Method for generating hydrocarbon molecules through energy radiation combined with ultrasonic vibration

Abstract

The present invention relates to a method for producing hydrocarbon molecules by 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 ultrasonic field, and irradiating the composite catalyst, the hydrogen-containing source and the carbon-containing source with energy to produce hydrocarbon molecules, wherein the composite catalyst comprises at least one nanometer substrate structure and at least one atomic site, and the atomic site comprises one or more than two chemical elements of Mn, Co, Fe, Ru, Rh, Al, Ag, Au, Pt, Pd, Cu, Ni, Zn, Ti, Os, Ir and La.

Description

Technical Field

[0001] The present invention relates to a method for catalytically generating hydrocarbon molecules through energy radiation and ultrasonic vibration, belonging to the fields of carbon dioxide utilization and renewable energy. Background Art

[0002] The greenhouse effect caused by a large increase in carbon dioxide poses a great threat to the environment, climate, and ecology of all mankind. Carbon dioxide capture, utilization, and storage technologies have attracted increasing attention, and scientists around the world have carried out a large number of research projects on these technologies. Artificial photosynthesis technology uses solar energy to convert carbon dioxide into organic compounds such as hydrocarbons and alcohols to achieve the storage and utilization of carbon dioxide and the recycling of energy, which is one of the most promising technologies.

[0003] In the past few decades, there has been an increasing interest in the field of converting solar energy into more useful energy. Some technologies have shown great promise in this field, but there is still a long way to go before commercialization. So far, most of the research work has only been able to successfully synthesize short-chain (C1-C2) hydrocarbon molecules, and their solar-to-chemical energy conversion efficiency is 1 or 2 orders of magnitude lower than that of natural photosynthesis. Although a few works can synthesize long-chain hydrocarbon molecules (>C3, even >C5), the current catalyst stability still cannot provide reliable support for industrialization. Therefore, the most important current work is to develop more efficient and stable catalysts.

[0004] Due to the plasmonic effect, plasmonic catalysts can achieve a great enhancement of local energy on the surface of nanostructures. Thus, under mild overall reaction conditions, catalytic reactions can be efficiently promoted, making reactions that cannot be achieved under normal temperature and pressure possible.

[0005] Since the concept of single-atom catalysis was proposed in recent years, it has received extensive attention and research. With the development of advanced characterization techniques, single-atom catalysts provide the possibility to clarify the structure-activity relationship of catalysts at the atomic and molecular levels and to connect heterogeneous catalysis with homogeneous catalysis. Single-atom catalysts exhibit different activities, selectivities, and stabilities from conventional nanocatalysts due to their special structures.

[0006] Therefore, by combining the advantages of plasmonic effects and single-atom catalysis, it is possible to develop artificial photosynthesis catalysts whose efficiency and stability can meet the requirements of commercialization.

[0007] Acoustic cavitation occurs when a liquid is exposed to high-intensity ultrasound; cavitation refers to the formation of low-pressure cavities (also known as vacuum bubbles or cavities) in a liquid, which grow from small to large, oscillate briefly, and then implode successively, instantaneously generating high pressure and high temperature. During the cavitation process, the intense explosion of bubbles can produce an instantaneous high temperature of up to 5000 °C and an instantaneous high pressure of up to 1000 atm, generating free radicals (containing unpaired electrons and showing very high activity), which cause many chemical (sonochemical) reactions, such as pollutant oxidation, sterilization, polymerization, desulfurization, degradation of long-chain molecules, etc. At the same time, a flow current, extremely fast microjets (with a speed of up to 500 m / s), and a huge shear force are generated in the cavitation field, promoting various physical and mechanical effects, such as emulsification, particle fragmentation, cell disruption, homogenization, dispersion, degassing, etc. Wu Xiaolin et al. studied the alkylation reaction in a tubular fixed bed with a solid acid as a catalyst and benzene and long-chain olefins as raw materials in an ultrasonic field (Wu Xiaolin et al., Preliminary study on the alkylation reaction of benzene and long-chain olefins in an ultrasonic field, Zhejiang Chemical Industry, Vol. 37, No. 2, 2006); Chinese Patent Application CN105368487A discloses the use of ultrasonic action to send ultrasonic energy (such as cavitation force, shear, microjet, shock wave microconvection, local hot spots, etc.) to heavy oil to drive hydroconversion under low-pressure hydrogen conditions (such as less than 500 psig) that are not conventionally considered suitable for treating heavy oil. The above-mentioned literatures all involve the hydrocracking of long-chain organic compounds, using conventional catalysts for the reaction, failing to utilize new catalytic means such as plasmon effects, unable to synthesize hydrocarbon molecules from small molecules such as CO2, and also unable to use green energy such as solar energy, and the waste liquid generated also has a certain pollution to the environment. Summary of the Invention

[0008] Based on the technical problems existing in the background art, the present invention elucidates a novel plasmon catalytic technology. The plasmon catalyst includes atomic sites, such as single atomic sites and / or atomic clusters containing 2 - 25 atoms, and provides a unique method for preparing hydrocarbon molecules by using CO or CO2 from industrial flue gas or the atmosphere through light radiation and / or thermal radiation in the presence of a cost-effective catalyst.

