Method for generating hydrocarbon molecules by magnetic field-assisted energy radiation

Abstract

A method for generating hydrocarbon molecules by magnetic field-assisted energy radiation, comprising: in the presence of an external magnetic field, making a composite catalyst come into contact with at least one hydrogen-containing source; and performing energy radiation on the composite catalyst and the hydrogen-containing source to generate hydrogen molecules, wherein the composite catalyst comprises at least one nano-substrate structure and at least one atomic site, and the atomic site comprises one or more chemical elements selected from the group consisting of Mn, Co, Fe, Al, Cu, Ni, Zn, Ti, La, Ru, Rh, Ag, Au, Pt, Pd, Os, and Ir.

Description

Method for generating hydrogen molecules by magnetic field-assisted energy radiation Technical Field

[0001] The present invention relates to a method for producing hydrogen through magnetic field-assisted energy radiation catalysis, and in particular to a composite catalyst and its application in energy radiation catalysis producing hydrogen. Background Art

[0002] In the new energy sector, hydrogen energy is widely considered the most ideal, pollution-free, green energy source of the new century. This is because the only product of hydrogen combustion is water. Hydrogen is the most abundant element in nature, widely present in water, mineral fuels, and various carbohydrates. Hydrogen is also a major industrial raw material and the most important industrial and specialty gas. It is used as a key raw material for the synthesis of ammonia, methanol, and hydrochloric acid, as well as a reducing agent in metallurgy and a hydrodesulfurization agent in petroleum refining.

[0003] However, traditional hydrogen production methods consume enormous amounts of conventional energy, making hydrogen energy prohibitively expensive and significantly limiting its widespread application. Scientists have therefore considered utilizing inexhaustible, inexpensive solar energy as a primary energy source in the hydrogen production process, offering a broader prospect for hydrogen energy development. Scientists have discovered that photocatalytic materials can harness solar energy to split water into the oxygen and hydrogen necessary for fuel cells. They have hailed this technology, which produces hydrogen and oxygen using only sunlight and water, as "one of humanity's ideal technologies."

[0004] Due to the plasmon effect, plasmon metal catalysts can achieve a significant enhancement of local energy on the surface of nanostructures. Thus, under mild overall reaction conditions, the catalytic reaction is efficiently promoted, making reactions that cannot be achieved at room temperature and pressure possible. In recent years, it has been possible to decompose water into hydrogen and oxygen, but so far, there is still a need to develop more efficient, stable and cost-effective catalysts. The proposal of single-atom catalysis has also received widespread attention and research. Due to its special structure, it exhibits activity, selectivity and stability that are different from conventional nanocatalysts. Combining the advantages of the plasmon effect and single-atom catalysis, it is possible to develop hydrogen production catalysts with efficiency, stability and cost that can meet commercial requirements.

[0005] In addition, applying specific external auxiliary means in the catalytic reaction may play a certain promoting role. The catalytic process involves the migration of effective charges, etc., so increasing the external magnetic field may affect the catalytic activity. In the prior art, magnetic field-assisted catalysis basically uses dynamic magnetic fields such as moving magnetic fields and alternating magnetic fields to generate Lorentz forces to make the charges move in a directional manner, thereby affecting the catalytic effect. However, on the one hand, this dynamic magnetic field method requires additional energy input, and on the other hand, the generation of Lorentz forces requires the catalyst to have a certain physical form to redistribute the charges macroscopically, and its effect on the catalytic effect is also relatively limited. Summary of the Invention

[0006] Based on the technical problems existing in the background technology, the present invention clarifies a new plasmon catalysis technology, which includes atomic sites, such as single atomic sites and / or atomic clusters containing 2-25 atoms, and provides a unique method for preparing hydrogen by decomposing a hydrogen source, preferably water, by light radiation and / or thermal radiation in the presence of a cost-effective catalyst, and the reaction yield is regulated by auxiliary means of applying an external magnetic field.

[0007] One aspect of the present invention is a method for producing hydrogen by magnetic field-assisted energy radiation, comprising:

[0008] In the presence of an external magnetic field, the composite catalyst is contacted with at least one hydrogen source, and energy is irradiated to the composite catalyst and the hydrogen source to generate hydrogen molecules, wherein

[0009] The composite catalyst comprises at least one nano-based structure and at least one atomic site, wherein the atomic site comprises one or more chemical elements selected from the group consisting of Mn, Co, Fe, Al, Cu, Ni, Zn, Ti, La, Ru, Rh, Ag, Au, Pt, Pd, Os, and Ir, and preferably comprises one or more chemical elements selected from the group consisting of Co, Fe, Mn, Ru, and Au.

[0010] In some embodiments, the external magnetic field is a static magnetic field, for example, it can be generated by a permanent magnet or a uniformly changing electric field, preferably generated by a permanent magnet. At the same time, there is no relative motion between the nanocatalyst and the external magnetic field, no Lorentz force is generated, and there is no macroscopic charge movement.

[0011] In certain embodiments, an external magnetic field is used to assist the catalytic reaction, thereby increasing the unit catalyst activity for producing hydrogen molecules, wherein the magnetic flux density of the external magnetic field is 0-400mT, preferably 100-400mT, and most preferably 200-300mT, and the unit catalyst activity for producing hydrogen molecules is increased by 0 to 50%, and increased by 30% to 50% within the preferred magnetic field flux density range.

[0012] In some embodiments, the energy radiation is selected from at least one of light radiation and heat radiation, preferably light radiation.

[0013] In certain embodiments, the distance between the nano-base structure and the atomic site is less than or equal to 5 nm, preferably less than or equal to 1 nm, more preferably less than 0.1 nm, and most preferably the two are in close contact.

[0014] In certain embodiments, the atomic sites are bound to the nano-based structure, for example, physically or chemically.

[0015] In certain embodiments, the mass percentage of the atomic sites to the nano-based structure is less than or equal to 50%, preferably 0.01% to 30%, preferably 0.01% to 5%, more preferably 0.1% to 2%, and most preferably 0.1% to 1%.

[0016] In certain embodiments, the atomic sites are loaded on the surface of the nano-based structure, or distributed in the internal pores or in the internal lattice of the nano-based structure. Preferably, the atomic sites are evenly distributed, and the interval between the atomic sites is 0.2-500nm, preferably 1-50nm, and more preferably 1-10nm.

