CN117550944A

CN117550944A - Method for producing hydrocarbon molecules by magnetic field assisted energy radiation

Info

Publication number: CN117550944A
Application number: CN202311524498.7A
Authority: CN
Inventors: 王琮; 霍海滨
Original assignee: Beijing Guanghe New Energy Technology Co ltd
Current assignee: Beijing Guanghe New Energy Technology Co ltd
Priority date: 2023-11-15
Filing date: 2023-11-15
Publication date: 2024-02-13

Abstract

A method for producing hydrocarbon molecules by magnetic field assisted energy radiation comprising contacting a plasmonic composite catalyst with at least one hydrogen containing source, at least one carbon containing source in the presence of an externally applied magnetic field; and energy irradiating the plasmonic composite catalyst, the hydrogen-containing source, and the carbon-containing source to produce hydrocarbon molecules, wherein the composite catalyst comprises at least one nano-substrate structure and at least one atomic site comprising one or more chemical elements of Mn, co, fe, ru, rh, al, ag, au, pt, pd, cu, ni, zn, ti, os, ir, la.

Description

Method for producing hydrocarbon molecules by magnetic field assisted energy radiation

Technical Field

The invention relates to a method for producing hydrocarbon molecules through magnetic field auxiliary energy radiation catalysis, belonging to the fields of carbon dioxide utilization and renewable energy sources.

Background

The greenhouse effect caused by the carbon dioxide greatly increased causes great threat to the whole human environment, climate and ecology. Carbon dioxide capture, utilization and sequestration technologies are becoming more and more important, and scientists around the world have conducted a vast array of research projects around these technologies. The artificial photosynthesis technology converts carbon dioxide into organic compounds such as hydrocarbons and alcohols by using solar energy, so as to realize the sealing and the utilization of the carbon dioxide and the recycling of energy, which is one of the most promising technologies.

In the last decades there has been an increasing interest in the field of solar energy conversion into more useful energy. Some technologies show great promise in this area, however, there is a long way to travel from commercialization. To date, most research works have solar chemical energy conversion efficiency 1 or 2 orders of magnitude lower than natural photosynthesis, and current catalyst stability still cannot provide reliable support for industrialization.

Due to the plasmonic effect, the plasmonic catalyst can achieve a great enhancement of localized energy on the nanostructure surface. Therefore, under the condition of mild overall reaction conditions, the catalytic reaction is efficiently promoted, so that the reaction which cannot be achieved at normal temperature and normal pressure is possible. The single-atom catalysis has also been widely studied and studied, and exhibits activities, selectivities and stabilities different from those of conventional nanocatalysts due to the special structure. By combining the advantages of the plasmon effect and the monoatomic catalysis, it is possible to develop an artificial photosynthetic catalyst which can meet the commercialization requirements in both efficiency and stability.

In addition, a certain promotion effect may be exerted by applying a specific external auxiliary means to the catalytic reaction. The catalytic process involves the migration of effective charges, etc., so that increasing the external magnetic field may have an effect on the catalytic activity. In the prior art, lorentz force is generated by basically adopting a moving magnetic field mode such as a moving magnetic field mode and an alternating magnetic field mode in magnetic field auxiliary catalysis mode so as to lead charges to directionally move, thereby influencing the catalysis effect. However, on the one hand, this dynamic magnetic field requires an additional energy input, and on the other hand, the lorentz force generation requires that the catalyst has a certain physical form to redistribute the charges macroscopically, and its influence on the catalytic effect is also limited.

Disclosure of Invention

Based on the technical problems of the prior art, the invention provides a novel plasmonic catalysis technology, wherein the plasmonic catalyst comprises atomic sites, such as single atomic sites and/or atomic clusters containing 2-25 atoms, and the invention provides a method for utilizing CO or CO from industrial flue gas or atmosphere in the presence of a cost-effective catalyst ₂ Unique methods for the preparation of hydrocarbon molecules by light and/or heat radiation, and by the aid of external magnetic fields, the yield of the reaction and the selectivity of the product are regulated.

One aspect of the invention is a method of producing hydrocarbon molecules by magnetic field assisted energy radiation comprising:

contacting a composite catalyst with at least one hydrogen-containing source, at least one carbon-containing source in the presence of an externally applied magnetic field, and energy irradiating the composite catalyst, the hydrogen-containing source, and the carbon-containing source to produce hydrocarbon molecules, wherein

The composite catalyst comprises at least one nano-substrate structure and at least one atomic site comprising one or more chemical elements of Mn, co, fe, ru, rh, al, ag, au, pt, pd, cu, ni, zn, ti, os, ir, la.

In some embodiments, the externally applied magnetic field is a static magnetic field, for example, it may be generated by a permanent magnet or a uniformly varying electric field, preferably by a permanent magnet, while there is no relative motion between the nanocatalyst and the externally applied magnetic field, no lorentz force is generated, and no macroscopic charge movement is present.

In certain embodiments, the catalytic reaction is assisted by an externally applied magnetic field having a magnetic flux density of 0-400mT, preferably 100-400mT, and most preferably 200-300mT, to increase the activity of the unit catalyst for the production of hydrocarbon molecules by 0-50% and by 30-50% over the preferred magnetic field flux density range.

In certain embodiments, the selectivity of propane in the product hydrocarbon molecule is enhanced by using an externally applied magnetic field having a magnetic flux density of 0-400mT, preferably 100-400mT, and most preferably 200-300mT, and a selectivity of 10% to 30% for propane in the product hydrocarbon molecule, and 20% to 30% in the preferred magnetic field flux density range.

In certain embodiments, the energy radiation is selected from at least one of optical radiation and thermal radiation, preferably optical radiation.

In certain embodiments, the distance between the nano-substrate structure and the atomic site is less than or equal to 5nm, preferably less than or equal to 1nm, more preferably less than 0.1nm, most preferably both are in intimate contact.

In certain embodiments, the atomic sites are bound to the nano-substrate structure, e.g., physically or chemically.

In certain embodiments, the mass percentage of the atomic sites to the nano-substrate structure is 50% or less, preferably 0.01% to 30%, preferably 0.01% to 5%, more preferably 0.1% to 2%, most preferably 0.1% to 1%.

In certain embodiments, the atomic sites are supported on the surface of the nano-substrate structure, in internal pores, or distributed in the internal lattice of the nano-substrate structure, preferably with a uniform distribution of the atomic sites. In a preferred embodiment, the separation between the atomic sites is 0.2-500nm, preferably 1-50nm, more preferably 1-10nm.

