CN105289723A

CN105289723A - Hydrocarbon conversion using carbon catalyst

Info

Publication number: CN105289723A
Application number: CN201510682767.1A
Authority: CN
Inventors: 谢昕; 武传胜
Original assignee: Henan Polytechnic Institute
Current assignee: Henan Polytechnic Institute
Priority date: 2015-10-20
Filing date: 2015-10-20
Publication date: 2016-02-03

Abstract

The invention discloses a carbon catalyst with catalytic activity. The catalyst is used in the processes of hydrocarbon dehydrogenation, hydrocarbon splitting decomposition, hydrocarbon coupling (such as C-C alkane coupling) and/or hydrocarbon replacement to provide hydrocarbon products such as oxidized graphene or oxidized graphite catalysts, and is suitable for various high-value chemical conversion. A method and the process with wide synthesis practicality can be applied to synthesis of a lot of high-value chemical matter in some wide preparing processes.

Description

The hydrocarbon of C catalyst is used to transform

Technical field

The invention relates to a kind of hydrocarbon of C catalyst that uses to transform.

Background technology

Cost in order to manufacture article needed for some high value organic chemicals and service is high must go against accepted conventions, and/or relies on the parent material of the accessory substance into petroleum industry.

Summary of the invention

The present invention describes the method and processing procedure with extensively synthesis practicality, can be applicable in the synthesis of some high value being used in extensive manufacture process and a large amount of chemical substance.Chemical hydrocarbon conversion provided by the invention cheaply and efficiently can be used in synthesis, and some is used on the hydrocarbon original material that production is row chemical product.The invention provides the method for the synthesis being used in low-molecular-weight saturated or fractional saturation organic compound.In a little example, these compounds are gas and/or are volatile compound.

The invention provides the processing procedure being used in dehydrogenation of hydrocarbons, hydrocarbon cracking, hydro carbons coupling (such as C-C alkane coupling) and/or hydro carbons and replacing, to provide hydrocarbon products.Dehydrogenation of hydrocarbons, hydrocarbon cracking, hydro carbons coupling (such as C-C alkane coupling) and/or the processing procedure of hydro carbons displacement of being used in of the present invention comprises, and hydro carbons is contacted with the carbon-based material of tool catalytic activity.In other words, synthetic method of the present invention comprises the use of the C catalyst of tool catalytic activity.In some embodiments, the C catalyst of this tool catalytic activity is the catalyst that graphene oxide derives or graphite oxide is derivative.

In, the invention provides one and be used in conversion

A () alkane parent material becomes olefin product (dehydrogenation);

B () alkane parent material becomes the alkane products (coupling) of one or more higher molecular weights;

C () alkane parent material becomes one or more substitution products (displacement);

D () higher alkane parent material becomes one or more lower paraffin hydrocarbon products (cracking);

E () cycloalkane parent material becomes alkane products or olefin product or its and combines (cracking);

Or the processing procedure of its combination any,

Comprise graphene oxide that the parent material in any (a)-(e) and tool catalytically active surface are modified or graphite oxide contacts, to provide product corresponding in (a)-(e).

In concrete example, the invention provides one and be used in processing procedure alkane parent material being converted into olefin product (dehydrogenation), comprise graphene oxide that alkane parent material and tool catalytically active surface are modified or graphite oxide contacts, to provide corresponding olefin product.In concrete example, the invention provides a kind of processing procedure being used in the alkane products (coupling) alkane parent material being converted into one or more higher molecular weights, comprise graphene oxide that alkane parent material and tool catalytically active surface are modified or graphite oxide contacts, to provide corresponding higher molecular weight products.In concrete example, the invention provides and be a kind ofly used in processing procedure alkane parent material being converted into one or more substitution products, comprise graphene oxide that alkane parent material and tool catalytically active surface are modified or graphite oxide contacts, to provide one or more corresponding substitution products.In concrete example, the invention provides one and be used in processing procedure higher alkane parent material being converted into one or more lower paraffin hydrocarbon products (cracking), comprise graphene oxide that higher alkane parent material and tool catalytically active surface are modified or graphite oxide contacts, to provide corresponding lower paraffin hydrocarbon product.In concrete example, the invention provides one and be used in processing procedure cycloalkane parent material being converted into alkane or olefin product or its combination (cracking), comprise graphene oxide that cycloalkane parent material and tool catalytically active surface are modified or graphite oxide contacts, to provide corresponding alkane or olefin product or its combination.In concrete example, it is a kind of processing procedure comprising cracking and coupling.In concrete example, it is a kind of processing procedure comprising cracking and dehydrogenation.In concrete example, it is a kind of processing procedure comprising displacement and dehydrogenation.

In the concrete example of above-mentioned processing procedure, the graphene oxide that this tool catalytically active surface is modified or graphite oxide are the graphene oxide that tool catalytically active surface is modified.

In the concrete example of above-mentioned processing procedure, the graphene oxide that this tool catalytically active surface is modified or graphite oxide are the graphite oxide that tool catalytically active surface is modified.

In the concrete example of above-mentioned processing procedure, the feature of the graphene oxide that this tool catalytically active surface is modified or graphite oxide is, at about 3150cm ^-1, 685cm ^-1, 280cm ^-1or 1140cm ^-1place has one or more fourier-transform infrared (FT-IR) feature.

In a little concrete example, the graphene oxide that this tool catalytically active surface is modified or graphite oxide have finishing and comprise one or more hydrogen peroxide terminated surface, epoxides terminated surface, ketone terminated surface, diketone terminated surface, aldehyde terminated surface, carboxy blocking surface, hydroxy-end capped surface, alcohol terminated surface, ether capped surface, dioxy cyclopropane terminated surface, quinone terminated surface, peroxy acid terminated surface, ester terminated surface, acid anhydride terminated surface or peracid ester terminated surface.

In a little concrete example, this tool catalytically active surface modify graphene oxide or graphite oxide there is finishing, comprise one or more peroxidating sealing gland end surfaces, epoxides terminated surface, ketone terminated surface, aldehyde terminated surface, carboxy blocking surface, hydroxy-end capped surface. alcohol terminated surface or ether capped surface.

In a little concrete example, the graphene oxide that this tool catalytically active surface is modified or graphite oxide have finishing, comprise one or more epoxides terminated surface, ketone terminated surface, aldehyde terminated surface, carboxy blocking surface, hydroxy-end capped surface or alcohol terminated surface.

In the further concrete example of this processing procedure, measure via x-ray photoelectron spectroscopy art (XPS), the graphene oxide that this tool catalytically active surface is modified or graphite oxide have at least fe25% carbon and at least about 0.01% oxygen.

In a little concrete example, measure via x-ray photoelectron spectroscopy art (XPS), the graphene oxide that this tool catalytically active surface is modified or the carbon of graphite oxide to oxygen ratio between about 1.5:1 with about between 1:1.5.

In a little concrete example, measure via x-ray photoelectron spectroscopy art (XPS), the graphene oxide that this tool catalytically active surface is modified or the carbon of graphite oxide to oxygen ratio between about 1:1 with about between 5:1.

In a little concrete example, measure via x-ray photoelectron spectroscopy art (XPS), the graphene oxide that this tool catalytically active surface is modified or the carbon of graphite oxide to oxygen ratio between about 1:1 with about between 4:1.

In a little concrete example, measure via x-ray photoelectron spectroscopy art (XPS), the carbon of the C catalyst of this tool catalytic activity is between about 1:1 with about between 3:1 to oxygen ratio.

In a little concrete example, measure via x-ray photoelectron spectroscopy art (XPS), the graphene oxide that this tool catalytically active surface is modified or the carbon of graphite oxide to oxygen ratio between about 2:1 with about between 3:1.