[0017] In some embodiments, the nano-based 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 their oxides, nitrides, sulfides, carbides, hydroxides, chlorides and metal-organic frameworks (MOFs), preferably metal-organic frameworks, TiO2, Al2O3 or CeO2.

[0018] In certain embodiments, the composite catalyst is a catalyst loaded with Co and Fe or bound to a metal organic framework (CoFe-MOF), a catalyst loaded with Co and Mn or bound to a metal organic framework (CoMn-MOF), a catalyst loaded with Fe and Co or bound to TiO2 (FeCo-TiO2), a catalyst loaded with Ru and Co or bound to TiO2 (RuCo-TiO2), a catalyst loaded with Ru or bound to Al2O3 (Ru-Al2O3), a catalyst loaded with Au or bound to Al2O3 (Au-Al2O3), or a catalyst loaded with Au or bound to CeO2 (Au-CeO2).

[0019] In a preferred embodiment, at least one dimension of the length, width, and height of the nanostructured substrate is about 1 nm to about 1000 nm, preferably about 70 nm to about 1000 nm, about 100 nm to about 800 nm, or about 200 nm to about 500 nm.

[0020] In a preferred embodiment, the nano-based structures each independently have a length, width, and height of about 1 nm to about 3000 nm, preferably, a length of about 100 nm to about 3000 nm, about 500 nm to about 2500 nm, or about 1000 nm to about 2000 nm, and / or a width or height of about 1 nm to about 1000 nm, about 70 nm to about 1000 nm, about 100 nm to about 800 nm, or about 200 nm to about 500 nm, or, the nano-based structures each independently have an aspect ratio of about 1 to about 20, preferably an aspect ratio of about 1 to about 10, or about 2 to about 8.

[0021] In certain embodiments, the nanostructures are shaped like spheres, spikes, flakes, needles, blades, columns, polyhedrons, three-dimensional pyramids, cubes, sheets, hemispheres, irregular three-dimensional shapes, porous structures, or any combination thereof.

[0022] In certain embodiments, the plurality of atomic sites are arranged in a pattern on the nano-based structure, preferably in a multi-layer arrangement, or the plurality of atomic sites are randomly dispersed in and / or on the surface of the nano-based structure.

[0023] In certain embodiments, the energy irradiation is such that the reaction is carried out at a temperature between about 20°C and about 500°C, preferably about 50°C to about 300°C, about 70°C to about 250°C, about 90°C to about 200°C, about 100°C to about 200°C, about 100°C to about 180°C, about 110°C to about 160°C, about 120°C to about 150°C, about 130°C to about 150°C, and the unit catalyst activity for producing hydrogen is greater than 0.2 μmol g -1 h -1 , preferably greater than 0.5 μmol g -1 h -1 , preferably greater than 3 μmol g -1 h -1 , preferably greater than 5 μmol g -1 h -1 , greater than 7 μmol g in the preferred temperature range -1 h -1 .

[0024] In some embodiments, light radiation or heat radiation is used to initiate the reaction and light radiation or heat radiation is used to continue the reaction, wherein the light radiation power is 200-1500 W / m 2 , preferably 200-1000W / m 2 , most preferably 500-1000W / m 2 .

[0025] In certain embodiments, the light radiation increases the temperature of the composite catalyst and the hydrogen-containing source, and is preferably the only source of temperature increase.

[0026] In certain embodiments, the hydrogen source is selected from the group consisting of water, saturated alcohols, carboxylic acids, phenols, and any combination thereof, preferably water.

[0027] In certain embodiments, when the atomic site comprises two or more chemical elements and is a single atom, the two or more elements may be arranged in an intermittent manner or in a random manner.

[0028] In some embodiments, when the atomic sites are atomic clusters, the composition of each atomic cluster may be the same or different. For example, each atomic cluster may contain a different elemental composition and / or a different number of atoms. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] FIG1 is a schematic diagram of a device for producing hydrogen through a magnetic field-assisted photocatalytic reaction.

[0030] FIG2 shows a schematic diagram of a device for producing hydrogen through a magnetic field-assisted thermocatalytic reaction.

[0031] FIG3 shows a high-resolution electron microscopy (HRTEM) image of the CoMn-MOF composite catalyst.

[0032] FIG4 shows a high-resolution electron microscopy (HRTEM) image of the RuCo-TiO2 composite catalyst. DETAILED DESCRIPTION

[0033] The present invention demonstrates that, unexpectedly, a hydrogen source, preferably water, can be converted into molecular hydrogen in the presence of a composite catalyst having plasmonic action, using light radiation and / or thermal radiation as energy input, assisted by a magnetic field.

[0034] Before further describing the present invention, the following sections collect certain terms used in the specification, examples, and appended claims. The definitions listed herein should be read and understood by those skilled in the art in light of the remainder of the present invention. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the art to which this invention belongs.

[0035] definition

[0036] As used herein, the term "catalyst" refers to a substance that increases the rate of a chemical reaction by reducing the activation energy of the reaction. This rate-increasing effect is known as "catalysis." Catalysts are not consumed in catalyzing reactions, so they can continue to catalyze further reactions of the reactants in small quantities.

[0037] As used herein, the term "plasmon donor" refers to a conductor whose real part of the dielectric constant is negative. When excited by electromagnetic radiation, a plasmon donor can provide surface plasmons.

[0038] As used herein, the term "temperature dependence" refers to a property that changes when the temperature changes by a given level. The temperature difference that changes the property can be any number of degrees, such as 0.1°C, 1°C, 5°C, 10°C, 100°C, or 1000°C.

[0039] As used herein, the term "chemical element" refers to a chemical substance composed of atoms with the same number of protons in their nuclei. Specifically, a chemical element is one listed in the periodic table of chemical elements. Chemical elements include both naturally occurring and synthetic elements. Chemical elements also include yet-to-be-discovered elements with more than 118 protons in their nuclei.

[0040] The terms "binding" or "loading" used in this article refer to physical or chemical binding or loading on the surface, internal pores or internal lattice, where physical methods include van der Waals forces, metallic bonds and other conventional physical binding methods, and chemical methods include ionic bonds, covalent bonds, coordination bonds and other conventional chemical binding methods.