In certain embodiments, the nano-substrate structure is selected from the group consisting of Mn, co, ce, fe, al, ca, ce, cu, ni, ti, zn, si, mo, bi,V, C, N and its oxide, nitride, sulfide, carbide, hydroxide, chloride and Metal Organic Framework (MOF), preferably metal organic framework, tiO ₂ Or Al ₂ O ₃ 。

In certain embodiments, the composite catalyst is a Co and Mn supported or bound to metal organic framework (CoMn-MOF) catalyst, fe supported or bound to Al ₂ O ₃ (Fe-Al) ₂ O ₃ ) Catalyst, co supported on or bound to Al ₂ O ₃ Of (Co-Al) ₂ O ₃ ) Catalyst, ru supported on or bound to Al ₂ O ₃ Of (Ru-Al) ₂ O ₃ ) Catalyst, ru and Fe supported on or bound to Al ₂ O ₃ Of (RuFe-Al) ₂ O ₃ ) The catalyst or Ru and Co are supported on and combined with Al ₂ O ₃ Of (RuCo-Al) ₂ O ₃ ) A catalyst.

In a preferred embodiment, at least one dimension of the nano-substrate structure in length, width, height is from about 1nm to about 1000nm, preferably from about 70nm to about 1000nm, from about 100nm to about 800nm, from about 200nm to about 500nm.

In preferred embodiments, the nano-substrate structures are each independently from about 1nm to about 3000nm in length, width, height, preferably from about 100nm to about 3000nm in length, from about 500nm to about 2500nm, or from about 1000nm to about 2000nm in length, and/or from about 1nm to about 1000nm in width or height, from about 70nm to about 1000nm, from about 100nm to about 800nm, or from about 200nm to about 500nm, or, each independently, from about 1 to about 20 aspect ratio, preferably from about 1 to about 10, or from about 2 to about 8 aspect ratio.

In certain embodiments, the shape of the nano-substrate structure is spherical, spines, flakes, needles, grass blades, cylinders, polyhedrons, three-dimensional pyramids, cubes, flakes, hemispheres, irregular three-dimensional shapes, porous structures, or any combination thereof.

In certain embodiments, a plurality of the atomic sites are arranged in a patterned configuration, preferably a multi-layer arrangement, on the nano-substrate structure, or a plurality of the atomic sites are randomly dispersed in and/or on the nano-substrate structure.

In certain embodiments, the energy radiation causes the reaction to proceed at a temperature between about 20 ℃ and about 500 ℃, preferably about 50 ℃ to about 300 ℃, about 70 ℃ to about 250 ℃, about 90 ℃ to about 200 ℃, about 100 ℃ to about 180 ℃, about 100 ℃ to about 150 ℃, about 110 ℃ to about 140 ℃, about 120 ℃ to about 140 ℃, and the unit catalyst activity to produce hydrocarbon molecules is greater than 18 μmol g ^-1 h ^-1 Greater than 50. Mu. Mol g at the preferred temperature range ^-1 h ^-1 。

In certain embodiments, the reaction is initiated using light or heat radiation having a light radiation power of 200-1500W/m and continued using light or heat radiation ² Preferably 200-1000W/m ² Most preferably 500-1000W/m ² 。

In certain embodiments, the optical radiation increases the temperature of the composite catalyst, the hydrogen-containing source, and the carbon-containing source, preferably the only source that increases the temperature.

In certain embodiments, the carbon-containing source is selected from the group consisting of CO ₂ 、CO、C _1-4 Hydrocarbons, synthesis gas, bicarbonate, and any combination thereof, or air, industrial fumes, tail gases or emissions containing more than one of these carbon-containing sources, preferably CO ₂ And CO.

In certain embodiments, the hydrogen-containing source is selected from the group consisting of water, H ₂ 、C _1-4 Hydrocarbons and any combination thereof, or air, industrial fumes, off-gases or emissions containing more than one of these hydrogen-containing sources, preferably water.

In some embodiments, when the atomic site contains two or more chemical elements and is a single atom, the two or more elements may be arranged at intervals or randomly.

In certain embodiments, where the atomic sites are clusters, the composition of each cluster may be the same or different, e.g., each cluster may contain a different elemental composition, and/or contain a different number of atoms.

Drawings

FIG. 1 shows a schematic diagram of an apparatus for producing hydrocarbon molecules by a magnetic field assisted photocatalytic reaction.

FIG. 2 shows a schematic diagram of an apparatus for producing hydrocarbon molecules by a magnetic field assisted thermocatalytic reaction.

FIG. 3 shows Co-Al ₂ O ₃ High resolution electron microscopy (HRTEM) of the composite catalyst.

Detailed Description

The invention demonstrates that, unexpectedly, CO can be driven by magnetic field assistance with optical and/or thermal radiation as energy input in the presence of a plasmonic complex catalyst ₂ Or CO and water to hydrocarbon molecules.

Before further describing the present invention, certain terms used in the specification, examples, and appended claims are collected in the following sections. The definitions set forth herein should be read and understood by those skilled in the art in light of the remainder of the present invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.

Definition of the definition

The term "catalyst" as used herein refers to a substance that exhibits an effect of increasing the rate of chemical reaction by decreasing the reaction activation energy. The rate-increasing effect is referred to as "catalysis". The catalyst is not consumed in the catalytic reaction so they can continue further reactions of the catalytic reactants with small amounts.

The term "plasmonic donor" as used herein refers to a conductor whose real part of the dielectric constant is negative. The plasmonic donor may provide a surface plasmon when excited by electromagnetic radiation.

The term "temperature dependence" as used herein refers to a property that can change when the temperature changes a given level. The temperature difference of the changing characteristic may be of any degree, such as 0.1 ℃, 1 ℃, 5 ℃, 10 ℃, 100 ℃, or 1000 ℃.

The term "chemical element" as used herein refers to a chemical substance consisting of atoms in the nucleus having the same number of protons. Specifically, the chemical element is an element recorded in the periodic table of chemical elements. Chemical elements include natural elements and synthetic elements. Chemical elements also include elements that have more than 118 protons in an as yet undiscovered nucleus.

The term "bonded" or "supported" as used herein refers to being physically or chemically bonded or supported in a surface, internal pore or internal lattice, wherein physical means include van der Waals forces, metallic bonds, and other conventional physical bonding means, and chemical means include ionic bonds, covalent bonds, coordination bonds, and other conventional chemical bonding means.