[0009] One aspect of the present invention is a method for generating hydrocarbon molecules by energy radiation, including:

[0010] In the presence of an ultrasonic field, bringing a composite catalyst into contact with at least one hydrogen-containing source and at least one carbon-containing source, and

[0011] Energy-radiating the composite catalyst, the hydrogen-containing source, and the carbon-containing source to generate hydrocarbon molecules, wherein

[0012] The composite catalyst comprises at least one nanoscale substrate structure and at least one atomic site, and the atomic site contains one or more chemical elements selected from Mn, Co, Fe, Ru, Rh, Al, Ag, Au, Pt, Pd, Cu, Ni, Zn, Ti, Os, Ir, and La.

[0013] In certain embodiments, the energy radiation is selected from at least one of light radiation and thermal radiation, preferably light radiation. In certain embodiments, the thermal radiation is preferably infrared radiation.

[0014] In certain embodiments, the ultrasonic field is emitted by an ultrasonic generator and conducted to the reactor via a metal bar.

[0015] In certain embodiments, an external ultrasonic field is used to assist the catalytic reaction, which improves the selectivity of propane in the product hydrocarbon molecules. The ultrasonic vibration frequency is 20 kHz to about 1 MHz, preferably about 100 - 800 kHz, more preferably 200 - 500 kHz; the power density of the ultrasonic vibration is 100 - 800 W / L, preferably 200 - 600 W / L, more preferably 300 - 500 W / L; the selectivity of propane in the product hydrocarbon molecules is 5% to 30%, and is 10% to 30% within the preferred ultrasonic frequency and power density range.

[0016] In certain embodiments, the distance between the nanoscale substrate 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.

[0017] In certain embodiments, the atomic site is combined with the nanoscale substrate structure, for example, by physical or chemical means.

[0018] In certain embodiments, the mass percentage of the atomic site to the nanoscale substrate 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%.

[0019] In certain embodiments, the atomic site is loaded on the surface of the nanoscale substrate structure, in the internal pores, or distributed in the internal lattice of the nanoscale substrate structure, and preferably each atomic site is evenly distributed. In a preferred embodiment, the distance between each atomic site is 0.2 - 500 nm, preferably 1 - 50 nm, more preferably 1 - 10 nm.

[0020] In some embodiments, the nano-substrate structure is selected from the group consisting of Mn, Co, Ce, Fe, Al, Ca, 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, or Al2O3.

[0021] In some embodiments, the composite catalyst is a (CoMn-MOF) catalyst with Co and Mn loaded or bonded to a metal-organic framework, an (Fe-Al2O3) catalyst with Fe loaded or bonded to Al2O3, a (Co-Al2O3) catalyst with Co loaded or bonded to Al2O3, a (Ru-Al2O3) catalyst with Ru loaded or bonded to Al2O3, a (RuFe-Al2O3) catalyst with Ru and Fe loaded or bonded to Al2O3, or a (RuCo-Al2O3) catalyst with Ru and Co loaded or bonded to Al2O3.

[0022] In a preferred embodiment, at least one dimension of the nano-substrate structure 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.

[0023] In a preferred embodiment, the nano-substrate structures are each independently about 1 nm to about 3000 nm in length, width, and height. Preferably, the length is 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, and / or the width or height is 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. Alternatively, 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.

[0024] In some embodiments, the shape of the nano-substrate structure is spherical, spiky, flaky, needle-shaped, grass-leaf-shaped, cylindrical, polyhedral, three-dimensional conical, cubic, sheet-shaped, hemispherical, irregular three-dimensional shape, porous structure, or any combination thereof.

[0025] In some embodiments, a plurality of the atomic sites are patterned and arranged on the nano-substrate structure, preferably in a multi-layer arrangement, or a plurality of the atomic sites are randomly dispersed in and / or on the surface of the nano-substrate structure.

[0026] In certain embodiments, the energy radiation causes the reaction to proceed at a temperature between about 20 °C and about 800 °C, preferably between about 20 °C and about 500 °C, preferably between about 50 °C and about 300 °C, between about 70 °C and about 250 °C, between about 90 °C and about 200 °C, between about 100 °C and about 200 °C, between about 100 °C and about 180 °C, between about 100 °C and about 150 °C, between about 110 °C and about 140 °C, between about 120 °C and about 140 °C.

[0027] In certain embodiments, the unit catalyst activity for producing hydrocarbon molecules is greater than 3 μmol g -1 h -1 , and is greater than 5 μmol g -1 h -1 in the preferred temperature range, and is greater than 8 μmol g -1 h -1 in the preferred temperature range and under the preferred vibration frequency. More preferably, the unit catalyst activity for producing hydrocarbon molecules is greater than 18 μmol g -1 h -1 , and is greater than 30 μmol g - 1 h -1 .

[0028] In certain embodiments, the reaction is initiated using light radiation or thermal radiation in combination with ultrasonic vibration, and the reaction is continued using the combined action of light radiation or thermal radiation and ultrasonic vibration, wherein the light radiation power of the light radiation is 200 - 1500 W / m 2 , preferably 200 - 1000 W / m 2 , and most preferably 500 - 1000 W / m 2 ; the ultrasonic vibration frequency is between about 20 kHz and about 1 MHz, preferably about 100 - 800 kHz, and more preferably 200 - 500 kHz.