[0041] As used herein, the term "alloy" refers to a mixture of metals or a mixture of metals and other elements. An alloy is defined by the properties of the metallic bonding. An alloy can be a solid solution of a metallic element (a single phase) or a mixture of two or more metallic phases (solutions of two or more).

[0042] The term "saturated alcohol" as used herein refers to a saturated hydrocarbon compound substituted with an -OH group, such as C1-C 15 Saturated alcohols, preferably C1-C8 saturated alcohols, more preferably C1-C4 saturated alcohols, such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol.

[0043] The term "carboxylic acid" as used herein refers to a saturated hydrocarbon compound substituted with a -COOH group, such as C1-C 15 Carboxylic acids, preferably C1-C8 carboxylic acids, more preferably C1-C4 carboxylic acids, such as formic acid, acetic acid, propionic acid, isopropionic acid, butyric acid, isobutyric acid.

[0044] The term "phenols" as used herein refers to compounds containing an -OH group directly attached to an aromatic ring, wherein the aromatic ring is a monocyclic, bicyclic or tricyclic ring containing 5 to 25 carbon atoms, preferably 5 to 20 carbon atoms, most preferably 5 to 15 carbon atoms, and more preferably 6 to 12 carbon atoms, such as benzene and naphthalene.

[0045] As used herein, the term "metal-organic framework (MOF)" refers to an organic-inorganic hybrid material with intramolecular pores or a metal-organic framework structure with a periodic network structure formed by self-assembly of organic ligands and metal ions or clusters. MOFs may contain transition metals, rare earth metals, main group metals such as alkali metals and alkaline earth metals, and the like as metallic elements, for example, Cu, Zn, Cd, Fe, Ti, Mn, Al, and Co, preferably Ti, and may also contain non-metallic elements such as O, N, S, P, and halogens (e.g., F, Cl, Br, I). MOFs can be prepared by methods known in the art, such as solvent evaporation, diffusion, hydrothermal or solvothermal methods, ultrasound, and microwave methods.

[0046] The term "specific catalyst activity" as used herein refers to the number of moles of product produced per unit mass of active catalyst per unit time under certain reaction conditions. Specifically, specific catalyst activity = number of moles of reaction product / mass of active catalyst / reaction time.

[0047] The term "close contact" used herein means that there is substantially no gap between the two, for example, the distance between the two is less than or equal to 1 nm, less than or equal to 0.1 nm, or substantially 0 nm, preferably forming a metallic bond or a coordination bond.

[0048] 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.

[0049] All numerical designations used herein, such as pH values, temperatures, times, concentrations, amounts, and molecular weights, including ranges, are approximate and, where appropriate, vary by increments of 0.1 or 1.0 (+) or (-). It will be understood that, although not always explicitly stated, all numerical designations may be preceded by the term "about."

[0050] 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 fully described, and the same range can be broken down into at least equal halves, thirds, quarters, fifths, tenths, etc. As a non-limiting example, each range discussed herein can be readily broken down into a lower third, a middle third, an upper third, etc.

[0051] Those skilled in the art will also understand that all language such as "up to," "at least," "above," "below," etc., are inclusive of the recited numbers and refer to ranges that can be subsequently subdivided into the sub-ranges discussed above.

[0052] As used herein, "optional" or "optionally" means that the subsequently described event or circumstance can or cannot occur, and that the description includes instances where said event or circumstance occurs and instances where it does not.

[0053] Plasmonic composite catalysts

[0054] One aspect of the present invention is a plasmonic composite catalyst that generates hydrogen molecules through light radiation and / or heat radiation.

[0055] Without wishing to be bound by theory, the plasmon composite catalyst of the present invention can enhance the absorption of light radiation and / or thermal radiation close to its plasmon resonance wavelength, interact with the raw materials in the reaction to reduce the activation energy of the reaction, thereby enabling the reaction to be initiated by light radiation and / or thermal radiation and increasing the reaction rate.

[0056] The plasmonic composite catalyst of the present invention comprises two structures: atomic sites and a nano-based structure, wherein the atomic sites and the nano-based structure are in contact with each other. In a preferred embodiment, the mass percentage of the atomic sites and the nano-based structure in the plasmonic composite catalyst is less than or equal to 50%, preferably 0.01% to 30%, preferably 0.01% to 5%, more preferably 0.1% to 2%, and most preferably 0.1% to 1%.

[0057] Atomic sites

[0058] The term "atomic site" as used in the present invention refers to mutually independent metal single atoms and / or mutually independent atomic clusters comprising 2-25, preferably 2-20 metal atoms, wherein the metal single atoms and / or the atomic clusters are stably bound or loaded 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 atoms in the metal single atoms or the atomic clusters exist in a valence state between 0 valence and the highest valence state normally present in the metal, and the average valence state of the metal atoms is, for example, 0 to +4 valence, or 0 to +3 valence, or 0 to +2 valence, or 0 to +1 valence, preferably 0 valence. The interatomic distance in the atomic clusters is less than 1 nm, preferably 0.1-0.5 nm.

[0059] The atoms in the atomic sites are combined with the atoms in the nano-based structure by physical or chemical means, such as van der Waals forces, metallic bonds and other conventional physical bonding methods, or ionic bonds, covalent bonds, coordination bonds and other conventional chemical bonding methods, such as forming alloys through metallic bonds, or forming complexes through coordination bonds.

[0060] When the atomic sites are independent single metal atoms, the interactions between the metal atoms and the atoms in the nanostructured substrate can prevent the metal atoms from agglomerating, making them more stable. In some embodiments, within the catalytic metal single atom sites, all catalytic metals exist as isolated atoms, i.e., the dispersion of the catalytic metal atoms is 100%, which maximizes the utilization of the catalytic metal atoms. Preferably, all catalytic metal atoms are directly fixed to the surface of the nanostructured substrate, forming 100% of the interface atoms, which maximizes the utilization of the metal-substrate interface interactions to optimize catalytic performance.

[0061] When the atomic sites are independent metal atom clusters, the metal atom clusters are physically or chemically combined with the atoms in the nano-based structure, and the metal atom clusters are stably dispersed on and / or in the nano-based structure.