The term "alloy" as used herein refers to a mixture of metals or a mixture of metals and other elements. The alloy is defined by metallic bonding (metallic bonding) properties. The alloy may be a solid solution of a metallic element (single phase) or a mixture of metallic phases (two or more solutions).

The term "metal-organic framework (MOF)" as used herein refers to an organic-inorganic hybrid material having intramolecular pores or a metal-organic framework structure having a periodic network structure formed by self-assembly of an organic ligand and metal ions or clusters. The MOF may contain a transition metal, a rare earth metal, a main group metal such as an alkali metal and an alkaline earth metal, etc. as metal elements, for example, cu, zn, cd, fe, ti, mn, al and Co, preferably Ti, and further contain a non-metal element such as O, N, S, P, halogen (e.g., F, cl, br, I), etc. MOFs can be prepared by methods known in the art such as evaporation of solvents, diffusion, hydrothermal or solvothermal methods, ultrasonic and microwave methods, and the like.

The term "activity per unit catalyst" as used herein refers to the number of moles of product produced per unit time per unit mass of active catalyst under certain reaction conditions. Specifically, unit catalyst activity = moles of reaction product/active catalyst mass/reaction time.

The term "intimate contact" as used herein means that there is substantially no gap between the two, e.g., a distance of 1nm or less, 0.1nm or less, or substantially 0nm, between the two, preferably forming a metal bond or a coordination bond.

The term "C" as used herein _1-4 Hydrocarbons "include C ₁ 、C ₂ 、C ₃ And C ₄ Hydrocarbons such as methane, ethane, n-propane, iso-propane, n-butane and iso-butane.

As used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise.

All numerical designations used herein, such as pH, temperature, time, concentration, content and molecular weight, including ranges, are approximations, with (+) or (-) changes occurring in 0.1 or 1.0 increments as appropriate. It will be understood that all numbers may be preceded by the term "about", although not always explicitly indicated.

As will be understood by those skilled in the art, for any and all purposes, particularly in terms of providing a written description, all ranges disclosed herein also encompass any and all possible subranges and combinations of subranges thereof. Any listed range can be readily identified as sufficiently descriptive, and the same range can be broken down into at least equal halves, thirds, quarters, fifths, tenths, etc. As a non-limiting example, each of the ranges discussed herein can be readily broken down into a lower third, a middle third, an upper third, and the like.

It will also be understood by those skilled in the art that all language, such as "up to", "at least", "above", "below", and the like, includes the recited numbers and refers to ranges that may be subsequently subdivided into subranges as discussed above.

As used herein, "optional" or "optionally" means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where said event or circumstance occurs and instances where it does not.

Plasmon composite catalyst

One aspect of the present invention is a plasmonic composite catalyst for generating hydrocarbon molecules by optical and/or thermal radiation.

Without wishing to be bound by theory, the plasmonic composite catalyst of the invention may enhance absorption of optical and/or thermal radiation near its plasmonic resonance wavelength, interact with the starting materials in the reaction to reduce the activation energy of the reaction, thereby enabling the reaction to be initiated by optical and/or thermal radiation, and increase the reaction rate.

The plasmon composite catalyst of the present invention comprises two structures: an atomic site and a nano-substrate structure, wherein the atomic site and the nano-substrate structure are in contact with each other. In a preferred embodiment, the mass percentage of the atomic sites to the nano-substrate structure in the plasmonic composite catalyst is 50% or less, preferably 0.01% to 30%, preferably 0.01% to 5%, more preferably 0.1% to 2%, most preferably 0.1% to 1%.

Atomic site

The term "atomic sites" as used herein refers to individual metal monoatoms and/or clusters of atoms comprising 2 to 25, preferably 2 to 20, metal atoms that are stably bound or supported on the surface of the nano-substrate structure and/or in the internal pores and/or internal lattice, preferably uniformly distributed on the nano-substrate structure, more preferably uniformly distributed on the surface of the nano-substrate structure. The metal monoatoms or atoms in the cluster of atoms are present in a valence state between 0 and the highest valence state in which the metal is typically present, the average valence state of the metal atoms being, for example, 0 to +4, or 0 to +3, or 0 to +2, or 0 to +1, preferably 0. The atomic distance between atoms in the atomic clusters is less than 1nm, preferably 0.1-0.5nm.

The atoms in the atomic sites are physically or chemically bound to the atoms in the nano-substrate structure, such as by van der Waals forces, metal bonds, and other conventional physical binding means, or ionic bonds, covalent bonds, coordination bonds, and other conventional chemical binding means, such as by metal bonds forming an alloy, or by coordination bonds forming a complex.

When the atomic sites are mutually independent metal monoatoms, the interaction between the metal monoatoms and atoms in the nano-substrate structure can prevent the metal monoatoms from agglomerating, so that the metal monoatoms are more stable. In some embodiments, in the single-atom sites of the catalytic metal, all the catalytic metal is present in the form of isolated atoms, i.e., the catalytic metal atoms have a dispersity of 100%, so that the catalytic metal atoms can be utilized to the maximum; preferably, all the catalytic metal atoms are directly fixed on the surface of the nano-substrate structure, and the catalytic metal atoms form 100% of interface atoms, so that the catalytic performance can be optimized by maximally utilizing the interaction between metal and substrate interface.

When the atomic sites are mutually independent metal atom clusters, the metal atom clusters are physically or chemically bound to atoms in the nano-substrate structure. The metal clusters are stably dispersed on and/or in the nano-substrate structure.

When the atomic site is a single atom of a single metal element, in some embodiments, the single metal element acts as both a plasmonic donor and a catalytic property donor, the nano-substrate structure providing physical support; in other embodiments, the single metallic element acts as a plasmonic donor, and the nano-substrate structure provides physical support and acts as a catalytic property donor.

When the atomic sites are metal clusters, in some embodiments, some of the clusters containing a particular element act as plasmonic donors and others of the clusters containing a particular element act as catalytic property donors, the nano-substrate structure providing physical support; in other embodiments, the clusters of atoms act as plasmonic donors, and the nano-substrate structure provides physical support and acts as a catalytic property donor.

In other embodiments, the atomic sites and the nano-substrate structure cooperate to provide physical support as a plasmonic donor and a catalytic property donor.