[0029] In certain embodiments, the light radiation raises the temperature of the composite catalyst, the hydrogen source, and the carbon source, and is preferably the sole source for raising the temperature.

[0030] In certain embodiments, the carbon source is selected from the group consisting of CO2, CO, C 1-4 hydrocarbons, syngas, bicarbonates, and any combination thereof, or air, industrial flue gas, tail gas, or emissions containing one or more of these carbon sources, preferably CO2 and CO.

[0031] In certain embodiments, the hydrogen source is selected from the group consisting of water, H2, C 1-4 hydrocarbons, and any combination thereof, or air, industrial flue gas, tail gas, or emissions containing one or more of these hydrogen sources, preferably water.

[0032] In some embodiments, when there are more than two chemical elements at the atomic site and it is a single atom, the more than two elements may be arranged at intervals or randomly arranged.

[0033] In some embodiments, when the atomic site is an atomic cluster, the composition of each atomic cluster may be the same or different. For example, each atomic cluster may contain different elemental compositions and / or contain different numbers of atoms.

[0034] In the plasmon-catalyzed reaction of the present invention, the ultrasonic field is conducive to the focusing of energy on the surface of the nanocatalyst. At the same time, when the product is generated on the catalyst surface, the presence of the ultrasonic field is also conducive to the rapid desorption of the product, accelerating the production rate of the product. Therefore, by combining the ultrasonic field and energy radiation, the rate of the catalytic reaction can be accelerated, achieving the purpose of increasing the yield and even changing the selectivity of some products. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 Shows a transmission electron microscope (TEM) image of the CoMn-MOF composite catalyst.

[0036] Figure 2 Shows a transmission electron microscope (TEM) image of the Fe-Al2O3 composite catalyst.

[0037] Figure 3 Shows a structural diagram of the photo-combined ultrasonic vibration catalytic reaction system of the present invention.

[0038] Figure 4 Shows a structural diagram of the thermal-combined ultrasonic vibration catalytic reaction system of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0039] The present invention elucidates that, unexpectedly, in the presence of a composite catalyst with plasmonic effects, CO2 or CO and water can be converted into hydrocarbon molecules by using light radiation and / or thermal radiation combined with ultrasonic vibration as the energy input.

[0040] Before further describing the present invention, certain terms used in the specification, examples, and additional claims are collected in the following sections. The definitions listed herein should be read and understood by those skilled in the art in light of the rest 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 the present invention pertains.

[0041] Definition

[0042] As used herein, the term "catalyst" refers to a substance that exhibits the effect of increasing the rate of a chemical reaction by lowering the activation energy of the reaction. The rate-increasing effect is referred to as "catalysis". Catalysts are not consumed in a catalytic reaction, so they can continue to catalyze the further reaction of reactants in small amounts.

[0043] 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, the plasmon donor can provide surface plasmons.

[0044] As used herein, the term "temperature dependence" refers to a property that can vary when the temperature is changed by a given level. The temperature difference that changes the property can be any degree, such as 0.1 °C, 1 °C, 5 °C, 10 °C, 100 °C, or 1000 °C.

[0045] As used herein, the term "chemical element" refers to a chemical substance composed of atoms with the same number of protons in the atomic nucleus. Specifically, a 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 with more than 118 protons in the atomic nucleus that have not yet been discovered.

[0046] As used herein, the term "binding" or "loading" means physically or chemically binding or loading on the surface or in the internal lattice, where the physical means include van der Waals forces, metallic bonds, and other conventional physical binding methods, and the chemical means include ionic bonds, covalent bonds, coordination bonds, and other conventional chemical binding methods.

[0047] As used herein, the term "alloy" refers to a mixture of metals or a mixture of metals and other elements. Alloys are defined by the properties of metallic bonding. An alloy can be a solid solution of metallic elements (single phase) or a mixture of metallic phases (two or more solutions).

[0048] 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 the self-assembly of organic ligands and metal ions or clusters. MOF can contain transition metals, rare earth metals, main group metals such as alkali metals and alkaline earth metals, etc. as metal elements, such as containing Cu, Zn, Cd, Fe, Ti, Mn, Al, and Co, preferably containing Ti, and also containing non-metal elements such as O, N, S, P, halogens (such as F, Cl, Br, I), etc. MOF can be prepared by methods known in the prior art such as the evaporation solvent method, diffusion method, hydrothermal or solvothermal method, ultrasonic and microwave methods, etc.

[0049] As used herein, the term "unit catalyst activity" refers to the number of moles of product produced per unit mass of active catalyst per unit time under certain reaction conditions. Specifically, unit catalyst activity = moles of reaction product / mass of active catalyst / reaction time.

[0050] As used herein, the term "in close contact" 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, and preferably a metal bond or a coordination bond is formed.

[0051] As used herein, the term "C 1-4 hydrocarbons" includes C1, C2, C3, and C4 hydrocarbons, such as methane, ethane, n-propane, isopropane, n-butane, and isobutane, cyclopropane, cyclobutane, ethylene, propylene, isopropylene, 1-butene, 2-butene, isobutene, acetylene, propyne, 1-butyne, 2-butyne, etc.

