyclic ring, a heterocyclic olefin, and the like, or R and R' together form a ring, carrying dioxycyclopropane and attached to the surface.

"醌 end surface" means Pair of oxime groups or An orthoquinone group attached to the surface of graphene oxide or graphite oxide, wherein R is a bond or any suitable divalent group, such as an alkylene group, an arylene group, a cycloalkylene group, an alkenylene group, an alkynylene group, or a hetero An aryl group, a cycloalkenylene group, a heterocyclic alkylene group, a heterocyclic alkenylene group, and the like, and R' is R, H or any suitable monovalent group attached to the surface, such as an alkyl group, an aryl group, or a ring. An alkyl group, an alkene, an alkyne, a heteroaryl group, a cyclic olefin, a heterocyclic ring, a heterocyclic olefin, and the like, or R and R' together form a fused ring attached to the surface.

"Nitro-terminated surface" means that the -R-NO ₂ group is attached to the surface of graphene oxide or graphite oxide, where R is a bond or any suitable divalent group, such as an alkylene group, an arylene group, or a ring arylene group. Alkyl, alkenylene, alkynylene, heteroarylene, cycloalkenylene, heterocycloalkylene, heterocycloalkylene and the like.

"Nitroso-terminated surface" means that the -R-NO group is attached to the surface of graphene oxide or graphite oxide, where R is a bond or any suitable divalent group, such as an alkylene group, an arylene group, or a ring arylene group. Alkyl, alkenylene, alkynylene, heteroarylene, cycloalkenylene, heterocycloalkylene, heterocycloalkylene and the like.

"Iodine-terminated surface", "bromo-terminated surface", "fluorine-terminated surface" and "chlorine-terminated surface" refer to a -RX group attached to the surface of graphene oxide or graphite oxide, where R a bond or any suitable divalent group such as an alkylene group, an arylene group, a cycloalkylene group, an alkenylene group, an alkynylene group, a heteroarylene group, a cycloalkenylene group, a heterocyclic alkylene group, a heterocyclic ring Alkenylene and similar groups, and X is F, Cl, Br or I.

"Alkane" means a linear saturated hydrocarbon of 1 to 50 carbon atoms, or 3 to 50 carbon atoms Branched saturated hydrocarbon groups such as methane, ethane, propane, butane (including all isomeric forms), pentane (including all isomeric forms) and analogs.

"Cycloalkyl" or "cycloalkane" means a cyclic saturated monovalent hydrocarbon radical of three to ten carbon atoms in which one or two carbon atoms may be substituted by a pendant oxy group, such as cyclopropyl, cyclobutyl, Cyclopentyl or cyclohexyl and similar groups. In some embodiments, a cycloalkyl group is covalently bonded to a surface as described herein.

"Hydrocarbon" means a compound containing a carbon-carbon bond and a carbon-hydrogen bond. The carbon-carbon bond in the hydrocarbon can be a saturated C-C bond or a -C=C- bond or a -c≡c- bond or any combination thereof.

The "active C-H bond" refers to a C-H bond which is located near the group so that hydrogen can be easily taken off. For example, the active C-H bond of ethylbenzene is present at the benzylic position.

Carbon catalyst

The ability of various carbon-based materials to catalyze a very large number of potential chemical reactions has not been explored to date. To date, these efforts have relied on the use of relatively high surface areas inherent in carbon-based materials to enhance the activity of transition metal-based catalysts. For example, metal catalysts have been placed on graphene-based materials to take advantage of the high surface area of such materials and to enhance the activity of transition metal-based catalysts. Although non-carbon materials (such as metals, metal oxides, non-metals, and non-metal oxides) have been placed on carbon or derivatized carbon surfaces (such as graphene oxide materials) to form supported catalysts, the catalytic activity is attributed. It is a non-carbon material, and the carbon or derivatized carbon surface is only used to support the metal catalyst. Conversely, the carbon catalysts described herein are themselves catalytically active. When an additional catalytically active material is present (e.g., an optional solid acid catalyst), the carbon catalyst is still catalytically active, and the resulting material can be expressed as a catalyst mixture of a carbon catalyst and a solid acid catalyst.

The importance of the role of the catalyst morphology in hydrocarbon conversion is hereby recognized. The carbon catalysts (e.g., graphite oxide or graphene oxide) described herein contain accessible edges and/or corners that can immobilize reactive surface groups and/or provide a higher reactive species surface richness degree.

The carbon catalysts (e.g., graphene oxide and/or graphite oxide) described herein and processes involving the use of the carbon catalysts are industrially and commercially important chemicals for use in large quantities of synthesis that are otherwise difficult to produce or otherwise expensive to produce. . In addition, some useful chemical reactions involving organic materials do not have available catalysts and are therefore too slow or too expensive. In some embodiments, the carbon catalysts provided herein (eg, graphene oxide and/or graphite oxide) provide access to such previously thorny chemical reactions, such as hydrocarbon-hydrocarbon coupling, hydrocarbon dehydrogenation and/or displacement, and/or Or lysate. The broad-spectrum catalysts described herein are capable of catalyzing various chemical reactions using various initial products (starting materials) and providing non-toxic alternatives to other catalysts and/or reactions. The broad-spectrum catalysts provided herein and methods of using such catalysts overcome the absence of one or more existing catalysts and/or processes.

In some embodiments, the carbon catalysts described herein are catalysts based on graphene oxide and/or graphite oxide. In some such embodiments, the carbon catalyst is a graphene oxide and/or graphite oxide that is a surface modified graphene oxide or surface modified graphite oxide produced using surface modification as described herein.

In additional embodiments, the carbon catalyst is amorphous carbon (eg, carbon black, lamp black, activated charcoal, or the like). In one aspect, an amorphous carbon dehydrogenation catalyst is provided. In one embodiment, the amorphous carbon dehydrogenation catalyst has an initial oxygen content of at least 7%; in further embodiments, the amorphous dehydrogenation catalyst also has a defined pore diameter of from about 2 nm to about 50 nm, accounting for less than 50 % of the total pore volume.

In another embodiment, the amorphous carbon dehydrogenation catalyst has an initial oxygen content of at least 10%. In another embodiment, the amorphous carbon dehydrogenation catalyst has an initial oxygen content of at least 15%. In another embodiment, the amorphous carbon dehydrogenation catalyst has an initial oxygen content of at least 20%. In another embodiment, the amorphous carbon dehydrogenation catalyst has an initial oxygen content of at least 25%. In another embodiment, the amorphous carbon dehydrogenation catalyst has an initial oxygen content of at least 30%. In a further specific example of any of the above mentioned amorphous carbon dehydrogenation catalysts, the material A further feature is that the pore diameter is defined from about 2 nm to about 50 nm, accounting for less than 50% of the total pore volume.

In another embodiment, the amorphous carbon dehydrogenation catalyst has an initial oxygen content of from about 7% to about 50%. In another embodiment, the amorphous carbon dehydrogenation catalyst has an initial from about 7% to about 20%. Oxygen content. In another embodiment, the amorphous carbon dehydrogenation catalyst has an initial oxygen content of from about 10% to about 30%. In a further embodiment of any of the above mentioned amorphous carbon dehydrogenation catalysts, the material is further characterized by defining a pore diameter from about 2 nm to about 50 nm, accounting for less than 50% of the total pore volume.

In another embodiment, the amorphous carbon dehydrogenation catalyst has a particle size of from about 12 to about 1250 mesh (or from about 10 microns to about 1700 microns). In another embodiment, the amorphous carbon dehydrogenation catalyst has a particle size of from about 100 to about 400 mesh (or from about 37 microns to about 150 microns).

In another embodiment, the amorphous carbon dehydrogenation catalyst does not exhibit a defined X-ray diffraction pattern. In another embodiment, the amorphous carbon dehydrogenation catalyst is substantially non-porous. In another embodiment, the amorphous carbon dehydrogenation catalyst is substantially non-porous and does not exhibit a defined X-ray diffraction pattern.

In some embodiments, the amorphous carbon-carbon catalyst is substantially free of transition metals. In another embodiment, the amorphous carbon catalyst (e.g., amorphous carbon dehydrogenation catalyst) further comprises another layer of catalytically active carbonaceous material that is chemically absorbed or physically absorbed onto the amorphous carbon material.

In another aspect, the oxidized amorphous carbon dehydrogenation catalyst is formed by oxidizing a first amorphous carbon catalyst having a degree of oxidation of from about 2% to about 5% by contacting the first amorphous carbon catalyst with an oxidizing agent. From about 7% to about 50% oxidation. In some embodiments, the oxidizing agent is selected from one or more of the group consisting of nitric acid, potassium peroxymonosulfate complex salt, O ₂ , H ₂ O ₂ , KMnO ₄ , NaClO ₃ , KClO _{4 ,} and plasma-excited oxygen species.

In another aspect, it is a carbon supported carbon catalyst. In a specific example, the carbon branch The supported carbon catalyst has a carbon support region and a catalytic region. In some embodiments, the carbon support region of the carbon supported carbon catalyst comprises non-sized amorphous carbon, charcoal or coke. In some embodiments, the ratio of the carbon support zone to the catalytic zone is less than 10:1, less than 5:1, less than 2:1, about 1:1, greater than 1:2, greater than 1:5, or greater than 10:1.

In another embodiment, the carbon supported carbon catalyst has a preferential adsorption affinity of at least 10:1 for a predetermined reactant compared to a predetermined byproduct. In another embodiment, the carbon supported carbon catalyst has a preferential adsorption affinity of at least 15:1 for a predetermined reactant compared to a predetermined byproduct. In another embodiment, the carbon supported carbon catalyst has a preferential adsorption affinity of at least 20:1 for a predetermined reactant compared to a predetermined by-product.

In another embodiment, the carbon supported carbon catalyst has a preferential adsorption affinity of at least 10:1 for a predetermined alkane or naphthenic reactant compared to hydrogen. In another embodiment, the carbon supported carbon catalyst has a preferential adsorption affinity of at least 15:1 for a predetermined alkane or naphthenic reactant compared to hydrogen. In another embodiment, the carbon supported carbon catalyst has a preferential adsorption affinity of at least 20:1 for a predetermined alkane or naphthenic reactant compared to hydrogen. In another embodiment, the carbon supported carbon catalyst has at least about 25% carbon and at least about 5% oxygen as measured by X-ray photoelectron spectroscopy (XPS).

In another embodiment, the catalytic region of the carbon supported carbon catalyst can optionally comprise surface modified graphene oxide, graphite oxide, mesoporous carbon, carbon nanotubes or amorphous activated charcoal or a combination thereof. In another embodiment, the catalytic zone of the carbon supported carbon catalyst can optionally comprise surface modified graphene oxide, graphite oxide or amorphous activated charcoal or a combination thereof.

In another embodiment, the catalytic zone of the carbon supported carbon catalyst is a dehydrogenation zone.

In another embodiment, the catalytic region of the carbon supported carbon catalyst has a peroxide end surface, a hydroxyl end surface, a carboxyl end surface, a ketone end surface, an epoxide end surface, and a dioxane ring. Propane capped surface or a combination thereof. In some embodiments, the catalytic region of the carbon supported carbon catalyst has a peroxide terminated surface. In some embodiments, the catalytic region of the carbon supported carbon catalyst has a hydroxyl terminated surface. In some specific examples, the The catalytic zone of the carbon supported carbon catalyst has a carboxyl terminated surface. In some embodiments, the catalytic zone of the carbon supported carbon catalyst has a ketone capping surface. In some embodiments, the catalytic region of the carbon supported carbon catalyst has an epoxide capping surface. In some embodiments, the catalytic region of the carbon supported carbon catalyst has a dioxopane end capping surface.

In another embodiment, the catalytic region of the carbon supported carbon catalyst has one or more Fourier Transform Infrared at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^{-1 ,} and 1140 cm ^-1 . (FT-IR)) Features. In another embodiment, the catalytic region of the carbon supported carbon catalyst has a spectrum exhibiting a C(1s) peak at about 286 eV and/or a photoelectron spectroscopy (XPS) exhibiting an oxygen (1s) peak at about 530 eV. . In another embodiment, the catalytic region of the carbon supported carbon catalyst has a spectrum of Raman spectroscopy exhibiting characteristics at about 1350 and/or 1575 cm ^-1 .

Method for preparing catalytically active carbon catalyst

In one aspect, a carbon catalyst suitable for use in converting a hydrocarbon such as propane to propylene as described herein is an oxidized graphite, such as a catalyst based on graphene oxide or graphite oxide. Graphene oxide or graphite oxide used as a catalyst in the present disclosure is produced by a known method. For example, modified graphene oxide or graphite oxide is formed by oxidizing graphite in concentrated sulfuric acid using KMnO ₄ and NaNO ₃ as described in WS Hummer Jr. REOffeman, J. Am. Chem. Soc. 80 :1339 (1958) and A. Lerf et al. J. PhysChem. B 102 : 4477-4482 (1998), the relevant portions of each of which are incorporated herein by reference. Graphene oxide or graphite oxide can also be produced by oxidizing graphite in H ₂ SO ₄ and fuming HNO ₃ using NaClO ₃ as described in the following literature: L. Staudenmaier, Ber . Dtsch. Chem . Ges. 31 : 1481 -1487 (1898); L. Stuadenmaier, Ber . Dtsch. Chem . Ges. 32 : 1394-1399 (1899); T. Nakajima et al. Carbon 44 : 537-538 (2006), the relevant parts of which are The reference is incorporated herein. Graphene oxide or graphite oxide can also be prepared via a Brodie reaction.

When a large amount of strong oxidizing agents and acids (such as KMnO ₄ and H ₂ SO ₄ ) are used, which are not suitable for large-scale commercialization, milder and ready-to-use oxidizing agents such as hydrogen peroxide and Oxone (peroxymonosulfuric acid) can be used. Hydrogen potassium complex salt; KHSO ₅ ) instead of KMnO ₄ is covered herein. Optionally, the carbon material can be oxidized via thermal cracking, a process that oxidizes the carbon surface using ambient molecular oxygen (O ₂ ).

In some embodiments, a method for forming a catalytically active graphene oxide or a catalytically active graphite oxide from a nascent catalyst comprises providing the nascent catalyst to a reaction chamber (or "reaction vessel"), the nascent The catalyst comprises graphene or graphite on a solid support. The nascent catalyst is then heated in the reaction chamber to elevated temperature. The nascent catalyst is then contacted with a chemical oxidant.

In some embodiments, the chemical oxidizing agent comprises at least one or more selected from the group consisting of potassium permanganate, hydrogen peroxide, organic peroxides, peroxyacids, cerium-containing species (eg, tetrapropylammonium perruthenate or other Perchlorate), lead-containing species (such as lead tetraacetate), chromium-containing species (such as chromium oxide or chromic acid), iodine-containing species (such as periodate), sulfur-containing oxidants (such as potassium peroxymonosulfate) Salt or sulfur dioxide), molecular oxygen, ozone, chlorine-containing species (such as chlorate or perchlorate or hypochlorite), sodium perborate, nitrogenous species (such as nitrous oxide or dinitrogen tetroxide), Silver-containing species (such as silver oxide), cerium-containing species (such as osmium tetroxide), 2,2'-dithiodisulfide, cerium-containing species (such as ammonium cerium nitrate), benzoquinone, Des Martin oxidant (Dess Martin periodinane) ), chloroperoxypanoic acid, molybdenum-containing species (such as molybdenum oxide), N-oxides (such as pyridinium N-oxide), vanadium-containing species (such as vanadium oxide), (2,2,6,6-tetramethyl) A material consisting of a group consisting of piperidin-1-yl)oxide (TEMPO) or an iron-containing species such as potassium ferricyanide.

In other embodiments, the chemical oxidant is a plasma-excited species containing an oxidizing species. In one example, the chemical oxidant comprises a plasma excited species of O ₂ , H ₂ O ₂ , NO, NO ₂ or other chemical oxidant. In this example, the nascent catalyst in the reaction chamber is in continuous contact with the plasma-exciting species of the oxidizing species, such as at least about 0.01 seconds, or 0.1 seconds, or 1 second, or 10 seconds, or 30 seconds, or 1 minute, or 5 minutes, or 10 minutes, or 15 minutes, or 20 minutes, or 30 minutes, or 1 hour, or 2 hours, or 3 hours, or 4 hours, or 5 hours, or 6 hours, or 12 hours , or 1 day, or 2 days, or 3 days, or 4 days, or 5 days, or 6 days, or 1 week, or 2 weeks, or 3 weeks, or 1 month, or 2 months, or 3 Month, or 4 months, or 5 months, or a predetermined period of 6 months. Alternatively, the nascent catalyst in the reaction chamber is in pulsating contact with the plasma-exciting species containing the oxidizing species, for example at least about 0.1 second, or 1 second, or 10 seconds, or 30 seconds, or 1 minute, or 10 minutes, or 30 minutes, or 1 hour, or 2 hours, or 3 hours, or 4 hours, or 5 hours, or 6 hours, or 12 hours, or 1 day, or 2 days, or 3 days, or 4 days, or 5 days , or 6 days, or 1 week, or 2 weeks, or 3 weeks, or 1 month, or 2 months, or 3 months, or 4 months, or 5 months, or 6 months of pulsation. In some cases, the nascent catalyst is exposed to a chemical oxidant for a time between about 0.1 seconds and 100 days.

In some cases, the nascent catalyst is heated during exposure to a chemical oxidant. In one example, the nascent catalyst is heated at a temperature between about 20 ° C and 3000 ° C, or 20 ° C and 2000 ° C, or between about 100 ° C and 2000 ° C.

Alternatively, a method for forming a catalytically active graphene oxide or a catalytically active graphite oxide catalyst from a nascent catalyst comprises providing a nascent catalyst comprising graphene or graphite into a reaction chamber. The reaction chamber has a holder or receptacle to support one or more nascent catalysts. The nascent catalyst is then contacted with one or more acids. In some examples, the one or more acids include sulfuric acid. In some examples, the nascent catalyst is previously treated with potassium persulfate prior to contacting the nascent catalyst with one or more acids. The nascent catalyst is then contacted with a chemical oxidant. The nascent catalyst is then contacted with hydrogen peroxide.

As a further alternative, the method for forming a catalytically active graphene oxide or catalytically active graphite oxide catalyst from a nascent catalyst comprises providing a nascent catalyst comprising graphene or graphite into a reaction chamber. The nascent catalyst is then contacted with one or more acids. In some examples, before the nascent catalyst is contacted with one or more acids, The nascent catalyst was previously treated with potassium persulfate. In some examples, the one or more acids include sulfuric acid and nitric acid. The nascent catalyst is then contacted with sodium chlorate, potassium chlorate and/or potassium perchlorate.

In some embodiments, a method for forming a catalytically active carbon catalyst comprises providing a carbonaceous material in a reaction chamber and causing a carbonaceous material and an oxidizing chemical in the reaction chamber (also referred to herein as " The chemical oxidant") is contacted for a predetermined period of time until the carbon to oxygen ratio of the carbonaceous material is less than or equal to about 1,000,000 to 1. In some examples, the ratio is determined via elemental analysis, such as XPS. In some embodiments, the time sufficient to achieve the carbon to oxygen ratio is at least about 0.1 seconds, or 1 second, or 10 seconds, or 30 seconds, or 1 minute, or 10 minutes, or 30 minutes, or 1 hour, or 2 hours, or 3 hours, or 4 hours, or 5 hours, or 6 hours, or 12 hours, or 1 day, or 2 days, or 3 days, or 4 days, or 5 days, or 6 days, or 1 week , or 2 weeks, or 3 weeks, or 1 month, or 2 months, or 3 months, or 4 months, or 5 months, or 6 months. In some examples, the carbonaceous material is contacted with the chemical oxidant until the carbon to oxygen ratio is less than or equal to about 500,000 to 1, or 100,000 to 1, or 50,000 to 1, or 10,000, as determined by elemental analysis. More than 1, or 5,000 to 1, or 1,000 to 1, or 500 to 1, or 100 to 1, or 50 to 1, or 10 to 1, or 5 to 1, or 1 to 1.

As an alternative, a method for forming oxidized and catalytically active graphite or oxidizing and catalytically active graphene comprises providing graphite or graphene in a reaction chamber and contacting the graphite or graphene with an oxidizing chemical Until the infrared spectroscopy spectrum of the graphite or graphene exhibits one or more FT-IR characteristics at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 . In these specific examples, the catalytically active carbon catalyst having one or more FT-IR characteristics at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 comprises surface-modified oxidation Graphene or graphite oxide.