Nano-substrate structure

The term "nano-substrate structure" as used herein refers to a structure having a size range of nano-scale, i.e., at least one dimension of length, width, height, is from about 1nm to about 1000nm, preferably from about 70nm to about 1000nm, from about 100nm to about 800nm, from about 200nm to about 500nm. The nano-substrate structure can have dimensions exceeding 1000nm, for example, having a length in the micrometer scale range, such as 1 μm to 5 μm. In some cases, tubes and fibers having only two dimensions in the nanometer range are also considered nanobase structures. Materials with nano-base structures may exhibit significantly different size-related properties than those observed in bulk materials.

The nano-substrate structures of the present invention are each independently from about 1nm to about 3000nm long, wide, high. The length is preferably from about 100nm to about 3000nm, more preferably from about 500nm to about 2500nm, and still more preferably from about 1000nm to about 2000nm. The width or height thereof is preferably from about 1nm to about 1000nm, preferably from about 70nm to about 1000nm, more preferably from about 100nm to about 800nm, still more preferably from about 200nm to about 500nm.

The nano-substrate structures of the present invention each independently have an aspect ratio (i.e., ratio of length to width/height) of from about 1 to about 20, preferably from about 1 to about 10, or from about 2 to about 8. The nano-substrate structures of the present invention can also have a relatively low aspect ratio, such as about 1 to about 2.

The nano-substrate structures of the present invention each independently have the following shape: spherical, spined, flake, needle, grass leaf, cylindrical, polyhedral, three-dimensional pyramidal, cubical, flaky, hemispherical, irregular three-dimensional shape, porous structure, or any combination thereof.

The nano-substrate structure is selected from the group consisting of Mn, co, ce, fe, al, ca, ce, cu, ni, ti, zn, si, mo, bi, V, C, N and oxides, nitrides, sulfides, carbides, hydrocarbon molecular oxides, chlorides, and metal organic frameworks thereof.

The term "nano-substrate structure" as used herein comprises more than 25 atoms, preferably more than 30 atoms.

The plurality of the nano-substrate structures of the present invention can be arranged in a patterned configuration on a substrate, preferably a multi-layer arrangement, or the plurality of the nano-substrate structures can be randomly dispersed in a medium. For example, the nano-substrate structure may be bound to a matrix. In this case, the nano-base structures are not substantially aggregated with each other, but are arranged or stacked in a regular form. Alternatively, a plurality of nano-substrate structures can be dispersed in a liquid medium, wherein each nano-substrate structure can be freely moved relative to other nano-substrate structures.

For example, the nano-substrate structure may have a spike-like or grass-like geometry. Optionally, the nano-substrate structure is a lamellar geometry having a relatively thin thickness. Preferably, the nano-base structure has a nano-jungle, nano-grass, and/or nano-snow flake configuration. The nano-base structure may have a relatively large aspect ratio, and such a nano-base structure may be constructed in the form of nanospikes, nano-snow flakes, or nanoneedles. The aspect ratio may be from about 1 to about 20, from about 1 to about 10, or from about 2 to about 8. Preferably, the length of the nano-substrate structure may be about 100nm to about 3000nm, about 500nm to about 2500nm, or about 1000nm to about 2000nm; the width or height may be from about 1nm to about 1000nm, from about 70nm to about 1000nm, from about 100nm to about 800nm, or from about 200nm to about 500nm.

The nano-substrate structure may be bonded to a substrate. Thus, the nano-substrate structures do not substantially aggregate together, but are arranged in an orderly fashion. The matrix may be formed of a metal or polymeric material (e.g., polyimide, PTFE, polyester, polyethylene, polypropylene, polystyrene, polyacrylonitrile, etc.).

In other examples, the nano-substrate structure has a shape of sphere, cylinder, polyhedron, three-dimensional cone, cube, platelet, hemisphere, irregular three-dimensional shape, porous structure, or any combination thereof. Such nano-substrate structures are each independently from about 1nm to about 1000nm long, wide, high, about 70nm to about 1000nm, about 100nm to about 800nm, or about 200nm to about 500nm.

In addition, the plasmonic atomic catalyst of the invention can function in various states, such as dispersed, aggregated, or attached/grown on other material surfaces. In a preferred embodiment, the plasmonic atomic catalyst is dispersed in a medium, preferably a reactant of the reaction, such as water.

Method for producing hydrocarbon molecules by magnetic field assistance

Another aspect of the invention is a method for producing hydrocarbon molecules by magnetic field assisted optical and/or thermal radiation comprising the steps of:

Contacting a plasmonic composite catalyst with at least one hydrogen-containing source and at least one carbon-containing source in the presence of an externally applied magnetic field; and, light and/or heat irradiating the plasmonic composite catalyst, the hydrogen-containing source, and the carbon-containing source to produce hydrocarbon molecules.

The reaction of the present invention may be carried out with the aid of an externally applied magnetic field. Under the catalysis of the plasmon composite catalyst, the reaction for synthesizing hydrocarbon molecules is initiated by the combined action of energy radiation, namely optical radiation and/or thermal radiation, and an external magnetic field. Without wishing to be bound by theory, the plasmonic composite catalyst is capable of converting and transmitting the energy of light radiation and heat radiation, thereby allowing the reaction of the invention to continue. Within a specific temperature range, increasing the temperature may result in higher energy conversion for the production of hydrocarbon molecules. Without wishing to be bound by theory, the magnetic field assist may catalyze spin-oriented electrons in the d energy band of the active element and accumulate at the active site interface, promoting the progress of the catalytic reaction. Therefore, in a preferred embodiment of the present invention, the element of the atomic site contained in the plasmon composite catalyst is mainly an element having d-band electrons.

For example, the use of an externally applied magnetic field to assist the catalytic reaction increases the activity of the unit catalyst for the production of hydrocarbon molecules, the magnetic flux density of the externally applied magnetic field being in the range of 0-400mT, preferably 100-400mT, most preferably 200-300mT, the activity of the unit catalyst for the production of hydrocarbon molecules being increased by 0 to 50% and being increased by 30 to 50% within the preferred magnetic flux density range.

For another example, the use of an externally applied magnetic field to assist in the catalytic reaction increases the selectivity of propane in the product hydrocarbon molecule, the magnetic flux density of the externally applied magnetic field being in the range of 0-400mT, preferably 100-400mT, most preferably 200-300mT, and the selectivity of propane in the product hydrocarbon molecule being in the range of 10% to 30%, and in the preferred magnetic field magnetic flux density range being 20% to 30%.