[0052] Unless the context clearly indicates otherwise, in this specification and the appended claims, the singular forms "a", "an", and "the" include the plural forms.

[0053] All numerical identifiers used herein, such as pH values, temperatures, times, concentrations, contents, and molecular weights, including ranges, are approximate values and are subject to (+) or (-) variations in increments of 0.1 or 1.0 where appropriate. It will be understood that although not always explicitly stated, the term "about" can precede all numerical identifiers.

[0054] As will be understood by those skilled in the art, for any and all purposes, particularly in providing a written description, all ranges disclosed herein also cover any and all possible sub-ranges and combinations of their sub-ranges. Any listed range can be readily recognized as fully described and can be decomposed into at least equal halves, thirds, quarters, fifths, tenths, etc. As a non-limiting example, each range discussed herein can be readily decomposed into lower thirds, middle thirds, upper thirds, etc.

[0055] Those skilled in the art will also understand that all languages, such as "at most", "at least", "above", "below", etc., include the recited numbers and refer to ranges that can subsequently be subdivided into the sub-ranges discussed above.

[0056] As used herein, "optional" or "optionally" means that the subsequently described event or circumstance can or cannot occur, and the description includes instances where the event or circumstance occurs and instances where the event or circumstance does not occur.

[0057] Plasmonic composite catalyst

[0058] On one hand, the present invention relates to a plasmon composite catalyst for generating hydrocarbon molecules by combining optical radiation and / or thermal radiation with ultrasonic vibration.

[0059] Without wishing to be bound by theory, the plasmon composite catalyst of the present invention can enhance the absorption of optical 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, so that the reaction can be initiated by combining optical radiation and / or thermal radiation with ultrasonic vibration, and increase the reaction rate.

[0060] The plasmon composite catalyst of the present invention comprises two structures: atomic sites and a nano-substrate structure, wherein the atomic sites 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 plasmon 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%.

[0061] Atomic site

[0062] The term "atomic sites" used in the present invention refers to independent metal single atoms and / or independent atomic clusters comprising 2 - 25, preferably 2 - 20 metal atoms, wherein the metal single atoms and / or the atomic clusters are stably bonded or supported on the surface and / or in the internal lattice of the nano-substrate structure, preferably uniformly distributed in the nano-substrate structure, and 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 commonly present in metals. 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 cluster is less than 1 nm, preferably 0.1 - 0.5 nm.

[0063] The atoms in the atomic sites are combined with the atoms in the nano-substrate structure by physical or chemical means, such as by van der Waals forces, metallic bonds and other conventional physical bonding means, or ionic bonds, covalent bonds, coordination bonds and other conventional chemical bonding means, such as forming an alloy by metallic bonds or forming a complex by coordination bonds.

[0064] When the atomic sites are independent metal single atoms, the interaction between the metal single atoms and the atoms in the nano-substrate structure can prevent the aggregation of the metal single atoms and make them more stable. In some embodiments, in the catalytic metal single atom sites, all the catalytic metals exist in the form of isolated atoms, that is, the dispersion of the catalytic metal atoms is 100%, so that the catalytic metal atoms can be utilized to the maximum extent; preferably, all the catalytic metal atoms are directly fixed on the surface of the nano-substrate structure, and the catalytic metal atoms form 100% interface atoms, and the metal-substrate interface interaction can be utilized to the maximum extent to optimize the catalytic performance.

[0065] When the atomic sites are independent metal atom clusters, the metal atom clusters are combined with the atoms in the nano-substrate structure by physical or chemical means. The metal atom clusters are stably dispersed on and / or in the nano-substrate structure.

[0066] When the atomic sites are single atoms of a single metal element, in some embodiments, the single metal element serves as both a plasmon donor and a catalytic property donor, and the nano-substrate structure provides a physical support function; in other embodiments, the single metal element serves as a plasmon donor, and the nano-substrate structure provides a physical support function and serves as a catalytic property donor.

[0067] When the atomic sites are metal atom clusters, in some embodiments, some atom clusters containing specific elements serve as plasmon donors, and some atom clusters containing specific elements serve as catalytic property donors, and the nano-substrate structure provides a physical support function; in other embodiments, the atom clusters serve as plasmon donors, and the nano-substrate structure provides a physical support function and serves as a catalytic property donor.

[0068] In other embodiments, the atomic sites and the nano-substrate structure act together as both a plasmon donor and a catalytic property donor, and the nano-substrate structure provides a physical support function.

[0069] Nanoscale substrate structure

[0070] As used herein, the term "nanoscale substrate structure" refers to a structure having a size range in the nanoscale, i.e., at least one of the length, width, and height 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. The nanoscale substrate structure can have dimensions exceeding 1000 nm. For example, it can have a length in the micron scale range, such as 1 μm to 5 μm. In some cases, tubular and fibrous materials with only two dimensions in the nanoscale are also considered nanoscale substrate structures. Materials with nanoscale substrate structures can exhibit significantly different size-related properties compared to those observed in bulk materials.