[0062] When the atomic site is a single atom of a single metal element, in some embodiments, the single metal element acts as both a plasmon donor and a catalytic property donor, and the nano-based structure provides physical support; in other embodiments, the single metal element acts as a plasmon donor, and the nano-based structure provides physical support and serves as a catalytic property donor.

[0063] When the atomic sites are metal atomic clusters, in some embodiments, some atomic clusters containing specific elements act as plasmon donors, other atomic clusters containing specific elements act as catalytic property donors, and the nano-based structure provides physical support; in other embodiments, the atomic clusters act as plasmon donors, and the nano-based structure provides physical support and acts as a catalytic property donor.

[0064] In other embodiments, the atomic sites and the nano-based structure act together as both plasmon donors and catalytic property donors, and the nano-based structure provides physical support.

[0065] Nanostructured substrate

[0066] As used herein, the term "nanosubstrate structure" refers to a structure having a size range of the nanometer scale, i.e., at least one of the length, width, and height dimensions is from about 1 nm to about 1000 nm, preferably from about 70 nm to about 1000 nm, from about 100 nm to about 800 nm, or from about 200 nm to about 500 nm. A nanosubstrate structure can have a dimension exceeding 1000 nm, for example, having a length in the micrometer scale range, such as 1 μm to 5 μm. In some cases, tubular objects and fibers having only two dimensions in the nanometer range are also considered nanosubstrate structures. Materials having nanosubstrate structures can exhibit size-related properties that are significantly different from those observed in bulk materials.

[0067] The nanobase structures of the present invention each independently have a length, width, and height of about 1 nm to about 3000 nm. Preferably, the length is about 100 nm to about 3000 nm, more preferably about 500 nm to about 2500 nm, and even more preferably about 1000 nm to about 2000 nm. Preferably, the width or height is about 1 nm to about 1000 nm, preferably about 70 nm to about 1000 nm, more preferably about 100 nm to about 800 nm, and even more preferably about 200 nm to about 500 nm.

[0068] The nano-based structures of the present invention each independently have an aspect ratio (i.e., the ratio of length to width / height) of about 1 to about 20, preferably an aspect ratio of about 1 to about 10, or about 2 to about 8. The nano-based structures of the present invention can also have a relatively low aspect ratio, for example, about 1 to about 2.

[0069] The nano-based structures of the present invention each independently have the following shapes: sphere, spike, flake, needle, blade, column, polyhedron, three-dimensional cone, cube, sheet, hemisphere, irregular three-dimensional shape, porous structure or any combination thereof.

[0070] The nano-based 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 their oxides, nitrides, sulfides, carbides, hydroxides, chlorides and metal-organic frameworks.

[0071] The term "nano-based structure" as used herein comprises more than 25, preferably more than 30 atoms.

[0072] The present invention can be a plurality of nano-base structures arranged in a patterned manner on a substrate, preferably in a multi-layer arrangement, or a plurality of nano-base structures can be randomly dispersed in a medium. For example, the nano-base structures can be attached to a substrate. In this case, the nano-base structures generally do not aggregate with each other, but are arranged or stacked in a regular pattern. Alternatively, a plurality of nano-base structures can be dispersed in a liquid medium, wherein each nano-base structure can move freely relative to the other nano-base structures.

[0073] For example, the nano-based structure can have a spike-like or blade-like geometry. Optionally, the nano-based structure is a flake-like geometry with a relatively thin thickness. Preferably, the nano-based structure has a nano-jungle, nano-grass, and / or nano-snowflake structure. The nano-based structure can have a relatively large aspect ratio, such that the nano-based structure can adopt the structure of nano-spikes, nano-snowflakes, or nano-needles. The aspect ratio can 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-based structure can be from about 100 nm to about 3000 nm, from about 500 nm to about 2500 nm, or from about 1000 nm to about 2000 nm; the width or height can be from about 1 nm to about 1000 nm, from about 70 nm to about 1000 nm, from about 100 nm to about 800 nm, or from about 200 nm to about 500 nm.

[0074] The nanostructures can be bound to a matrix. Thus, the nanostructures are generally not aggregated together, but arranged in an ordered manner. The matrix can be formed of a metal or a polymer material (e.g., polyimide, PTFE, polyester, polyethylene, polypropylene, polystyrene, polyacrylonitrile, etc.).

[0075] In other examples, the nano-based structures have a spherical, cylindrical, polyhedral, three-dimensional pyramidal, cubic, plate-like, hemispherical, irregular three-dimensional shape, porous structure or any combination thereof. Such nano-based structures are each independently about 1 nm to about 1000 nm in length, width, and height, about 70 nm to about 1000 nm, about 100 nm to about 800 nm, or about 200 nm to about 500 nm.

[0076] In addition, the plasmon atom catalyst of the present invention can function in various states, such as dispersed, aggregated, or attached / grown on the surface of other materials. In a preferred embodiment, the plasmon atom catalyst is dispersed in a medium, which is preferably a reactant of the reaction, such as water.

[0077] Method for generating hydrogen molecules by magnetic field assistance

[0078] Another aspect of the present invention is a method for generating hydrogen molecules by magnetic field-assisted light radiation and / or thermal radiation, comprising the following steps:

[0079] contacting a plasmonic composite catalyst with at least one hydrogen-containing source in the presence of an applied magnetic field; and

[0080] The plasmon composite catalyst and the hydrogen source are irradiated with light and / or heat to generate hydrogen molecules.

[0081] The reaction of the present invention is carried out under the condition of an external magnetic field assistance. Under the catalytic action of the plasmon composite catalyst, the reaction of the hydrogen source is triggered by the combined action of energy radiation, i.e. light radiation and / or heat radiation, and an external magnetic field. The reaction of decomposing the hydrogen source, preferably water, to produce hydrogen molecules is an endothermic reaction. Without being bound by theory, the plasmon composite catalyst can convert and transfer the energy of light radiation and heat radiation, thereby allowing the reaction of the present invention to continue. Within a specific temperature range, increasing the temperature can lead to a higher energy conversion rate for producing hydrogen molecules. Without being bound by theory, magnetic field assistance can catalyze the generation of spin-oriented electrons in the d energy band of the active element, and gather at the interface of the active site, thereby promoting the progress of the catalytic reaction. Therefore, in a preferred embodiment of the present invention, the elements of the atomic sites contained in the plasmon composite catalyst are mainly elements with d energy band electrons.