In some embodiments, the C catalyst of this tool catalytic activity is a kind of heterogeneous catalysis.In a little concrete example, the C catalyst of this tool catalytic activity provides reaction solution pH, is neutral when disperseing in the reactive mixture.In some embodiments, the C catalyst of this tool catalytic activity provides reaction solution pH, is acid when disperseing in the reactive mixture.In other concrete examples, the C catalyst of this tool catalytic activity provides reaction solution pH, is alkalescence when disperseing in the reactive mixture.In a little concrete example, the C catalyst of this tool catalytic activity is present on solid support.In some embodiments, the C catalyst of this tool catalytic activity is present in solid support.

Concerning or hereinafter described any concrete example, the invention provides multiple processing procedure above, wherein this processing procedure comprises further this reactant is contacted with co-catalyst.In a little concrete example, this co-catalyst is a kind of oxidation catalyst.In some embodiments, this co-catalyst is a kind of zeolite.

Concerning above or hereinafter described any concrete example, the invention provides multiple processing procedure, wherein this processing procedure comprises extra oxidant further.A little above or in the concrete example of hereinafter described method and/or processing procedure, the method comprises solvent-free reaction.In the method concrete example that some is above or hereinafter described, the method comprises one or more gas reactants and contacts with C catalyst.

Accompanying drawing explanation

Fig. 1 shows the illustrative example of modified graphene oxide in the method and example be used in this disclosure or graphite oxide (MG).

The illustrative x-ray photoelectron spectroscopy art (XPS) that the sample of Fig. 2 display to prepared graphene oxide or graphite oxide carries out.

Detailed description of the invention

The cracking at naphtha is dependent in the manufacture of original material (such as low molecular weight alkanes or alkene).Naphtha is natural gas condensates or takes from oil, coal or a kind of composition of product of distillation of mud coal.Naphtha is the mixture that hydrocarbon seethes with excitement in certain temperature range, contains some low-molecular-weight and the volatile part of liquid hydrocarbon in oil.For example, 95% propylene of current production is out manufactured as the accessory substance of cracking naphtha.But just on the decrease, and ethane cracking device cannot produce the propylene as callable accessory substance in the supply of propylene.Therefore, in the industry cycle avoid being dependent on while oil (a kind of natural resources day by day reduced), needs can manufacture the method for high-value goods (such as low-molecular-weight hydrocarbon).

The invention provides for use low cost parent material to manufacture high-value chemical method and processing procedure.The present invention is to provide, low-molecular-weight is saturated, the practical technique of fractional saturation or unsaturated organic compound to utilize the C catalyst of some tool catalytic activity (graphene oxide of such as finishing and/or graphite oxide) to synthesize.In a little example, these compounds are gas and/or are volatile compound.In a little example, these compounds cover six carbon.In a little example, these compounds cover five carbon.In a little example, these compounds cover four carbon.In a little example, these compounds cover three carbon.In a little example, these compounds comprise two to six carbon.In a little example, these compounds comprise two to five carbon.In a little example, these compounds comprise two to four carbon.In a little example, these compounds comprise two to three carbon.In a little example, these compounds comprise three carbon.

Needs can overcome the disappearance of one or more existing catalyst and catalysis can use the broad-spectrum catalyst of the various chemical reactions (such as hydrocarbon conversion) of extensive initial reactant or parent material.

Cognitive to various and be commercially obtainablely used in the relevant limitation of method that catalytic hydrocarbon reacts at present at this.For example, although base can provide the reaction rate of viable commercial at the catalyst of transition metal, the use of metallic catalyst has various disappearance, such as the metallic pollution of products therefrom.This, especially has problems for product being used in health or biological use or other to the industry that there is responsive purposes at metal to being.The C catalyst (such as graphene oxide and/or graphite oxide) being used in hydrocarbon conversion (such as propane becomes the conversion of propylene) of the present invention does not have transition metal in fact, can generate the pure hydro carbons not having metal pollutant.

The another disappearance of metallic catalyst is, metallic catalyst does not have selective usually in hydrocarbon reaction.Base is generally oxidative dehydrogenation (ODH) in the dehydrogenation of hydrocarbons of transition metal, and needs a high proportion of oxygen/hydrocarbon, causes undesired oxidized byproduct.In a little concrete example, C catalyst provided by the invention (such as graphene oxide or graphite oxide) can allow the dynamic Control of some hydrocarbon reaction (such as dehydrogenation), with increase hydrocarbon conversion in selective.

As another example of disappearance that the metal-based catalyst arrived in this cognition is described, base may manufacture quite expensive at the catalyst of transition metal, and adopts the processing procedure of this catalyst may need considerable initial sum maintenance cost.On the contrary, the technology of carbon-supported catalysts of the present invention (such as graphene oxide and/or graphite oxide) can improve existing manufacturing facility, therefore reduces any initial cost using the new technology of the commercially valuable hydro carbons of large-scale production relevant with lifting.Shale gas (comprising dry or wet shale gas) is very abundant, and can easily be transported to existing manufacturing facility.Therefore, multi-functional technology of the present invention can not be subject to the availability of parent material and/or obtain the obstruction of cost of parent material.

The present invention describes the processing procedure being used in hydrocarbon conversion, and this conversion relates to the use of C catalyst, and it has the convenience of benefit and the heterogeneous process of synthesizing without metal concurrently.Method provided by the invention is friendly to environment, because they reduce in production plant using base in the demand of the catalyst of metal.Moreover, reduce production stage, thus reduce the cost of article and manufacturing service.

The typical hydrocarbon parent material being used in hydrocarbon conversion often has sulfur-containing impurities, and it pollutes the catalyst of base at metal.The advantage of the C catalyst (such as graphene oxide and/or graphite oxide derive catalyst) of tool catalytic activity of the present invention is, catalyst is not subject to the pollution of the impurity (such as sulfur-containing impurities) that usually can pollute other catalyst (such as base is at the catalyst of transition metal).

Another advantage is, the C catalyst (such as modified graphene oxide and/or graphite oxide) of tool catalytic activity of the present invention is renewable, thus reduces industrial waste and reduce article and manufacturing cost.C catalyst of the present invention and the parent material utilizing the processing procedure of this C catalyst can activate relative passivity, such as hydro carbons, and be useful in the activation of c h bond and/or C-C key.

Some catalyst previously used, such as mesoporous carbon, can manufacture coke in reaction process, C catalyst of the present invention (such as graphene oxide and/or graphite oxide derive catalyst) overcomes this shortcoming.Moreover the catalyst previously used has hole, it can postpone product from the outside diffusion of central hole structure, and C catalyst of the present invention (such as graphene oxide and/or graphite oxide derive catalyst) overcomes this shortcoming.In addition, base can block reactor at the catalyst of mesopore and/or amorphous carbon and/or activated carbon by coked result, and carbon of the present invention urges agent (such as graphene oxide and/or graphite oxide derive catalyst) to overcome this shortcoming.

Some previously described catalyst (such as fullerene associated materials or crystalline carbon material) has disappearance.Site, edge or the defect site tool challenge of possibility tool catalytic activity is introduced in fullerene associated materials or crystalline carbon.On the contrary, the C catalyst (such as modified graphene oxide and/or graphite oxide) of tool catalytic activity provided by the invention overcomes this latent defect of fullerene associated materials; In a little example, compare at the material of base at fullerene, catalyst provided by the invention (such as graphene oxide and/or graphite oxide) has and shows the Unit Weight number at higher edge or site, corner.Compare and/or crystalline carbon associated materials relevant at fullerene, the C catalyst (such as modified graphene oxide and/or graphite oxide) of tool catalytic activity provided by the invention comprises the site, edge of higher percent for dusty material.