[0071] Each of the nanoscale substrate structures of the present invention independently has a length, width, and height of from about 1 nm to about 3000 nm. Its length is preferably from about 100 nm to about 3000 nm, more preferably from about 500 nm to about 2500 nm, and still more preferably from about 1000 nm to about 2000 nm. Its width or height is preferably from about 1 nm to about 1000 nm, preferably from about 70 nm to about 1000 nm, more preferably from about 100 nm to about 800 nm, and still more preferably from about 200 nm to about 500 nm.

[0072] Each of the nanoscale substrate structures of the present invention independently has an aspect ratio (i.e., the 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 nanoscale substrate structures of the present invention can also have a relatively low aspect ratio, such as from about 1 to about 2.

[0073] Each of the nanoscale substrate structures of the present invention independently has the following shapes: spherical, spiky, flaky, needle-like, grass-leaf-like, cylindrical, polyhedral, three-dimensional conical, cubic, sheet-like, hemispherical, irregular three-dimensional shape, porous structure, or any combination thereof.

[0074] The nanoscale substrate structures are selected from the group consisting of Mn, Co, Ce, Fe, Al, Ca, Cu, Ni, Ti, Zn, Si, Mo, Bi, V, C, N, and their oxides, nitrides, sulfides, carbides, hydrocarbon molecule oxides, chlorides, and metal-organic frameworks.

[0075] As used herein, the term "nanoscale substrate structure" contains more than 25, preferably more than 30 atoms.

[0076] The multiple nano-substrate structures of the present invention can be patterned and arranged on a substrate, preferably in a multi-layer arrangement, or the multiple nano-substrate structures can be randomly dispersed in a medium. For example, the nano-substrate structures can be combined with a substrate. In this case, the nano-substrate structures generally do not aggregate with each other, but are arranged or stacked in a regular form. Alternatively, multiple nano-substrate structures can be dispersed in a liquid medium, where each nano-substrate structure can move freely relative to other nano-substrate structures.

[0077] For example, the nano-substrate structure can have a spiky or grass-leaf-like geometric structure. Optionally, the nano-substrate structure is a flaky geometric structure with a relatively thin thickness. Preferably, the nano-substrate structure has a nano-jungle, nano-grass, and / or nano-snowflake structure. The nano-substrate structure can have a relatively large aspect ratio, and such a nano-substrate structure can adopt the structure of nano-spikes, nano-snowflakes, or nano-needles. The aspect ratio can be about 1 to about 20, about 1 to about 10, or about 2 to about 8. Preferably, the length of the nano-substrate structure can be about 100 nm to about 3000 nm, about 500 nm to about 2500 nm, or about 1000 nm to about 2000 nm; the width or height can be 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.

[0078] The nano-substrate structures can be combined with a substrate. Therefore, the nano-substrate structures generally do not aggregate together, but are arranged in an orderly manner. The substrate can be formed of a metal or polymer material (such as polyimide, PTFE, polyester, polyethylene, polypropylene, polystyrene, polyacrylonitrile, etc.).

[0079] In other examples, the nano-substrate structures have a shape of a sphere, cylinder, polyhedron, three-dimensional cone, cube, sheet, hemisphere, irregular three-dimensional shape, porous structure, or any combination thereof. Each of such nano-substrate structures independently has a length, width, and 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.

[0080] In addition, the plasmonic atomic catalyst of the present invention can act in various states, such as being dispersed, aggregated, or attached / grown on the surface of other materials. In a preferred embodiment, the plasmonic atomic catalyst is dispersed in a medium, which is preferably a reactant of the reaction, such as water.

[0081] Method for generating hydrocarbon molecules by energy radiation combined with an ultrasonic field

[0082] Another aspect of the present invention is a method for generating hydrocarbon molecules by light radiation and / or thermal radiation, comprising the following steps:

[0083] In the presence of an ultrasonic field, a plasmonic composite catalyst is brought into contact with at least one hydrogen-containing source and at least one carbon-containing source; and

[0084] Under the action of an ultrasonic field, the plasmonic composite catalyst, the hydrogen-containing source and the carbon-containing source are subjected to light radiation and / or heat radiation to produce hydrocarbon molecules.

[0085] Under the catalytic action of the plasmonic composite catalyst, energy radiation, namely light radiation and / or heat radiation, combined with ultrasonic vibration, initiates the reaction for synthesizing hydrocarbon molecules. Without wishing to be bound by theory, the plasmonic composite catalyst can convert and transfer the energy of light radiation, heat radiation and ultrasonic vibration, so that the reaction of the present invention can proceed continuously. Within a specific temperature range, increasing the temperature can lead to a higher energy conversion rate for producing hydrocarbon molecules.