Regeneration of used catalyst

In some embodiments, a method for regenerating a spent catalyst, such as a catalytically active carbon catalyst (eg, graphene oxide and/or graphite) as described herein, includes providing the used in a reaction chamber or vessel. The catalyst and the used catalyst are contacted with a chemical oxidant. In some examples, the chemical oxidant comprises one or more materials selected from the group above. In other examples, the chemical oxidant is a plasma-excited species containing an oxidizing species. In one example, the chemical oxidant comprises a plasma excited species of O ₂ , H ₂ O ₂ , NO, NO ₂ or other chemical oxidant. In some embodiments, the spent catalyst is in continuous or pulsating contact with the chemical oxidant, as described above. Contact of the spent catalyst with the chemical oxidant produces a carbon catalyst having a catalytically active material. In one example, a spent catalyst coated with graphene or graphite (or other carbonaceous but oxygen deficient material) can form a layer of catalytically active graphene oxide or graphite oxide.

Other methods of preparing graphene or graphite oxide having catalytically active oxidation are also encompassed within the scope of the disclosure, as described in PCT International Application No. PCT/US2011/38327 (WO 2011/150325), the disclosure of which is incorporated herein. Used as a reference. Various variations of catalytically active graphene oxide or graphite oxide are also encompassed within the scope of the present disclosure, including variations in island shape, coverage and/or adsorption sites, such as the co-pending PCT International Application PCT/US2011/38334 (WO 2011/150329), the disclosure of which is incorporated herein by reference.

The advantage of catalytically active graphene oxide or graphite oxide to catalyze the conversion of a hydrocarbon as described herein (e.g., conversion of propane to propylene) is that the carbon catalyst is heterogeneous, i.e., it does not dissolve in the reaction mixture. Many starting materials, such as alcohols, aldehydes, alkynes, methylketones, olefins, methylbenzenes, thiols, and disubstituted methylenes, and their reaction products, are soluble in many A variety of different organic solvents. In a chemical reaction comprising such dissolved starting materials, the graphene oxide or graphite oxide remains as a suspended solid throughout the chemical reaction. In some of the above methods, the graphene oxide or graphite oxide can be removed from the reaction product using simple mechanical means such as filtration, centrifugation, deposition or other suitable mechanical separation techniques, excluding more complex techniques such as chromatography. Method or distillation) to remove reminders The need for chemicals.

After the catalytic reaction, the graphene oxide or graphite oxide is in a different chemical form or in the same chemical form. For example, in one embodiment, the hydrocarbon conversion described herein (eg, conversion of propane to propylene) causes slow reduction or oxygen removal of the graphene oxide or graphite oxide and loss of functional groups. The altered graphene oxide or graphite oxide left after the catalysis is put into other uses or regenerated. For example, after the catalytic reaction, the graphene oxide or graphite oxide is in a reduced form. This material is quite similar to graphene or graphite and can be used simply for graphene or graphite applications. For example, reduced graphene oxide can be used in energy storage devices or field effect transistors. Alternatively, the reduced graphene oxide or graphite oxide is reoxidized to be regenerated into the graphene oxide or graphite oxide catalyst. In a further embodiment, the graphene oxide or graphite oxide used in the reaction is regenerated in situ after the reaction and is in the same form as the start of the reaction. The reoxidation process is the same as that used to produce the graphene oxide or graphite oxide catalyst, such as Hummers, Staudenmaier or Brodie. Thus, the carbon catalysts described herein provide an economical alternative to metal based catalysts.

In some embodiments of the invention, carbon catalysts configured for use in cracking, displacement, dehydrogenation, and/or hydrocarbon coupling reactions are described. In some embodiments of the invention, carbon catalysts configured for use in the activation of C-H bonds in a hydrocarbon reaction are described. Such carbon catalysts can achieve reaction rates that meet and even exceed the reaction rates of transition metal based catalysts, but reduce, if not excluded, contamination problems associated with transition metal based catalyst use.

In one embodiment, the carbon catalyst of any of the converted catalysts described herein is a catalytically active graphene oxide or graphite oxide comprising one or more oxygen-containing functionalities. An exemplary graphene oxide or graphite oxide catalyst is shown in Figure 1. In a specific embodiment, the graphene oxide or graphite oxide-based carbon catalyst (eg, graphene oxide and/or graphite oxide) described herein contains surface groups, including hydroxyl groups, alcohols, and epoxides. One or more of a class, a ketone, an aldehyde or a carboxylic acid. In some cases, at least some of the oxygen-containing functional groups are used to oxidize organic species, such as alkanes or cycloalkanes. In other examples, oxygen is used as the terminal oxidant. Various specific examples of the invention describe carbon oxide catalysts of graphene oxide having various compositions, concentrations and island shapes, coverage and absorption sites.

The carbon-containing catalysts provided herein include unsupported catalytically active graphene oxide or catalytically active graphite oxide, and graphene oxide or graphite oxide on a solid support, such as a carbon-containing solid support or a metal-containing Solid support (for example, TiO ₂ , Al ₂ O ₃ ). In an alternative embodiment, the solid support is a polymer and the catalytically active graphite oxide or graphene oxide is dispersed in the polymer. In some embodiments, a catalyst having catalytically active graphene oxide and/or catalytically active graphite oxide on a solid support is provided. Examples of such solid supports include carbon nitride, boron nitride, boron nitride carbon, and the like. In other embodiments, a catalyst having a catalytically active carbon and oxygen containing material and a cocatalyst (e.g., carbon nitride, boron nitride, boron nitride carbon, and the like) is provided.

In further embodiments, the carbon-containing catalysts provided herein include unsupported catalytically active graphene or catalytically active graphite oxide, and graphene oxide or graphite oxide in a solid support, such as zeolites, polymers, and/or Metal-containing solid support (for example, TiO ₂ , Al ₂ O ₃ ). In some embodiments, a catalyst having catalytically active graphene oxide and/or catalytically active graphite oxide in a polymer support is provided. In a further embodiment, catalytically active graphene oxide and/or catalytic activity is provided in an amorphous solid, such as activated charcoal, coal fly ash, bio ash or pumice. A catalyst for graphite oxide. In other embodiments, a catalyst having a catalytically active carbon and oxygen containing material and a cocatalyst (e.g., carbon nitride, boron nitride, boron nitride carbon, and the like) is provided.

Metal content

In some embodiments, the heterogeneous catalytically active graphene oxide or graphite oxide catalyst (or other carbon and oxygen containing catalyst or carbon catalyst) is substantially free of metal, particularly It is a transition metal. In some embodiments, a heterogeneous catalytically active surface modified graphene oxide or graphite oxide catalyst (or other carbon and oxygen containing catalyst or carbon catalyst) suitable for use in the reactions described herein comprises less than the weight of the catalyst. 5% transition metal. In some embodiments, a heterogeneous catalytically active surface modified graphene oxide or graphite oxide catalyst (or other carbon and oxygen containing catalyst or carbon catalyst) suitable for use in the reactions described herein comprises less than the weight of the catalyst. 2% transition metal. In some embodiments, a heterogeneous catalytically active surface modified graphene oxide or graphite oxide catalyst (or other carbon and oxygen containing catalyst or carbon catalyst) suitable for use in the reactions described herein comprises less than the weight of the catalyst. 1% transition metal. In some embodiments, a heterogeneous catalytically active surface modified graphene oxide or graphite oxide catalyst (or other carbon and oxygen containing catalyst or carbon catalyst) suitable for use in the reactions described herein comprises less than the weight of the catalyst. 0.5% transition metal. In some embodiments, a heterogeneous catalytically active surface modified graphene oxide or graphite oxide catalyst (or other carbon and oxygen containing catalyst or carbon catalyst) suitable for use in the reactions described herein comprises less than the weight of the catalyst. 0.1% transition metal. In some embodiments, a heterogeneous catalytically active surface modified graphene oxide or graphite oxide catalyst (or other carbon and oxygen containing catalyst or carbon catalyst) suitable for use in the reactions described herein comprises less than the weight of the catalyst. 0.01% transition metal. In some embodiments, a heterogeneous catalytically active surface modified graphene oxide or graphite oxide catalyst (or other carbon and oxygen containing catalyst or carbon catalyst) suitable for use in the reactions described herein comprises less than the weight of the catalyst. 0.001% transition metal.

In some examples, the heterogeneous catalyst has a relatively low concentration of metal (eg, transition metal) selected from the group consisting of W, Fe, Ta, Ni, Au, Ag, Rh, Ru, Pd, Pt, Ir, Co. , a group consisting of Mn, Os, Zr, Zn, Mo, Re, Cu, Cr, V, Ti, and Nb. In one embodiment, the heterogeneous catalyst has a transition metal concentration of less than or equal to about 50 ppm, about 20 ppm, as measured by an atomic absorption spectrometer or mass spectrometer (eg, inductively coupled plasma mass spectrometer or "ICP-MS"). 10 ppm, about 5 ppm, about 1 Ppm ("parts per million"), or 0.5 ppm, or 0.1 ppm, or 0.06 ppm, or 0.01 ppm, or 0.001 ppm, or 0.0001 ppm, or 0.00001 ppm. In another embodiment, the heterogeneous catalyst has a metal content (% by mole) of less than about 0.0001%, or less than about 0.000001%, or less than about 0.000001%.

In some instances, heterogeneous catalytically active graphene oxide or graphite oxide catalysts (or other carbon and oxygen containing catalysts) have a relatively low manganese content. In one example, the molecule has a manganese content of less than about 1 ppm, or 0.5 ppm, or 0.1 ppm, or 0.06 ppm, as measured by an atomic absorption spectrometer or mass spectrometer (eg, inductively coupled plasma mass spectrometer or "ICP-MS"). , or 0.01 ppm, or 0.001 ppm, or 0.0001 ppm, or 0.00001 ppm.

In some cases, the catalysts provided herein have a certain degree of transition metal content. As an example, a carbon catalyst suitable for use in any of the reactions described herein includes graphene oxide or graphite oxide and has a transition metal content of between about 1 ppm and about 50% by weight, based on the weight of the catalyst. In some examples, the carbon catalyst has a transition metal content of between about 1 ppm and about 25% by weight, based on the weight of the catalyst, or between about 1 ppm and about 10% by weight of the catalyst, or by weight of the catalyst. Between about 1 ppm and about 5%, or between about 1 ppm and about 1% by weight of the catalyst, or between about 10 ppm and about 50% by weight of the catalyst, or as a catalyst The weight is between about 100 ppm and about 50%, or between about 1000 ppm and about 50% by weight of the catalyst, or between about 10 ppm and about 25% by weight of the catalyst, or The catalyst weight is between about 100 ppm and about 25%, or between about 1000 ppm and about 25% by weight of the catalyst, or between about 10 ppm and about 10% by weight of the catalyst, or Between about 100 ppm and about 10% by weight of the catalyst, or between about 1000 ppm and about 10% by weight of the catalyst, or between about 10 ppm and about 5% by weight of the catalyst, Or between about 100 ppm and about 5% by weight of the catalyst, or between about 1000 ppm and about 5% by weight of the catalyst, or by weight of the catalyst To about 10 ppm, and Between about 1%, or between about 100 ppm and about 1% by weight of the catalyst, or between about 1000 ppm and about 1% by weight of the catalyst.

In some cases, the transition metal content of the carbon catalyst is via an atomic absorption spectrometer (AAS) or other elemental analysis technique, such as an X-ray photoelectron spectroscopy (XPS) or a mass spectrometer (eg, an inductively coupled plasma mass spectrometer or "ICP- MS") to determine.

In some embodiments, the carbon catalyst has a low concentration of transition metal selected from the group consisting of W, Fe, Ta, Ni, Au, Ag, Rh, Ru, Pd, Pt, Ir, Co, Mn, Os, Zr, In the group consisting of Zn, Mo, Re, Cu, Cr, V, Ti, and Nb. In some embodiments, the carbon catalyst has a metal content (% by mole) of more than about 0.0001% and up to about 50 mole % of the total weight of the catalyst, or more than about 0.001% and up to about 50 mole % of the total weight of the catalyst. More than about 0.01% and up to about 50 mole % of total catalyst weight, more than about 0.1% and up to about 50 mole % of total catalyst weight, more than about 0.0001% and up to about 25 mole % of total catalyst By weight, or more than about 0.001% and up to about 25 mole % of total catalyst weight, more than about 0.01% and up to about 25 mole % of total catalyst weight, more than about 0.1% and up to about 25 mole % Total catalyst weight, more than about 0.0001% and up to about 10 mole % of total catalyst weight, or more than about 0.001% and up to about 10 mole % of total catalyst weight, more than about 0.01% and up to about 10 moles % catalyst total weight, more than about 0.1% and up to about 10 mole % of total catalyst weight, more than about 0.0001% and up to about 5 mole % of total catalyst weight, or more than about 0.001% and up to about 5 Mole% of total catalyst weight, more than about 0.01% and up to about 5 mole % of total catalyst weight, more than about 0.1% and up to about 5 mole % Total catalyst weight, more than about 0.0001% and up to about 1 mole percent of total catalyst weight, or more than about 0.001% and up to about 1 mole percent total catalyst weight, more than about 0.01% and up to about 1 mole % total catalyst weight, more than about 0.1% and up to about 1 mole % of total catalyst weight.

surface

In some specific examples, having catalytically active graphene oxide or graphite oxide The non-transition metal catalyst has a surface configured to contact a reactant such as a hydrocarbon for dehydrogenation, displacement, cracking or coupling. In some examples, the catalyst has a surface that is terminated by one or more hydrogen peroxide, hydroxyl (OH), epoxide, ketone, aldehyde or carboxylic acid groups. In some embodiments, a catalytically active carbon catalyst (eg, graphene oxide or graphite oxide) comprises an electron-rich surface group to coordinate the redox process. In some embodiments, the catalytically active carbon catalyst (eg, graphene oxide or graphite oxide) comprises a Lewis basic site that can extract hydrogen from the CH bond of a hydrocarbon such as propane. To produce a dehydrogenation product (such as propylene).

In one embodiment, the catalyst has a surface comprising one or more species (or "surface groups") selected from the group consisting of hydroxyl, alkyl, aryl, alkenyl, alkynyl, epoxide, Peroxide, peroxy acid, aldehyde, keto, ether, carboxylic or carboxylate, peroxide or hydroperoxide, lactone, thiolactone, decylamine, sulfur Endoamine, mercapto, anhydride, ester, carbonate, acetal, hemiacetal, ketal, hemi-ketal, amine, hydroxylamine, amine acetal, semi-amine acetal, Carbamate groups, isocyanate groups, isothiocyanate groups, cyanamides, hydrazines, hydrazines, carbodiimides, hydrazines, oxime ethers, N-heterocycles, N-oxides, hydroxylamines, hydrazines, Amidamide, thiourea, urea, isourea, thiourea, isothiourea, enamine, enol ether, aliphatic, aromatic, phenolic, mercaptan, thioether, thioester, disulfide Ester, disulfide, hydrazine, hydrazine, sultone, sulfinic acid, sulfenamide, sulfenyl ester, sulfonic acid, sulfite group, sulfate group, sulfonate group, sulfonamide, sulfonium sulfonate Base halide, thiocyanate group Mercaptan, thioaldehyde, S-heterocyclic ring, fluorenyl group, trimethylsulfonyl group, phosphine, phosphate group, guanidinium phosphate, thiophosphate group, thiophosphoric acid amide, phosphonate group, hypophosphite group ( Phosphine, phosphite, phosphate, phosphonic acid diester, phosphine oxide, amine, imine, decylamine, aliphatic decylamine, aromatic decylamine, halogen, chloro, iodine, fluoro, bromo , mercapto halide, mercapto fluoride, mercapto chloride, mercapto bromide, mercapto iodide, mercapto cyanide, hydrazine, ketene, α-β unsaturated ester, α-β unsaturated Ketone, α-β unsaturated aldehyde, anhydride, azide, diazo, diazotide, nitrate group, Nitrate, nitroso, nitrile, nitrite, orthoester, orthocarbonate, O-heterocycle, borane, boric acid, borate, hydrazine, dioxopane, diketone and the like The group formed. In one example, the surface groups are disposed on the surface of each of the reactive sites of the catalyst.

Carbon content

In some embodiments, the catalytically active graphene oxide or graphite oxide catalyst (or other carbon and oxygen containing catalyst) has at least about 25%, or 30%, or 35%, or 40%, or 45%, or 50. %, or 55%, or 60%, or 65%, or 70%, or 75%, or 80%, or 85%, or 90%, or 95%, or 99%, or 99.99% carbon content (Mo ear%). The remainder of the catalyst is oxygen, or one or more of the other surface groups described herein, or one or more selected from the group consisting of hydrogen, oxygen, boron, nitrogen, sulfur, phosphorus, fluorine, chlorine, bromine, and iodine. The elements in the group that is composed. In some embodiments, the graphene oxide or graphite oxide has at least about 0.01%, or 1%, or 5%, or 15%, or 20%, or 25%, or 30%, or 35%, or 40%, Or 45%, or 50% oxygen content. In some embodiments, the surface modified graphene oxide or graphite oxide catalyst (MG) has a carbon content of at least about 15%, 20%, 25%, 30%, 35%, 40%, 45%, or 50% and at least An oxygen content of about 0.001%, 0.01%, 0.1% or 1%. For example, the graphene oxide or graphite oxide catalyst described herein has a carbon content of at least about 25% and an oxygen content of at least about 0.01%. In another example, the graphene oxide or graphite oxide catalyst described herein has a carbon content of at least about 25% and an oxygen content of at least about 1%. In another example, the graphene oxide or graphite oxide catalyst described herein has a carbon content of at least about 50% and an oxygen content of at least about 10%. The measurement of oxygen content is carried out with the aid of various surface or volume analysis spectroscopy techniques. As an example, the oxygen content is measured by X-ray photoelectron spectroscopy (XPS) or mass spectrometry (eg, inductively coupled plasma mass spectrometry or "ICP-MS").

In some embodiments, the carbon catalyst has at least about 0.1:1, or 0.5:1, or 1:1, or 1.5:1, or 2:1, or 2.5:1, or 3:1, or 3.5:1, Or 4:1, or 4.5:1, or 5:1, Or 5.5:1, or 6:1, or 6.5:1, or 7:1, or 7.5:1, or 8:1, or 8.5:1, or 9:1, or 9.5:1, or 10:1, Or a total carbon to oxygen ratio of 100:1, or 1000:1, or 10,000:1, or 100,000:1, or 1,000,000:1. In some examples, the carbon catalyst has at least about 0.1:1, or 0.5:1, or 1:1, or 1.5:1, or 2:1, or 2.5:1, or 3:1, or 3.5:1, or 4:1, or 4.5:1, or 5:1, or 5.5:1, or 6:1, or 6.5:1, or 7:1, or 7.5:1, or 8:1, or 8.5:1, or 9:1, or 9.5:1, or 10:1, or 100:1, or 1000:1, or 10,000:1, or 100,000:1, or 1,000,000:1 surface carbon to oxygen ratio.

pH

In some instances, a heterogeneous catalytically active carbon catalyst (eg, graphene oxide or graphite oxide catalyst or other carbon and oxygen containing catalyst) provides a solution between about 0.1 and about 14 when dispersed in a solution. pH. In some instances, a heterogeneous catalytically active carbon catalyst (eg, graphene oxide or graphite oxide catalyst or other carbon and oxygen containing catalyst) provides an acidic reaction solution pH when dispersed in a solution (eg, between about 0.1) To a pH between about 6.9). In some instances, a heterogeneous catalytically active carbon catalyst (eg, graphene oxide or graphite oxide catalyst or other carbon and oxygen containing catalyst) provides a basic reaction solution pH when dispersed in a solution (eg, pH is between Between about 7.1 and about 14). In some instances, a heterogeneous catalytically active carbon catalyst (eg, graphene oxide or graphite oxide catalyst or other carbon and oxygen containing catalyst) provides a neutral reaction solution pH when dispersed in a solution (eg, a pH of about 7) ).

As an example, in one embodiment, "acidic graphene oxide or graphite oxide" having a solution pH of 1-3 is provided relative to the pH of the solution of 4-6, by removing certain water-containing washes in the preparation of the material. Optional steps to prepare. Generally, after the synthesis of the graphene oxide or graphite oxide catalyst in an acid, the graphene oxide or the graphite oxide is washed with a large amount of water to remove the acid. When the number of washing steps is reduced, a graphene oxide or graphite oxide catalyst having a large amount of external acid absorbed on the surface thereof may be formed, and the pH of the solution is lower than the pH at which the catalyst is prepared by washing the material with water.

In another embodiment, graphene oxide or graphite oxide is alkalized by exposure to a base. The alkaline graphene oxide or graphite oxide catalyst is via a dispersion of graphene oxide or graphite oxide in water with a non-nucleophilic base such as potassium carbonate or sodium hydrogencarbonate or an organic base such as pyridinium or Triethylamine) was stirred together and prepared by separating the obtained product by filtration. These carbon catalysts exhibit a significantly higher pH when dispersed in water (e.g., pH = about 8).

Accordingly, depending on the choice of substrate (e.g., whether the starting material is sensitive to acid or to base), a suitable carbon catalyst is prepared which provides an acidic or basic pH upon dispersion in solution.