Multifunctional C catalyst of the present invention and utilize the processing procedure of this C catalyst (such as graphene oxide and/or graphite oxide) to can be applicable in various organic reaction, comprises and does not limit in hydrocarbon-hydrocarbon (such as C-C) coupling, alkane displacement, alkane and/or cycloalkane cracking and alkane and/or cycloalkane dehydrogenation.C catalyst of the present invention (such as graphene oxide and/or graphite oxide) comprises the reactivity of higher concentration and/or selective site on surface, and overcomes low overall activity and/or the reactivity of previous described carbon-supported catalysts.

This revealing method also can be applicable in pharmaceuticals industry.For example, chalcone is the important precursor of important materials in flavonoids and other pharmacy, and also has a lot of purposes at the outer of pharmaceuticals industry.In addition, the reaction (such as manufacturing reaction of medicine or agricultural products) that metal can allow in worry metallic pollution is lacked in graphene oxide or graphite oxide, or the reaction that metallic pollution can be harmful to (such as product wherein will experience and further reacts or be used in further application, and this reaction or application responsive to metallic pollution) in use these methods.

As noted before, the invention provides the method being used in following reaction:

A () alkane parent material transfers olefin product (dehydrogenation) to;

B () alkane parent material transfers the alkane products (coupling) of one or more higher molecular weights to;

C () alkane parent material transfers one or more substitution products (displacement) to;

D () higher alkane parent material transfers one or more lower paraffin hydrocarbon products (cracking) to;

E () cycloalkane parent material transfers alkane products or olefin product or its to and combines (cracking); Or its combination any;

Comprise and the parent material in any (a)-(e) is contacted, to provide product corresponding in (a)-(e) with the C catalyst (graphene oxide that catalytically active surface of such as having is modified or graphite oxide) of tool catalytic activity.

In specific embodiments, with regard to above-mentioned reaction (4) (such as propane transfers the dehydrogenation of propylene to), the C catalyst of this tool catalytic activity is graphene oxide or the graphite oxide material of the modification of a kind of tool catalytically active surface, it is characterized in that:

(1) at about 3150cm ^-1, 1685cm ^-1, 1280cm " or 1140cm ^-1place has one or more FT-IR feature.

(2) at about 3150cm ^-1, 1685cm ^-1, 1280cm ^-1or 1140cm ^-1place has one or more FT-IR feature; And finishing, it comprises one or more hydrogen peroxide terminated surface, epoxides terminated surface, ketone terminated surface, aldehyde terminated surface, carboxy blocking surface, hydroxy-end capped surface, alcohol terminated surface, lactone terminated surface, quinone terminated surface, acid anhydride terminated surface or ether capped surface.

(3) at about 3150cm ^-1, 1685cm ^-1, 1280cm ^-1or 1140cirf ¹place has one or more FT-IR feature; And finishing, it comprises one or more epoxides terminated surface, peroxide terminated surface, ketone terminated surface, aldehyde terminated surface, carboxy blocking surface, hydroxy-end capped surface, alcohol terminated surface, quinone terminated surface or ether capped surface.

(4) at about 3150cm ^-1, 1685cm ^-1, 1280cm ^-1or 1140cm ^-1place has one or more FT-IR feature; And finishing, it comprises one or more epoxides terminated surface, ketone terminated surface, aldehyde terminated surface, carboxy blocking surface, hydroxy-end capped surface or alcohol terminated surface.

(5) at about 3150cm ^-1, 1685cm ^-1, 1280cm ^-1or 1140cm ^-1place has one or more FT-IR feature; And finishing, it comprises one or more hydrogen peroxide terminated surface, epoxides terminated surface, ketone terminated surface, aldehyde terminated surface, carboxy blocking surface, hydroxy-end capped surface, alcohol terminated surface, lactone terminated surface, quinone terminated surface, acid anhydride terminated surface or ether capped surface; And measure, at least about 25% carbon with at least about 0.01% oxygen via x-ray photoelectron spectroscopy art (XPS).

(6) at about 3150cm ^-1, 1685cm ^-1, 1280cm ^-1or 1140cm ^{_ 1}place has one or more FT-IR feature; And finishing, it comprises one or more epoxides terminated surface, peroxide terminated surface, ketone terminated surface, aldehyde terminated surface, carboxy blocking surface, hydroxy-end capped surface, alcohol terminated surface, quinone terminated surface or ether capped surface; And measure, at least about 25% carbon with at least about 0.01% oxygen via x-ray photoelectron spectroscopy art (XPS).

(7) at about 3150cm ^-1, 1685cm ^-1, 1280cm ^-1or 1140cm ^-1place has one or more FT-IR feature; And finishing, it comprises one or more epoxides terminated surface, ketone terminated surface, aldehyde terminated surface, carboxy blocking surface, hydroxy-end capped surface or alcohol terminated surface; Measure, at least about 25% carbon with at least about 0.01% oxygen via x-ray photoelectron spectroscopy art (XPS).

(8) at about 3150cm ^-1, 1685cm ^-1, 1280cm ^{_ 1}or 1140crrf ¹place has one or more FT-IR feature; And finishing, it comprises one or more hydrogen peroxide terminated surface, epoxides terminated surface, ketone terminated surface, aldehyde terminated surface, carboxy blocking surface, hydroxy-end capped surface, alcohol terminated surface, lactone terminated surface, quinone terminated surface, acid anhydride terminated surface or ether capped surface; And measure via x-ray photoelectron spectroscopy art (XPS), catalyst so far carbon is between about 1:1 with about between 1:1.5 to oxygen ratio.

(9) at about 3150cm ^-1, 1685cm ^-1, 1280cm ^-1or 1140cm ^-1place has one or more FT-IR feature; And finishing, it comprises one or more epoxides terminated surface, peroxide terminated surface, ketone terminated surface, aldehyde terminated surface, carboxy blocking surface, hydroxy-end capped surface, alcohol terminated surface, quinone terminated surface or ether capped surface; And measure via x-ray photoelectron spectroscopy art (XPS), the carbon of catalyst is between about 1:1 with about between 1:1.5 to oxygen ratio.

(10) at about 3150cm ^-1, 1685cm ^-1, 1280cm ^-1or 1140cm ^-1place has one or more FT-IR feature; And finishing, it comprises one or more epoxides terminated surface, ketone terminated surface, aldehyde terminated surface, carboxy blocking surface, hydroxy-end capped surface or alcohol terminated surface; And measure via x-ray photoelectron spectroscopy art (XPS), the carbon of this catalyst is between about 1:1 with about between 1:1.5 to oxygen ratio.

(11) at about 3150cm ^-1, 1685cm ^-1, 1280cm ^-1or 1140cm ^-1place has one or more FT-IR feature; And finishing, it comprises one or more hydrogen peroxide terminated surface, epoxides terminated surface, ketone terminated surface, aldehyde terminated surface, carboxy blocking surface, hydroxy-end capped surface, alcohol terminated surface, lactone terminated surface, quinone terminated surface, acid anhydride terminated surface or ether capped surface; And measure via x-ray photoelectron spectroscopy art (XPS), the carbon of this catalyst is between about 1:1 with about between 5:1 to oxygen ratio.

(12) at about 3150cm ^-1, 1685cm ^-1, 1280cirf ¹or 1140cm ^-1place has one or more FT-IR feature; And finishing, it comprises one or more epoxides terminated surface, peroxide terminated surface, ketone terminated surface, aldehyde terminated surface, carboxy blocking surface, hydroxy-end capped surface, alcohol terminated surface, quinone terminated surface or ether capped surface; And measure via x-ray photoelectron spectroscopy art (XPS), the carbon of this catalyst is between about 1:1 with about between 5:1 to oxygen ratio.

(13) at about 3150cm ^-1, 1685cm ^-1, 1280cm ^-1or 1140cm ^-1place has one or more FT-IR feature; And finishing, it comprises one or more epoxides terminated surface, ketone terminated surface, aldehyde terminated surface, carboxy blocking surface, hydroxy-end capped surface or alcohol terminated surface; And measure via x-ray photoelectron spectroscopy art (XPS), the carbon of this catalyst is between about 1:1 with about between 5:1 to oxygen ratio.