[0086] As used herein, the term "ultrasonic vibration" refers to the high-frequency vibration effect generated when ultrasonic waves propagate in a medium. In the reaction of the present invention, the ultrasonic vibration frequency is from about 20 kHz to about 1 MHz, preferably about 100 - 800 kHz, more preferably 200 - 500 kHz; the power density of the ultrasonic vibration is 100 - 800 W / L, preferably 200 - 600 W / L, more preferably 300 - 500 W / L. Without wishing to be bound by theory, in the present invention, the energy of ultrasonic vibration initiates a cavitation effect in the reaction system, and the instantaneous high temperature, high pressure and shear force generated can promote the dissociation of molecules and the formation of free radicals, which is beneficial to the occurrence of chemical reactions for producing hydrocarbon molecules; at the same time, ultrasonic vibration also plays a certain promoting role in the thermal electron focusing on the catalyst surface, which is beneficial to the plasmonic effect, and after the reaction, it is also more beneficial for the products that are originally easily adsorbed on the catalyst surface to desorb as soon as possible, so that the reaction rate will not slow down due to saturation of the catalyst surface.

[0087] In certain specific embodiments of the present invention, the ultrasonic vibration is emitted by an ultrasonic generator and conducted to the reactor via a metal bar. Specifically, the ultrasonic generator is adjusted to the required frequency and power, and the metal bar is directly in contact with the outer surface of the reactor to produce a conduction effect. It should be understood that the application method of the ultrasonic field is not limited to this, as long as the ultrasonic vibration with the required frequency and power can be conducted to the reactor.

[0088] In the catalytic hydrocarbon production reaction of the present invention, the main raw materials can be gaseous molecules, so the effect of ultrasonic vibration on liquids is not very obvious for the reaction of the present invention. Without wishing to be bound by theory, in the plasmonic catalytic reaction, the increase in the ultrasonic field mainly enhances the focusing effect of energy on the surface of the nano-catalyst and the desorption effect of the products from the surface of the nano-catalyst.

[0089] The light radiation and / or heat radiation step is carried out 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 temperatures, the unit catalyst activity for producing hydrocarbon molecules is greater than 18 μmol g -1 h -1 , and greater than 50 μmol g -1 h -1 in the preferred temperature range; the selectivity of propane in the product hydrocarbon molecules is 5% to 30%, and 10% to 30% in the preferred ultrasonic frequency and power density range.

[0090] As used herein, the term "heat" refers to the thermal energy transferred from one system to another as a result of heat exchange. The thermal energy can be transferred from an external heat source to the reaction system, or it can be carried by one reaction component and transferred to other reaction components. In other words, a reaction component that carries thermal energy before the reaction is also referred to as an internal heat source. In certain embodiments, heat radiation increases the temperature of the plasmon composite catalyst, the hydrogen source, and the carbon source in the reaction of the present invention.

[0091] In the reaction of the present invention, energy radiation and ultrasonic vibration are used as energy sources, where the energy radiation simulates the wavelength composition and intensity of sunlight, so it can increase the temperature of the irradiated catalyst and reaction mixture. When the radiation intensity reaches a certain specific level, the temperature of the plasmon composite catalyst, the hydrogen source, and the carbon source is increased by light radiation. Preferably, the energy radiation is the sole source for increasing the temperature.

[0092] In the reaction of the present invention, after the reaction starts, the reaction continues under energy radiation and an ultrasonic field. In the reaction of the present invention, the energy radiation power is lower than the sunlight radiation power (i.e., the solar constant). For example, the energy radiation power is 200 - 1500 W / m 2 , preferably 200 - 1000 W / m 2 , most preferably 500 - 1000 W / m 2 . The energy radiation can be sunlight or light emitted by an artificial light source, and the wavelength of the energy radiation is between about 250 nm and about 1 μm.

[0093] The light radiation of the present invention can itself increase the reaction temperature to the desired temperature without additional heating.

[0094] The thermal radiation of the present invention is similar to light radiation and originates from blackbody radiation generated by a high-temperature heat source. According to Planck's law, its radiation intensity has a specific wavelength distribution; the thermal radiation adopted in the present invention has its strongest wavelength in the infrared wavelength region ranging from about 2 μm to 10 μm; the catalytic reaction effect generated by the plasmon composite catalyst in the present invention under the action of thermal radiation is related to the wavelength of the thermal radiation used. Without wishing to be bound by theory, the thermal radiation excitation method used in the present invention is different from the direct heat conduction adopted in traditional thermal catalysis, but rather the plasmon catalyst directly absorbs the thermal radiation wave (or light radiation wave) close to the resonance wavelength, thereby exciting the catalytic reaction and enhancing the catalytic effect. In the present invention, the thermal radiation is preferably infrared radiation.

[0095] The reaction time varies according to the size of the reaction, radiation intensity, temperature, and other factors. The reaction is continuously carried out using a perfect device and continuously adding a hydrogen source and a carbon source. The reaction time can be more than 0.1 hour, preferably from 0.1 hour to 1000 hours, preferably from 0.1 hour to 500 hours, preferably from 0.5 hour to 100 hours, preferably from 1 hour to 50 hours, preferably from 2 hours to 30 hours, and most preferably from 4 hours to 20 hours.

[0096] The reaction can be carried out under low pressure, normal pressure, or high pressure, and an 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 from 1 bar to 30 bar, preferably from 1 bar to 20 bar, preferably from 1 bar to 10 bar, and more preferably from 1.5 bar to 5 bar.

[0097] Reaction raw materials

[0098] The carbon source is selected from the group consisting of CO2, CO, C 1-4 hydrocarbons, syngas, bicarbonates, and any combination thereof, or air, industrial flue gas, tail gas, or emissions containing one or more of these carbon sources, preferably CO2 and CO.