Stoichiometry and catalyst dosage

In some embodiments, for the reaction (eg, dehydrogenation, cracking, displacement, and/or coupling) of any of the catalytically active carbon catalysts (eg, graphene oxide or graphite oxide) described herein, graphene oxide or The amount of graphite oxide used is any value between 0.01% by weight and 1000% by weight. As used herein, % by weight (wt%) refers to the weight of the catalyst compared to the weight of one or more reactants. In a specific embodiment, the graphene oxide or graphite oxide catalyst may constitute at least 0.01% by weight, between 0.01% and 5% by weight, between 5% and 50% by weight, and between 50% by weight and Between 200% by weight, between 200% and 400% by weight, between 400% and 1000% by weight or at most 1000% by weight. The amount of catalyst used can vary depending on the type of reaction. For example, the reaction of the catalyst on the C-H bond can work effectively at higher amounts of catalyst, such as up to 400% by weight. Other reactions work effectively with less catalyst weight, such as as little as 0.01% by weight.

In some cases, groups present on the surface of the catalytically active carbon catalyst (eg, peroxide groups covalently bonded to graphene oxide or graphite oxide) are modified to provide stoichiometric control of the reaction.

Reaction time

In some embodiments, the duration of the reaction (eg, dehydrogenation, cracking, displacement, and/or coupling) of any of the catalytically active carbon catalysts (eg, graphene oxide or graphite oxide) described herein ( For example, more than about 10%, about 20%, about 30%, about 40%, about 50%, about 60%, about 70%, about 80%, about 90%, about 95% or about 100% of the starting material conversion The product is from a few seconds to a few minutes, from a few minutes to a few hours, or from hours to days, or from days to weeks. In one embodiment, the reaction duration is from about 1 second to about 5 minutes for the reaction of any of the catalytically active carbon catalyst media described herein. In one embodiment, the reaction duration is from about 5 minutes to about 30 minutes for the reaction of any of the catalytically active carbon catalyst media described herein. In one embodiment, the reaction duration is from about 30 minutes to about 60 minutes for the reaction of any of the catalytically active carbon catalyst media described herein. In one embodiment, the reaction duration is from about 60 minutes to about 4 hours for the reaction of any of the catalytically active carbon catalyst media described herein. In one embodiment, the reaction duration is from about 4 hours to about 8 hours for the reaction of any of the catalytically active carbon catalyst media described herein. In one embodiment, the reaction duration is from about 8 hours to about 12 hours for the reaction of any of the catalytically active carbon catalyst media described herein. In one embodiment, the reaction duration is from about 8 hours to about 24 hours for the reaction of any of the catalytically active carbon catalyst media described herein. In one embodiment, the reaction duration is from about 24 hours to about 2 days for the reaction of any of the catalytically active carbon catalyst media described herein. In one embodiment, the reaction duration is from about 1 day to about 3 days for the reaction of any of the catalytically active carbon catalyst media described herein. In one embodiment, the reaction duration is from about 1 day to about 5 days for the reaction of any of the catalytically active carbon catalyst media described herein. In one embodiment, the reaction duration is from about 1 day to about 6 days for the reaction of any of the catalytically active carbon catalyst media described herein. In one embodiment, the reaction duration is from about 1 day to about 1 week, 2 weeks, 3 weeks, or longer for the reaction of any of the catalytically active carbon catalyst media described herein.

temperature reflex

In some embodiments, the reaction (eg, dehydrogenation, cleavage, displacement, and/or coupling) of any of the catalytically active carbon catalyst media described herein is between about -78 ° C, -65 ° C, and -50. °C, -25°C, -15°C, -10°C, -5°C, 0°C, 5°C, 10°C, 15°C, 20°C, 25°C, 35°C, 50°C, 60°C, 80°C and about 25 The temperature is between °C, 50 ° C, 100 ° C, 150 ° C, 200 ° C, 250 ° C, 300 ° C, 400 ° C, 500 ° C, 600 ° C, 700 ° C, 800 ° C, 900 ° C or about 1000 ° C.

In some embodiments, the reaction is between about -78 ° C and about 1000 ° C for any of the catalytically active carbon catalyst media described herein (eg, dehydrogenation, cracking, displacement, and/or coupling). The temperature is carried out. In some embodiments, the reaction is between about -78 ° C and about 800 ° C for any of the catalytically active carbon catalyst media described herein (eg, dehydrogenation, cracking, displacement, and/or coupling). The temperature is carried out. In some embodiments, the reaction is between about -50 ° C and about 1000 ° C for any of the catalytically active carbon catalyst media described herein (eg, dehydrogenation, cracking, displacement, and/or coupling). The temperature is carried out. In some embodiments, the reaction is between about -50 ° C and about 800 ° C for any of the catalytically active carbon catalyst media described herein (eg, dehydrogenation, cracking, displacement, and/or coupling). The temperature is carried out.

In some embodiments, the reaction is between about -25 ° C and about 1000 ° C for any of the catalytically active carbon catalyst media described herein (eg, dehydrogenation, cracking, displacement, and/or coupling). The temperature is carried out. In some embodiments, the reaction is between about -25 ° C and about 800 ° C for any of the catalytically active carbon catalyst media described herein (eg, dehydrogenation, cracking, displacement, and/or coupling). The temperature is carried out.

In some embodiments, the reaction (eg, dehydrogenation, cleavage, displacement, and/or coupling) of any of the catalytically active carbon catalyst media described herein is between about 0 ° C and about 1000 ° C. Perform at temperature. In some embodiments, the reaction of any of the catalytically active carbon catalyst media described herein (eg, dehydrogenation, cracking, displacement, and/or coupling) The reaction is carried out at a temperature between about 0 ° C and about 800 ° C. In some embodiments, the reaction (eg, dehydrogenation, cleavage, displacement, and/or coupling) of any of the catalytically active carbon catalyst media described herein is between about 0 ° C and about 600 ° C. Perform at temperature. In some embodiments, the reaction (eg, dehydrogenation, cleavage, displacement, and/or coupling) of any of the catalytically active carbon catalyst media described herein is between about 0 ° C and about 500 ° C. Perform at temperature. In some embodiments, the reaction (eg, dehydrogenation, cleavage, displacement, and/or coupling) of any of the catalytically active carbon catalyst media described herein is between about 0 ° C and about 450 ° C. Perform at temperature. In some embodiments, the reaction (eg, dehydrogenation, cleavage, displacement, and/or coupling) of any of the catalytically active carbon catalyst media described herein is between about 0 ° C and about 400 ° C. Perform at temperature. In some embodiments, the reaction (eg, dehydrogenation, cleavage, displacement, and/or coupling) of any of the catalytically active carbon catalyst media described herein is between about 0 ° C and about 350 ° C. The temperature is carried out. In some embodiments, the reaction (eg, dehydrogenation, cleavage, displacement, and/or coupling) of any of the catalytically active carbon catalyst media described herein is between about 0 ° C and about 300 ° C. The temperature is carried out. In some embodiments, the reaction (eg, dehydrogenation, cleavage, displacement, and/or coupling) of any of the catalytically active carbon catalyst media described herein is between about 0 ° C and about 200 ° C. Perform at temperature. In some embodiments, the reaction (eg, dehydrogenation, cleavage, displacement, and/or coupling) of any of the catalytically active carbon catalyst media described herein is between about 0 ° C and about 100 ° C. Perform at temperature.

In some embodiments, the reaction (eg, dehydrogenation, cleavage, displacement, and/or coupling) of any of the catalytically active carbon catalyst media described herein is between about 25 ° C and about 1000 ° C. Perform at temperature. In some embodiments, the reaction (eg, dehydrogenation, cleavage, displacement, and/or coupling) of any of the catalytically active carbon catalyst media described herein is between about 25 ° C and about 800 ° C. Perform at temperature. In some embodiments, reactions to any of the catalytically active carbon catalyst media described herein (eg, Dehydrogenation, cleavage, displacement, and/or coupling), the reaction is carried out at a temperature between about 25 ° C and about 600 ° C. In some embodiments, the reaction (eg, dehydrogenation, cleavage, displacement, and/or coupling) of any of the catalytically active carbon catalyst media described herein is between about 25 ° C and about 500 ° C. Perform at temperature. In some embodiments, the reaction (eg, dehydrogenation, cleavage, displacement, and/or coupling) of any of the catalytically active carbon catalyst media described herein is between about 25 ° C and about 450 ° C. Perform at temperature. In some embodiments, the reaction (eg, dehydrogenation, cleavage, displacement, and/or coupling) of any of the catalytically active carbon catalyst media described herein is between about 25 ° C and about 400 ° C. Perform at temperature. In some embodiments, the reaction (eg, dehydrogenation, cleavage, displacement, and/or coupling) of any of the catalytically active carbon catalyst media described herein is between about 25 ° C and about 300 ° C. Perform at temperature. In some embodiments, the reaction (eg, dehydrogenation, cleavage, displacement, and/or coupling) of any of the catalytically active carbon catalyst media described herein is between about 25 ° C and about 200 ° C. Perform at temperature. In some embodiments, the reaction (eg, dehydrogenation, cleavage, displacement, and/or coupling) of any of the catalytically active carbon catalyst media described herein is between about 25 ° C and about 100 ° C. Perform at temperature.

In some embodiments, the reaction (eg, dehydrogenation, cleavage, displacement, and/or coupling) of any of the catalytically active carbon catalyst media described herein is between about 50 ° C and about 1000 ° C. Perform at temperature. In some embodiments, the reaction (eg, dehydrogenation, cleavage, displacement, and/or coupling) of any of the catalytically active carbon catalyst media described herein is between about 50 ° C and about 800 ° C. Perform at temperature. In some embodiments, the reaction (eg, dehydrogenation, cleavage, displacement, and/or coupling) of any of the catalytically active carbon catalyst media described herein is between about 50 ° C and about 600 ° C. Perform at temperature. In some embodiments, the reaction (eg, dehydrogenation, cleavage, displacement, and/or coupling) of any of the catalytically active carbon catalyst media described herein is between about 50 ° C and about 500 ° C. Perform at temperature. In some specific examples, for any The reaction (e.g., dehydrogenation, cracking, displacement, and/or coupling) of the catalytically active carbon catalyst media described herein is carried out at a temperature between about 50 ° C and about 400 ° C. In some embodiments, the reaction (eg, dehydrogenation, cleavage, displacement, and/or coupling) of any of the catalytically active carbon catalyst media described herein is between about 50 ° C and about 300 ° C. Perform at temperature. In some embodiments, the reaction (eg, dehydrogenation, cleavage, displacement, and/or coupling) of any of the catalytically active carbon catalyst media described herein is between about 50 ° C and about 200 ° C. Perform at temperature. In some embodiments, the reaction (eg, dehydrogenation, cleavage, displacement, and/or coupling) of any of the catalytically active carbon catalyst media described herein is between about 50 ° C and about 150 ° C. Perform at temperature. In some embodiments, the reaction (eg, dehydrogenation, cleavage, displacement, and/or coupling) of any of the catalytically active carbon catalyst media described herein is between about 50 ° C and about 100 ° C. Perform at temperature.

In some embodiments, the reaction (eg, dehydrogenation, cleavage, displacement, and/or coupling) of any of the catalytically active carbon catalyst media described herein is between about 75 ° C and about 1000 ° C. Perform at temperature. In some embodiments, the reaction (eg, dehydrogenation, cleavage, displacement, and/or coupling) of any of the catalytically active carbon catalyst media described herein is between about 75 ° C and about 800 ° C. Perform at temperature. In some embodiments, the reaction (eg, dehydrogenation, cleavage, displacement, and/or coupling) of any of the catalytically active carbon catalyst media described herein is between about 75 ° C and about 600 ° C. Perform at temperature. In some embodiments, the reaction (eg, dehydrogenation, cleavage, displacement, and/or coupling) of any of the catalytically active carbon catalyst media described herein is between about 75 ° C and about 500 ° C. Perform at temperature. In some embodiments, the reaction (eg, dehydrogenation, cleavage, displacement, and/or coupling) of any of the catalytically active carbon catalyst media described herein is between about 75 ° C and about 450 ° C. Perform at temperature. In some embodiments, the reaction (eg, dehydrogenation, cleavage, displacement, and/or coupling) of any of the catalytically active carbon catalyst media described herein is between about 75 ° C and about It is carried out at a temperature between 400 °C. In some embodiments, the reaction (eg, dehydrogenation, cleavage, displacement, and/or coupling) of any of the catalytically active carbon catalyst media described herein is between about 75 ° C and about 300 ° C. Perform at temperature. In some embodiments, the reaction (eg, dehydrogenation, cleavage, displacement, and/or coupling) of any of the catalytically active carbon catalyst media described herein is between about 75 ° C and about 200 ° C. Perform at temperature.

In some embodiments, the reaction (eg, dehydrogenation, cleavage, displacement, and/or coupling) of any of the catalytically active carbon catalyst media described herein is between about 100 ° C and about 1000 ° C. Perform at temperature. In some embodiments, the reaction (eg, dehydrogenation, cleavage, displacement, and/or coupling) of any of the catalytically active carbon catalyst media described herein is between about 100 ° C and about 800 ° C. Perform at temperature. In some embodiments, the reaction (eg, dehydrogenation, cleavage, displacement, and/or coupling) of any of the catalytically active carbon catalyst media described herein is between about 100 ° C and about 600 ° C. Perform at temperature. In some embodiments, the reaction (eg, dehydrogenation, cleavage, displacement, and/or coupling) of any of the catalytically active carbon catalyst media described herein is between about 200 ° C and about 600 ° C. Perform at temperature. In some embodiments, the reaction (eg, dehydrogenation, cleavage, displacement, and/or coupling) of any of the catalytically active carbon catalyst media described herein is between about 300 ° C and about 600 ° C. Perform at temperature. In some embodiments, the reaction (eg, dehydrogenation, cleavage, displacement, and/or coupling) of any of the catalytically active carbon catalyst media described herein is between about 400 ° C and about 600 ° C. Perform at temperature. In some embodiments, the reaction (eg, dehydrogenation, cleavage, displacement, and/or coupling) of any of the catalytically active carbon catalyst media described herein is between about 200 ° C and about 500 ° C. Perform at temperature. In some embodiments, the reaction (eg, dehydrogenation, cleavage, displacement, and/or coupling) of any of the catalytically active carbon catalyst media described herein is between about 300 ° C and about 500 ° C. Perform at temperature.

pressure

In some embodiments, the reaction is carried out at atmospheric pressure for the reaction (e.g., dehydrogenation, cracking, displacement, and/or coupling) of any of the catalytically active carbon catalyst media described herein. In some embodiments, the reaction (eg, dehydrogenation, cracking, displacement, and/or coupling) of any of the catalytically active carbon catalyst media described herein is between about 0.1 atm and about 150 atm. Under pressure. In some embodiments, the reaction (eg, dehydrogenation, cracking, displacement, and/or coupling) of any of the catalytically active carbon catalyst media described herein is between about 1 atm and about 150 atm. Under pressure. In some embodiments, the reaction (eg, dehydrogenation, cracking, displacement, and/or coupling) of any of the catalytically active carbon catalyst media described herein is between about 5 atm and about 150 atm. Under pressure. In some embodiments, the reaction (eg, dehydrogenation, cracking, displacement, and/or coupling) of any of the catalytically active carbon catalyst media described herein is between about 10 atm and about 150 atm. Under pressure. In some embodiments, the reaction (eg, dehydrogenation, cracking, displacement, and/or coupling) of any of the catalytically active carbon catalyst media described herein is between about 20 atm and about 150 atm. Under pressure. In some embodiments, the reaction (eg, dehydrogenation, cracking, displacement, and/or coupling) of any of the catalytically active carbon catalyst media described herein is between about 50 atm and about 150 atm. Under pressure. In some embodiments, the reaction (eg, dehydrogenation, cracking, displacement, and/or coupling) of any of the catalytically active carbon catalyst media described herein is between about 100 atm and about 150 atm. Under pressure. In some embodiments, the reaction (eg, dehydrogenation, cracking, displacement, and/or coupling) of any of the catalytically active carbon catalyst media described herein is between about 1 atm and about 100 atm. Under pressure. In some embodiments, the reaction (eg, dehydrogenation, cracking, displacement, and/or coupling) of any of the catalytically active carbon catalyst media described herein is between about 5 atm and about 50 atm. Under pressure. In some embodiments, the reaction of any of the catalytically active carbon catalyst media described herein (eg, dehydrogenation, cracking, displacement, and/or coupling), the reaction is carried out at a pressure of between about 10 atm and about 50 atm. In some embodiments, the reaction is carried out at atmospheric pressure for the reaction (e.g., dehydrogenation, cracking, displacement, and/or coupling) of any of the catalytically active carbon catalyst media described herein. In some embodiments, the reaction (eg, dehydrogenation, cracking, displacement, and/or coupling) of any of the catalytically active carbon catalyst media described herein is between about 1 atm and about 5 atm. Under pressure. In some embodiments, the reaction is carried out at ambient atmospheric pressure for the reaction (e.g., dehydrogenation, cracking, displacement, and/or coupling) of any of the catalytically active carbon catalyst media described herein. In some embodiments, the reaction (eg, dehydrogenation, cracking, displacement, and/or coupling) of any of the catalytically active carbon catalyst media described herein is between about 0.1 atm and about 1 atm. Under pressure. In some embodiments, the reaction is carried out at a pressure of about 1 atm for any of the catalytically active carbon catalyst media described herein (e.g., dehydrogenation, cracking, displacement, and/or coupling).

time

In some embodiments, the catalyst is contacted with the reactant for about 0.01 seconds, or 0.1 second, for any of the catalytically active carbon catalyst media described herein (eg, dehydrogenation, cracking, displacement, and/or coupling). , or 1 second, or 10 seconds, or 30 seconds, or 1 minute, or 5 minutes, or 10 minutes, or 15 minutes, or 20 minutes, or 30 minutes, or 1 hour, or 2 hours, or 3 hours, or 4 hours, or 5 hours, or 6 hours, or 12 hours, or 24 hours, to about 1 minute, or 5 minutes, or 10 minutes, or 15 minutes, or 20 minutes, or 30 minutes, or 1 hour, or 2 Hours, or 3 hours, or 4 hours, or 5 hours, or 6 hours, or 12 hours, or a period of time between 24 hours, 48 hours, 72 hours, 5 days, 1 week, 2 weeks, 3 weeks, or any The appropriate length of time.

Oxidation

In some embodiments, the reaction (eg, dehydrogenation, cracking, displacement, and/or coupling) of any of the catalytically active carbon catalyst media described herein is carried out under ambient atmosphere get on. In some embodiments, the reaction is carried out under an inert atmosphere for the reaction (e.g., dehydrogenation, cracking, displacement, and/or coupling) of any of the catalytically active carbon catalyst media described herein. In some embodiments, the reaction (eg, dehydrogenation, cracking, displacement, and/or coupling) of any of the catalytically active carbon catalyst media described herein is carried out by filling the reaction chamber with a starting material for the gas. .

In a further embodiment, for any of the catalytically active carbon catalyst media described herein (eg, dehydrogenation, cracking, displacement, and/or coupling), the reaction mixture is further oxidized with an additional stream of oxygen to allow for control Reaction product and/or reaction efficiency and/or conversion ratio. In other embodiments, the reaction mixture is further oxidized with a sacrificial chemical oxidant such as ozone, hydrogen peroxide, potassium oxone, potassium permanganate, organic peroxide, peroxyacid, Perrhenate, lead tetraacetate, chromium oxide, periodate, potassium peroxymonosulfate complex, sulfur dioxide, chlorate, perchlorate, hypochlorite, perborate, nitrate, mono-oxidation Dinitrogen, dinitrogen tetroxide, silver oxide, osmium tetroxide, 2,2'-disulfide dichloride, cerium ammonium nitrate, benzoquinone, Des Martin oxidant, Swern oxidation reagent, molybdenum oxide, N-oxidation Pyridinium, vanadium oxide, TEMPO, potassium ferricyanide or the like.

The catalytically active carbon catalysts (e.g., graphene oxide and/or graphite oxide) described herein can also be prepared by varying the amount of oxidizing agent and acid used in the reaction mixture to produce varying degrees of oxidation. Variants with reduced oxygen content also have the desired reactivity. On the other hand, carbon catalysts which have a variability in oxidation, including those which are porous and have a high surface area but have a lower oxygen function, also have the desired activity. Advantageously, the hydrocarbon conversions described herein (e.g., conversion of propane to propylene) are cleaner compared to other processes and exhibit reduced and/or negligible amounts of by-products. Accordingly, modifications to the physical structure of the carbon catalyst, including surface area and porosity, and configuration of oxidation and/or surface groups, to improve reaction efficiency are encompassed by the specific examples presented herein.

Pass (Passes)

In some embodiments, the reactant (e.g., gaseous reactant) can pass through the catalyst once for any of the catalytically active carbon catalyst media described herein (e.g., dehydrogenation, cracking, displacement, and/or coupling). In an alternative embodiment, multiple passes may be utilized to improve conversion efficiency and/or reaction yield.