The photoirradiation and/or heat radiation step is performed at a temperature between about 20 ℃ to about 800 ℃, about 20 ℃ to about 500 ℃, about 50 ℃ to about 300 ℃, about 70 ℃ to about 250 ℃, about 90 ℃ to about 200 ℃, about 100 ℃ to about 180 ℃, about 100 ℃ to about 150 ℃, about 110 ℃ to about 140 ℃, about 120 ℃ to about 140 ℃, and the like. At the above temperature, the unit catalyst activity for producing hydrocarbon molecules is greater than 18. Mu. Mol g ^-1 h ^-1 Greater than 50. Mu. Mol g at the preferred temperature range ^-1 h ^-1 。

The term "heat" as used herein refers to thermal energy transferred from one system to another as a result of heat exchange. The thermal energy may be transferred from an external heat source to the reaction system or may be carried by one reaction component to the other reaction component. In other words, the reaction components carrying thermal energy prior to reaction are also referred to as internal heat sources. In certain embodiments, the temperature of the plasmonic composite catalyst, the hydrogen-containing source, and the carbon-containing source in the reaction of the invention may also be increased by an external heat source.

In the reaction of the present invention, the optical radiation mimics the wavelength composition and intensity of sunlight, so that it can raise the temperature of the catalyst and reaction mixture being irradiated. When the radiation intensity reaches a certain specific level, the temperature of the plasmon composite catalyst, the hydrogen-containing source, and the carbon-containing source is raised by the optical radiation. Preferably, the optical radiation is the only source of elevated temperature.

In the reaction of the present invention, after the reaction starts, the reaction proceeds under light irradiation. The term "light" as used herein refers to electromagnetic waves having wavelengths between about 250nm and about 2000 nm. In other words, light refers to radiation of visible light. Preferably, in the reaction of the present invention, the optical radiation power is lower than the solar radiation power (i.e., solar constant). For example, the optical radiation power is 20 0-1500W/m ² Preferably 200-1000W/m ² Most preferably 500-1000W/m ² . The optical radiation may be sunlight or light emitted by an artificial light source, the optical radiation having a wavelength between about 250nm and about 2000 nm.

In certain embodiments of the invention, the optical radiation itself may raise the reaction temperature to the desired temperature without additional heating.

The term "thermal radiation" as used in the present invention refers to energy transfer in a form similar to that of light radiation, originating from blackbody radiation generated by a high-temperature heating element, the radiation intensity of which has a specific wavelength distribution according to the planck's law; the heat radiation employed in the present invention has its strongest wavelength in the infrared wavelength region ranging from about 2um to 10 um; the catalytic reaction effect of the plasmon composite catalyst under the action of heat radiation is related to the adopted heat radiation wavelength. Without wishing to be bound by theory, the thermal radiation excitation mode used in the invention is different from the direct thermal conduction adopted by traditional thermal catalysis, but the plasmon catalyst directly absorbs the thermal radiation wave (or optical radiation wave) close to the resonance wavelength, so as to excite the catalytic reaction and promote the catalytic effect.

The reaction time varies depending on the size of the reaction, the intensity of the radiation, the temperature and other factors, and the reaction is continued using a well-established apparatus with continuous addition of the hydrogen-containing source and the carbon-containing source. The reaction time may be 0.1 hours or more, preferably 0.1 hours to 1000 hours, preferably 0.1 hours to 500 hours, preferably 0.5 hours to 100 hours, preferably 1 hour to 50 hours, preferably 2 hours to 30 hours, most preferably 4 hours to 20 hours.

The reaction may be carried out at low, normal or high pressure, and an appropriate reaction pressure may be selected according to the size of the reaction, the intensity of radiation, the temperature and other factors, for example, the reaction pressure may be at least 1bar, for example, 1bar to 30bar,1bar to 20bar, preferably 1bar to 10bar, more preferably 1.5bar to 5bar.

Reaction raw materials

The carbon-containing source is selected from CO ₂ 、CO、C _1-4 Hydrocarbons, synthesis gas, bicarbonateAny combination thereof, or air, industrial fumes, exhaust gases or emissions containing more than one of these carbon-containing sources, preferably CO ₂ And CO.

The hydrogen-containing source is selected from water, H ₂ 、C _1-4 Hydrocarbons and any combination thereof, or air, industrial fumes, off-gases or emissions containing more than one of these hydrogen-containing sources, preferably water.

As can be seen from the above-described reaction raw materials, the carbon-containing source and the hydrogen-containing source that can be used in the present invention are widely present in industrial waste gas, waste water, flue gas, combustion emission, automobile exhaust, and the like, and therefore can be used as the reaction raw material of the present invention, thereby facilitating the recycling of industrial waste.

Reaction product

The reaction of the present invention is capable of producing hydrocarbon molecules. Without wishing to be bound by theory, the reaction mechanism of the present invention may include the decomposition and recombination of various reactant feedstock molecules at the atomic sites and nano-substrate structures of the plasmonic composite catalyst.

Examples

Example 1 preparation of plasmonic composite catalyst

₂ ₃ ₂ ₃ The preparation method of the Co-AlO (Co is loaded or combined with AlO) composite catalyst comprises the following steps:

3g of nano-active alumina (Al) ₂ O ₃ Gamma crystalline form, 10-20 nm), 2.7g lithium chloride (LiCl), 3.3g potassium chloride (KCl) and 60mg cobalt chloride hexahydrate (CoCl) ₂ ·6H ₂ O) adding an agate mortar and grinding for 30 minutes. Spreading the ground powder on the bottom of a quartz boat, and putting the quartz boat into a tube furnace. Nitrogen (N) was first introduced at a flow rate of 80mL/min for 30 minutes ₂ ) The flow of nitrogen is kept unchanged, the tube furnace is heated to 500 ℃ at a heating rate of 8 ℃/min, and after calcination for 4 hours, the tube furnace is cooled to room temperature. The calcined sample was placed in a 500mL beaker, 500mL deionized water was added, and the mixture was immersed for about 4 hours. Pouring out the soaked supernatant, washing with deionized water for 6 times, separating with 8000rpm centrifuge, and adding 80deg.COven drying for 12h to obtain Co-Al with 0.5% load used in the experiment ₂ O ₃ A composite catalyst.

Co-Al loading of 0.25% and 1% can also be obtained by adjusting the addition amount of cobalt chloride hexahydrate ₂ O ₃ A composite catalyst. FIG. 3 shows Co-Al ₂ O ₃ The yellow circles in the transmission electron microscope image of the plasmon composite catalyst mark the atomic sites (only partially marked) prepared on the nano substrate, and the atomic sites can be uniformly distributed on the substrate and are spaced by about 1-10nm.