(14) at about 3150cm ^-1, 1685cm ^-1, 1280cm ^-1or 1140cm ^-1place has one or more FT-IR feature; And finishing, it comprises one or more hydrogen peroxide terminated surface, epoxides terminated surface, ketone terminated surface, aldehyde terminated surface, carboxy blocking surface, hydroxy-end capped surface, alcohol terminated surface, lactone terminated surface, quinone terminated surface, acid anhydride terminated surface or ether capped surface; And measure via x-ray photoelectron spectroscopy art (XPS), the carbon of this catalyst is between about 1.5:1 with about between 2:1 to oxygen ratio.

(15) at about 3150cm ^-1, 1685cm ^-1, 1280cm ^-1or 1140cm ^-1place has one or more FT-IR feature; And finishing, it comprises one or more epoxides terminated surface, peroxide terminated surface, ketone terminated surface, aldehyde terminated surface, carboxy blocking surface, hydroxy-end capped surface, alcohol terminated surface, quinone terminated surface or ether capped surface; And measure via x-ray photoelectron spectroscopy art (XPS), the carbon of this catalyst is between about 1.5:1 with about between 2:1 to oxygen ratio.

(16) at about 3150m ^-1, 1685cm ^-1, 1280cm ^-1or 1140cm ^-1place has one or more FT-IR feature; And finishing, it comprises one or more epoxides terminated surface, ketone terminated surface, aldehyde terminated surface, carboxy blocking surface, hydroxy-end capped surface or alcohol terminated surface; And measure via x-ray photoelectron spectroscopy art (XPS), the carbon of this catalyst is between about 1.5:1 with about between 2:1 to oxygen ratio.

(17) at about 3150cm ^-1685cm ^-1, 1280cm ^-1or 1140cm ^-1place has one or more FT-IR feature; And finishing, it comprises one or more hydrogen peroxide terminated surface, epoxides terminated surface, ketone terminated surface, aldehyde terminated surface, carboxy blocking surface, hydroxy-end capped surface, alcohol terminated surface, lactone terminated surface, quinone terminated surface, acid anhydride terminated surface or ether capped surface; And measure via x-ray photoelectron spectroscopy art (XPS), the carbon of this catalyst is between about 2:1 with about between 3:1 to oxygen ratio.

(18) at about 3150cm ^-1, 1685cm* ¹, 1280cmf ¹or 1140cm ^-1place has one or more FT-IR feature; And finishing, it comprises one or more epoxides terminated surface, peroxide terminated surface, ketone terminated surface, aldehyde terminated surface, carboxy blocking surface, hydroxy-end capped surface, alcohol terminated surface, quinone terminated surface or ether capped surface; And measure via x-ray photoelectron spectroscopy art (XPS), the carbon of this catalyst is between about 2:1 with about between 3:1 to oxygen ratio.

(19) at about 3150cm ^-1, 1685cm ^-1, 1280cm ^{_ 1}or 1140cm ^-1place has one or more FT-IR feature; And finishing, it comprises one or more epoxides terminated surface, ketone terminated surface, aldehyde terminated surface, carboxy blocking surface, hydroxy-end capped surface or alcohol terminated surface; And measure via x-ray photoelectron spectroscopy art (XPS), the carbon of this catalyst is between about 2:1 with about between 3:1 to oxygen ratio.

In specific embodiments, for above-mentioned reaction (b) (such as methane and ethane transfer the coupling of propane to), the C catalyst of this tool catalytic activity is graphene oxide or the graphite oxide material of the modification of tool catalytically active surface, it is characterized in that:

(1) at about 3150cm ^-1, 1685cm ^-1, 1280cm ^-1or 1140cm ^-1place has one or more FT-IR feature.

(3) at about 3150cm ^-1, 1685cm ^-1, 1280cm ^-1or 1140cmf ¹place has one or more FT-IR feature; And finishing, it comprises one or more epoxides terminated surface, peroxide terminated surface, ketone terminated surface, aldehyde terminated surface, carboxy blocking surface, hydroxy-end capped surface, alcohol terminated surface, quinone terminated surface or ether capped surface.

(4) at about 3150cm ^-1, 1685cm ^-1, 1280cirf ¹or 1140cm ^-1place has one or more FT-IR feature; And finishing, it comprises one or more epoxides terminated surface, ketone terminated surface, aldehyde terminated surface, carboxy blocking surface, hydroxy-end capped surface or alcohol terminated surface.

(6) at about 3150cm ^-1, 1685cm ^-1, 1280cm ^-1or 1140cm ^-1place has one or more FT-IR feature; And finishing, it comprises one or more epoxides terminated surface, peroxide terminated surface, ketone terminated surface, aldehyde terminated surface, carboxy blocking surface, hydroxy-end capped surface, alcohol terminated surface, quinone terminated surface or ether capped surface; And measure, at least about 25% carbon with at least about 0.01% oxygen via x-ray photoelectron spectroscopy art (XPS).

(7) at about 3150cm ^-1, 1685cm ^-1, 1280cir ^-1or 1140cm ^-1place has one or more FT-IR feature; And finishing, it comprises one or more epoxides terminated surface, ketone terminated surface, aldehyde terminated surface, carboxy blocking surface, hydroxy-end capped surface or alcohol terminated surface; Measure, at least about 25% carbon with at least about 0.01% oxygen via x-ray photoelectron spectroscopy art (XPS).

(8) at about 3150cm ^-1, 1685cm ^-1, 1280cm ^-1or 1140cm ^-1place has one or more FT-IR feature; And finishing, it comprises one or more hydrogen peroxide terminated surface, epoxides terminated surface, ketone terminated surface, aldehyde terminated surface, carboxy blocking surface, hydroxy-end capped surface, alcohol terminated surface, lactone terminated surface, quinone terminated surface, acid anhydride terminated surface or ether capped surface; And measure via x-ray photoelectron spectroscopy art (XPS), the carbon of this catalyst is between about 1:1 with about between 1:1.5 to oxygen ratio.

(9) at about 3150cm ^-1, 1685cm ^-1, 1280cm ^-1or 1140cm ^{_ 1}place has one or more FT-IR feature; And finishing, it comprises one or more epoxides terminated surface, peroxide terminated surface, ketone terminated surface, aldehyde terminated surface, carboxy blocking surface, hydroxy-end capped surface, alcohol terminated surface, quinone terminated surface or ether capped surface; And measure via x-ray photoelectron spectroscopy art (XPS), the carbon of this catalyst is between about 1:1 with about between 1:1.5 to oxygen ratio.

(10) at about 3150cm ^-1, 1685cm ^-1, 1280cm ^-1or 1140cm ^-1place has one or more FT-IR feature; And finishing, it comprises one or more epoxides end-blocking Zhi face, ketone terminated surface, aldehyde terminated surface, carboxy blocking surface, hydroxy-end capped surface or alcohol terminated surface; And measure via x-ray photoelectron spectroscopy art (XPS), the carbon of this catalyst is between about 1:1 with about between 1:1.5 to oxygen ratio.

(11) at about 3150cm ^-1685cm ^-1, 1280cm ^-1or 1140cm Shu place has one or more FT-IR feature; And finishing, it comprises one or more hydrogen peroxide terminated surface, epoxides terminated surface, ketone terminated surface, aldehyde terminated surface, carboxy blocking surface, hydroxy-end capped surface, alcohol terminated surface, lactone terminated surface, quinone terminated surface, acid anhydride terminated surface or ether capped surface; And measure via x-ray photoelectron spectroscopy art (XPS), the carbon of this catalyst is between about 1:1 with about between 5:1 to oxygen ratio.