Catalyst form

The carbon catalyst used in the reactions can be in various forms. The catalyst can be a powder having a particle size ranging from 10 nm to 100 μm. The catalyst can be compressed into pellets, rings, honeycomb-like structures or other forms that facilitate the loading into the reactor. Substance formation can be accomplished by calcination or sintering of the carbon catalyst itself. Forming and molding can also be enhanced by incorporating polymeric binders, organic resins, surfactants, or metallic species. These forming agents may be included in the range of from 0.01% by weight to up to 95% by weight of the mass load. A variety of polymer materials and resins are effective in this role, including polyethylene, polypropylene, polyethers, polyether oximes, polytetrafluoroethylene, polyesters, polyurethanes, polyamines, polystyrene Classes, polyoxins, Nafion, phenolic resins and polyelectrolytes or ionic polymers. The polymers or resins may be acidic, neutral or basic. Likewise, the surfactants and metallic species can be acidic, neutral or basic. In a further embodiment, the catalytically active carbon catalyst can be applied to or deposited on the surface of the reaction vessel.

The available surface area of the catalytically active carbon catalyst can optionally be modified along with multiple passes of the reactants to improve conversion efficiency and/or reaction yield.

The materials incorporated into the catalyst for bonding, shaping and/or molding may exhibit catalytic activity or cocatalytic activity with the carbon catalyst in the desired reaction, or they may be bystand species.

Solvent

In some embodiments, suitable for any of the catalytically active carbon catalyst media described herein (eg, dehydrogenation, cracking, displacement, and/or coupling), any suitable solvent The carbon catalyst has a solvent of low reactivity. In one embodiment, a chlorinated solvent such as dichloromethane, chloroform, tetrachloromethane, dichloroethane, and the like is used. In other cases, solvents such as acetonitrile or DMF are used. In some embodiments, water can be used as a solvent. Suboptimal solvents include solvents such as methanol, ethanol and/or tetrahydrofuran.

In a further optional embodiment, the reaction is solvent free. In another example, the reaction comprises a liquid reactant that is contacted with a catalytically active carbon catalyst as described herein, which reaction is thus free of additional solvent. In another example, the reaction comprises a solid reactant that is contacted with a catalytically active carbon catalyst as described herein, wherein upon heating, the solid melts to form a liquid reactant.

Gas phase reaction

In a further embodiment, the reaction comprises a gaseous reactant (e.g., propane) that is contacted with a heated, catalytically active carbon catalyst as described herein. In such cases, the gas phase reaction can occur under vacuum, ambient atmospheric pressure, or at elevated pressure (e.g., in a bomb reactor or high pressure reactor).

Reactor system

In some embodiments, any of the reactions described herein are batch reactions. In other embodiments, any of the reactions described herein are flow reactions. An exemplary reactor system is described in PCT International Application No. PCT/US2011/38327 (WO 2011/150325), the disclosure of which is incorporated herein by reference. It will be appreciated that any suitable reactor or reaction system can be used in conjunction with the process and catalytically active carbon catalysts described herein.

In some examples, the reactor operates under vacuum. In some embodiments, the reactor is at a pressure of less than about 760 Torr, or 1 Torr, or 1 x 10 ^-3 Torr, or 1 x 10 ^-4 Torr, or 1 x 10 ^-5 Torr, or 1 x 10 ^-6 Torr, or 1 x 10 ^-7 Torr, Operates at lower pressures. In other examples, the reactor 315 operates at high pressure. In some embodiments, the reactor 315 is at a pressure of at least about 1 atm, or 2 atm, or 3 atm, or 4 atm, or 5 atm, or 6 atm, or 7 atm, or 8 atm, or 9 atm, Or operate at 10 atm, or 20 atm, or 50 atm, or higher.

In some embodiments, the reactor is a plug flow reactor, a continuous stirred tank reactor, a semi-batch reactor, or a catalytic reactor. In some cases, the catalytic reactor is a shell and tube reactor or a fluidized bed reactor. In other cases, the reactor includes several parallel reactors. This can help to keep the size of each reactor within predetermined limits while meeting processing requirements. For example, if 500 liters/hour of propylene is required, but the reactor can provide 250 liters/hour, the two reactors in parallel will achieve the desired propylene output. In some instances, a flow reactor can be employed to improve the conversion due to the superior interaction of the reactants (e.g., propane) with the catalyst (higher concentrations result in increased reaction rates).

Conversion

In some embodiments, the number of conversions of the reaction for any of the catalytically active carbon catalyst media described herein is on the order of from 10" ⁵ to about 1,000,000 or greater. In some embodiments, the number of conversions for the reaction of any of the catalytically active carbon catalyst media described herein is on the order of from 10" ⁴ to about 10<^4> . In an exemplary embodiment, for the reaction of any of the catalytically active carbon catalyst media described herein, the number of conversions of the reaction is on the order of 10 ^-2 (expressed as the number of moles of product per catalyst mass).

Cocatalyst

In some embodiments, the reaction mixture can optionally further comprise a cocatalyst for the reaction of any of the catalytically active carbon catalyst media described herein. In one embodiment, such cocatalysts are, for example, carbon nitride, boron nitride, boron nitride carbon, and the like. In some embodiments, the cocatalyst is an oxidation catalyst (e.g., titanium dioxide, manganese dioxide). In some embodiments, the cocatalyst is a dehydrogenation catalyst (eg, Pd/ZnO). In some embodiments, the cocatalyst is a zeolite.

Co-reagents

In a further optional embodiment, the reaction of any of the carbon catalyst media described herein can optionally be carried out in the presence of a co-reagent. In one embodiment, such co-agents are additional oxidizing agents such as ozone, hydrogen peroxide, oxone, molecular oxygen or the like, and optionally regenerate the carbon in situ catalyst. In another embodiment, the additional reagent can be a complementary reagent that synergizes with the procedures described herein, such as a Dess Martin oxidation reagent or a Sven oxidation reagent. In a further embodiment, the co-reagent absorbs reaction by-products (e.g., hydrogen).

A cocatalyst and catalyst supported on graphite oxide and a catalyst operating in the presence of graphite oxide or other carbon catalyst:

Graphene oxide or graphite oxide and other carbon catalysts are expected to be active when graphene oxide or graphite oxide and other carbon catalysts are used in conjunction with other catalytic molecules or materials. The catalysts may be metal-containing, organic, inorganic or macromolecular and may operate via different or identical reaction mechanisms in which catalysis based on graphene oxide or graphite oxide is carried out. The catalysts may be supported on graphene oxide or graphite oxide via chemisorption (e.g., by interaction with linkages of chemical functionality present on graphene oxide or graphite oxide) or physical adsorption. The catalysts (graphene oxide or graphite oxide or added species) may be enhanced by co-chemical effects between graphene oxide or graphite oxide and the catalyst, or may be available from the high surface area of graphene oxide or graphite oxide The reaction site benefits. Metal-containing, organic, inorganic or macromolecular catalysts can also be used in the presence of graphene oxide or graphite oxide, wherein there is no interaction between the two and graphene oxide or graphite oxide operates alone as a bystander species. The catalyst retains its inherent reactivity and is not affected by the presence of graphene oxide or graphite oxide.

Graphite intercalation compound as a catalyst:

It is expected that graphene oxide or graphite oxide and other carbon catalysts are active in forming an intercalation compound (IC). When these materials are formed from graphite-based materials, these materials are referred to as graphite intercalation compounds (GIC). IC and GIC are inserted by inserting small molecules or polymers It is formed by entering an interlayer region of a stacked structure of graphite and other similar carbon materials. The intercalant may be metallic (eg, metal salts, coordination complexes), organic (eg, aryl or aliphatic species), inorganic (eg, mineral acid) or macromolecules, and exhibit diverse chemical properties ( For example, ionic, various functional groups and various physical states (ie, gases, liquids, solids). These ICs and GICs can be catalytically or stoichiometrically reactive and can be considered as non-covalently functionalized carbon catalysts. The reactivity of the GIC can be the result of the carbon material itself or the intercalation or a combination thereof. Although the carbon material or intercalation material can enhance the inherent reactivity of each other, the carbon material or the intercalation material can also be an inert bystand species.

Carbon catalyst catalyzed conversion

A catalytically active carbon catalyst comprising surface modified graphene oxide or graphite oxide is used to activate an unactivated substrate (e.g., a hydrocarbon). In these reactions, graphene oxide or graphite oxide exerts its catalytic effect via one or more exemplary properties, such as acidic, oxidative, dehydrogenating, redox or any combination thereof.

Dehydrogenation

Graphene oxide or graphite oxide is used to catalyze dehydrogenation reactions such as dehydrogenation of alkanes to olefins or dehydrogenation of olefins to alkynes. This dehydrogenation chemistry is practical when this reaction is combined with other reactions.

In a particular embodiment, graphene oxide or graphite oxide is used to catalyze the dehydrogenation of alkane to olefins, including the dehydrogenation of linear and linear alkanes. In a further embodiment, graphene oxide or graphite oxide is used to catalyze the dehydrogenation of olefins to alkynes, including dehydrogenation of terminal or non-terminal olefins. In other embodiments, graphene oxide or graphite oxide is used to catalyze the conversion of saturated or partially saturated cyclic alkanes (eg, cyclohexane, methylcyclohexane, and the like) to aromatic compounds (eg, benzenes, toluene, and the like). Dehydrogenation reaction of the similar substance).

In a further aspect, the perturbation of the electronic properties of the substrate (eg, via incorporation of push electrons or pull electron substituents) does not significantly affect the isolated yield of the desired product. Thus, a push electron group (eg, a methoxy group, a dialkylamino group, or any other electron-withdrawing group) or a pull-electron group is included. The substrate of the group (e.g., nitro, halo or any other electron withdrawing group) is suitable for dehydrogenation in the presence of a carbon catalyst as described herein.

Thus, the dehydrogenation process has broad synthetic utility in the presence of a catalytically active carbon catalyst as presented herein.

In an exemplary embodiment, the dehydrogenation reaction is carried out at a temperature between 100 ° C and 600 ° C in the presence of less than 1% by weight to 1000% by weight of graphene oxide or graphite oxide for a duration of 6-48 hour.

It will be appreciated that any combination of catalyst amount, reaction time, solvent and reaction temperature as described in the above paragraphs is encompassed within the scope of any specific examples described above or below.

Dynamic control of hydrocarbon dehydrogenation reaction

R is H or any hydrocarbyl group or two R groups form a ring.

In one aspect, the importance of reaction kinetics is recognized here. In one aspect, the extent to which an alkane (e.g., propane) is converted to an olefin (e.g., propylene) varies with reaction time and temperature. As an example, for the conversion of propane to propylene using the processes described herein (as described in Examples 4 and 3), about 1 hour was observed relative to the amount of unreacted propane in the crude mixture after 1 hour. % propylene. The conversion increases over time, indicating that no balance has been established. At 168 hours, approximately 10% of propylene was observed in the crude NMR spectrum (see Figures 3 and 4). It seems that the catalyst reactivity was not lost due to prolonged heating, and no by-products were observed.

Tables 1-4 below show comparative data for the processes described herein and certain other processes.

Source: Lei Liu et al., Chem. Commun. , 2011, 47 , 8334-8336

Source: Zeeshan Nawaz et al . , Ind.Eng.Chem.Res . , 2010, 49 , 4614-4619

As seen in Tables 1 and 2, the conversion of propane to propylene increased over time, indicating that equilibrium has not been established, i.e., when the temperature is as low as about 400 ° C, the reaction is under power control. Conversely, Tables 3 and 4 show the results of methods using other catalysts and/or higher reaction temperatures. The data in Tables 3 and 4 show that as the reaction time increases, the conversion decreases, that is, the higher temperature favors the reverse reaction (hydrogenation of propylene to propane), and the thermodynamic product is propane, which causes a longer reaction time. The down conversion is reduced.

Accordingly, the importance of power control for hydrocarbon dehydrogenation is recognized here. Accordingly, the processes provided herein utilize lower temperatures and/or lower pressures relative to other methods (eg, temperatures below 600 ° C or below 500 ° C, and pressures of about 1 atmosphere or between about 1 A reaction time of between 5 atmospheres and for several days or weeks is obtained to obtain a kinetically favorable forward reaction product, that is, a dehydrogenated hydrocarbon.

Propane to propylene

In one embodiment, provided herein is a process for converting propane to propylene comprising reacting propane with a catalytically active carbon catalyst (eg, any of the carbon catalysts described herein (eg, graphene oxide and/or graphite oxide)) contact. A suitable reaction temperature and/or pressure is selected for the gas reaction.

In one embodiment, the starting material is high purity propane. In this example, the reaction product is high purity propylene. In an alternative embodiment, a low purity propane (eg one or Mixtures of various low molecular weight gases, such as methane, ethane, propane, butane and/or isobutylene and/or sulfur-containing impurities, can be used in the reaction. In this example, the reaction product comprises a mixture of one or more olefins, including propylene, which is further purified using standard procedures. Furthermore, the catalyst was not contaminated by the presence of sulfur-containing impurities in the starting material (low purity propane).

The reaction is carried out by contacting the gaseous reactant with a graphene oxide or graphite oxide carbon catalyst as described herein. As described in more detail herein, conversion efficiency is controlled by varying temperature, pressure, and/or catalyst usage. By way of example, in some instances, the conversion of propane to propylene occurs at a temperature of from about 400 ° C to about 600 ° C and at a pressure of from about 1 atmosphere to about 20 atmospheres for a period of from about 10 minutes to about 60 minutes. By way of example, in some instances, conversion of propane to propylene occurs at a temperature of from about 400 ° C to about 450 ° C and a pressure of about 1 atmosphere for about 160 hours, 1 week, 10 days, 2 weeks, or longer. period.

Ethane to ethylene

In one embodiment, provided herein is a process for converting ethane to ethylene comprising reacting ethane with a catalytically active carbon catalyst (eg, any of the carbon catalysts described herein (eg, graphene oxide and/or graphite oxide) (for example, graphene oxide and/or graphite oxide)) contact. A suitable reaction temperature and/or pressure is selected for the gas reaction.

In one embodiment, the starting material is high purity ethane. In this example, the reaction product is high purity ethylene. In an alternative embodiment, low purity ethane (e.g., a mixture of one or more low molecular weight gases such as methane, ethane, propane, and/or butane) can be used in the reaction. In this example, the reaction product comprises a mixture of one or more olefins, including ethylene, which is further purified using standard procedures.

The reaction is carried out by contacting the gaseous reactant with a graphene oxide or graphite oxide carbon catalyst as described herein. As described in more detail herein, conversion efficiency is controlled by varying temperature, pressure, and/or catalyst usage. As an example, in some cases The conversion of ethane to ethylene occurs at a temperature of from about 200 ° C to about 450 ° C and a pressure of from about 1 atm to about 5 atm for about 10 minutes to about 60 minutes, or longer, such as 8 hours, 1 Days, 4 days, 1 week, or 2 weeks.

Conversion of butane to 1-butene

In one embodiment, a process for converting butane to 1-butene is provided herein, comprising reacting butane with a catalytically active carbon catalyst (eg, any of the carbon catalysts described herein (eg, graphene oxide and/or Graphite oxide (for example, graphene oxide and/or graphite oxide) is contacted. A suitable reaction temperature and/or pressure is selected for the gas reaction.

In one embodiment, the starting material is high purity butane. In this example, the reaction product is high purity 1-butene. In an alternative embodiment, low purity butane (e.g., a mixture of one or more low molecular weight gases such as methane, ethane, propane, and/or butane) can be used in the reaction. In this example, the reaction product comprises a mixture of one or more olefins, including 1-butene, which is further purified using standard procedures.

The reaction is carried out by contacting the gaseous reactant with a graphene oxide or graphite oxide carbon catalyst as described herein. As described in more detail herein, conversion efficiency is controlled by varying temperature, pressure, and/or catalyst usage. By way of example, in some instances, the conversion of butane to 1-butene occurs at a temperature of from about 200 ° C to about 600 ° C, and at a pressure of from about 1 atmosphere to about 20 atmospheres, for a period of from about 1 minute to about 60 minutes. Or longer, such as 8 hours, 1 day, 4 days, 1 week, or 2 weeks.

Conversion of butane to 2-butene

In one embodiment, provided herein is a process for converting butane to 2-butene comprising reacting butane with a catalytically active carbon catalyst (eg, any of the carbon catalysts described herein (eg, graphene oxide and/or Or graphite oxide)) contact. A suitable reaction temperature and/or pressure is selected for the gas reaction.

In one embodiment, the starting material is high purity butane. In this example, the reaction product is high purity 2-butene. In an alternative embodiment, low purity butane (eg one or Mixtures of various low molecular weight gases, such as methane, ethane, propane and/or butane, can be used in the reaction. In this example, the reaction product comprises a mixture of one or more olefins, including 2-butene, which is further purified using standard procedures.

The reaction is carried out by contacting the gaseous reactant with a graphene oxide or graphite oxide carbon catalyst as described herein. As described in more detail herein, conversion efficiency is controlled by varying temperature, pressure, and/or catalyst usage. By way of example, in some instances, the conversion of butane to 2-butene occurs at a temperature of from about 200 ° C to about 600 ° C, and at a pressure of from about 1 atmosphere to about 20 atmospheres, for a period of from about 1 minute to about 60 minutes. Or longer, such as 8 hours, 1 day, 4 days, 1 week, or 2 weeks.

Conversion of butane to butadiene

In one embodiment, provided herein is a process for converting butane to butadiene comprising reacting butane with a catalytically active carbon catalyst (eg, any of the carbon catalysts described herein (eg, graphene oxide and/or Graphite oxide)) contact. A suitable reaction temperature and/or pressure is selected for the gas reaction.

In one embodiment, the starting material is high purity butane. In this example, the reaction product is a high purity butadiene. In an alternative embodiment, low purity butane (e.g., a mixture of one or more low molecular weight gases such as methane, ethane, propane, and/or butane) can be used in the reaction. In this example, the reaction product comprises a mixture of one or more olefins, including butadiene, which is further purified using standard procedures.

The reaction is carried out by contacting the gaseous reactant with a graphene oxide or graphite oxide carbon catalyst as described herein. As described in more detail herein, conversion efficiency is controlled by varying temperature, pressure, and/or catalyst usage. By way of example, in some instances, the conversion of butane to butadiene occurs at a temperature of from about 200 ° C to about 600 ° C and a pressure of from about 1 atmosphere to about 20 atmospheres for from about 1 minute to about 60 minutes, or For a longer period of time, such as 8 hours, 1 day, 4 days, 1 week, or 2 weeks.

Alkane-alkane coupling Methane to propane

In one embodiment, provided herein is a process for converting methane to propane comprising reacting methane with a catalytically active carbon catalyst (eg, any of the carbon catalysts described herein (eg, graphene oxide and/or graphite oxide)) contact. A suitable reaction temperature and/or pressure is selected for the gas reaction.

In one embodiment, the starting material is high purity methane. In this example, the reaction product is high purity propane. In an alternative embodiment, low purity methane (e.g., a mixture of one or more low molecular weight gases such as methane, ethane, propane, and/or butane) can be used in the reaction. In this example, the reaction product comprises a mixture of one or more alkanes, including propane, which is further purified using standard procedures.

The reaction is carried out by contacting the gaseous reactant with a graphene oxide or graphite oxide carbon catalyst as described herein. As described in more detail herein, conversion efficiency is controlled by varying temperature, pressure, and/or catalyst usage. By way of example, in some instances, the conversion of methane to propane occurs at a temperature of from about 400 ° C to about 800 ° C, and at a pressure of from about 1 atmosphere to about 20 atmospheres, for a period of from about 1 minute to about 60 minutes, or longer. For example, 8 hours, 1 day, 4 days, 1 week, or 2 weeks.

Conversion of methane to butane

In one embodiment, provided herein is a process for converting methane to butane comprising reacting methane with a catalytically active carbon catalyst (eg, any of the carbon catalysts described herein (eg, graphene oxide and/or graphite oxide) )contact. A suitable reaction temperature and/or pressure is selected for the gas reaction.

In one embodiment, the starting material is high purity methane. In this example, the reaction product is high purity butane. In an alternative embodiment, low purity methane (e.g., a mixture of one or more low molecular weight gases such as methane, ethane, propane, and/or butane) can be used in the reaction. In this example, the reaction product comprises a mixture of one or more alkanes, including butane, which is further purified using standard procedures.

The reaction is carried out by contacting the gaseous reactant with a graphene oxide or graphite oxide carbon catalyst as described herein. As described in more detail herein, conversion efficiency is controlled by varying temperature, pressure, and/or catalyst usage. By way of example, in some instances, the conversion of methane to butane occurs at a temperature of from about 400 ° C to about 800 ° C and a pressure of from about 1 atmosphere to about 20 atmospheres for from about 1 minute to about 60 minutes, or longer. The period is, for example, 8 hours, 1 day, 4 days, 1 week, or 2 weeks.