[0099] The hydrogen source is selected from the group consisting of water, H2, C 1-4 hydrocarbons, and any combination thereof, or air, industrial flue gas, tail gas, or emissions containing one or more of these hydrogen sources, preferably water.

[0100] As can be seen from the above reaction raw materials, the carbon sources and hydrogen sources that can be used in the present invention widely exist in industrial waste gas, wastewater, flue gas, combustion emissions, automobile exhaust, etc. Therefore, they can be used as reaction raw materials for the present invention, which is conducive to the recycling of industrial waste.

[0101] Reaction products

[0102] The reaction of the present invention can produce hydrocarbon molecules. Without being 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 nanostructured substrates of the plasmon composite catalyst.

[0103] Example

[0104] Preparation of plasmonic composite catalyst in Example 1

[0105] Preparation method of Co - Al2O3 (Co supported or combined with Al2O3) composite catalyst:

[0106] Weigh 3 g of nano-activated alumina (Al2O3, γ-crystalline form, 10 - 20 nm), 2.7 g of lithium chloride (LiCl), 3.3 g of potassium chloride (KCl), and 60 mg of cobalt(II) chloride hexahydrate (CoCl2·6H2O) and add them to an agate mortar, then grind for 30 minutes. Spread the ground powder at the bottom of a quartz boat and place it in a tube furnace. First, pass nitrogen (N2) at a flow rate of 80 mL / min for 30 minutes. Keeping the nitrogen gas flow rate unchanged, heat the tube furnace to 500 °C at a heating rate of 8 °C / min, calcine for 4 hours, and then cool to room temperature. Put the calcined sample into a 500 mL beaker, add 500 mL of deionized water, and soak for about 4 hours. Pour out the supernatant after soaking, wash the solution 6 times with deionized water and centrifuge at 8000 rpm, and then dry in an oven at 80 °C for 12 h to obtain the 0.5% loading Co-Al2O3 composite catalyst used in the experiment.

[0107] By adjusting the addition amount of cobalt(II) chloride hexahydrate, Co-Al2O3 composite catalysts with loadings of 0.25% and 1% can also be obtained respectively.

[0108] Preparation method of CoMn - MOF (Co and Mn supported or combined with MOF) composite catalyst:

[0109] (1) Synthesis of metal-organic framework (MOF) substrate

[0110] Add 4.2 mL of isopropyl titanate and 7.06 g of terephthalic acid to a mixed solution containing 108 mL of N,N-dimethylformamide and 12 mL of methanol. Stir the mixture at 25 °C for 30 min using a magnetic stirrer until a transparent and homogeneous solution is obtained. Transfer this solution to a 200 mL stainless steel autoclave, place the autoclave in an oven and heat to 150 °C, and react for 16 hours. After cooling to room temperature, wash 3 times with methanol, centrifuge, and dry in an oven at 80 °C for 16 hours to obtain the MOF substrate for standby. Characterized by SEM, the morphology of the MOF substrate is columnar nanoparticles with a diameter of 700 nm and a height of 200 nm.

[0111] (2) Preparation of CoMn-MOF catalyst

[0112] Add 2 g of the MOF substrate and 100 mL of methanol to a 250 mL beaker and stir evenly with a magnetic stirrer. Take another 100 mL beaker, weigh 18 mg of manganese nitrate tetrahydrate (Mn(NO3)2·4H2O) and 12 mg of cobalt nitrate hexahydrate (Co(NO3)2·6H2O), add 20 mL of methanol and stir to dissolve. Pour the mixed solution into the MOF dispersion. After stirring for 1 h, wash with methanol, filter and separate using a Buchner funnel, and dry in an oven at 80 °C for 16 h to obtain the CoMn-MOF catalyst, with the loading amounts of Co and Mn both being approximately 0.5%.

[0113] Figure 1 The transmission electron microscopy image of the CoMn-MOF plasmonic composite catalyst is shown. The circles in the figure mark the atomic sites prepared on the nano substrate (only partially marked). It can be seen that the atomic sites are relatively evenly distributed on the substrate, and the spacing between the atomic sites is about 1 - 10 nm.

[0114] Preparation method of Fe - Al2O3 (Fe supported or combined with Al2O3) composite catalyst:

[0115] (1) Put 0.125 g of iron acetylacetonate and 50 g of aluminum acetylacetonate evenly into a 100 mL zirconia ball milling jar.

[0116] (2) Add 50 zirconia balls with a diameter of 6 mm and 20 zirconia balls with a diameter of 10 mm to the above jar, and ball mill for 10 h using a planetary ball mill at a rotation speed of 400 rpm / min.

[0117] (3) Place the taken-out powder in a porcelain boat and calcine in a muffle furnace under an air atmosphere. The calcination time is 5 h and the temperature is 400 °C.

[0118] (4) Take out the calcined product to obtain the Fe-Al2O3 composite catalyst with a loading amount of approximately 0.25%.