(12) at about 3150cm ^-1, 1685cm], 1280cm ^-1or 1140cm ^-1place has one or more FT-IR feature; And finishing, it comprises one or more epoxides terminated surface, peroxide terminated surface, ketone terminated surface, aldehyde terminated surface, carboxy blocking surface, hydroxy-end capped surface, alcohol terminated surface, quinone terminated surface or ether capped surface; And measure via x-ray photoelectron spectroscopy art (XPS), the carbon of this catalyst is between about 1:1 with about between 5:1 to oxygen ratio.

(13) at about 3150cm* ^1-1685cm ^-1, 1280cm ^-1or 1140cm ^-1place has one or more FT-IR feature; And finishing, it comprises one or more epoxides terminated surface, ketone terminated surface, aldehyde terminated surface, carboxy blocking surface, hydroxy-end capped surface or alcohol terminated surface; And measure via x-ray photoelectron spectroscopy art (XPS), the carbon of this catalyst is between about 1:1 with about between 5:1 to oxygen ratio.

(14) at about 3150cm ^-1, 1685cm ^-1, 1280cm ^-1or 1140cm ^-1place has one or more FT-IR feature; And finishing, it comprises one or more hydrogen peroxide terminated surface, epoxides terminated surface, ketone terminated surface, aldehyde terminated surface, carboxy blocking surface, hydroxy-end capped surface, alcohol terminated surface, lactone terminated surface, quinone terminated surface, acid anhydride terminated surface or ether capped surface; And measure via x-ray photoelectron spectroscopy art (XPS), the carbon of this catalyst is between about 1.5:1 and about 2:1 to oxygen ratio.

(16) at about 3150cm ^-1, 1685cm ^-1, 1280cm ^-1or 1140cm ^-1place has one or more FT-IR feature; And finishing, it comprises one or more epoxides terminated surface, ketone terminated surface, aldehyde terminated surface, carboxy blocking surface, hydroxy-end capped surface or alcohol terminated surface; And measure via x-ray photoelectron spectroscopy art (XPS), the carbon of this catalyst is between about 1.5:1 with about between 2:1 to oxygen ratio.

(17) at about 3150cm ^-1, 1685cm ^-1, 1280cm ^-1or 1140cm ^-1place has one or more FT-IR feature; And finishing, it comprises one or more hydrogen peroxide terminated surface, epoxides terminated surface, ketone terminated surface, aldehyde terminated surface, carboxy blocking surface, hydroxy-end capped surface, alcohol terminated surface, lactone terminated surface, quinone terminated surface, acid anhydride terminated surface or ether capped surface; And measure via x-ray photoelectron spectroscopy art (XPS), the carbon of this catalyst is between about 2:1 with about between 3:1 to oxygen ratio.

(18) at about 3150cm ^-1, 1685cm ^-1, 1280cm ^-1or 1140cm ^-1place has one or more FT-IR feature; And finishing, it comprises one or more epoxides terminated surface, peroxide terminated surface, ketone terminated surface, aldehyde terminated surface, carboxy blocking surface, hydroxy-end capped surface, alcohol terminated surface, quinone terminated surface or ether capped surface; And measure via x-ray photoelectron spectroscopy art (XPS), the carbon of this catalyst is between about 2:1 with about between 3:1 to oxygen ratio.

(19) at about 3150cm ^-1, 1685cm ^-1, 1280cm ^-1or 1140cm ^-1place has one or more FT-IR feature; And finishing, it comprises one or more epoxides terminated surface, ketone terminated surface, aldehyde terminated surface, carboxy blocking surface, hydroxy-end capped surface or alcohol turnip end surfaces; And measure via x-ray photoelectron spectroscopy art (XPS), the carbon of this catalyst is between about 2:1 with about between 3:1 to oxygen ratio.

In specific embodiments, with regard to above-mentioned reaction (c) (such as ethane transfers the displacement of methane and propane to), the C catalyst of this tool catalytic activity is graphene oxide or the graphite oxide material of the modification of tool catalytically active surface, it is characterized in that:

(2) at about 3150cm ^-1, 1685cm ^-1, 1280cmf ¹or 1140cmf ¹place has one or more FT-IR feature; And finishing, it comprises one or more hydrogen peroxide terminated surface, epoxides terminated surface, ketone terminated surface, aldehyde terminated surface, carboxy blocking surface, hydroxy-end capped surface, alcohol terminated surface, lactone terminated surface, quinone terminated surface, acid anhydride terminated surface or ether capped surface.

(3) at about 3150cm ^-1, 1685cm ^-1, 1280cm " or 1140cm ^-shu place has one or more FT-IR feature; And finishing, it comprises one or more epoxides terminated surface, peroxide terminated surface, ketone terminated surface, aldehyde terminated surface, carboxy blocking surface, hydroxy-end capped surface, alcohol terminated surface, quinone terminated surface or ether capped surface.

(4) at about 3150cm ^-1, 1685cm ^-1, 1280cm ^-1or 1140 place there is one or more FT-IR feature; And finishing, it comprises one or more epoxides terminated surface, ketone terminated surface, aldehyde terminated surface, carboxy blocking surface, hydroxy-end capped surface or alcohol terminated surface.

(5) at about 3150cm ^-1, 1685cm], 1280cmf ¹or 1140cm ^-1place has one or more FT-IR feature; And finishing, it comprises one or more hydrogen peroxide terminated surface, epoxides terminated surface, ketone terminated surface, aldehyde terminated surface, carboxy blocking surface, hydroxy-end capped surface, alcohol terminated surface, lactone terminated surface, quinone terminated surface, acid anhydride terminated surface or ether capped surface; And measure, at least about 25% carbon with at least about 0.01% oxygen via x-ray photoelectron spectroscopy art (XPS).

(9) at about 3150cm ^-1, 1685cm ^-1, 1280cm ^-1or 1140cm ^-1place has one or more FT-IR feature; And finishing, it comprises one or more epoxides terminated surface, peroxide terminated surface, ketone terminated surface, aldehyde terminated surface, carboxy blocking surface, hydroxy-end capped surface, alcohol terminated surface, quinone terminated surface or ether capped surface; And measure via x-ray photoelectron spectroscopy art (XPS), the carbon of this catalyst is between about 1:1 with about between 1:1.5 to oxygen ratio.

(12) at about 3150cm ^-1, 1685cm ^-1, 1280cm ^-1or 1140cm ^-1place has one or more FT-IR feature; And finishing, it comprises one or more epoxides terminated surface, peroxide terminated surface, ketone terminated surface, aldehyde terminated surface, carboxy blocking surface, hydroxy-end capped surface, alcohol terminated surface, quinone terminated surface or ether capped surface; And measure via x-ray photoelectron spectroscopy art (XPS), the carbon of this catalyst is between about 1:1 with about between 5:1 to oxygen ratio.

(16) at about 3150cm ^-1, 1685cm ^-1, 1280cm* ¹or 1140cm ^-1place has one or more FT-IR feature; And finishing, it comprises one or more epoxides terminated surface, ketone terminated surface, aldehyde terminated surface, carboxy blocking surface, hydroxy-end capped surface or alcohol terminated surface; And measure via x-ray photoelectron spectroscopy art (XPS), the carbon of this catalyst is between about 1.5:1 with about between 2:1 to oxygen ratio.

In specific embodiments, with regard to above-mentioned reaction (d) (such as hexane transfers the cracking of methane and/or ethane and/or propane and/or butane or its combination to), the C catalyst of this tool catalytic activity is graphene oxide or the graphite oxide material of the modification of tool catalytically active surface, it is characterized in that:

(1) at about 3150cm ^-1685cm ^-1, 1280cm ^-1or 1140cm " place has one or more FT-IR feature.