Conversion of ethane to butane

In one embodiment, provided herein is a process for converting ethane to butane comprising reacting ethane with a catalytically active carbon catalyst (eg, any of the carbon catalysts described herein (eg, graphene oxide and/or oxidation) Graphite)) contact. A suitable reaction temperature and/or pressure is selected for the gas reaction.

In one embodiment, the starting material is high purity ethane. In this example, the reaction product is high purity butane. In an alternative embodiment, low purity ethane (e.g., a mixture of one or more low molecular weight gases such as methane, ethane, propane, and/or butane) can be used in the reaction. In this example, the reaction product comprises a mixture of one or more alkanes, including butane, which is further purified using standard procedures.

The reaction is carried out by contacting the gaseous reactant with a graphene oxide or graphite oxide carbon catalyst as described herein. As described in more detail herein, conversion efficiency is controlled by varying temperature, pressure, and/or catalyst usage. By way of example, in some instances, the conversion of ethane to butane occurs at a temperature of from about 400 ° C to about 800 ° C, and at a pressure of from about 1 atmosphere to about 20 atmospheres, for a period of from about 1 minute to about 60 minutes, or more For a long period of time, such as 8 hours, 1 day, 4 days, 1 week, or 2 weeks.

Alkane replacement

Graphene oxide or graphite oxide and other carbon catalysts are active in the coupling of various alkanes. For example, methane gas reacts with graphene oxide or graphite oxide to form higher alkanes such as pentane, heptane, octane or decane. Products of alkane coupling include but not Limited to linear and branched alkanes such as neopentane, isopentane, n-pentane and the like. In some embodiments, the alkane is catalyzed by graphene oxide or graphite oxide and other carbon catalysts to form a polymeric material, such as to convert methane to polyethylene. The alkane starting materials used in these coupling reactions include gases, liquids, and solid alkanes such as methane, ethane, propane, butane, pentane, hexane, heptane, octadecane, nonadecane, and the like. The products of these coupling reactions include, but are not limited to, higher alkanes, unfunctionalized alkanes, and polyalkanes, as shown by the elevations shown below.

In a further embodiment, provided herein are methods for coupling an organic compound, comprising: (a) contacting the organic compound with a catalytically active carbon catalyst (eg, graphene oxide and/or graphite oxide) as described herein; (b) converting the organic compound to form a coupling product with the aid of the catalytically active carbon catalyst.

In some embodiments, the catalytically active carbon catalyst is an oxidized graphite. In some embodiments, the catalytically active carbon catalyst is graphene oxide or graphite oxide. In some embodiments, the organic compound comprises an alkane. In some embodiments, the alkane comprises a linear alkane. In some embodiments, the alkane comprises a branched alkane. In some embodiments, the alkane comprises methane, ethane, propane, butane, pentane, hexane, heptane, octadecane or nonadecane. In some embodiments, the alkane comprises an isomer of butane, pentane, hexane, heptane, octadecane or pentadecane. In some embodiments, the coupling product comprises an alkane. In some embodiments, the coupling product comprises linear or branched alkane. In some embodiments, the coupling product comprises a polyalkane.

Ethane to propane

In one embodiment, provided herein is a process for converting ethane to propane comprising reacting ethane with a catalytically active carbon catalyst (eg, any of the carbon catalysts described herein (eg, graphene oxide and/or graphite oxide) ))contact. A suitable reaction temperature and/or pressure is selected for the gas reaction.

In one embodiment, the starting material is high purity ethane. In this example, the reaction product is high purity propane. In an alternative embodiment, low purity ethane (e.g., a mixture of one or more low molecular weight gases such as methane, ethane, propane, and/or butane) can be used in the reaction. In this example, the reaction product comprises a mixture of one or more alkanes (e.g., propane and methane), including propane, which is further purified using standard procedures.

The reaction is carried out by contacting the gaseous reactant with a graphene oxide or graphite oxide carbon catalyst as described herein. As described in more detail herein, conversion efficiency is controlled by varying temperature, pressure, and/or catalyst usage. By way of example, in some instances, the conversion of methane to propane occurs at a temperature of from about 400 ° C to about 800 ° C, and at a pressure of from about 1 atmosphere to about 20 atmospheres, for a period of from about 1 minute to about 60 minutes, or longer. For example, 8 hours, 1 day, 4 days, 1 week, or 2 weeks.

Pyrolysis Conversion of hexane to methane

In one embodiment, provided herein is a process for converting hexane to methane, comprising reacting hexane with a catalytically active carbon catalyst (eg, any of the carbon catalysts described herein (eg, graphene oxide and/or graphite oxide) ))contact. A suitable reaction temperature and/or pressure is selected for the reaction.

In one embodiment, the starting material is high purity hexane. In this example, the reaction product is a mixture of high purity methane gas and/or low molecular weight hydrocarbons. In an alternative embodiment, low purity hexane (e.g., a mixture of one or more low molecular weight alkanes and/or olefins) can be used in the reaction. In this example, the reaction product contains one or more gases The mixture, including methane, was further purified using standard procedures.

The reaction is carried out by contacting the reactants with a graphene oxide or graphite oxide carbon catalyst as described herein. As described in more detail herein, conversion efficiency is controlled by varying the temperature and/or amount of catalyst. By way of example, in some instances, conversion of hexane to methane occurs at a temperature of from about 400 ° C to about 800 ° C or about 1000 ° C, and a pressure of from about 1 atmosphere to about 20 atmospheres for from about 1 minute to about 60 minutes. , or longer, such as 8 hours, 1 day, 4 days, 1 week, or 2 weeks.

Conversion of hexane to ethane

In one embodiment, provided herein is a process for converting hexane to ethane comprising reacting hexane with a catalytically active carbon catalyst (eg, any of the carbon catalysts described herein (eg, graphene oxide and/or oxidation) Graphite)) contact. A suitable reaction temperature and/or pressure is selected for the reaction.

In one embodiment, the starting material is high purity hexane. In this example, the reaction product is a mixture of high purity ethane gas and/or low molecular weight hydrocarbons. In an alternative embodiment, low purity hexane (e.g., a mixture of one or more low molecular weight alkanes and/or olefins) can be used in the reaction. In this example, the reaction product comprises a mixture of one or more gases, including ethane, which is further purified using standard procedures.

The reaction is carried out by contacting the reactants with a graphene oxide or graphite oxide carbon catalyst as described herein. As described in more detail herein, conversion efficiency is controlled by varying the temperature and/or amount of catalyst. By way of example, in some instances, the conversion of hexane to ethane occurs at a temperature of from about 400 ° C to about 800 ° C or about 1000 ° C, and at a pressure of from about 1 atmosphere to about 20 atmospheres, for a period of from about 1 minute to about 60. Minutes, or longer, such as 8 hours, 1 day, 4 days, 1 week, or 2 weeks.

Hexane to propane

In one embodiment, provided herein is a process for converting hexane to propane comprising reacting hexane with a catalytically active carbon catalyst (eg, any of the carbon catalysts described herein) Contact (for example, graphene oxide and/or graphite oxide). A suitable reaction temperature and/or pressure is selected for the reaction.

In one embodiment, the starting material is high purity hexane. In this example, the reaction product is a mixture of high purity propane gas and/or low molecular weight hydrocarbons. In an alternative embodiment, low purity hexane (e.g., a mixture of one or more low molecular weight alkanes and/or olefins) can be used in the reaction. In this example, the reaction product comprises a mixture of one or more gases, including propane, which is further purified using standard procedures.

The reaction is carried out by contacting the reactants with a graphene oxide or graphite oxide carbon catalyst as described herein. As described in more detail herein, conversion efficiency is controlled by varying the temperature and/or amount of catalyst. By way of example, in some instances, the conversion of hexane to propane occurs at a temperature of from about 400 ° C to about 800 ° C or about 1000 ° C, and at a pressure of from about 1 atmosphere to about 20 atmospheres, for a period of from about 1 minute to about 60 minutes. , or longer, such as 8 hours, 1 day, 4 days, 1 week, or 2 weeks.

Conversion of hexane to butane

In one embodiment, provided herein is a process for converting hexane to butane comprising reacting hexane with a catalytically active carbon catalyst (eg, any of the carbon catalysts described herein (eg, graphene oxide and/or oxidation) Graphite)) contact. A suitable reaction temperature and/or pressure is selected for the reaction.

In one embodiment, the starting material is high purity hexane. In this example, the reaction product is a mixture of high purity butane gas and/or low molecular weight hydrocarbons. In an alternative embodiment, low purity hexane (e.g., a mixture of one or more low molecular weight alkanes and/or olefins) can be used in the reaction. In this example, the reaction product comprises a mixture of one or more gases, including butane, which is further purified using standard procedures.

The reaction is carried out by contacting the reactants with a graphene oxide or graphite oxide carbon catalyst as described herein. As described in more detail herein, conversion efficiency is controlled by varying the temperature and/or amount of catalyst. As an example, in some cases, hexane Conversion to butane occurs at a temperature of from about 400 ° C to about 800 ° C or about 1000 ° C, and a pressure of from about 1 atmosphere to about 20 atmospheres, for a period of from about 1 minute to about 60 minutes, or a longer period of time, such as 8 hours, 1 Days, 4 days, 1 week, or 2 weeks.

Pyrolysis and dehydrogenation Conversion of hexane to propylene

In one embodiment, provided herein is a process for converting hexane to propylene comprising reacting hexane with a catalytically active carbon catalyst (eg, any of the carbon catalysts described herein (eg, graphene oxide and/or graphite oxide) ))contact. A suitable reaction temperature and/or pressure is selected for the reaction.

In one embodiment, the starting material is high purity hexane. In this example, the reaction product is a mixture of high purity propylene gas and/or low molecular weight hydrocarbons. In an alternative embodiment, low purity hexane (e.g., a mixture of one or more low molecular weight alkanes and/or olefins) can be used in the reaction. In this example, the reaction product comprises a mixture of one or more gases, including propylene, which is further purified using standard procedures.

The reaction is carried out by contacting the reactants with a graphene oxide or graphite oxide carbon catalyst as described herein. As described in more detail herein, conversion efficiency is controlled by varying the temperature and/or amount of catalyst. By way of example, in some instances, the conversion of hexane to propylene occurs at a temperature of from about 400 ° C to about 800 ° C or about 1000 ° C, and at a pressure of from about 1 atmosphere to about 20 atmospheres, for a period of from about 1 minute to about 60 minutes. , or longer, such as 8 hours, 1 day, 4 days, 1 week, or 2 weeks.

Conversion of hexane to butene or butadiene

In one embodiment, provided herein is a process for converting hexane to butane or butadiene comprising reacting hexane with a catalytically active carbon catalyst (eg, any of the carbon catalysts described herein (eg, graphene oxide) And / or graphite oxide)) contact. A suitable reaction temperature and/or pressure is selected for the reaction.

In one embodiment, the starting material is high purity hexane. In this example, the counter The product should be a mixture of high purity butadiene or butadiene gas and/or low molecular weight hydrocarbons. In an alternative embodiment, low purity hexane (e.g., a mixture of one or more low molecular weight alkanes and/or olefins) can be used in the reaction. In this example, the reaction product comprises a mixture of one or more gases, including butadiene or butadiene, which is further purified using standard procedures.

The reaction is carried out by contacting the reactants with a graphene oxide or graphite oxide carbon catalyst as described herein. As described in more detail herein, conversion efficiency is controlled by varying the temperature and/or amount of catalyst. By way of example, in some instances, the conversion of hexane to butadiene occurs at a temperature of from about 400 ° C to about 800 ° C or about 1000 ° C, and at a pressure of from about 1 atmosphere to about 20 atmospheres, for about 1 minute to about 60 minutes, or longer, such as 8 hours, 1 day, 4 days, 1 week, or 2 weeks.

Reaction with graphite oxide/solid acid catalyst mixture

The specific examples herein also encompass reactions catalyzed by a mixture of graphite oxide and a solid acid such as zeolite, clay, layered clay or aluminum phosphate. The catalytic activity of graphene oxide or graphite oxide can optionally be modified and/or improved using a solid acid catalyst as a cocatalyst. The solid acid catalyst is optionally a zeolite catalyst comprising a zeolite selected from the group consisting of faujasite (FAU), zeolite socony mobil-5 (ZSM-5), mordenite (MOR) or ferrierite (FERierite (FER) )) zeolite catalyst. The specific examples in this paper also cover synthetic analogues of the following materials: faujasite, sodalite, analcime, Tobermorite, Cancrinite, Clintobermorite and / or X, Y, A, P type zeolite, derived from waste aluminosilicates such as, for example, zeolites obtained from Ceramatec (Salt Lake City, Utah). The zeolite catalyst may optionally incorporate graphene oxide or graphite oxide in solution or in a solid state. The amount of zeolite used can range widely from about 0.01 to about 1000% by weight. The reaction conditions catalyzed by the graphene oxide or graphite oxide/solid acid catalyst mixture are similar to the graphene or graphite oxide catalyzed hydrocarbon conversion described herein (eg, conversion of propane to The reaction conditions used for propylene).

Some specific examples

As described above, methods are provided for the following reactions: (a) conversion of an alkane starting material to an olefin product (dehydrogenation); (b) conversion of an alkane starting material to one or more higher molecular weight alkane products (coupling (c) conversion of the alkane starting material to one or more displacement products (replacement); (d) conversion of the higher alkane starting material to one or more lower alkane products (cracking); (e) conversion of the naphthenic starting material to An alkane product or an olefin product or a combination thereof (cracking); or any combination thereof; comprising the starting material of any of (a)-(e) with a catalytically active carbon catalyst (eg, graphene oxide having catalytically active surface modification) Or graphite oxide) contact to provide the corresponding product in (a)-(e).

(A)

In a specific embodiment, in view of the above reaction (a) (for example, dehydrogenation of propane to propylene), the catalytically active carbon catalyst is a catalytically active surface-modified graphene oxide or graphite oxide material, which is characterized. Lie in:

(1) One or more FT-IR characteristics at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 .

(2) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more hydrogen peroxide capping Surface, epoxide end surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface, alcohol end surface, lactone end surface, tantalum end surface, anhydride end surface or Ether capped surface.

(3) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more epoxide caps Surface, peroxide end surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface, alcohol end surface, rhodium end surface or ether end surface.

(4) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more epoxide caps Surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface or alcohol end surface.

(5) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more hydrogen peroxide capping Surface, epoxide end surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface, alcohol end surface, lactone end surface, tantalum end surface, anhydride end surface or An ether terminated surface; and at least about 25% carbon and at least about 0.01% oxygen as measured by X-ray photoelectron spectroscopy (XPS).

(6) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more epoxide caps Surface, peroxide end surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface, alcohol end surface, rhodium end surface or ether end surface; and via X-ray photoelectron spectroscopy (XPS) measures at least about 25% carbon and at least about 0.01% oxygen.

(7) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more epoxide caps Surface, ketone capping surface, aldehyde capping surface, carboxyl terminated surface, hydroxyl terminated surface or alcohol terminated surface; at least about 25% carbon and at least about 0.01% oxygen as measured by X-ray photoelectron spectroscopy (XPS).

(8) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more hydrogen peroxide capping Surface, epoxide end surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface, alcohol end surface, lactone end surface, tantalum end surface, anhydride end surface or The ether terminated surface; and the catalyst has a carbon to oxygen ratio of between about 1:1 and about 1:1.5 as measured by X-ray photoelectron spectroscopy (XPS).

(9) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more epoxide caps Surface, peroxide end surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface, alcohol end surface, rhodium end surface or ether end surface; and via X-ray photoelectron spectroscopy The catalyst has a carbon to oxygen ratio of between about 1:1 and about 1:1.5 as measured by XPS.

(10) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more epoxide caps Surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface or alcohol end surface; and the carbon to oxygen ratio of the catalyst is measured by X-ray photoelectron spectroscopy (XPS) 1:1 and about 1:1.5.

(11) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more hydrogen peroxide capping Surface, epoxide end surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface, alcohol end surface, lactone end surface, tantalum end surface, anhydride end surface or The ether terminated surface; and the catalyst has a carbon to oxygen ratio of between about 1:1 and about 5:1 as measured by X-ray photoelectron spectroscopy (XPS).

(12) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more epoxide caps Surface, peroxide end surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface, alcohol end surface, rhodium end surface or ether end surface; and via X-ray photoelectron spectroscopy The catalyst has a carbon to oxygen ratio of between about 1:1 and about 5:1 as measured by XPS.

(13) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more epoxide caps Surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface or alcohol end surface; and the carbon to oxygen ratio of the catalyst is measured by X-ray photoelectron spectroscopy (XPS) Between 1:1 and about 5:1.

(14) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more hydrogen peroxide capping Surface, epoxide end surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface, alcohol end surface, lactone end surface, tantalum end surface, anhydride end surface or The ether terminated surface; and the catalyst has a carbon to oxygen ratio of between about 1.5:1 and about 2:1 as measured by X-ray photoelectron spectroscopy (XPS).

(15) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more epoxide caps Surface, peroxide end surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface, alcohol end surface, rhodium end surface or ether end surface; and via X-ray photoelectron spectroscopy The catalyst has a carbon to oxygen ratio of between about 1.5:1 and about 2:1 as measured by XPS.

(16) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more epoxide caps Surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface or alcohol end surface; and the carbon to oxygen ratio of the catalyst is measured by X-ray photoelectron spectroscopy (XPS) 1.5:1 and about 2:1.

(17) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more hydrogen peroxide capping Surface, epoxide end surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface, alcohol end surface, lactone end surface, tantalum end surface, anhydride end surface or The ether terminated surface; and the catalyst has a carbon to oxygen ratio of between about 2:1 and about 3:1 as measured by X-ray photoelectron spectroscopy (XPS).

(18) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more epoxide caps Surface, peroxide end surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface, alcohol end surface, rhodium end surface or ether end surface; and via X-ray photoelectron spectroscopy The catalyst has a carbon to oxygen ratio of between about 2:1 and about 3:1 as measured by XPS.

(19) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more epoxide caps Surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface or alcohol end surface; and the carbon to oxygen ratio of the catalyst is measured by X-ray photoelectron spectroscopy (XPS) 2:1 and about 3:1.

(20) Any one of the above (1) to (19), wherein the main surface is modified to be a hydrogen peroxide-terminated surface.

(21) Any one of the above (1) to (19), wherein the main surface modification is a hydroxyl terminated surface.

(22) Any one of the above (1) to (19), wherein the main surface modification is a carboxyl terminated surface.

(23) Any one of the above (1) to (19), and wherein the major surface modification is an epoxide capping surface.

(24) Any one of the above (1) to (19), wherein the main surface modification is an ether terminated surface.

(25) Any one of the above (1) to (19), wherein the main surface modification is an anhydride-terminated surface.

(26) Any one of the above (1) to (19), and wherein the main surface modification is a ruthenium capping surface.

(27) Any one of the above (1) to (19), wherein the main surface modification is lactone end capping surface.

(28) Any one of the above (1) to (19), wherein the main surface modification is an aldehyde-terminated surface.

(29) Any one of the above (1) to (19), and wherein the main surface is modified to a ketone-terminated surface.

(30) Any one of the above (1) to (19), wherein the main surface modification is an alcohol-terminated surface.

(31) Any one of the above (1) to (19), wherein the detectable surface modification is a hydrogen peroxide-terminated surface.

(32) Any one of the above (1) to (19), wherein the detectable surface modification is a hydroxyl terminated surface.

(33) Any one of the above (1) to (19), wherein the detectable surface modification is a carboxyl terminated surface.

(34) Any one of the above (1) to (19), wherein the detectable surface modification is an epoxide capping surface.

(35) Any one of the above (1) to (19), wherein the detectable surface modification is an ether terminated surface.

(36) Any one of the above (1) to (19), and wherein the detectable surface modification is an anhydride-terminated surface.

(37) Any one of the above (1) to (19), wherein the detectable surface modification is a ruthenium capping surface.

(38) Any one of the above (1) to (19), and wherein the detectable surface modification is a lactone end-capped surface.

(39) Any one of the above (1) to (19), wherein the detectable surface modification is an aldehyde-terminated surface.

(40) Any one of the above (1) to (19), wherein the detectable surface modification is a ketone seal End surface.

(41) Any one of the above (1) to (19), wherein the detectable surface modification is an alcohol-terminated surface.

(B)

In a specific embodiment, for the above reaction (b) (for example, coupling of methane and ethane to propane), the catalytically active carbon catalyst is a graphene oxide or graphite oxide material having catalytically active surface modification. Features are:

(1) One or more FT-IR characteristics at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 .

(2) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more hydrogen peroxide capping Surface, epoxide end surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface, alcohol end surface, lactone end surface, tantalum end surface, anhydride end surface or Ether capped surface.