₂ ₃ ₂ ₃ ₂ ₃ Fe-AlO (Fe supported on or bound to AlO), ru-AlO(Ru load or junction) ₂ ₃ ₂ ₃ Is combined with AlO), ruFe-AlO ₂ ₃ ₂ ₃ ₂ ₃ Preparation method of (Ru and Fe are loaded or combined with AlO) and RuCo-AlO (Ru and Co are loaded or combined with AlO) composite catalyst The method comprises the following steps:

(1) 0.125g of iron acetylacetonate and 50g of aluminum acetylacetonate were placed uniformly in a 100mL zirconia ball mill pot.

(2) 50 zirconia pellets having a diameter of 6mm and 20 zirconia pellets having a diameter of 10mm were charged into the above-mentioned pot, and ball-milled using a planetary ball mill at a rotation speed of 400rpm/min for 10 hours.

(3) And placing the taken powder into a porcelain boat, and roasting in the atmosphere of muffle furnace air. The calcination time was 5 hours and the temperature was 400 ℃.

(4) Taking out the roasted product to obtain Fe-Al with the loading capacity of about 0.25% ₂ O ₃ A composite catalyst.

(5) Ru-Al with a loading of about 0.25% was obtained by substituting 0.125g of iron acetylacetonate with 0.125g of ruthenium acetylacetonate in the above preparation ₂ O ₃ A composite catalyst; the RuFe-Al with Ru and Fe loading of about 0.125% can be obtained by replacing 0.125g of ferric acetylacetonate with 0.0625g of ruthenium acetylacetonate and 0.0625g of ferric acetylacetonate or with 0.0625g of ruthenium acetylacetonate and 0.0625g of cobalt acetylacetonate in the preparation process ₂ O ₃ Composite catalyst and RuCo-Al with Ru and Co loading of about 0.125% ₂ O ₃ A composite catalyst.

CoMn-MOF (Co and Mn supported or bound to MOF) composite catalyst is prepared by the following steps:

1. synthetic Metal Organic Framework (MOF) substrates

4.2mL of isopropyl titanate and 7.06g of terephthalic acid were added to a mixed solution containing 108mL of N, N-dimethylformamide and 12mL of methanol. The mixture was stirred at 25 ℃ for 30min using magnetic force until a clear homogeneous solution was obtained. This solution was transferred to a 200mL stainless steel autoclave, which was placed in an oven and heated to 150℃for 16 hours. After cooling to room temperature, washing with methanol for 3 times, centrifuging, and drying in an oven at 80 ℃ for 16 hours to obtain the MOF substrate for later use. The morphology of the MOF substrate is characterized by SEM and is columnar nano particles with the diameter of 700nm and the height of 200 nm.

2. Preparation of CoMn-MOF catalyst

In a 250mL beaker, 2g of MOF substrate and 100mL of methanol were added and stirred well using magnetic force. Another 100mL beaker was weighed, 18mg of manganese nitrate tetrahydrate (Mn (NO) ₃ ) ₂ ·4H ₂ O) and 12mg of cobalt nitrate hexahydrate (Co (NO) ₃ ) ₂ · ₆ H ₂ O), adding 20mL of methanol, stirring and dissolving. The mixture was poured into the MOF dispersion. After stirring for 1h, washing with methanol, filtering and separating with a buchner funnel, drying in an oven at 80 ℃ for 16 hours, a CoMn-MOF catalyst was obtained, with Co and Mn loadings of about 0.5%.

₂ ₂ The preparation method of the FeCo-TiO (Fe and Co are loaded or combined with TiO) composite catalyst comprises the following steps:

0.2g of titanium dioxide (TiO ₂ Anatase, 5-10nm, hydrophilic) was placed in a 500mL beaker, 200mL deionized water was then added thereto, and 100mL of 1mol/L ammonium carbonate ((NH) was added thereto after 15 minutes of magnetic stirring ₄ ) ₂ CO ₃ ) The solution was stirred for an additional 5min and labeled as solution A. 0.0014g of cobalt nitrate hexahydrate (Co (NO) ₃ ) ₂ .6H ₂ O) and 0.0015g of ferric nitrate nonahydrate (Fe (NO) ₃ ) ₃ .9H ₂ O) was dissolved in 100mL deionized water and sonicated for 10min, which was slowly added dropwise to the solution A above. After the formed suspension is aged for 2.5 hours at room temperature, the formed precipitate is centrifugally washed for 3 times by deionized water with the rotating speed of 12500rpm, and then is dried for 12 hours at 60 ℃ in an oven to obtain FeCo-TiO ₂ A composite catalyst.

Example 2 photocatalytic reactions to produce hydrocarbon molecules

The catalyst is a CoMn-MOF composite catalyst prepared according to example 1, the MOF (metal organic framework) is of a nano-substrate structure, the MOF mainly comprises Ti metal elements, and the morphology of the MOF substrate is columnar nano-particles with the diameter of 700nm and the height of 200nm through SEM characterization; the atomic sites comprise Co and Mn, are clusters formed by 2-4 metals, are distributed on the surface of the MOF, and have an interval of 5-10nm.

Into a sealable pressure-bearing glass tube of 35mL volume was charged 1.5g CoMn-MOF composite catalyst and 2mL of ultra-pure water, using CO ₂ Exhausting the air in spite of the internal air, charging 4bar CO ₂ . The glass tube is horizontally placed on the glass wool, so that the catalyst and water are uniformly spread, and the catalyst and water are vertically irradiated from above by using a halogen lamp with controllable voltage. The incident light intensity was about 1000W/m ² . A thermocouple was attached to the lower half of the glass tube to monitor temperature. The temperature of the glass tube is controlled to be 135+/-5 ℃ and the continuous illumination is carried out for 18 hours to carry out photocatalysis reaction. After the reaction, the outlet end of the reaction tube was connected to a gas chromatography flame ionization detector (GC-FID) and a gas chromatography thermal conductivity detector (GC-TCD) for product analysis.

Through measurement and analysis, C in the product after the stable reaction ₁ -C ₃ The hydrocarbon product concentration was about 1637.5ppm, calculated to correspond to a loading of single atoms of catalyst activity, of about 64.98. Mu. Mol g per catalyst activity ^-1 h ^-1 。

Example 3 magnetic field assisted photocatalytic reaction to produce hydrocarbon molecules

A photocatalytic reaction was performed in the same manner as in example 2 except that a magnetic field was applied using the same CoMn-MOF composite catalyst as in example 2.