[0082] For example, using an external magnetic field to assist the catalytic reaction improves the unit catalyst activity of producing hydrogen molecules. The magnetic flux density of the external magnetic field is 0-400mT, preferably 100-400mT, and most preferably 200-300mT. The unit catalyst activity of producing hydrogen molecules is increased by 0 to 50%, and is increased by 30% to 50% within the preferred magnetic field flux density range.

[0083] The light irradiation and / or heat irradiation step is performed at a temperature between about 20°C and about 800°C, about 20°C and about 500°C, about 50°C and about 300°C, about 70°C and about 250°C, about 90°C and about 200°C, about 100°C and about 200°C, about 100°C and about 180°C, about 110°C and about 160°C, about 120°C and about 150°C, about 130°C and about 150°C, etc. At the above temperature, the unit catalyst activity of hydrogen production is greater than 0.2 μmol g -1 h -1 , preferably greater than 0.5 μmol g -1 h -1 , preferably greater than 3 μmol g -1 h -1 , preferably greater than 5 μmol g -1 h -1 , greater than 7 μmol g in the preferred temperature range -1 h-1 .

[0084] As used herein, the term "heat" refers to heat energy transferred from one system to another as a result of heat exchange. Heat energy can be transferred to the reaction system from an external heat source, or it can be carried by one reaction component and transferred to other reaction components. In other words, the reaction component that carries heat energy before the reaction is also referred to as an internal heat source. In certain embodiments, the temperature of the plasmon composite catalyst and the hydrogen-containing source in the reaction of the present invention can also be increased by an external heat source.

[0085] In the reaction of the present invention, light radiation mimics the wavelength composition and intensity of sunlight, thus increasing the temperature of the irradiated catalyst and reactants. When the radiation intensity reaches a certain level, the temperature of the plasmonic composite catalyst and hydrogen-containing source is increased by light radiation. Preferably, light radiation is the sole source of the temperature increase.

[0086] In the reaction of the present invention, after the reaction is started, the reaction continues under light radiation. The term "light" as used herein refers to electromagnetic waves with a wavelength between about 250nm and about 2000nm. In other words, light refers to the radiation of visible light. Preferably, in the reaction of the present invention, the light radiation power is lower than the solar radiation power (i.e., the solar constant). For example, the light radiation power is 200-1500W / m 2 , preferably 200-1000W / m 2 , most preferably 500-1000W / m 2 The light radiation may be sunlight or light emitted by an artificial light source, and the wavelength of the light radiation is between about 250 nm and about 2000 nm.

[0087] In certain embodiments of the present invention, light irradiation itself can increase the reaction temperature to the desired temperature without the need for additional heating.

[0088] The term "thermal radiation" used in the present invention refers to a form of energy transfer similar to light radiation, which comes from blackbody radiation generated by a high-temperature heating element. According to Planck's law, its radiation intensity has a specific wavelength distribution; the thermal radiation used in the present invention has the strongest wavelength in the infrared wavelength region of about 2um to 10um; the catalytic reaction effect produced by the plasmon composite catalyst in this invention under the action of thermal radiation is related to the wavelength of the thermal radiation used. Without being bound by theory, the thermal radiation excitation method used in the present invention is different from the direct heat conduction used in traditional thermal catalysis. Instead, the plasmon catalyst directly absorbs thermal radiation waves (or light radiation waves) close to the resonance wavelength, thereby stimulating the catalytic reaction and enhancing the catalytic effect.

[0089] The reaction time varies depending on the size of the reaction, radiation intensity, temperature, and other factors. The reaction is carried out continuously using a complete apparatus and with the continuous addition of a hydrogen source. The reaction time can 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, and most preferably 4 hours to 20 hours.

[0090] The reaction can be carried out at low pressure, normal pressure or high pressure, and the appropriate reaction pressure can be selected according to the size of the reaction, radiation intensity, temperature and other factors. For example, the reaction pressure can be at least 1 bar, such as 1 bar to 30 bar, 1 bar to 20 bar, preferably 1 bar to 10 bar, and more preferably 1.5 bar to 5 bar.

[0091] Reaction raw materials

[0092] In the reaction of the present invention, the reaction raw materials include a hydrogen source, such as water, saturated alcohols, carboxylic acids and phenols, preferably water, such as pure water or hard water, which can be in gaseous or liquid state.

[0093] Reaction products

[0094] The reaction of the present invention can produce hydrogen molecules. Without wishing to be bound by theory, the reaction mechanism of the present invention may include the decomposition and recombination of various reaction raw material molecules on the atomic sites and nano-base structure of the plasmonic composite catalyst.

[0095] Example

[0096] Example 1 Preparation of composite catalyst

[0097] The CoFe-MOF (Co and Fe loaded or bound to MOF) composite catalyst and the CoMn-MOF (Co and Mn loaded or bound to MOF) composite catalyst were prepared by the following method:

[0098] 4.2 mL of isopropyl titanate and 7.06 g of terephthalic acid were added to a mixed solution containing 108 mL of N,N-dimethylformamide and 12 mL of methanol. The mixture was stirred magnetically at 25°C for 30 minutes until a transparent, homogeneous solution was obtained. This solution was transferred to a 200 mL stainless steel autoclave, which was placed in an oven and heated to 150°C for 16 hours. After cooling to room temperature, the mixture was washed with methanol three times, centrifuged, and dried in an oven at 80°C for 16 hours to obtain the MOF substrate, which was then used. Scanning electron microscopy (SEM) revealed the MOF substrate to be columnar nanoparticles with a diameter of 700 nm and a height of 200 nm.

[0099] Add 2g of MOF substrate and 100mL of methanol to a 250mL beaker and stir magnetically. In another 100mL beaker, weigh 8.8mg of ferric nitrate nonahydrate (Fe(NO3)3·9H2O) and 12mg of cobalt nitrate hexahydrate (Co(NO3)2·6H2O), add 20mL of methanol, and stir to dissolve. Pour the mixture into the MOF dispersion. After stirring for 1 hour, wash with methanol, separate the mixture using a Buchner funnel, and dry it in an oven at 80°C for 16 hours to obtain the CoFe-MOF composite catalyst.