(3) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more epoxide caps Surface, peroxide end surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface, alcohol end surface, rhodium end surface or ether end surface.

(4) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more epoxide caps Surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface or alcohol end surface.

(5) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more hydrogen peroxide capping Surface, epoxide end surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface, alcohol end surface, lactone end surface, tantalum end surface, anhydride end surface or An ether terminated surface; and at least about 25% carbon and at least about 0.01% oxygen as measured by X-ray photoelectron spectroscopy (XPS).

(6) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more epoxide caps Surface, peroxide end surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface, alcohol end surface, rhodium end surface or ether end surface; and via X-ray photoelectron spectroscopy (XPS) measures at least about 25% carbon and at least about 0.01% oxygen.

(7) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more epoxide caps Surface, ketone capping surface, aldehyde capping surface, carboxyl terminated surface, hydroxyl terminated surface or alcohol terminated surface; at least about 25% carbon and at least about 0.01% oxygen as measured by X-ray photoelectron spectroscopy (XPS).

(8) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more hydrogen peroxide capping Surface, epoxide end surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface, alcohol end surface, lactone end surface, tantalum end surface, anhydride end surface or The ether terminated surface; and the catalyst has a carbon to oxygen ratio of between about 1:1 and about 1:1.5 as measured by X-ray photoelectron spectroscopy (XPS).

(9) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more epoxide caps Surface, peroxide end surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface, alcohol end surface, rhodium end surface or ether end surface; and via X-ray photoelectron spectroscopy The catalyst has a carbon to oxygen ratio of between about 1:1 and about 1:1.5 as measured by XPS.

(10) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more epoxide caps Surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface or alcohol end surface; and the carbon to oxygen ratio of the catalyst is measured by X-ray photoelectron spectroscopy (XPS) 1:1 and about 1:1.5.

(11) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more hydrogen peroxide capping Surface, epoxide end surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface, alcohol end surface, lactone end surface, tantalum end surface, anhydride end surface or The ether terminated surface; and the catalyst has a carbon to oxygen ratio of between about 1:1 and about 5:1 as measured by X-ray photoelectron spectroscopy (XPS).

(12) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more epoxide caps Surface, peroxide end surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface, alcohol end surface, rhodium end surface or ether end surface; and via X-ray photoelectron spectroscopy The catalyst has a carbon to oxygen ratio of between about 1:1 and about 5:1 as measured by XPS.

(13) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more epoxide caps Surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface or alcohol end surface; and the carbon to oxygen ratio of the catalyst is measured by X-ray photoelectron spectroscopy (XPS) Between 1:1 and about 5:1.

(14) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more hydrogen peroxide capping Surface, epoxide end surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface, alcohol end surface, lactone end surface, tantalum end surface, anhydride end surface or The ether terminated surface; and the catalyst has a carbon to oxygen ratio of between about 1.5:1 and about 2:1 as measured by X-ray photoelectron spectroscopy (XPS).

(15) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more epoxide caps Surface, peroxide end surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface, alcohol end surface, rhodium end surface or ether end surface; and via X-ray photoelectron spectroscopy The catalyst has a carbon to oxygen ratio of between about 1.5:1 and about 2:1 as measured by XPS.

(16) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more epoxide caps Surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface or alcohol end surface; and the carbon to oxygen ratio of the catalyst is measured by X-ray photoelectron spectroscopy (XPS) 1.5:1 and about 2:1.

(17) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more hydrogen peroxide capping Surface, epoxide end surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface, alcohol end surface, lactone end surface, tantalum end surface, anhydride end surface or The ether terminated surface; and the catalyst has a carbon to oxygen ratio of between about 2:1 and about 3:1 as measured by X-ray photoelectron spectroscopy (XPS).

(18) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more epoxide caps Surface, peroxide end surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface, alcohol end surface, rhodium end surface or ether end surface; and via X-ray photoelectron spectroscopy The catalyst has a carbon to oxygen ratio of between about 2:1 and about 3:1 as measured by XPS.

(19) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more epoxide caps Surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface or alcohol end surface; and the carbon to oxygen ratio of the catalyst is measured by X-ray photoelectron spectroscopy (XPS) 2:1 and about 3:1.

(20) Any one of the above (1) to (19), wherein the main surface is modified to be a hydrogen peroxide-terminated surface.

(21) Any one of the above (1) to (19), wherein the main surface modification is a hydroxyl terminated surface.

(22) Any one of the above (1) to (19), wherein the main surface modification is a carboxyl terminated surface.

(23) Any one of the above (1) to (19), and wherein the major surface modification is an epoxide capping surface.

(24) Any one of the above (1) to (19), wherein the main surface modification is an ether terminated surface.

(25) Any one of the above (1) to (19), wherein the main surface modification is an anhydride-terminated surface.

(26) Any one of the above (1) to (19), and wherein the main surface modification is a ruthenium capping surface.

(27) Any one of the above (1) to (19), wherein the main surface modification is a lactone end-capped surface.

(28) Any one of the above (1) to (19), wherein the main surface modification is an aldehyde-terminated surface.

(29) Any one of the above (1) to (19), and wherein the main surface is modified to a ketone-terminated surface.

(30) Any one of the above (1) to (19), wherein the main surface modification is an alcohol-terminated surface.

(31) Any one of the above (1) to (19), wherein the detectable surface modification is a hydrogen peroxide-terminated surface.

(32) Any one of the above (1) to (19), wherein the detectable surface modification is a hydroxyl terminated surface.

(33) Any one of the above (1) to (19), wherein the detectable surface modification is a carboxyl terminated surface.

(34) Any one of the above (1) to (19), wherein the detectable surface modification is an epoxide capping surface.

(35) Any one of the above (1) to (19), wherein the detectable surface modification is an ether terminated surface.

(36) Any one of the above (1) to (19), and wherein the detectable surface modification is an anhydride-terminated surface.

(37) Any one of the above (1) to (19), wherein the detectable surface modification is a ruthenium capping surface.

(38) Any one of the above (1) to (19), and wherein the detectable surface modification is a lactone end-capped surface.

(39) Any one of the above (1) to (19), wherein the detectable surface modification is an aldehyde-terminated surface.

(40) Any one of the above (1) to (19), wherein the detectable surface modification is a ketone-terminated surface.

(41) Any one of the above (1) to (19), wherein the detectable surface modification is an alcohol-terminated surface.

(C)

In a specific embodiment, in the case of the above reaction (c) (for example, the conversion of ethane to methane and propane), the catalytically active carbon catalyst is a graphene oxide or graphite oxide material having catalytically active surface modification. Features are:

(1) One or more FT-IR characteristics at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 .

(2) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more hydrogen peroxide capping Surface, epoxide end surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface, alcohol end surface, lactone end surface, tantalum end surface, anhydride end surface or Ether capped surface.

(3) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more epoxide caps Surface, peroxide end surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface, alcohol end surface, rhodium end surface or ether end surface.

(4) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more epoxide caps Surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface or alcohol end surface.

(5) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more hydrogen peroxide capping Surface, epoxide end surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface, alcohol end surface, lactone end surface, tantalum end surface, anhydride end surface or An ether terminated surface; and at least about 25% carbon and at least about 0.01% oxygen as measured by X-ray photoelectron spectroscopy (XPS).

(6) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more epoxide caps Surface, peroxide end surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface, alcohol end surface, rhodium end surface or ether end surface; and via X-ray photoelectron spectroscopy (XPS) measures at least about 25% carbon and at least about 0.01% oxygen.

(7) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more epoxide caps Surface, ketone capping surface, aldehyde capping surface, carboxyl terminated surface, hydroxyl terminated surface or alcohol terminated surface; at least about 25% carbon and at least about 0.01% oxygen as measured by X-ray photoelectron spectroscopy (XPS).

(8) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more hydrogen peroxide capping Surface, epoxide end surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface, alcohol end surface, lactone end surface, tantalum end surface, anhydride end surface or The ether terminated surface; and the catalyst has a carbon to oxygen ratio of between about 1:1 and about 1:1.5 as measured by X-ray photoelectron spectroscopy (XPS).

(9) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more epoxide caps Surface, peroxide end surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface, alcohol end surface, rhodium end surface or ether end surface; and via X-ray photoelectron spectroscopy The catalyst has a carbon to oxygen ratio of between about 1:1 and about 1:1.5 as measured by XPS.

(10) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more epoxide caps Surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface or alcohol end surface; and the carbon to oxygen ratio of the catalyst is measured by X-ray photoelectron spectroscopy (XPS) 1:1 and about 1:1.5.

(11) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more hydrogen peroxide capping Surface, epoxide end surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface, alcohol end surface, lactone end surface, tantalum end surface, anhydride end surface or The ether terminated surface; and the catalyst has a carbon to oxygen ratio of between about 1:1 and about 5:1 as measured by X-ray photoelectron spectroscopy (XPS).

(12) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more epoxide caps Surface, peroxide end surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface, alcohol end surface, rhodium end surface or ether end surface; and via X-ray photoelectron spectroscopy The catalyst has a carbon to oxygen ratio of between about 1:1 and about 5:1 as measured by XPS.

(13) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more epoxide caps Surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface or alcohol end surface; and the carbon to oxygen ratio of the catalyst is measured by X-ray photoelectron spectroscopy (XPS) Between 1:1 and about 5:1.

(14) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more hydrogen peroxide capping Surface, epoxide end surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface, alcohol end surface, lactone end surface, tantalum end surface, anhydride end surface or The ether terminated surface; and the catalyst has a carbon to oxygen ratio of between about 1.5:1 and about 2:1 as measured by X-ray photoelectron spectroscopy (XPS).

(15) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more epoxide caps Surface, peroxide end surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface, alcohol end surface, rhodium end surface or ether end surface; and via X-ray photoelectron spectroscopy The catalyst has a carbon to oxygen ratio of between about 1.5:1 and about 2:1 as measured by XPS.

(16) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more epoxide caps Surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface or alcohol end surface; and the carbon to oxygen ratio of the catalyst is measured by X-ray photoelectron spectroscopy (XPS) 1.5:1 and about 2:1.

(17) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more hydrogen peroxide capping Surface, epoxide end surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface, alcohol end surface, lactone end surface, tantalum end surface, anhydride end surface or The ether terminated surface; and the catalyst has a carbon to oxygen ratio of between about 2:1 and about 3:1 as measured by X-ray photoelectron spectroscopy (XPS).

(18) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more epoxide caps Surface, peroxide end surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface, alcohol end surface, rhodium end surface or ether end surface; and via X-ray photoelectron spectroscopy The catalyst has a carbon to oxygen ratio of between about 2:1 and about 3:1 as measured by XPS.

(19) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more epoxide caps Surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface or alcohol end surface; and the carbon to oxygen ratio of the catalyst is measured by X-ray photoelectron spectroscopy (XPS) 2:1 and about 3:1.

(20) Any one of the above (1) to (19), wherein the main surface is modified to be a hydrogen peroxide-terminated surface.

(21) Any one of the above (1) to (19), wherein the main surface modification is a hydroxyl terminated surface.

(22) Any one of the above (1) to (19), wherein the main surface modification is a carboxyl terminated surface.

(23) Any one of the above (1) to (19), wherein the main surface modification is an epoxide End surface.

(24) Any one of the above (1) to (19), wherein the main surface modification is an ether terminated surface.

(25) Any one of the above (1) to (19), wherein the main surface modification is an anhydride-terminated surface.

(26) Any one of the above (1) to (19), and wherein the main surface modification is a ruthenium capping surface.

(27) Any one of the above (1) to (19), wherein the main surface modification is a lactone end-capped surface.

(28) Any one of the above (1) to (19), wherein the main surface modification is an aldehyde-terminated surface.

(29) Any one of the above (1) to (19), and wherein the main surface is modified to a ketone-terminated surface.

(30) Any one of the above (1) to (19), wherein the main surface modification is an alcohol-terminated surface.

(31) Any one of the above (1) to (19), wherein the detectable surface modification is a hydrogen peroxide-terminated surface.

(32) Any one of the above (1) to (19), wherein the detectable surface modification is a hydroxyl terminated surface.

(33) Any one of the above (1) to (19), wherein the detectable surface modification is a carboxyl terminated surface.

(34) Any one of the above (1) to (19), wherein the detectable surface modification is an epoxide capping surface.

(35) Any one of the above (1) to (19), wherein the detectable surface modification is an ether terminated surface.

(36) Any one of the above (1) to (19), wherein the detectable surface modification is an anhydride seal End surface.

(37) Any one of the above (1) to (19), wherein the detectable surface modification is a ruthenium capping surface.

(38) Any one of the above (1) to (19), and wherein the detectable surface modification is a lactone end-capped surface.

(39) Any one of the above (1) to (19), wherein the detectable surface modification is an aldehyde-terminated surface.

(40) Any one of the above (1) to (19), wherein the detectable surface modification is a ketone-terminated surface.

(41) Any one of the above (1) to (19), wherein the detectable surface modification is an alcohol-terminated surface.

(D)

In a specific embodiment, the catalytically active carbon catalyst is in the case of the above reaction (d) (for example, the conversion of hexane to methane and/or ethane and/or propane and/or butane or a combination thereof). A graphene oxide or graphite oxide material having a catalytically active surface modification characterized by:

(1) One or more FT-IR characteristics at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 .

(2) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more hydrogen peroxide capping Surface, epoxide end surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface, alcohol end surface, lactone end surface, tantalum end surface, anhydride end surface or Ether capped surface.

(3) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more epoxide caps Surface, peroxide end surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface, alcohol end surface, rhodium end surface or ether end surface.

(4) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more epoxide caps Surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface or alcohol end surface.

(5) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more hydrogen peroxide capping Surface, epoxide end surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface, alcohol end surface, lactone end surface, tantalum end surface, anhydride end surface or An ether terminated surface; and at least about 25% carbon and at least about 0.01% oxygen are measured via X-ray photoelectron spectroscopy (XPS).

(6) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more epoxide caps Surface, peroxide end surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface, alcohol end surface, rhodium end surface or ether end surface; and via X-ray photoelectron spectroscopy (XPS) measures at least about 25% carbon and at least about 0.01% oxygen.

(7) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more epoxide caps Surface, ketone capping surface, aldehyde capping surface, carboxyl terminated surface, hydroxyl terminated surface or alcohol terminated surface; at least about 25% carbon and at least about 0.01% oxygen as measured by X-ray photoelectron spectroscopy (XPS).

(8) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more hydrogen peroxide capping Surface, epoxide end surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface, alcohol end surface, lactone end surface, tantalum end surface, anhydride end surface or The ether terminated surface; and the catalyst has a carbon to oxygen ratio of between about 1:1 and about 1:1.5 as measured by X-ray photoelectron spectroscopy (XPS).

(9) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more epoxide caps Surface, peroxide end surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface, alcohol end surface, rhodium end surface or ether end surface; and via X-ray photoelectron spectroscopy The catalyst has a carbon to oxygen ratio of between about 1:1 and about 1:1.5 as measured by XPS.

(10) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more epoxide caps Surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface or alcohol end surface; and the carbon to oxygen ratio of the catalyst is measured by X-ray photoelectron spectroscopy (XPS) 1:1 and about 1:1.5.

(11) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more hydrogen peroxide capping Surface, epoxide end surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface, alcohol end surface, lactone end surface, tantalum end surface, anhydride end surface or The ether terminated surface; and the catalyst has a carbon to oxygen ratio of between about 1:1 and about 5:1 as measured by X-ray photoelectron spectroscopy (XPS).

(12) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more epoxide caps Surface, peroxide end surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface, alcohol end surface, rhodium end surface or ether end surface; and via X-ray photoelectron spectroscopy The catalyst has a carbon to oxygen ratio of between about 1:1 and about 5:1 as measured by XPS.

(13) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more epoxide caps Surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface or alcohol end surface; and the carbon to oxygen ratio of the catalyst is measured by X-ray photoelectron spectroscopy (XPS) Between 1:1 and about 5:1.

(14) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more hydrogen peroxide capping Surface, epoxide end surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface, alcohol end surface, lactone end surface, tantalum end surface, anhydride end surface or The ether terminated surface; and the catalyst has a carbon to oxygen ratio of between about 1.5:1 and about 2:1 as measured by X-ray photoelectron spectroscopy (XPS).

(15) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more epoxide caps Surface, peroxide end surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface, alcohol end surface, rhodium end surface or ether end surface; and via X-ray photoelectron spectroscopy The catalyst has a carbon to oxygen ratio of between about 1.5:1 and about 2:1 as measured by XPS.

(16) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more epoxide caps Surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface or alcohol end surface; and the carbon to oxygen ratio of the catalyst is measured by X-ray photoelectron spectroscopy (XPS) 1.5:1 and about 2:1.

(17) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more hydrogen peroxide capping Surface, epoxide end surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface, alcohol end surface, lactone end surface, tantalum end surface, anhydride end surface or The ether terminated surface; and the catalyst has a carbon to oxygen ratio of between about 2:1 and about 3:1 as measured by X-ray photoelectron spectroscopy (XPS).

(18) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more epoxide caps Surface, peroxide end surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface, alcohol end surface, rhodium end surface or ether end surface; and via X-ray photoelectron spectroscopy The catalyst has a carbon to oxygen ratio of between about 2:1 and about 3:1 as measured by XPS.

(19) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more epoxide caps Surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface or alcohol end surface; and the carbon to oxygen ratio of the catalyst is measured by X-ray photoelectron spectroscopy (XPS) 2:1 and about 3:1.

(20) Any one of the above (1) to (19), wherein the main surface is modified to be a hydrogen peroxide-terminated surface.

(21) Any one of the above (1) to (19), wherein the main surface modification is a hydroxyl terminated surface.

(22) Any one of the above (1) to (19), wherein the main surface modification is a carboxyl terminated surface.

(23) Any one of the above (1) to (19), and wherein the major surface modification is an epoxide capping surface.

(24) Any one of the above (1) to (19), wherein the main surface modification is an ether terminated surface.

(25) Any one of the above (1) to (19), wherein the main surface modification is an anhydride-terminated surface.

(26) Any one of the above (1) to (19), and wherein the main surface modification is a ruthenium capping surface.

(27) Any one of the above (1) to (19), wherein the main surface is modified to a lactone end-capped surface.

(28) Any one of the above (1) to (19), wherein the main surface modification is an aldehyde end-capped surface.

(29) Any one of the above (1) to (19), and wherein the main surface is modified to a ketone-terminated surface.

(30) Any one of the above (1) to (19), wherein the main surface modification is an alcohol-terminated surface.

(31) Any one of the above (1) to (19), wherein the detectable surface modification is a hydrogen peroxide-terminated surface.

(32) Any one of the above (1) to (19), wherein the detectable surface modification is a hydroxyl terminated surface.

(33) Any one of the above (1) to (19), wherein the detectable surface modification is a carboxyl terminated surface.

(34) Any one of the above (1) to (19), wherein the detectable surface modification is an epoxide capping surface.

(35) Any one of the above (1) to (19), wherein the detectable surface modification is an ether terminated surface.

(36) Any one of the above (1) to (19), and wherein the detectable surface modification is an anhydride-terminated surface.

(37) Any one of the above (1) to (19), wherein the detectable surface modification is a ruthenium capping surface.

(38) Any one of the above (1) to (19), and wherein the detectable surface modification is a lactone end-capped surface.

(39) Any one of the above (1) to (19), wherein the detectable surface modification is an aldehyde-terminated surface.

(40) Any one of the above (1) to (19), wherein the detectable surface modification is a ketone-terminated surface.

(41) Any one of the above (1) to (19), wherein the detectable surface modification is an alcohol-terminated surface.

(E)

In a specific embodiment, the catalytically active carbon catalyst is a catalytically active surface in the case of the above reaction (e) (for example, the conversion of cyclohexane to methane and/or ethane and/or propane or a combination thereof). A modified graphene oxide or graphite oxide material characterized by:

(1) One or more FT-IR characteristics at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 .

(2) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more hydrogen peroxide capping Surface, epoxide end surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface, alcohol end surface, lactone end surface, tantalum end surface, anhydride end surface or Ether capped surface.

(3) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more epoxide caps Surface, peroxide end surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface, alcohol end surface, rhodium end surface or ether end surface.

(4) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more epoxide caps Surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface or alcohol end surface.

(5) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more hydrogen peroxide capping Surface, epoxide end surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface, alcohol end surface, lactone end surface, tantalum end surface, anhydride end surface or An ether terminated surface; and at least about 25% carbon and at least about 0.01% oxygen as measured by X-ray photoelectron spectroscopy (XPS).

(6) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more epoxide caps Surface, peroxide end surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface, alcohol end surface, rhodium end surface or ether end surface; and via X-ray photoelectron spectroscopy (XPS) measures at least about 25% carbon and at least about 0.01% oxygen.