(2) at about 3150cm ^-1, 1685cm ^-1, 1280cm ^-1or 1140cm ^{_ 1}place has one or more FT-IR feature; And finishing, it comprises one or more hydrogen peroxide terminated surface, epoxides terminated surface, ketone terminated surface, aldehyde terminated surface, carboxy blocking surface, hydroxy-end capped surface, alcohol terminated surface, lactone terminated surface, quinone terminated surface, acid anhydride terminated surface or ether capped surface.

(3) at about 3150cm ^-1, 1685cm ^-1, 1280cm] or 1140cm ^]place has one or more FT-IR feature; And finishing, it comprises one or more epoxides terminated surface, peroxide terminated surface, ketone terminated surface, aldehyde terminated surface, carboxy blocking surface, hydroxy-end capped surface, alcohol terminated surface, quinone terminated surface or ether capped surface.

(4) at about 3150cm ^-1, 1685cm ^-1, 1280cm ^-1or 1140cm ^{_ 1}place has one or more FT-IR feature; And finishing, it comprises one or more epoxides terminated surface, ketone terminated surface, aldehyde terminated surface, carboxy blocking surface, hydroxy-end capped surface or alcohol terminated surface.

(5) at about 3150cm ^-1, 1685cm ^-1, 1280cm ^-1or 1140cm ^-1place has one or more FT-IR feature; And finishing, it comprises one or more hydrogen peroxide terminated surface, epoxides terminated surface, ketone terminated surface, aldehyde terminated surface, carboxy blocking surface, hydroxy-end capped surface, alcohol terminated surface, lactone terminated surface, quinone terminated surface, acid anhydride terminated surface or ether capped surface; And measure at least about 25% carbon with at least about 0.01% oxygen via x-ray photoelectron spectroscopy art (XPS).

(6) at about 3150cm ^-1, 1685cm ^-1, 1280crrf ¹or 1140cm ^-1place has one or more FT-IR feature; And finishing, it comprises one or more epoxides terminated surface, peroxide terminated surface, ketone terminated surface, aldehyde terminated surface, carboxy blocking surface, hydroxy-end capped surface, alcohol terminated surface, quinone terminated surface or ether capped surface; And measure at least about 25% carbon with at least about 0.01% oxygen via x-ray photoelectron spectroscopy art (XPS).

(7) at about 3150cm ^-1, 1685cm* ¹, 1280cmf ¹or 1140cm ^-1place has ~, individual or multiple FT-IR feature; And finishing, it comprises one or more epoxides terminated surface, ketone terminated surface, aldehyde terminated surface, carboxy blocking surface, hydroxy-end capped surface or alcohol terminated surface; Measure, at least about 25% carbon with at least about 0.01% oxygen via x-ray photoelectron spectroscopy art (XPS).

(8) at about 3150cm ^-1, 1685cm* ¹, 1280cm ^{_ 1}or 1140cm ^-1place has one or more FT-IR feature; And finishing, it comprises one or more hydrogen peroxide terminated surface, epoxides terminated surface, ketone terminated surface, aldehyde terminated surface, carboxy blocking surface, hydroxy-end capped surface, alcohol terminated surface, lactone terminated surface, quinone terminated surface, acid anhydride terminated surface or ether capped surface; And measure via x-ray photoelectron spectroscopy art (XPS), the carbon of this catalyst is between about 1:1 with about between 1:1.5 to oxygen ratio.

(10) at about 3150cm ^-1, 1685cm ^-1, 1280cm. Shu or 1140cm ^-1place has one or more FT-IR feature; And finishing, it comprises one or more epoxides terminated surface, ketone terminated surface, aldehyde terminated surface, carboxy blocking surface, hydroxy-end capped surface or alcohol terminated surface; And measure via x-ray photoelectron spectroscopy art (XPS), the carbon of this catalyst is between about 1:1 with about between 1:1.5 to oxygen ratio.

(11) at about 3150cm* ¹, 1685cm ^-1, 1280cm ^-1or 1140cm ^-1place has one or more FT-IR feature; And finishing, it comprises one or more hydrogen peroxide terminated surface, epoxides terminated surface, ketone terminated surface, aldehyde terminated surface, carboxy blocking surface, hydroxy-end capped surface, alcohol terminated surface, lactone terminated surface, quinone terminated surface, acid anhydride terminated surface or ether capped surface; And measure via x-ray photoelectron spectroscopy art (XPS), the carbon of this catalyst is between about 1:1 with about between 5:1 to oxygen ratio.

(13) at about 3150cm ^-1, 1685cm ^-1, 1280cm ^-1or 1140cm] place has one or more FT-IR feature; And finishing, it comprises one or more epoxides terminated surface, ketone terminated surface, aldehyde terminated surface, carboxy blocking surface, hydroxy-end capped surface or alcohol terminated surface; And measure via x-ray photoelectron spectroscopy art (XPS), the carbon of this catalyst is between about 1:1 with about between 5:1 to oxygen ratio.

(14) at about 3150cm ^-1, 1685cm], 1280cm ^-1or 1140cm ^-1place has one or more FT-IR feature; And finishing, it comprises one or more hydrogen peroxide terminated surface, epoxides terminated surface, ketone terminated surface, aldehyde terminated surface, carboxy blocking surface, hydroxy-end capped surface, alcohol terminated surface, lactone terminated surface, quinone terminated surface, acid anhydride terminated surface or ether capped surface; And measure via x-ray photoelectron spectroscopy art (XPS), the carbon of this catalyst is between about 1.5:1 with about between 2:1 to oxygen ratio.

In specific embodiments, with regard to above-mentioned reaction (e) (such as cyclohexane transfers the cracking of methane and/or ethane and/or propane or its combination to), the C catalyst of this tool catalytic activity is graphene oxide or the graphite oxide material of the modification of tool catalytically active surface, it is characterized in that:

(1) at about 3150cm ^-1, 1685cm ^-1280cm ^-1or 1140cm ^-1place has one or more FT-IR feature.

(3) at about 3150cm ^-1, 1685cm ^-1280cm ^-1or 1140cm ^-1place has one or more FT-IR feature; And finishing, it comprises one or more epoxides terminated surface, peroxide terminated surface, ketone terminated surface, aldehyde terminated surface, carboxy blocking surface, hydroxy-end capped surface, alcohol terminated surface, quinone terminated surface or ether capped surface.

(5) at about 3150cm ^-1, 1685cm ^-1, 1280cm ^-1or 1140cm ^-1place has one or more FT-IR feature; And finishing, it comprises one or more hydrogen peroxide terminated surface, epoxides terminated surface, ketone terminated surface, aldehyde terminated surface, carboxy blocking surface, hydroxy-end capped surface, alcohol terminated surface, lactone terminated surface, quinone terminated surface, acid anhydride terminated surface or ether capped surface; And measure, at least about 25 private carbon with at least about 0.01% oxygen via x-ray photoelectron spectroscopy art (XPS).

(6) at about 3150cm ^-1, 1685cm ^-1, 1280cm ^-1or 1140cm ^-1place has one

Or multiple FT-IR feature; And finishing, it comprises one or more epoxides terminated surface, peroxide terminated surface, ketone terminated surface, aldehyde terminated surface, carboxy blocking surface, hydroxy-end capped surface, alcohol terminated surface, quinone terminated surface or ether capped surface; And measure, at least about 25% carbon with at least about 0.01% oxygen via x-ray photoelectron spectroscopy art (XPS).

(8) at about 3150cm ^-1, 1685cm ^-1, 1280cm " or 1140cm-Shu place there is one or more FT-IR feature; And finishing, it comprises one or more hydrogen peroxide terminated surface, epoxides terminated surface, ketone terminated surface, aldehyde terminated surface, carboxy blocking surface, hydroxy-end capped surface, alcohol terminated surface, lactone terminated surface, quinone terminated surface, acid anhydride terminated surface or ether capped surface; And measure via x-ray photoelectron spectroscopy art (XPS). the carbon of this catalyst is between about 1:1 with about between 1:1.5 to oxygen ratio.