[0100] The CoMn-MOF composite catalyst was obtained by replacing the ferric nitrate nonahydrate in the above process with 8.8 mg of MnCl₂. A high-resolution electron microscopy (HRTEM) image of the CoMn-MOF composite catalyst is shown in Figure 3. The yellow circles in the image indicate the atomic sites (only partially shown) prepared on the nanostructured substrate. The atomic sites are uniformly distributed on the substrate, with spacing of approximately 1-10 nm.

[0101] XPS was used to characterize the chemical bonding (coordination bonding) of Co, Mn, Fe and the atoms in the MOF substrate in the obtained composite catalyst.

[0102] The FeCo-TiO2 (Fe and Co loaded or bound to TiO2) composite catalyst and the RuCo-TiO2 (Ru and Co loaded or bound to TiO2) composite catalyst were prepared by the following method:

[0103] 0.2g of titanium dioxide (TiO2, anatase, 5-10nm, hydrophilic) was weighed and placed in a 500mL beaker. 200mL of deionized water was then added. After 15 minutes of magnetic stirring, 100mL of a 1mol / L ammonium carbonate ((NH4)2CO3) solution was added and stirred for 5 minutes. This solution is designated Solution A. 0.0014g of cobalt nitrate hexahydrate (Co(NO3)2·6H2O) and 0.0015g of ferric nitrate nonahydrate (Fe(NO3)3·9H2O) were dissolved in 100mL of deionized water and sonicated for 10 minutes. The solution was then slowly added dropwise to Solution A. The resulting suspension was aged at room temperature for 2.5 hours. The resulting precipitate was washed three times with deionized water by centrifugation at 12,500 rpm and then dried in an oven at 60°C for 12 hours to obtain the FeCo-TiO2 composite catalyst.

[0104] A RuCo-TiO2 composite catalyst was obtained by replacing the cobalt nitrate and ferric nitrate mixed solution with a mixed solution containing 0.0020g of hydrated ruthenium trichloride (RuCl3·xH2O) and 0.0014g of cobalt nitrate hexahydrate (Co(NO3)2·6H2O). A high-resolution electron microscopy (HRTEM) image of the RuCo-TiO2 composite catalyst is shown in Figure 4. The yellow circles in the image indicate the atomic sites (only partially shown) prepared on the nanostructured substrate. The atomic sites are uniformly distributed across the substrate, with spacing of approximately 1-10nm.

[0105] The Ru-Al2O3 (Ru loaded on or combined with Al2O3) composite catalyst and the Au-Al2O3 (Au loaded on or combined with Al2O3) composite catalyst were prepared by the following method:

[0106] Dissolve 17.6 mg of ruthenium trichloride (RuCl3) in 5 mL of deionized water and ultrasonically mix at room temperature for 60 minutes. Then, add 2 g of activated alumina and ultrasonically mix at 40°C for 60 minutes. The resulting dry solid is collected and washed five times with deionized water to obtain a Ru-Al2O3 precursor. Slowly add 20 mL of sodium hydroxide (pre-adjusted to pH 12.0) and 0.4 g of solid sodium borohydride (NaBH4) to the precursor, stir thoroughly, and filter. The resulting solid is washed three times with deionized water and dried at 80°C under a nitrogen atmosphere to obtain the Ru-Al2O3 composite catalyst. Replace the RuCl3 in the above process with 3.4 mg of chloroauric acid (HAuCl4) to obtain the Au-Al2O3 composite catalyst.

[0107] The Au-CeO2 (Au loaded or combined with CeO2) composite catalyst was prepared by the following method:

[0108] 1.73 g of cerium nitrate hexahydrate (CeNO3·6H2O) and 0.0068 g of tetrachloroauric acid (HAuCl4·3H2O) were dissolved in 10 mL of deionized water. Once completely dissolved, the mixture was slowly added dropwise to 70 mL of 6 mol / L sodium hydroxide (NaOH) solution. After stirring at room temperature for 30 minutes, the suspension was transferred to a 100 mL stainless steel reactor lined with polytetrafluoroethylene and incubated at 120°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, the precipitate was collected by centrifugation, washed with deionized water until the pH of the washing solution reached 7, and then dried in an oven at 60°C for 12 hours. The dried sample was thoroughly ground and placed in a tube furnace at 5°C / min in air to 400°C, where it was held for 2 hours to obtain the Au-CeO2 composite catalyst used in the experiment.

[0109] Example 2 Photocatalytic reaction to produce hydrogen

[0110] The catalyst used is the CoMn-MOF composite catalyst prepared according to Example 1. The MOF (metal organic framework) is a nano-substrate structure. The MOF mainly contains Ti metal elements. SEM characterization shows that the MOF substrate is a columnar nanoparticle with a diameter of 700 nm and a height of 200 nm; the atomic sites contain Co and Mn, which are atomic clusters formed by 2-4 metal atoms, distributed on the MOF surface, and the atomic clusters are spaced 5-20 nm apart.

[0111] In a 35 mL sealable pressure-bearing glass tube, add 1 g of CoMn-MOF composite atomic catalyst and 1 mL of ultrapure water. Ar is used to displace the air inside, and then the tube is filled with 4 bar of Ar. The tube is placed flat on glass wool, so that the catalyst and water are evenly distributed. A voltage-controlled halogen lamp is used to illuminate the tube vertically from above. The incident light intensity is approximately 1000 W / m 2 A thermocouple was connected to the lower half of the glass tube to monitor the temperature. The temperature of the glass tube was controlled at 50°C ± 10°C, and the photocatalytic reaction was carried out under continuous illumination for 18 h.

[0112] After the photocatalytic reaction, the hydrogen content in the gas in the reaction tube was characterized by gas chromatography using a thermal conductivity detector (TCD). After the photocatalytic reaction using the CoMn-MOF composite catalyst, the hydrogen content was 1683 ppm. Calculation showed that the unit catalyst activity for hydrogen production was 0.528 μmol g -1 h -1 After the above reaction was carried out for 9 consecutive cycles (162 h), the catalytic activity of the catalyst for hydrogen production did not decrease.