(7) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more epoxide caps Surface, ketone capping surface, aldehyde capping surface, carboxyl terminated surface, hydroxyl terminated surface or alcohol terminated surface; at least about 25% carbon and at least about 0.01% oxygen as measured by X-ray photoelectron spectroscopy (XPS).

(8) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more hydrogen peroxide capping Surface, epoxide end surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface, alcohol end surface, lactone end surface, tantalum end surface, anhydride end surface or The ether terminated surface; and the catalyst has a carbon to oxygen ratio of between about 1:1 and about 1:1.5 as measured by X-ray photoelectron spectroscopy (XPS).

(9) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more epoxide caps Surface, peroxide end surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface, alcohol end surface, rhodium end surface or ether end surface; and via X-ray photoelectron spectroscopy The catalyst has a carbon to oxygen ratio of between about 1:1 and about 1:1.5 as measured by XPS.

(10) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more epoxide caps Surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface or alcohol end surface; and the carbon to oxygen ratio of the catalyst is measured by X-ray photoelectron spectroscopy (XPS) 1:1 and about 1:1.5.

(11) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more hydrogen peroxide capping Surface, epoxide end surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface, alcohol end surface, lactone end surface, tantalum end surface, anhydride end surface or The ether terminated surface; and the catalyst has a carbon to oxygen ratio of between about 1:1 and about 5:1 as measured by X-ray photoelectron spectroscopy (XPS).

(12) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more epoxide caps Surface, peroxide end surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface, alcohol end surface, rhodium end surface or ether end surface; and via X-ray photoelectron spectroscopy The catalyst has a carbon to oxygen ratio of between about 1:1 and about 5:1 as measured by XPS.

(13) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more epoxide caps Surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface or alcohol end surface; and the carbon to oxygen ratio of the catalyst is measured by X-ray photoelectron spectroscopy (XPS) Between 1:1 and about 5:1.

(14) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more hydrogen peroxide capping Surface, epoxide end surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface, alcohol end surface, lactone end surface, tantalum end surface, anhydride end surface or The ether terminated surface; and the catalyst has a carbon to oxygen ratio of between about 1.5:1 and about 2:1 as measured by X-ray photoelectron spectroscopy (XPS).

(15) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more epoxide caps Surface, peroxide end surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface, alcohol end surface, rhodium end surface or ether end surface; and via X-ray photoelectron spectroscopy The catalyst has a carbon to oxygen ratio of between about 1.5:1 and about 2:1 as measured by XPS.

(16) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more epoxide caps Surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface or alcohol end surface; and the carbon to oxygen ratio of the catalyst is measured by X-ray photoelectron spectroscopy (XPS) 1.5:1 and about 2:1.

(17) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more hydrogen peroxide capping Surface, epoxide end surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface, alcohol end surface, lactone end surface, tantalum end surface, anhydride end surface or The ether terminated surface; and the catalyst has a carbon to oxygen ratio of between about 2:1 and about 3:1 as measured by X-ray photoelectron spectroscopy (XPS).

(18) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more epoxide caps Surface, peroxide end surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface, alcohol end surface, rhodium end surface or ether end surface; and via X-ray photoelectron spectroscopy The catalyst has a carbon to oxygen ratio of between about 2:1 and about 3:1 as measured by XPS.

(19) having one or more FT-IR features at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 ; and surface modification comprising one or more epoxide caps Surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface or alcohol end surface; and the carbon to oxygen ratio of the catalyst is measured by X-ray photoelectron spectroscopy (XPS) 2:1 and about 3:1.

(20) Any one of the above (1) to (19), wherein the main surface is modified to be a hydrogen peroxide-terminated surface.

(21) Any one of the above (1) to (19), wherein the main surface modification is a hydroxyl terminated surface.

(22) Any one of the above (1) to (19), wherein the main surface modification is a carboxyl terminated surface.

(23) Any one of the above (1) to (19), and wherein the major surface modification is an epoxide capping surface.

(24) Any one of the above (1) to (19), wherein the main surface modification is an ether terminated surface.

(25) Any one of the above (1) to (19), wherein the main surface modification is an anhydride-terminated surface.

(26) Any one of the above (1) to (19), and wherein the main surface modification is a ruthenium capping surface.

(27) Any one of the above (1) to (19), wherein the main surface modification is a lactone end-capped surface.

(28) Any one of the above (1) to (19), wherein the main surface modification is an aldehyde-terminated surface.

(29) Any one of the above (1) to (19), and wherein the main surface is modified to a ketone-terminated surface.

(30) Any one of the above (1) to (19), wherein the main surface modification is an alcohol-terminated surface.

(31) Any one of the above (1) to (19), wherein the detectable surface modification is a hydrogen peroxide-terminated surface.

(32) Any one of the above (1) to (19), wherein the detectable surface modification is a hydroxyl group End surface.

(33) Any one of the above (1) to (19), wherein the detectable surface modification is a carboxyl terminated surface.

(34) Any one of the above (1) to (19), wherein the detectable surface modification is an epoxide capping surface.

(35) Any one of the above (1) to (19), wherein the detectable surface modification is an ether terminated surface.

(36) Any one of the above (1) to (19), and wherein the detectable surface modification is an anhydride-terminated surface.

(37) Any one of the above (1) to (19), wherein the detectable surface modification is a ruthenium capping surface.

(38) Any one of the above (1) to (19), and wherein the detectable surface modification is a lactone end-capped surface.

(39) Any one of the above (1) to (19), wherein the detectable surface modification is an aldehyde-terminated surface.

(40) Any one of the above (1) to (19), wherein the detectable surface modification is a ketone-terminated surface.

(41) Any one of the above (1) to (19), wherein the detectable surface modification is an alcohol-terminated surface.

F

For each of the specific examples of each of (A) , (B) , (C) , (D) or (E) above, the catalyst is substantially free of any transition metal (eg, the catalyst contains less than 0.1% of any The weight of the transition metal).

For each specific example of (A) , (B) , (C) , (D) or (E) above, or for each of the above (A) and (F) , (B) And for each specific example of (F) , (C) and (F) , (D) and (F) or (E) and (F) , the catalyst is used in an amount of (1-1) at about 0.1. Weight by weight to about 10% by weight of the starting material.

(1-2) at a weight of from about 0.1% by weight to about 1% by weight of the starting material.

(1-3) The weight of the starting material is from about 0.001% by weight to about 0.1% by weight.

(1-4) The weight of the starting material in the range of from about 10% by weight to about 50% by weight.

(1-5) The weight of the starting material in the range of from about 10% by weight to about 100% by weight.

(1-6) The weight of the starting material in the range of from about 100% by weight to about 500% by weight.

(1-7) The weight of the starting material in the range of from about 100% by weight to about 1000% by weight.

(1-8) The weight of the starting material in the range of from about 1000% by weight to about 10,000% by weight.

For each of (A) and (1-1), (A) and (1-2), (A) and (1-3), (A) and (1-4), (A) and (1- 5), (A) and (1-6), (A) and (1-7), (A) and (1-8), (A) and (F) and (1-1), (A) And (F) and (1-2), (A) and (F) and (1-3), (A) and (F) and (1-4), (A) and (F) and (1- 5), (A) and (F) and (1-6), (A) and (F) and (1-7), (A) and (F) and (1-8), (B) and 1-1), (B) and (1-2), (B) and (1-3), (B) and (1-4), (B) and (1-5), (B) and 1-6), (B) and (1-7), (A) and (1-8), (B) and (F) and (1-1), (B) and (F) and (1 2), (B) and (F) and (1-3), (B) and (F) and (1-4), (B) and (F) and (1-5), (B) and ( F) and (1-6), (B) and (F) and (1-7), (B) and (F) and (1-8), (C) and (1-1), (C) And (1-2), (C) and (1-3), (C) and (1-4), (C) and (1-5), (C) and (1-6), (C) and (1-7), (C) and (1-8), (C) and (F) and (1-1), (C) and (F) and (1-2), (C) and ( F) and (1-3), (C) and (F) and (1-4), (C) and (F) and (1-5), (C) and (F) and (1-6) , (C) and (F) and (1-7), (C) and (F) and (1-8), (D) and (1-1), (D) and (1-2), ( D) and (1-3), (D) and (1-4), (D) and (1-5), (D) and (1-6), (D) and (1-7), ( D) and (1-8), (A) and (F) And (1-1), (D) and (F) and (1-2), (D) and (F) and (1-3), (D) and (F) and (1-4), ( D) and (F) and (1-5) , (D) and (F) and (1-6), (D) and (F) and (1-7), (D) and (F) and 1-8), (E) and (1-1), (E) and (1-2), (E) and (1-3), (E) and (1-4), (E) and 1-5), (E) and (1-6), (E) and (1-7), (E) and (1-8), (E) and (F) and (1-1), ( E) and (F) and (1-2), (E) and (F) and (1-3), (E) and (F) and (1-4), (E) and (F) and Each specific of 1-5), (E) and (F) and (1-6), (E) and (F) and (1-7) or (E) and (F) and (1-8) For example, the reaction is carried out at the following temperature: (2-1) between about -78 ° C and room temperature.

(2-2) is between about room temperature and about 100 °C.

(2-3) is between about 100 ° C and about 300 ° C.

(2-4) is between about 200 ° C and about 400 ° C.

(2-4) is between about 300 ° C and about 500 ° C.

(2-5) is between about 400 ° C and about 450 ° C.

(2-6) is between about 400 ° C and about 500 ° C.

(2-7) is between about 400 ° C and about 600 ° C.

(3-1) For each of the specific examples described above, the reaction was carried out at a pressure of 1 atm.

(3-2) For each of the specific examples described above, the reaction is carried out at a pressure of between about 1-5 atm.

(3-3) For each of the specific examples described above, the reaction is carried out at a pressure of between about 0.1 and 1 atm.

(3-4) For each of the specific examples described above, the reaction is carried out at a pressure of between about 1-10 atm.

(3-5) For each of the specific examples described above, the reaction is carried out at a pressure of between about 1 and 50 atm.

(4-1) In the above specific example (3-1), the catalytically active carbon catalyst is a catalytically active surface-modified graphene oxide or graphite oxide, and the catalytically active surface-modified graphene oxide or Graphite oxide is a graphene oxide having a catalytically active surface modification.

(4-2) In the above specific example (3-1), the catalytically active carbon catalyst is a catalytically active surface-modified graphene oxide or graphite oxide, and the catalytically active surface-modified graphene oxide or Graphite oxide is a graphite oxide having a catalytically active surface modification.

(4-3) In the above specific example (3-2), the catalytically active carbon catalyst is urging The active surface-modified graphene oxide or graphite oxide, and the catalytically active surface-modified graphene oxide or graphite oxide is a catalytically active surface-modified graphene oxide.

(4-4) In the above specific example (3-2), the catalytically active carbon catalyst is a catalytically active surface-modified graphene oxide or graphite oxide, and the catalytically active surface-modified graphene oxide or Graphite oxide is a graphite oxide having a catalytically active surface modification.

(4-5) In the above specific example (3-3), the catalytically active carbon catalyst is a catalytically active surface-modified graphene oxide or graphite oxide, and the catalytically active surface-modified graphene oxide or Graphite oxide is a graphene oxide having a catalytically active surface modification.

(4-6) In the above specific example (3-3), the catalytically active carbon catalyst is a catalytically active surface-modified graphene oxide or graphite oxide, and the catalytically active surface-modified graphene oxide or Graphite oxide is a graphite oxide having a catalytically active surface modification.

(4-7) In the above specific example (3-4), the catalytically active carbon catalyst is a catalytically active surface-modified graphene oxide or graphite oxide, and the catalytically active surface-modified graphene oxide or Graphite oxide is a graphene oxide having a catalytically active surface modification.

(4-8) In the above specific example (3-4), the catalytically active carbon catalyst is a catalytically active surface-modified graphene oxide or graphite oxide, and the catalytically active surface-modified graphene oxide or Graphite oxide is a graphite oxide having a catalytically active surface modification.

(4-9) In the above specific example (3-5), the catalytically active carbon catalyst is a catalytically active surface-modified graphene oxide or graphite oxide, and the catalytically active surface-modified graphene oxide or Graphite oxide is a graphene oxide having a catalytically active surface modification.

(4-10) In the above specific example (3-5), the catalytically active carbon catalyst is a catalytically active surface-modified graphene oxide or graphite oxide, and the catalytically active surface-modified graphene oxide or Graphite oxide is a graphite oxide having a catalytically active surface modification.

(5-1) For (4-1), (4-2), (4-2), (4-3), (4-4), (4-5), (4-6), (4) For each of -7), (4-8), (4-9) or (4-10), the reaction is under power control.

(5-2) For (4-1), (4-2), (4-2), (4-3), (4-4), (4-5), (4-6), (4 -7) For each of (4-8), (4-9) or (4-10), the reaction is under thermodynamic control.

Although specific reaction conditions, conversions, and yields are specified herein, the above conditions, conversions, and yields can be applied to reactions catalyzed by any catalytically active carbon catalyst, including surface modified graphene oxide or graphite oxide. on.

Example

The invention will be better understood by reference to the following examples. The examples are merely provided to illustrate illustrative specific examples and are not to be construed as covering the entire scope of the invention.

Data for ¹ H and ¹³ C NMR were collected on a Varian Unity INOVA 400 MHz spectrometer. The chemical shift (δ) is reported in ppm with (CH ₃ ) ₄ Si as the magnetic field reference and the residual solvent peak as the internal standard ( ¹ H: CDCl ₃ , 7.24 ppm; C ₆ D ₆ , 7.15 ppm; C ₇ D ₈ , 7.09 ppm; ¹³ C: CDCl ₃ , 77.0 ppm; C ₆ D ₆ 128.0 ppm; C ₇ D ₈ , 137.5 ppm). Mass spectra (CI) were taken with a Karatos MS9 instrument and reported in m/z (relative intensity). IR spectra were recorded in the solid state in KBr using the Thermo Scientific Nicolet iS5 system with the iD3 Attenuated Total Reflection (ATR) accessory (twisted) or the Perkin-Elmer Spectrum BX system.

XPS spectra were recorded using a commercially available X-ray photoelectron spectrometer (Kratos Axis Ultra) using a monochromatic Al-K _alpha X-ray source (1486.5 eV), hybrid optics (using both magnetic and electrostatic lenses) and multi-channel plates (multi The -channel plate and the delay line detector are connected to a hemispherical analyzer. The photoelectron take-off angle is perpendicular to the surface of the sample and is 15°, 26°, 38°, 45° or 52° with respect to the X-ray beam. All spectra were recorded using a single scan and a 300 x 700 micron slit aperture, and a high resolution spectrum of each element was collected with a pass energy of 20 eV while the measurement record was collected by energy using 80 eV. The pressure measured in the analysis chamber during data acquisition is typically 4x10 ^-9 Torr.

The ToF-SIMS analysis was performed under static conditions using the IONTOF TOF-SIMS5 (4" version of the instrument, located at the Texas Materials Institute at the University of Texas at Austin. This instrument uses a 30 keV Bi ₃ ⁺ primary ion beam (primary ion) Beam), which is extracted from the Bi/Mn alloy source, and a 0.5 keV 铯sputtered ion beam, which is generated by a DSC-S gun that allows a maximum energy of 2 keV. The data acquisition is performed on the ION-TOF SurfaceLab On a PC-based workstation, it is connected to a PC to execute ION-TOF SurfaceLab 6 software and IGOR, which are used for data transfer and processing.

Example 1 - Preparation of graphene oxide or graphite oxide catalyst

Graphene oxide or graphite oxide used in some of the experiments in these examples was prepared according to the following method.

The modified Hummers method was used to prepare graphite oxide. The flake graphite was reacted with potassium permanganate (KMnO ₄ ) in concentrated sulfuric acid (H ₂ SO ₄ ) at 35 ° C for 4 hours to obtain surface-modified graphene oxide or graphite oxide (MG). The reaction of the reaction mixture is then terminated by dilution in deionized water followed by the addition of an aqueous solution of hydrogen peroxide (H ₂ O ₂ ). MG is insoluble in this mixture and is thus recovered by vacuum filtration followed by washing with excess water to remove residual metal salts and acids. Finally, the hygroscopic product was dried under vacuum to remove residual water to give the product as a dark brown powder. The mass balance of this reaction is depicted in Figure 1. The ratio of graphite to KMnO ₄ and H ₂ SO ₄ can optionally be varied to produce MGs having different degrees of oxidation.

Example 2: Preparation of graphite oxide

A 250 mL reaction flask was charged with natural flake graphite (1.56 g; SP-1 Bay Carbon Inc. or Alfa Aesar [99%; 7-10 μm]), 50 mL of concentrated sulfuric acid, 25 mL of fuming nitric acid and Stir the rod and then cool on an ice bath. The flask was then charged under stirring in NaClO ₃ (3.25 g; Note: In some instances, since KClO ₄ during the reaction of forming water-insoluble, NaClO _{3. 3} is more preferably KClO). Additional NaClO ₃ (3.25 g) was added every hour for 11 consecutive hours per day. This procedure is repeated for 3 days. The resulting mixture was poured into 2 L of deionized water. Next, the heterogeneous dispersion was filtered through a coarse fritted funnel or nylon membrane filter (0.2 μm, Whatman) with additional deionized water (3 L) and 6 N HCl (1 L Wash the separated material. The filtered solid was collected and dried under high vacuum to afford product (3.61 g) as a dark brown powder.

Example 3: Preparation of graphene oxide

A graphene substrate is provided in the reaction chamber. The substrate exhibited no one or more Fourier Transform Infrared (FT-IR) peaks at 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 . The plasma-excited species of oxygen are then directed from the plasma generator into the reaction chamber and brought into contact with the exposed surface of the graphene substrate. The graphene substrate is exposed to a plasma-excited species of oxygen until the FT-IR spectrum of the substrate exhibits one or more peaks at 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^{-1 ,} or 1140 cm ^-1 .

Example 4 Conversion of propane to propylene using graphene oxide or graphite oxide

The catalyst powder prepared in Example 1 was used as a catalyst for converting propane to propylene. A 30 mL glass reactor was charged with MG (50 mg; density ~2 g mL ^-1 ) and sealed with a rubber septum. The reactor was then evacuated (10 ^-3 Torr) and backfilled with propane (Praxair instrument fuel grade; 99.5% purity) to a pressure of 1 atm. The reactor was then heated to 400 ° C over various lengths of time (1-168 hours). The reaction was terminated by cooling to -78 ° C in a dry ice-isopropanol bath to concentrate the gas mixture. Then the septum was removed, 1-2 mL of CDCl ₃ was added to dissolve the crude product mixture. The slurry was then filtered using a syringe to remove the MG, resulting in a clear, colorless filtrate. When the solution was warmed to room temperature, partial dissolved gas evolution was observed, indicating that the solution was saturated. The solution was then analyzed by NMR spectroscopy to determine the product distribution (Fig. 3).

NMR analysis of the reaction mixture revealed complete conversion of propane to propylene. No observation To reaction by-products. A single impurity was observed in the NMR spectrum at a double peak between 1.18 and 1.20 ppm. This signal is consistent with isobutane, which is an impurity present in the fuel grade commercially available propane starting material. The specification sheet provided by the supplier (Praxair) states that this is the most abundant impurity in propane and is present at <3000 ppm. This impurity is not the product of the reaction. The instrumental limit of the NMR to detect reaction by-products is about 3000 ppm.

Optionally, the catalyst is recovered at the end of the reaction and reused under the same conditions without loss of conversion efficiency, demonstrating durable catalyst stability and pot life.

Example 5 Conversion of Ethane to Ethylene Using Graphene Oxide or Graphite Oxide

In a typical preparation, the high pressure tank is charged with graphene oxide or graphite oxide, ethane and a magnetic stir bar. The high pressure tank was then sealed under ambient atmosphere and heated at 400 ° C for 1 hour. The ethylene product was isolated using standard procedures.

Example 6 Conversion of methane to propane using graphene oxide or graphite oxide

In a typical preparation, the high pressure tank is filled with graphene oxide or graphite oxide, methane and a magnetic stir bar. The high pressure tank was then sealed under ambient atmosphere and maintained at room temperature for 7 days. The propane product was isolated using standard procedures.

Example 7 Conversion of Ethane to Propane Using Graphene Oxide or Graphite Oxide

In a typical preparation, the high pressure tank is charged with graphene oxide or graphite oxide, ethane and a magnetic stir bar. The autoclave was then sealed under ambient atmosphere and heated at 400 °C for 5 hours. The propane product was isolated using standard procedures.

Example 8 Conversion of Methane to Butane Using Graphene Oxide or Graphite Oxide

In a typical preparation, the high pressure tank is charged with graphene oxide or graphite oxide, ethane and a magnetic stir bar. The high pressure tank was then sealed under ambient atmosphere and heated at 120 °C for 3 hours. The butane product was isolated using standard procedures.