(10) at about 3150cm ^-1, 1685cm ^-1, 1280cm ^-1or 1140cm ^-1place has one or more FT-IR feature; And finishing, it comprises one or more epoxides terminated surface, ketone terminated surface, aldehyde terminated surface, carboxy blocking surface, hydroxy-end capped surface or alcohol terminated surface; And measure via x-ray photoelectron spectroscopy art (XP.S), the carbon of this catalyst is between about 1:1 with about between 1:1.5 to oxygen ratio.

(11) at about 3150cm ^-1, 1685cm ^-1, 1280cm ^-1or 1140cm ^-1place has one or more FT-IR feature; And finishing, its comprise one or more hydrogen peroxide terminated surface, epoxides terminated surface, ketone terminated surface, aldehyde terminated surface, carboxy blocking surface, hydroxy-end capped surface, alcohol terminated surface, lactone terminated surface, quinone terminated surface, acid anhydride end-blocking table *, face or ether capped surface; And measure via x-ray photoelectron spectroscopy art (XPS), the carbon of this catalyst is between about 1:1 with about between 5:1 to oxygen ratio.

(13) at about 3150cm ^-1, 1685cm ^-1, 1280cm ^{_ 1}or 1140cm ^-1place has one or more FT-IR feature; And finishing, it comprises one or more epoxides terminated surface, ketone terminated surface, aldehyde terminated surface, carboxy blocking surface, hydroxy-end capped surface or alcohol terminated surface; And measure via x-ray photoelectron spectroscopy art (XPS), the carbon of this catalyst is between about 1:1 with about between 5:1 to oxygen ratio.

(15) at about 3150cm ^-1, 1685cm ^-1, 1280cm ^-1or 1140cm ^-1place has plucks or multiple FT-IR feature; And finishing, it comprises one or more epoxides terminated surface, peroxide terminated surface, ketone terminated surface, aldehyde terminated surface, carboxy blocking surface, hydroxy-end capped surface, alcohol terminated surface, quinone terminated surface or ether capped surface; And measure via x-ray photoelectron spectroscopy art (XPS), the carbon of this catalyst is between about 1.5:1 with about between 2:1 to oxygen ratio.

(16) at about 3150cm ^-1, 1685cm], 1280cm ^-1or 1140cm ^-1place has one or more FT-IR feature; And finishing, it comprises one or more epoxides terminated surface, ketone terminated surface, aldehyde terminated surface, carboxy blocking surface, hydroxy-end capped surface or alcohol terminated surface; And measure via x-ray photoelectron spectroscopy art (XPS), the carbon of this catalyst is between about 1.5:1 with about between 2:1 to oxygen ratio.

(17) at about 3150cm ^-1, 1685cm ^-1, 1280cm ^-1or 1140cm ^-1place has one or more FT-IR feature; And finishing, it comprises one or more hydrogen peroxide terminated surface, epoxides terminated surface, ketone terminated surface, aldehyde terminated surface, carboxy blocking surface, hydroxy-end capped surface, alcohol terminated surface, lactone terminated surface, quinone terminated surface, acid anhydride terminated surface or ether capped surface; And measure via x-ray photoelectron spectroscopy art (XPS), the carbon of this catalyst is between about 2:1 and about 3:1 to oxygen ratio.

(18) at about 3150cm ^-1, 1685cm ^-1, 1280cm ^-1or 1140cm ^-1place has one or more FT-IR feature; And finishing, it comprises one or more epoxides terminated surface, peroxide terminated surface, ketone terminated surface, aldehyde terminated surface, carboxy blocking surface, hydroxy-end capped surface, alcohol terminated surface, quinone terminated surface or ether capped surface: and measure via x-ray photoelectron spectroscopy art (XPS), the carbon of this catalyst is between about 2:1 with about between 3:1 to oxygen ratio.

(19) at about 3150cm ^-1, 1685cm* ¹, 1280cm ^-1or 1140cm ^-1place has one or more FT-IR feature; And finishing, it comprises one or more epoxides terminated surface, ketone terminated surface, aldehyde terminated surface, carboxy blocking surface, hydroxy-end capped surface or alcohol terminated surface; And measure via x-ray photoelectron spectroscopy art (XPS), the carbon of this catalyst is between about 2:1 with about between 3:1 to oxygen ratio.

With regard to each concrete example of above-mentioned each (A), (B), (C), (D) or (E), this catalyst is in fact without any transition metal.With regard to each concrete example of above-mentioned (A), (B), (C), (D) or (E), or with regard to each concrete example of above described each (A) and (F), (B) and (F), (C) and (F), (D) and (F) or (E) and (F), this catalyst amount be (1-1) between about 0.1 % by weight to about 10 % by weight the weight of parent material.

(1-2) between about 0.1 % by weight to about 1 % by weight the weight of parent material.

(1-3) between about 0.001 % by weight to about 0 ^-1the weight of the parent material of % by weight.

(1-4) between about 10 % by weight to about 50 % by weight the weight of parent material.

(1-5) between about 10 % by weight to about 100 % by weight the weight of parent material.

(1-6) between about 100 % by weight to about 500 % by weight the weight of parent material.

(1-7) between about 100 % by weight to about 1,000 % by weight the weight of parent material.

(1-8) between about 1,000 % by weight to about 10,000 % by weight the weight of parent material.

With regard to each (A) and (1-1), 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) (A), 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) (B), and (1-8) (A), 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) (B), 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 (C) ^-1), 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) (C), and (1-1) (D), and (1-2) (D), (1-3), and (1-4) (D), and (1-5) (D), and (1-6) (D), and (1-7) (D), and (1-8) (D), and (F) and (1 (A) ^-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), 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 (1-5) (E), and (F) and (1-6) (E), and each concrete example of (F) and (1-7) or (E) and (F) and (1-8) (E), this reaction is carried out under following temperature:

(2-1) between about-78 DEG C and room temperature.

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

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

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

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

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

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

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

(3-1) with regard to above described each concrete example, this reaction is carried out under pressure 1atm.

(3-2) with regard to above described each concrete example, this reaction is carried out under about between 1-5atm at pressure.

(3-3) with regard to above described each concrete example, this reaction is carried out under about between 0.1-1atm at pressure.

(3-4) with regard to above described each concrete example, this reaction is carried out under about between 1-10atm at pressure.

(3-5) with regard to above described each concrete example, this reaction is carried out under about between 1-50atm at pressure.

(4-1) by above-mentioned concrete example (3-1), the C catalyst of this tool catalytic activity is graphene oxide or the graphite oxide of the modification of tool catalytically active surface, and the graphene oxide of this tool catalytically active surface modification or graphite oxide are the graphene oxide that tool catalytically active surface is modified.

(4-2) by above-mentioned concrete example (3-1), the C catalyst of this tool catalytic activity is graphene oxide or the graphite oxide of the modification of tool catalytically active surface, and the graphene oxide of this tool catalytically active surface modification or graphite oxide are the graphite oxide that tool catalytically active surface is modified.

(4-3) by above-mentioned concrete example (3-2), the C catalyst of this tool catalytic activity is graphene oxide or the graphite oxide of the modification of tool catalytically active surface, and the graphene oxide of this tool catalytically active surface modification or graphite oxide are the graphene oxide that tool catalytically active surface is modified.

(4-4) by above-mentioned concrete example (3-2), the C catalyst of this tool catalytic activity is graphene oxide or the graphite oxide of the modification of tool catalytically active surface, and the graphene oxide of this tool catalytically active surface modification or graphite oxide are the graphite oxide that tool catalytically active surface is modified.

(4-5) by above-mentioned concrete example (3-3), the C catalyst of this tool catalytic activity is graphene oxide or the graphite oxide of the modification of tool catalytically active surface, and the graphene oxide of this tool catalytically active surface modification or graphite oxide are the graphene oxide that tool catalytically active surface is modified.