A schematic of the apparatus for producing hydrocarbon molecules using the magnetic field assisted photocatalytic reaction used in example 3 is shown in fig. 1. In the reaction, two permanent magnets are placed in parallel near the pressure-bearing glass tube, and the magnetic flux density of the middle position of the two magnets is measured by a Gaussian meter. After the stabilization reaction, C in the product is measured ₁ -C ₃ The concentration of hydrocarbon products is calculated to obtain the activity of the unit catalyst and the selectivity of propane in the products. The corresponding results for example 2 and example 3 are shown in table 1:

TABLE 1

From the above experimental results, it is apparent that the unit catalyst activity of hydrocarbon molecules is improved to some extent by applying a magnetic field of a specific magnetic flux density, and the selectivity of propane in hydrocarbon products is increased.

Example 4 magnetic field assisted photocatalytic reaction to produce hydrocarbon molecules

Ru-Al prepared according to example 1 was used ₂ O ₃ Composite catalyst, ruCo-Al ₂ O ₃ Composite catalyst, fe-Al ₂ O ₃ Composite catalyst, feCo-TiO ₂ The composite catalyst was subjected to photocatalytic reaction in the same manner as in example 2 except that a magnetic field was applied. Obtaining C in the product after stable reaction through measurement and analysis ₁ -C ₃ The hydrocarbon product concentration was calculated to give a unit catalyst activity corresponding to the loading of the catalyst activity monoatoms. The reaction result data are shown in table 2:

TABLE 2

Example 5 temperature dependence of catalytic reactions to produce hydrocarbon molecules

Used catalystThe chemosing agent is Fe-Al prepared according to example 1 ₂ O ₃ A composite catalyst was subjected to photocatalytic reaction in the same manner as in example 2 except that the reaction temperature and the externally applied magnetic field, and the corresponding C was calculated ₁ -C ₃ Unit catalyst activity for hydrocarbon molecular yield. The results are shown in table 3:

TABLE 3 Table 3

From the above experimental results, it is known that the catalytic activity for producing hydrocarbon molecules in the photocatalytic reaction increases with increasing temperature in the range of 60 to 135 ℃. When the temperature exceeds 135 ℃, the catalytic activity of the produced hydrocarbon molecules is reduced.

Example 6 thermocatalytic reaction to produce hydrocarbon molecules

The catalyst used was Co-Al prepared according to example 1 ₂ O ₃ Composite catalyst, al ₂ O ₃ Is a nano-substrate structure, and is characterized by SEM, and the morphology of the nano-substrate structure is irregular-shaped particles with the diameter of 10-20 nm; single atoms of isolated Co metal distributed in Al ₂ O ₃ The surface and the pore space, the metal atom interval is 1-10nm.

1.5g Co-Al was added to a 30mL capacity sealable pressure-bearing stainless steel reaction tube ₂ O ₃ Composite catalyst and 2mL pure water with CO ₂ Exhausting the air in spite of the internal air, charging 4bar CO ₂ . After the reaction tube is tightly wound by the heating belt, the reaction tube is horizontally placed on glass wool, so that the catalyst and water are uniformly spread, and the temperature of the heating belt is controlled to be 135+/-5 ℃. After the reaction was carried out for 18 hours, the outlet of the reaction tube was connected to GC-FID and GC-TCD for analysis of the products.

For Co-Al with loading of 0.5% ₂ O ₃ Testing after thermal reaction of the composite catalyst, and stabilizing C in the reacted product ₁ -C ₃ The hydrocarbon product concentration was about 1278.8ppm, calculated to correspond to the loading of the catalyst activity monatomic, about 50.7. Mu. Mol g per catalyst activity ^-1 h ^-1 。

Example 7 magnetic field assisted thermocatalytic reaction to produce hydrocarbon molecules

The same Co-Al as in example 6 was used ₂ O ₃ The composite catalyst was subjected to a thermocatalytic reaction in the same manner as in example 6 except that a magnetic field was applied.

A schematic of the apparatus for producing hydrocarbon molecules using the magnetic field assisted thermocatalytic reaction used in example 7 is shown in fig. 2. During reaction, two permanent magnets are placed in parallel near the pressure-bearing reaction tube, and the magnetic flux density of the middle position of the two permanent magnets is measured by a Gaussian meter. After the stabilization reaction, C in the product is measured ₁ -C ₃ The concentration of hydrocarbon products is calculated to obtain the activity of the unit catalyst and the selectivity of propane in the products. The corresponding results for example 6 and example 7 are shown in table 4:

TABLE 4 Table 4

Example 8 magnetic field assisted thermocatalytic reaction to produce hydrocarbon molecules

Using the CoMn-MOF composite catalyst prepared according to example 1, feCo-TiO ₂ A composite catalyst was subjected to a thermocatalytic reaction in the same manner as in example 7, and C in the product after the stable reaction was obtained by measurement and analysis ₁ -C ₃ The hydrocarbon product concentration was calculated to give a unit catalyst activity corresponding to the loading of the catalyst activity monoatoms. The reaction result data are shown in Table 5:

TABLE 5

From the above experimental results, it was found that the activity per catalyst for generating hydrocarbon molecules and the propane selectivity in hydrocarbon products can be improved by applying a magnetic field having a constant magnetic flux density under other reaction conditions. In summary, the present invention provides a method for improving the reaction yield of a plasmonic catalyst for producing hydrocarbon molecules using energy radiation catalysis by applying an external static magnetic field. In the invention, the application of the external static magnetic field can improve the reaction yield and the propane selectivity in the product under various reaction conditions, has an improvement effect on the catalytic activity of various plasmon catalysts, and is beneficial to the commercial development and application of catalytic hydrocarbon production.

The methods described herein may be performed in any order that is logically possible, except the specific order disclosed.

The representative examples are intended to aid in the description of the invention and are not intended, nor should they be construed, to limit the scope of the invention. Indeed, many modifications of the invention and many other embodiments thereof, in addition to those shown and described herein, will become apparent to those skilled in the art, including the examples and the scientific and patent literature references cited herein. The embodiments contain important additional information, exemplifications and guidance that can be employed by the practice of the invention in its various embodiments and equivalents.