Example 9 Conversion of ethane to butane using graphene oxide or graphite oxide

In a typical preparation, the high pressure tank is filled with graphene oxide or graphite oxide, ethane. And a magnetic stir bar. The high pressure tank was then sealed under ambient atmosphere and heated at 40 ° C for 300 hours. The butane product was isolated using standard procedures.

Example 10 Conversion of Hexane to Methane Using Graphene Oxide or Graphite Graphite

In a typical preparation, the high pressure tank is charged with graphene oxide or graphite oxide, hexane, and a magnetic stir bar. The high pressure tank was then sealed under ambient atmosphere and heated at 100 °C for 2 hours. The methane product was isolated using standard procedures.

Example 11 Conversion of Hexane to Ethane Using Graphene Oxide or Graphite Oxide

In a typical preparation, the high pressure tank is charged with graphene oxide or graphite oxide, hexane, and a magnetic stir bar. The autoclave was then sealed under ambient atmosphere and heated at 100 °C for 4 hours. The ethane product was isolated using standard procedures.

Example 12 Conversion of Hexane to Propane Using Graphene Oxide or Graphite Oxide

In a typical preparation, the high pressure tank is charged with graphene oxide or graphite oxide, hexane, and a magnetic stir bar. The autoclave was then sealed under ambient atmosphere and heated at 100 °C for 6 hours. The propane product was isolated using standard procedures.

Example 13 Conversion of hexane to propylene using graphene oxide or graphite oxide

In a typical preparation, the high pressure tank is charged with graphene oxide or graphite oxide, hexane, and a magnetic stir bar. The high pressure tank was then sealed under ambient atmosphere and heated at 400 ° C for 80 hours. The propylene product was isolated using standard procedures.

Example 14 Conversion of Hexane to Butane Using Graphene Oxide or Graphite Oxide

In a typical preparation, the high pressure tank is charged with graphene oxide or graphite oxide, hexane, and a magnetic stir bar. The high pressure tank was then sealed under ambient atmosphere and heated at 50 °C for 10 hours. The butane product was isolated using standard procedures.

Example 15 Conversion of hexane to butene or butadiene using graphene oxide or graphite oxide

In a typical preparation, the high pressure tank is charged with graphene oxide or graphite oxide, hexane, and a magnetic stir bar. The high pressure tank was then sealed under ambient atmosphere and heated at 500 °C for 20 hours. The butene or butadiene product was isolated using standard procedures.

Example 16 Conversion of Butane to 1-butene using graphene oxide or graphite oxide

In a typical preparation, the high pressure tank is charged with graphene oxide or graphite oxide, hexane, and a magnetic stir bar. The high pressure tank was then sealed under ambient atmosphere and heated at 500 ° C for 1 minute. The 1-butene product was isolated using standard procedures.

Example 17 Conversion of Butane to 2-butene using graphene oxide or graphite oxide

In a typical preparation, the high pressure tank is charged with graphene oxide or graphite oxide, hexane, and a magnetic stir bar. The high pressure tank was then sealed under ambient atmosphere and heated at 1000 ° C for 30 seconds. The 2-butene product was isolated using standard procedures.

Example 18 Conversion of Butane to Butadiene Using Graphene Oxide or Graphite Oxide

In a typical preparation, the high pressure tank is charged with graphene oxide or graphite oxide, hexane, and a magnetic stir bar. The high pressure tank was then sealed under ambient atmosphere and heated at 800 ° C for 5 minutes. The butadiene product was isolated using standard procedures.

While a preferred embodiment of the invention has been shown and described herein, it will be apparent to those skilled in the art Numerous variations, changes, and substitutions will now occur to those skilled in the art without departing from the invention. It will be appreciated that the invention may be practiced with various alternatives to the specific examples of the invention described herein. The scope of the present invention is intended to be defined by the scope of the invention, and the methods and structures, and equivalents thereof, within the scope of the claims.

Claims (87)

One for converting (a) an alkane starting material to an olefin product (dehydrogenation); (b) an alkane starting material to one or more higher molecular weight alkane products (coupling); (c) an alkane starting material to be one or a plurality of displacement products (displacement); (d) a higher alkane starting material into one or more lower alkane products (cracking); (e) a cycloalkane starting material to an alkane product or an olefin product or a combination thereof (cracking); or any A combined process comprising contacting any of the starting materials in (a)-(e) with graphene oxide or graphite oxide having a catalytically active surface modification to provide a corresponding product of (a)-(e). The process of claim 1, wherein the catalytically active surface-modified graphene oxide or graphite oxide is a catalytically active surface-modified graphene oxide. The process of claim 1, wherein the catalytically active surface-modified graphene oxide or graphite oxide is a catalytically active surface-modified graphite oxide. The process of claim 1, wherein the catalytically active surface-modified graphene oxide or graphite oxide is characterized by having one or at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 Multiple Fourier Transform Infrared (FT-IR) features. The process of claim 1, wherein the catalytically active surface-modified graphene oxide or graphite oxide has a surface modification comprising one or more hydrogen peroxide-terminated surfaces, an epoxide-terminated surface, a ketone-terminated surface, Diketone-terminated surface, aldehyde-terminated surface, carboxyl-terminated surface, hydroxyl-terminated surface, alcohol-terminated surface, ether-terminated surface, dioxetane-terminated surface, ruthenium-terminated surface, peroxyacid-terminated surface , an ester capping surface, an anhydride capping surface or a peroxyacid ester capping surface. The process of claim 1, wherein the catalytically active surface-modified graphene oxide or Graphite oxide has a surface modification comprising one or more hydrogen peroxide capping surfaces, an epoxide capping surface, a ketone capping surface, an aldehyde capping surface, a carboxyl capping surface, a hydroxyl terminated surface, an alcohol capping surface Or ether terminated surface. The process of claim 1, wherein the catalytically active surface-modified graphene oxide or graphite oxide has a surface modification comprising one or more epoxide end-capping surfaces, a ketone-terminated surface, an aldehyde-terminated surface, and a carboxyl group seal. End surface, hydroxyl terminated surface or alcohol terminated surface. The process of claim 1 wherein the catalytically active surface modified graphene oxide or graphite oxide has at least about 25% carbon and at least about 0.01% oxygen as measured by X-ray photoelectron spectroscopy (XPS). The process of claim 1, wherein the catalytically active surface-modified graphene oxide or graphite oxide has a carbon to oxygen ratio of about 1.5:1 and about 1:1.5, as measured by X-ray photoelectron spectroscopy (XPS). between. The process of claim 1, wherein the catalytically active surface-modified graphene oxide or graphite oxide has a carbon to oxygen ratio of about 1:1 and about 5:1 as measured by X-ray photoelectron spectroscopy (XPS). between. The process of claim 1, wherein the catalytically active surface-modified graphene oxide or graphite oxide has a carbon to oxygen ratio of between about 2:1 and about 3:1 as measured by X-ray photoelectron spectroscopy (XPS). between. A process for the conversion of an alkane to an olefin under dynamic control comprising contacting an alkane with a catalytically active surface-modified graphene oxide or graphite oxide according to any one of claims 1 to 11 with respect to a less catalytically active surface modification In the presence of a catalyst of graphene oxide or graphite oxide, the temperature at which the alkane is converted to an olefin is at a low temperature. The process of claim 12, wherein the process provides a higher olefin yield and reduces the reverse reaction of the olefin hydrogenation. A process for converting propane to propylene comprising contacting propane with graphene oxide or graphite oxide having a catalytically active surface modification as claimed in any one of claims 1 to 11. A process for the conversion of ethane to ethylene comprising contacting ethane with graphene oxide or graphite oxide having a catalytically active surface modification as claimed in any one of claims 1 to 11. A process for converting methane to propane comprising contacting methane with graphene oxide or graphite oxide having a catalytically active surface modification as claimed in any one of claims 1 to 11. A process for the conversion of ethane to propane comprising contacting ethane with graphene oxide or graphite oxide having a catalytically active surface modification as claimed in any one of claims 1 to 11. A process for converting methane to butane comprising contacting methane with graphene oxide or graphite oxide having a catalytically active surface modification as claimed in any one of claims 1 to 11. A process for converting ethane to butane comprising contacting ethane with graphene oxide or graphite oxide having a catalytically active surface modification as claimed in any one of claims 1 to 11. A process for converting hexane to methane comprising contacting hexane with graphene oxide or graphite oxide having a catalytically active surface modification as claimed in any one of claims 1 to 11. A process for converting hexane to ethane comprising contacting hexane with graphene oxide or graphite oxide having a catalytically active surface modification as claimed in any one of claims 1 to 11. A process for the conversion of hexane to propane comprising contacting hexane with graphene oxide or graphite oxide having a catalytically active surface modification according to any one of claims 1 to 11. touch. A process for converting hexane to propylene comprising contacting hexane with graphene oxide or graphite oxide having a catalytically active surface modification as claimed in any one of claims 1 to 11. A process for converting hexane to butane comprising contacting hexane with graphene oxide or graphite oxide having a catalytically active surface modification as claimed in any one of claims 1 to 11. A process for converting hexane to butene or butadiene comprising contacting hexane with graphene oxide or graphite oxide having a catalytically active surface modification as claimed in any one of claims 1 to 11. A process for converting butane to 1-butene comprising contacting butane with graphene oxide or graphite oxide having a catalytically active surface modification as claimed in any one of claims 1 to 11. A process for converting butane to 2-butene comprising contacting butane with graphene oxide or graphite oxide having a catalytically active surface modification as claimed in any one of claims 1 to 11. A process for converting butane to butadiene comprising contacting butane with a graphene oxide or graphite oxide having a catalytically active surface modification as claimed in any one of claims 1 to 11. A process for alkane displacement comprising contacting the alkane with a graphene oxide or graphite oxide having a catalytically active surface modification as claimed in any one of claims 1 to 11. The process of claim 29, wherein the alkane is a C ₁ -C ₆ alkane, and the product derived from contacting the C ₁ -C ₆ alkane with the catalytically active surface-modified graphene oxide or graphite oxide is advanced and/or Or a mixture of lower C ₁ -C ₁₂ alkanes. A process for the dehydrogenation of an alkane comprising contacting the alkane with a graphene oxide or graphite oxide having a catalytically active surface modification as claimed in any one of claims 1 to 11. The process of claim 31, wherein the alkane is a C ₂ -C ₆ alkane, and the product obtained by contacting the C ₂ -C ₆ alkane with the catalytically active surface-modified graphene oxide or graphite oxide is one or more A mixture of C ₂ -C ₆ olefins. The process of claim 31, wherein the alkane is a C ₄ -C ₆ alkane, and the product obtained by contacting the C ₄ -C ₆ alkane with the catalytically active surface-modified graphene oxide or graphite oxide is one or more A mixture of C ₄ -C ₆ dienes. The process of any one of claims 1 to 11, wherein the process comprises a solventless reaction. The process of any one of claims 1 to 11, wherein the process comprises contacting one or more gaseous reactants with the catalytically active surface-modified graphene oxide or graphite oxide. A product formed according to the process of any one of claims 1 to 35. A propylene formed according to the process of claim 12. A reaction vessel comprising the starting material, product, and catalytically active surface-modified graphene oxide or graphite oxide according to any one of claims 1 to 35. The reaction vessel of claim 36, further comprising a heat source for heating the reaction vessel to a desired temperature, means for controlling the temperature of the reaction vessel, and means for determining the temperature within the reaction vessel. The reaction vessel of any of claims 38 and 39 is in the form of a fluidized bed reactor. The reaction vessel of any one of claims 38 to 39, further comprising a solid acid catalyst. A catalytically active surface-modified graphene oxide or graphite oxide in contact with propane and propylene. A reaction vessel comprising propane, propylene and graphene oxide or graphite oxide with catalytically active surface modification. A process for converting propane to propylene comprising propane and a catalytically active surface The modified graphene oxide or graphite oxide is contacted to provide propylene. The process of claim 44, wherein the catalytically active surface-modified graphene oxide or graphite oxide is a catalytically active surface-modified graphene oxide. The process of claim 44, wherein the catalytically active surface-modified graphene oxide or graphite oxide is a catalytically active surface-modified graphite oxide. The process of claim 44, wherein the catalytically active surface-modified graphene oxide or graphite oxide is characterized by having one or at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 Multiple FT-IR features. The process of claim 44, wherein the catalytically active surface-modified graphene oxide or graphite oxide has a surface modification comprising one or more hydrogen peroxide-terminated surfaces, an epoxide end surface, a ketone end surface , diketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end surface, alcohol end surface, ether end surface, dioxopane end surface, ruthenium end surface, peroxy acid end cap Surface, ester capping surface, anhydride capping surface or peroxyacid ester capping surface. The process of claim 44, wherein the catalytically active surface-modified graphene oxide or graphite oxide has a surface modification comprising one or more hydrogen peroxide capping surfaces, an epoxide capping surface, a ketone capping surface, An aldehyde capping surface, a carboxyl terminated surface, a hydroxyl terminated surface, an alcohol terminated surface, or an ether terminated surface. The process of claim 44, wherein the catalytically active surface-modified graphene oxide or graphite oxide has a surface modification comprising one or more epoxide capping surfaces, a ketone-terminated surface, an aldehyde-terminated surface, a carboxyl-terminated end Surface, hydroxyl terminated surface or alcohol terminated surface. The process of claim 44, wherein the catalytically active surface-modified graphene oxide or graphite oxide has at least about 25% carbon and at least about 0.01% oxygen, as measured by X-ray photoelectron spectroscopy (XPS). The process of claim 44, wherein the X-ray photoelectron spectroscopy (XPS) is performed. The catalytically active surface-modified graphene oxide or graphite oxide has a carbon to oxygen ratio of between about 1.5:1 and about 1:1.5. The process of claim 44, wherein the catalytically active surface-modified graphene oxide or graphite oxide has a carbon to oxygen ratio of between about 1:1 and about 5:1 as measured by X-ray photoelectron spectroscopy (XPS). between. The process of claim 44, wherein the catalytically active surface-modified graphene oxide or graphite oxide has a carbon to oxygen ratio of between about 2:1 and about 3:1 as measured by X-ray photoelectron spectroscopy (XPS). between. A process for the conversion of propane to propylene under dynamic control comprising contacting propane with a catalytically active surface-modified graphene oxide or graphite oxide according to any one of claims 44 to 54 for oxidation with less catalytically active surface modification. The temperature at which the temperature at which propane is converted to propylene is low in the presence of a catalyst of graphene or graphite oxide. A propylene prepared according to the process of claim 55. A saturated hydrocarbon group for converting (a) a hydrocarbon starting material to an unsaturated hydrocarbon group (dehydrogenation) on a hydrocarbon product; (b) a hydrocarbon starting material to one or more higher molecular weight hydrocarbons a product (coupling); (c) a hydrocarbon starting material as one or more replacement products (substitution); (d) a higher hydrocarbon starting material as one or more lower hydrocarbon products (cracking); or any combination thereof, including Any of the starting materials in (a)-(d) are contacted with a catalytically active carbon catalyst to provide the corresponding products in (a)-(d). The process of claim 57, wherein the carbon catalyst is selected from the group consisting of fullerene-related materials, amorphous carbon, crystalline carbon, mesoporous carbon, graphene oxide or graphite oxide-derived materials or activated carbon. The process of claim 57, wherein the carbon catalyst is selected from the group consisting of fullerene-related materials, amorphous carbon, crystalline carbon, graphene oxide or graphite oxide-derived materials or activated carbon. The process of claim 57, wherein the starting material in (a)-(d) is a material that does not comprise an active C-H bond. The process of claim 57, wherein the catalytically active carbon catalyst is a modified form of graphene oxide or graphite oxide. The process of claim 57, wherein the catalytically active carbon catalyst is characterized by having one or more Fourier transform infrared at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 FT-IR) features. The process of claim 57, wherein the catalytically active carbon catalyst is a graphene oxide or graphite oxide having a catalytically active surface modification. The process of claim 63, wherein the catalytically active surface-modified graphene oxide or graphite oxide is a catalytically active surface-modified graphene oxide. The process of claim 63, wherein the catalytically active surface-modified graphene oxide or graphite oxide is a catalytically active surface-modified graphite oxide. The process of claim 57, wherein the catalytically active carbon catalyst has a surface modification comprising one or more hydrogen peroxide capping surfaces, an epoxide capping surface, a ketone capping surface, a diketone capping surface, Aldehyde-terminated surface, carboxyl-terminated surface, hydroxyl-terminated surface, alcohol-terminated surface, ether-terminated surface, dioxoprene-terminated surface, ruthenium-terminated surface, peroxyacid-terminated surface, ester-terminated surface, An anhydride capping surface or a peroxyacid ester capping surface. The process of claim 57, wherein the catalytically active carbon catalyst has a surface modification comprising one or more hydrogen peroxide capping surfaces, an epoxide capping surface, a ketone capping surface, an aldehyde capping surface, a carboxyl group A capped surface, a hydroxyl terminated surface, an alcohol terminated surface or an ether terminated surface. The process of claim 57, wherein the catalytically active carbon catalyst has a surface repair Decorative, comprising one or more epoxide capping surfaces, a ketone capping surface, an aldehyde capping surface, a carboxyl capping surface, a hydroxyl terminated surface, or an alcohol capping surface. The process of claim 57, wherein the catalytically active carbon catalyst has at least about 25% carbon and at least about 0.01% oxygen as measured by X-ray photoelectron spectroscopy (XPS). The process of claim 57, wherein the catalytically active carbon catalyst has a carbon to oxygen ratio of between about 1.5:1 and about 1:1.5 as measured by X-ray photoelectron spectroscopy (XPS). The process of claim 57, wherein the catalytically active carbon catalyst has a carbon to oxygen ratio of between about 1:1 and about 5:1 as measured by X-ray photoelectron spectroscopy (XPS). The process of claim 57, wherein the catalytically active carbon catalyst has a carbon to oxygen ratio of between about 2:1 and about 3:1 as measured by X-ray photoelectron spectroscopy (XPS). A process for converting propane to propylene comprising contacting propane with a catalytically active carbon catalyst to provide propylene. The process of claim 73, wherein the carbon catalyst is selected from the group consisting of fullerene-related materials, amorphous carbon, crystalline carbon, mesoporous carbon, graphene oxide or graphite oxide-derived materials or activated carbon. The process of claim 73, wherein the carbon catalyst is selected from the group consisting of fullerene-related materials, amorphous carbon, crystalline carbon, graphene oxide or graphite oxide-derived materials or activated carbon. The process of claim 73, wherein the catalytically active carbon catalyst is a modified form of graphene oxide or graphite oxide. The process of claim 73, wherein the catalytically active carbon catalyst is characterized by having one or more Fourier transform infrared at about 3150 cm ^-1 , 1685 cm ^-1 , 1280 cm ^-1 or 1140 cm ^-1 FT-IR) features. The process of claim 73, wherein the catalytically active carbon catalyst is a graphene oxide or graphite oxide having a catalytically active surface modification. The process of claim 78, wherein the catalytically active surface-modified graphene oxide or graphite oxide is a graphene oxide having a catalytically active surface modification. The process of claim 78, wherein the catalytically active surface-modified graphene oxide or graphite oxide is a catalytically active surface-modified graphite oxide. The process of claim 73, wherein the catalytically active carbon catalyst has a surface modification comprising one or more hydrogen peroxide capping surfaces, an epoxide capping surface, a ketone capping surface, a diketone capping surface, Aldehyde-terminated surface, carboxyl-terminated surface, hydroxyl-terminated surface, alcohol-terminated surface, ether-terminated surface, dioxoprene-terminated surface, ruthenium-terminated surface, peroxyacid-terminated surface, ester-terminated surface, An anhydride capping surface or a peroxyacid ester capping surface. The process of claim 73, wherein the catalytically active carbon catalyst has a surface repair Ornament, which contains one or more hydrogen peroxide capping surfaces, epoxide end caps Surface, ketone end surface, aldehyde end surface, carboxyl end surface, hydroxyl end table Surface, alcohol terminated surface or ether terminated surface. The process of claim 73, wherein the catalytically active carbon catalyst has a surface repair Decorative, comprising one or more epoxide end surfaces, a ketone end surface, an aldehyde seal End surface, carboxyl terminated surface, hydroxyl terminated surface or alcohol terminated surface. The process of claim 73, wherein the catalytically active carbon catalyst has at least about 25% carbon and at least about 0.01% oxygen as measured by X-ray photoelectron spectroscopy (XPS). The process of claim 73, wherein the catalytically active carbon catalyst has a carbon to oxygen ratio of between about 1.5:1 and about 1:1.5 as measured by X-ray photoelectron spectroscopy (XPS). The process of claim 73, wherein the X-ray photoelectron spectroscopy (XPS) is performed The catalytically active carbon catalyst has a carbon to oxygen ratio of between about 1:1 and about 5:1. The process of claim 73, wherein the catalytically active carbon catalyst has a carbon to oxygen ratio of between about 2:1 and about 3:1 as measured by X-ray photoelectron spectroscopy (XPS).