[0113] Example 3 Magnetic Field-Assisted Photocatalytic Reaction for Hydrogen Generation

[0114] The photocatalytic reaction was carried out in the same manner as in Example 2 using the same CoMn-MOF composite catalyst as in Example 2, except that a magnetic field was applied.

[0115] The schematic diagram of the magnetic field-assisted photocatalytic reaction hydrogen production apparatus used in Example 3 is shown in Figure 1. During the reaction, two permanent magnets were placed parallel to each other near the pressure-bearing glass tube, and the magnetic flux density at the center of the two magnets was measured using a gaussmeter. After the reaction stabilized, the hydrogen content in the product was measured and calculated to obtain the specific catalyst activity. The corresponding results of Examples 2 and 3 are shown in Table 1:

[0116] Table 1

[0117] From the above experimental results, it can be seen that by applying a magnetic field with a specific magnetic flux density, the unit catalyst activity of hydrogen production is improved to a certain extent.

[0118] Example 4 Thermal Catalytic Reaction to Produce Hydrogen

[0119] The catalyst used was the same CoMn-MOF composite catalyst as in Example 2.

[0120] In a 35 mL sealable, pressure-bearing stainless steel tube, add 0.5 g of the CoMn-MOF composite catalyst and 6 mL of ultrapure water. Expel air with Ar and then fill with 4 bar of Ar. Wrap the tube tightly with heating tape and place it flat on glass wool. Maintain the heating tape temperature at 130°C ± 10°C and continue the reaction for 18 hours.

[0121] The gas after the reaction was characterized by gas chromatography in the same manner as in Example 2. After the thermal catalytic reaction using the CoMn-MOF composite catalyst, the hydrogen content was calculated to be 9184 ppm, and the unit catalyst activity of hydrogen production was approximately 5.766 μmol g -1 h -1 .

[0122] Example 5 Magnetic Field-Assisted Thermocatalytic Reaction for Hydrogen Production

[0123] The thermal catalytic reaction was carried out in the same manner as in Example 4 using the same CoMn-MOF composite catalyst as in Example 4, except that a magnetic field was applied.

[0124] The schematic diagram of the magnetic field-assisted thermocatalytic reaction hydrogen production apparatus used in Example 5 is shown in Figure 2. During the reaction, two permanent magnets were placed parallel to each other near the pressurized reaction tube, and the magnetic flux density at the center of the two magnets was measured using a gaussmeter. After the reaction stabilized, the hydrogen content in the product was measured and calculated to obtain the specific catalyst activity. The corresponding results of Examples 4 and 5 are shown in Table 2:

[0125] Table 2

[0126] From the above experimental results, it can be seen that by applying a magnetic field with a specific magnetic flux density, the unit catalyst activity of hydrogen production is improved to a certain extent.

[0127] Example 6 Temperature dependence of the magnetic field-assisted catalytic reaction for hydrogen production

[0128] The photocatalytic reaction was carried out in the same manner as in Example 2, using the same CoMn-MOF composite catalyst as in Example 2, except for the reaction temperature and applied magnetic field. The unit catalyst activity corresponding to the hydrogen molecular production was calculated. The results are shown in Table 3:

[0129] Table 3

[0130] The experimental results above show that the energy conversion efficiency of hydrogen production in the photocatalytic reaction increases with temperature within the range of 50 to 150°C. However, when the temperature exceeds 150°C, the energy conversion efficiency of hydrogen production decreases as side reactions increase.

[0131] Example 7 Thermal Catalytic Reaction to Produce Hydrogen

[0132] Using a RuCo-TiO2 composite catalyst, 0.2 g of the RuCo-TiO2 composite catalyst was added to a 35 mL sealable pressure-bearing stainless steel tube, and a thermal catalytic reaction was carried out in the same manner as in Example 4. The temperature was controlled at 130°C ± 10°C, and the reaction was continued for 18 hours.

[0133] The gas after the reaction was characterized by gas chromatography in the same manner as in Example 2. The calculated hydrogen content was 6863 ppm, and the unit catalyst activity for hydrogen production was approximately 10.77 μmol g -1 h -1 After the above reaction was carried out for 10 cycles (180 h), the catalytic activity of the catalyst for hydrogen production did not decrease.

[0134] Example 8 Magnetic Field-Assisted Thermocatalytic Reaction for Hydrogen Production

[0135] The same RuCo-TiO2 composite catalyst as in Example 7 was used, and the thermal catalytic reaction was carried out in the same manner as in Example 7 except that a magnetic field was applied.

[0136] During the reaction, two permanent magnets were placed parallel to each other near the pressurized reaction tube, and the magnetic flux density at the center of the two magnets was measured using a gaussmeter. After the reaction stabilized, the hydrogen content in the product was measured and calculated to obtain the specific catalyst activity. The corresponding results for Examples 7 and 8 are shown in Table 4:

[0137] Table 4

[0138] From the above experimental results, it can be seen that by applying a magnetic field with a specific magnetic flux density, the unit catalyst activity of hydrogen production is improved to a certain extent.

[0139] Example 9 Catalytic reaction to produce hydrogen

[0140] The CoFe-MOF composite catalyst, FeCo-TiO2 composite catalyst, Ru-Al2O3 composite catalyst, Au-Al2O3 composite catalyst, and Au-CeO2 composite catalyst prepared according to Example 1 were used to carry out photocatalytic and / or thermal catalytic reactions to produce hydrogen.

[0141] The photocatalytic reaction was carried out in the same manner as in Example 2, except for the reaction temperature and the applied magnetic field. The thermocatalytic reaction was carried out in the same manner as in Example 4, except for the applied magnetic field. The unit catalyst activity corresponding to the hydrogen molecular production was calculated, and the reaction result data are shown in Table 5:

[0142] Table 5

[0143] From the above experimental results, it can be seen that when other reaction conditions remain unchanged, the unit catalyst activity of hydrogen production can be improved by applying a magnetic field with a certain magnetic flux density.

[0144] In summary, the present invention provides a method for improving the reaction yield of hydrogen production using plasmonic catalysts using energy radiation catalysis, using the aid of an external static magnetic field. In the present invention, the application of an external static magnetic field can improve reaction yields under various reaction conditions and enhance the catalytic activity of various plasmonic catalysts, facilitating the commercial development and application of catalytic hydrogen production.