Claims

1. A method for producing hydrocarbon molecules by magnetic field assisted energy radiation, comprising

Contacting a plasmonic composite catalyst with at least one hydrogen-containing source and at least one carbon-containing source in the presence of an externally applied magnetic field; and

energy irradiating the plasmonic composite catalyst, the hydrogen containing source and the carbon containing source to produce hydrocarbon molecules, wherein

The composite catalyst comprises at least one nano-substrate structure and at least one atomic site comprising one or more chemical elements of Mn, co, fe, ru, rh, al, ag, au, pt, pd, cu, ni, zn, ti, os, ir, la, preferably one or more of Co, fe, mn, ru, au.

2. The method of claim 1, wherein

The external magnetic field is a static magnetic field, preferably a static magnetic field generated by a permanent magnet or a uniformly varying electric field, and more preferably a static magnetic field generated by a permanent magnet.

3. The method of claim 1 or 2, wherein

The magnetic flux density of the externally applied magnetic field is 0-400mT, preferably 100-400mT, and most preferably 200-300mT.

4. A method as claimed in any one of claims 1 to 3, wherein

The selectivity of propane in the product hydrocarbon molecule is 10% to 30%, preferably 20% to 30%.

5. The method of any one of claims 1 to 4, wherein

The energy radiation is selected from at least one of optical radiation and thermal radiation, preferably optical radiation.

6. The method of any one of claims 1 to 5, wherein

The distance between the nano-substrate structure and the atomic site is less than or equal to 5nm, preferably less than or equal to 1nm, more preferably less than 0.1nm, most preferably both are in intimate contact.

7. The method of any one of claims 1 to 6, wherein

The atomic sites are bound to the nano-substrate structure, for example physically or chemically.

8. The method of any one of claims 1 to 7, wherein

The mass percentage of the atomic sites to the nano-substrate structure is 50% or less, preferably 0.01% to 30%, preferably 0.01% to 5%, more preferably 0.1% to 2%, and most preferably 0.1% to 1%.

9. The method of any one of claims 1 to 8, wherein

In certain embodiments, the atomic sites are supported on the surface of the nano-substrate structure, in internal pores, or distributed in the internal lattice of the nano-substrate structure, preferably with uniform distribution of the atomic sites, and

the space between the atomic sites is 0.2-500nm, preferably 1-50nm, more preferably 1-10nm.

10. The method of any one of claims 1 to 9, wherein

When the atomic site contains more than two chemical elements and is a single atom, the more than two elements are arranged at intervals or randomly.

11. The method of any one of claims 1 to 10, wherein

When the atomic sites are clusters, the composition of each cluster is the same, or each cluster comprises a different elemental composition and/or comprises a different number of atoms.

12. The method of any one of claims 1 to 11, wherein

The nano-substrate structure is selected from the group consisting of Mn, co, ce, fe, al, ca, ce, cu, ni, ti, zn, si, mo, bi, V, C, N and oxides, nitrides, sulfides, carbides, hydroxides, chlorides, and Metal Organic Frameworks (MOFs), preferably metal organic frameworks, tiO ₂ Or Al ₂ O ₃ 。

13. The method of any one of claims 1 to 12, wherein

The composite catalyst is Co and Mn supported or combined with a metal organic framework (CoMn-MOF), fe supported or combined with Al ₂ O ₃ Catalyst (Fe-Al) ₂ O ₃ ) Co loading or bondingIn Al ₂ O ₃ Catalyst (Co-Al) ₂ O ₃ ) Loaded with Ru or bound to Al ₂ O ₃ Catalyst (Ru-Al) ₂ O ₃ ) Loaded with or bound to Al, ru and Fe ₂ O ₃ Catalyst (RuFe-Al) ₂ O ₃ ) Or Ru and Co supported or bonded to Al ₂ O ₃ Catalyst (RuCo-Al) ₂ O ₃ )。

14. The method of any one of claims 1 to 13, wherein

At least one dimension of the nano-substrate structure in length, width, and height is from about 1nm to about 1000nm, preferably from about 70nm to about 1000nm, from about 100nm to about 800nm, and from about 200nm to about 500nm.

15. The method of any one of claims 1 to 14, wherein

The nano-substrate structures are each independently from about 1nm to about 3000nm long, wide, high, preferably from about 100nm to about 3000nm long, from about 500nm to about 2500nm, or from about 1000nm to about 2000nm long, and/or from about 1nm to about 1000nm wide or high, from about 70nm to about 1000nm, from about 100nm to about 800nm, or from about 200nm to about 500nm, or

The nano-substrate structures each independently have an aspect ratio of about 1 to about 20, preferably about 1 to about 10, or about 2 to about 8.

16. The method of any one of claims 1 to 15, wherein

The shape of the nano-substrate structure is spherical, spiny, thin sheet, needle-like, grass leaf, cylindrical, polyhedral, three-dimensional cone, cube, flake, hemispherical, irregular three-dimensional shape, porous structure or any combination thereof.

17. The method of any one of claims 1 to 16, wherein

A plurality of said atomic sites are arranged in a patterned configuration, preferably a multi-layer arrangement, or

A plurality of the atomic sites are randomly dispersed in and/or on the nano-substrate structure.

18. The method of any one of claims 1 to 17, wherein

The energy radiation causes the reaction to proceed at a temperature of between about 20 ℃ and about 500 ℃, preferably between about 50 ℃ and about 300 ℃, between about 70 ℃ and about 250 ℃, between about 90 ℃ and about 200 ℃, between about 100 ℃ and about 180 ℃, between about 100 ℃ and about 150 ℃, between about 110 ℃ and about 140 ℃, between about 120 ℃ and about 140 ℃.

19. The method of any one of claims 1 to 18, wherein

Initiating the reaction using light or heat radiation and allowing the reaction to proceed using light or heat radiation, wherein

The optical radiation power of the optical radiation is 200-1500W/m ² Preferably 200-1000W/m ² Most preferably 500-1000W/m ² 。

20. The method of any one of claims 1 to 19, wherein

The optical radiation increases the temperature of the composite catalyst, the hydrogen-containing source and the carbon-containing source, preferably the only source of increased temperature.

21. The method of any one of claims 1 to 20, wherein

The carbon-containing source is selected from the group consisting of CO ₂ 、CO、C _1-4 Hydrocarbons, synthesis gas, bicarbonate, and any combination thereof, or air, industrial fumes, tail gases or emissions containing more than one of these carbon-containing sources, preferably CO ₂ And CO.

22. The method of any one of claims 1 to 21, wherein

The hydrogen-containing source is selected from water, H ₂ 、C _1-4 Hydrocarbons or any combination thereof, or more than one kind of hydrocarbonThe air, industrial fumes, tail gas or emissions of these hydrogen-containing sources are preferably water.