(4-6) by above-mentioned concrete example (3-3), the C catalyst of this tool catalytic activity is graphene oxide or the graphite oxide of the modification of tool catalytically active surface, and the graphene oxide of this tool catalytically active surface modification or graphite oxide are the graphite oxide that tool catalytically active surface is modified.

(4-7) by above-mentioned concrete example (3-4), the C catalyst of this tool catalytic activity is graphene oxide or the graphite oxide of the modification of tool catalytically active surface, and the graphene oxide of this tool catalytically active surface modification or graphite oxide are the graphene oxide that tool catalytically active surface is modified.

(4-8) by above-mentioned concrete example (3-4), the C catalyst of this tool catalytic activity is graphene oxide or the graphite oxide of the modification of tool catalytically active surface, and the graphene oxide of this tool catalytically active surface modification or graphite oxide are the graphite oxide that tool catalytically active surface is modified.

(4-9) by above-mentioned concrete example (3-5), the C catalyst of this tool catalytic activity is the graphene oxide modified of tool catalytically active surface or graphite oxide, and this tool catalytically active surface is modified. graphene oxide or graphite oxide be the graphene oxide that tool catalytically active surface is modified.

(4-10) by above-mentioned concrete example (3-5), the C catalyst of this tool catalytic activity is graphene oxide or the graphite oxide of the modification of tool catalytically active surface, and the graphene oxide of this tool catalytically active surface modification or graphite oxide are the graphite oxide that tool catalytically active surface is modified.

Although specify specific reaction condition, conversion and productive rate in the present invention, above-mentioned condition, conversion and productive rate can be applicable in the reaction of any C catalyst through tool catalytic activity (comprising graphene oxide or the graphite oxide of finishing) institute's catalysis.

The preparation of graphene oxide or graphite oxide catalyst, according to following method, prepares graphene oxide or the graphite oxide of use a little experiments in these embodiments.

Use modified Hummers method to prepare graphite oxide.At 35 DEG C, flake graphite and potassinm permanganate (KMn0 ₄) at the concentrated sulfuric acid (H ₂s0 ₄) in reaction 4 hours, the graphene oxide of obtained finishing or graphite oxide (MG).Then, in deionized water, then hydrogen peroxide (H is added via dilution ₂0 ₂) aqueous solution, stop the reaction of this reactant mixture.MG is not dissolved in this mixture, thus then washs to remove residual metal salt and acid with excessive water via vacuum filtration, reclaims.Finally, this hygroscopic products dry is to remove residual water under vacuo, obtains in dark brown pulverous product.The mass balance equation of this reaction describes in FIG.Optionally change graphite and KMn0 ₄and H ₂s0 ₄ratio, to produce the MG with different degree of oxidation.

Graphite+KMn0 ₄+ H ₂s0 ₄+ H ₂0 ₂+ water+MG+ waste water 1 matter equivalent 3 matter equivalent 10 matter equivalent 2 matter equivalent 20 matter equivalent 2 matter equivalent 34 matter equivalent Example 2: being prepared in 250mL reaction flask of graphite oxide loads natural flake graphite (1.56g; SP ^-1or AlfaAesar [99% BayCarbonInc.; 7 ^-10fim]), the concentrated sulfuric acid of 50mL, the fuming nitric aicd of 25mL and stirring rod, then cool on ice bath.Then under agitation NaC10 is loaded by flask ₃(3.25g; Please note: in a little example, by the KC10 during reaction formed ₄be not dissolved in water, NaC10 ₃comparatively KC10 ₃be preferred).Continuous 11 hours of every day reinstalled NaC10 time per ₃(3.25g).This program repeats 3 days.The mixture of gained is poured in 2L deionized water.Then, by this Heterodisperse liquid, by scalping glass funnel (coarsefrittedfunnel) or nylon membrane filter, (0.2 is i, Whatman) filter, wash with 6NHC1 (1L) material be separated by extra deionized water (3L).Collect the solid leached, and dry under a high vacuum, to provide in dark brown pulverous product (3.61g).

The preparation of graphene oxide provides Graphene base material in the reaction chamber.This base material is at 3150cm ^-1, 1685cm ^-1, 1280cm ^-1or 1140cm ^]do not represent one or more fourier-transform infrared (FT-IR) peak.Then, the electricity slurry of oxygen excites species to be directed to this reative cell from electricity slurry generator, and makes it contact with the exposed surface of Graphene base material.This Graphene base material be exposed to oxygen electricity slurry excite species under until the FT-IR spectrum of base material is at 3150cm ^-1, 1685cm ^-1, 1280cm ^-1or 1140cm ^-1show one or more peak.

In typical case's preparation, in pressure pan, load graphene oxide or graphite oxide, hexane and magnetic stirring bar.Then under ambient air, this pressure pan is sealed, and heat 5 minutes at 800 DEG C.Standardization program is used to isolate butadiene product.

Claims

1. one kind is used in conversion

A () alkane parent material becomes olefin product (dehydrogenation);

Or the processing procedure of its combination any,

2. as the processing procedure of claims 1, it is characterized in that, the graphene oxide that this tool catalytically active surface is modified or graphite oxide are the graphene oxide that tool catalytically active surface is modified.

3. as the processing procedure of claims 1, it is characterized in that, the graphene oxide that this tool catalytically active surface is modified or graphite oxide are the graphite oxide that tool catalytically active surface is modified.

4. as the processing procedure of claims 1, it is characterized in that, the feature of the graphene oxide that this tool catalytically active surface is modified or graphite oxide is, at about 3150cm ^-1, 1685cm ^-1, 1280cm ^-1or 1140cm ^-1place has one or more fourier-transform infrared (FT-IR) feature.

5. as the processing procedure of claims 1, it is characterized in that, the graphene oxide that this tool catalytically active surface is modified or graphite oxide have finishing, and it comprises one or more hydrogen peroxide terminated surface, epoxides terminated surface, ketone terminated surface, diketone terminated surface, aldehyde terminated surface, carboxy blocking surface, hydroxy-end capped surface, alcohol terminated surface, ether capped surface, dioxy cyclopropane terminated surface, quinone terminated surface, peroxy acid terminated surface, ester terminated surface, acid anhydride terminated surface or peracid ester terminated surface.

6. as the processing procedure of claims 1, it is characterized in that, the graphene oxide that this tool catalytically active surface is modified or graphite oxide have finishing, and it comprises one or more hydrogen peroxide terminated surface, epoxides terminated surface, ketone terminated surface, aldehyde terminated surface, carboxy blocking surface, hydroxy-end capped surface, alcohol terminated surface or ether capped surface.

7. as the processing procedure of claims 1, it is characterized in that, the graphene oxide that this tool catalytically active surface is modified or graphite oxide have finishing, and it comprises one or more epoxides terminated surface, ketone terminated surface, aldehyde terminated surface, carboxy blocking surface, hydroxy-end capped surface or alcohol terminated surface.

8. as the processing procedure of claims 1, it is characterized in that, measure via x-ray photoelectron spectroscopy art (XPS), the graphene oxide that this tool catalytically active surface is modified or graphite oxide have the carbon at least about 25% and the oxygen at least about 0.01%.

9. as the processing procedure of claims 1, it is characterized in that, measure via x-ray photoelectron spectroscopy art (XPS), the carbon of the graphene oxide that this tool catalytically active surface is modified or graphite oxide is between about 1.5:1 with about between 1:1.5 to oxygen ratio.

10. as the processing procedure of claims 1, it is characterized in that, measure via x-ray photoelectron spectroscopy art (XPS), the carbon of the graphene oxide that this tool catalytically active surface is modified or graphite oxide is between about 1:1 with about between 5:1 to oxygen ratio.