[0145]

[00106] Methods described herein can be performed in any order that is logically possible, except in the specific order disclosed.

[0146] The representative examples are intended to help illustrate the present invention and are not intended to, and should not be construed as, limiting the scope of the present invention. Indeed, various modifications of the present 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 examples contain important additional information, illustrations, and guidance that can be employed in the practice of the present invention in its various embodiments and equivalents.

Claims

1. A method for producing hydrogen by magnetic field assisted energy radiation, comprising: The composite catalyst is contacted with at least one hydrogen-containing source in the presence of an external magnetic field, and energy irradiation to the composite catalyst and the hydrogen source to generate hydrogen molecules, wherein The composite catalyst comprises at least one nano-based structure and at least one atomic site, wherein the atomic site comprises one or more chemical elements selected from the group consisting of Mn, Co, Fe, Al, Cu, Ni, Zn, Ti, La, Ru, Rh, Ag, Au, Pt, Pd, Os, and Ir, and preferably comprises one or more chemical elements selected from the group consisting of Co, Fe, Mn, Ru, and Au.

2. The method of claim 1, wherein The externally applied magnetic field is a static magnetic field, preferably a static magnetic field generated by a permanent magnet or a uniformly changing electric field, more preferably a static magnetic field generated by a permanent magnet.

3. The method according to claim 1 or 2, wherein The magnetic flux density of the external magnetic field is 0-400 mT, preferably 100-400 mT, and most preferably 200-300 mT.

4. The method according to any one of claims 1 to 3, wherein The energy radiation is selected from at least one of light radiation and heat radiation, preferably light radiation.

5. The method according to any one of claims 1 to 4, wherein The distance between the nano-base structure and the atomic site is less than or equal to 5 nm, preferably less than or equal to 1 nm, more preferably less than 0.1 nm, and most preferably the two are in close contact.

6. The method according to any one of claims 1 to 5, wherein The atomic sites are bound to the nano-based structure, for example, physically or chemically.

7. The method according to any one of claims 1 to 6, wherein The mass ratio of the atomic sites to the nano-based structure is less than or equal to 50%, preferably 0.01% to 30%, preferably 0.01% to 5%, more preferably 0.1% to 2%, and most preferably 0.1% to 1%.

8. The method according to any one of claims 1 to 7, wherein In some embodiments, the atomic sites are supported on the surface of the nano-based structure, in the internal pores, or distributed in the internal lattice of the nano-based structure, preferably, the atomic sites are uniformly distributed, and The interval between each atomic site is 0.2-500 nm, preferably 1-50 nm, more preferably 1-10 nm.

9. The method according to any one of claims 1 to 8, wherein When the atomic site includes two or more chemical elements and is a single atom, the two or more elements are arranged in an intermittent manner or randomly.

10. The method according to any one of claims 1 to 8, wherein When the atomic sites are atomic clusters, the composition of each atomic cluster is the same, or each atomic cluster contains a different elemental composition and / or contains a different number of atoms.

11. The method according to any one of claims 1 to 10, wherein The nano-based 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 their oxides, nitrides, sulfides, carbides, hydroxides, chlorides and metal-organic frameworks (MOFs), preferably metal-organic frameworks, TiO2, Al2O3 or CeO2.

12. The method of any one of claims 1 to 11, wherein The composite catalyst is a catalyst loaded with Co and Fe or combined with a metal organic framework (CoFe-MOF), a catalyst loaded with Co and Mn or combined with a metal organic framework (CoMn-MOF), a catalyst loaded with Fe and Co or combined with TiO2 (FeCo-TiO2), a catalyst loaded with Ru and Co or combined with TiO2 (RuCo-TiO2), a catalyst loaded with Ru or combined with Al2O3 (Ru-Al2O3), a catalyst loaded with Au or combined with Al2O3 (Au-Al2O3) or a catalyst loaded with Au or combined with CeO2 (Au-CeO2).

13. The method of any one of claims 1 to 12, wherein At least one dimension of the length, width and height of the nano-base structure is about 1 nm to about 1000 nm, preferably about 70 nm to about 1000 nm, about 100 nm to about 800 nm, about 200 nm to about 500 nm.

14. The method of any one of claims 1 to 13, wherein The nano-based structures are each independently about 1 nm to about 3000 nm in length, width, and height, preferably about 100 nm to about 3000 nm in length, about 500 nm to about 2500 nm in length, or about 1000 nm to about 2000 nm in length, and / or about 1 nm to about 1000 nm in width or height, about 70 nm to about 1000 nm in width, about 100 nm to about 800 nm in width, or about 200 nm to about 500 nm in height, or The nano-based 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.

15. The method of any one of claims 1 to 14, wherein The nano-based structure has a shape of sphere, spike, flake, needle, blade, column, polyhedron, three-dimensional cone, cube, sheet, hemisphere, irregular three-dimensional shape, porous structure or any combination thereof.

16. The method of any one of claims 1 to 15, wherein A plurality of said atomic sites are arranged in a pattern on said nanostructured substrate, preferably in a multi-layer arrangement, or A plurality of the atomic sites are randomly dispersed in the nano-based structure and / or on the surface.

17. The method of any one of claims 1 to 16, wherein The energy radiation allows the reaction to proceed at a temperature between 20°C and about 500°C, preferably about 50°C to about 300°C, about 70°C to about 250°C, about 90°C to about 200°C, about 100°C to about 200°C, about 100°C to about 180°C, about 110°C to about 160°C, about 120°C to about 150°C, about 130°C to about 150°C.

18. The method of any one of claims 1 to 17, wherein The reaction is initiated using light radiation or heat radiation, and the reaction is continued using light radiation or heat radiation, wherein The light radiation power of the light radiation is 200-1500W / m 2 , preferably 200-1000W / m 2 , most preferably 500-1000W / m 2 .

19. The method of any one of claims 1 to 18, wherein The light radiation increases the temperature of the composite catalyst and the hydrogen-containing source and is preferably the only source of increased temperature.

20. The method of any one of claims 1 to 19, wherein The hydrogen source is selected from the group consisting of water, saturated alcohols, carboxylic acids, phenols and any combination thereof, preferably water.

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