[0119] Figure 2 The transmission electron microscopy image of the Fe-Al2O3 plasmonic composite catalyst is shown. After SEM characterization, its morphology is irregular-shaped particles with a diameter of 500 - 1000 nm; isolated single Fe metal atoms are distributed on the surface and pores of Al2O3, and the spacing between the metal atoms is 1 - 5 nm.

[0120] Ru - Al2O3 (Ru supported or combined with Al2O3), RuFe - Al2O3 (Ru and Fe supported or combined with Al2O3), RuCo - Al2O3 (Ru and Co supported or combined with Al2O3) composite catalyst preparation method:

[0121] (1) Put 0.125 g of ruthenium acetylacetonate and 50 g of aluminum acetylacetonate evenly into a 100 mL zirconia ball milling jar.

[0122] (2) Add 50 zirconia balls with a diameter of 6 mm and 20 zirconia balls with a diameter of 10 mm into the above-mentioned tank, and ball mill for 10 h using a planetary ball mill at a rotation speed of 400 rpm / min.

[0123] (3) Place the taken-out powder in a porcelain boat and calcine it in the air atmosphere of a muffle furnace. The calcination time is 5 h and the temperature is 400 °C.

[0124] (4) Take out the calcined product to obtain the Ru-Al2O3 composite catalyst with a loading of about 0.25%.

[0125] (5) Replace 0.125 g of ruthenium acetylacetonate with 0.0625 g of ruthenium acetylacetonate and 0.0625 g of iron acetylacetonate, or replace it with 0.0625 g of ruthenium acetylacetonate and 0.0625 g of cobalt acetylacetonate in the above preparation process, then the RuFe-Al2O3 composite catalyst with the loadings of Ru and Fe both being about 0.125% and the RuCo-Al2O3 composite catalyst with the loadings of Ru and Co both being about 0.125% can be obtained.

[0126] Preparation method of FeCo - TiO2 (Fe and Co supported or combined with TiO2) composite catalyst:

[0127] Weigh 0.2 g of titanium dioxide (TiO2, anatase, 5 - 10 nm, hydrophilic type) and place it in a 500 mL beaker. Then add 200 mL of deionized water to it. After magnetic stirring for 15 minutes, add 100 mL of 1 mol / L ammonium carbonate ((NH4)2CO3) solution to it and continue stirring for 5 min, which is marked as solution A. Dissolve 0.0014 g of cobalt(II) nitrate hexahydrate (Co(NO3)2·6H2O) and 0.0015 g of iron(III) nitrate nonahydrate (Fe(NO3)3·9H2O) in 100 mL of deionized water and ultrasonicate for 10 min, and slowly drip it into the above-mentioned solution A. After the formed suspension is aged at room temperature for 2.5 h, the formed precipitate is centrifugally washed 3 times with deionized water at a rotation speed of 12,500 rpm, and then dried in an oven at 60 °C for 12 h to obtain the FeCo-TiO2 composite catalyst.

[0128] Visible - light catalytic reaction for generating hydrocarbon molecules in Example 2

[0129] The catalyst is the CoMn-MOF composite catalyst prepared according to Example 1. The MOF (metal-organic framework) is a nanoscale substrate structure. The main component of the MOF is TiO2. After SEM characterization, the morphology of the MOF substrate is columnar nanoparticles with a diameter of 700 nm and a height of 200 nm; the atomic sites include Co and Mn, which are atomic clusters formed by 2 - 4 metals and are distributed on the surface of the MOF. The interval between the atomic clusters is about 1 - 10 nm, as Figure 1 shown.

[0130] In a sealable pressure-bearing glass tube with a volume of 35 mL, 1.5 g of CoMn-MOF composite catalyst and 2 mL of ultrapure water were added. The air in the tube was evacuated with CO2 and 4 bar of CO2 was filled. The glass tube was placed flat on glass wool to evenly spread the catalyst and water. A halogen lamp with a controllable voltage, wavelength range of 340 - 800 nm, was vertically irradiated from above. The incident light intensity was about 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 135 °C ± 5 °C, and continuous light irradiation was carried out for 18 h for the photocatalytic reaction. After the reaction, the outlet end of the reaction tube was connected to a gas chromatograph flame ionization detector (GC-FID) and a gas chromatograph thermal conductivity detector (GC-TCD) for product analysis.

[0131] After measurement and analysis, the concentration of C1-C3 hydrocarbon products in the product after stable reaction was about 1637.5 ppm. It can be calculated that, corresponding to the loading amount of catalytically active single atoms, the unit catalytic activity was about 64.98 μmol / g / h.

[0132] Photocatalytic reaction for generating hydrocarbon molecules under ultrasonic field in Example 3

[0133] Using the same CoMn-MOF composite catalyst as in Example 2, the photocatalytic reaction was carried out in the same manner as in Example 2, and on this basis, a sieve frame sheet metal connection was connected to the surface of the reactor to conduct ultrasonic waves. The vibration frequency of the ultrasonic waves was 250 kHz, and the ultrasonic power density was 320 W / L. The reaction system was as Figure 3 shown.

[0134] After the reaction, product analysis was carried out in the same manner as in Example 2. After measurement and analysis, C1-C3 hydrocarbon products were observed in the product after stable reaction, and the total concentration was about 2027 ppm. It can be calculated that, corresponding to the loading amount of catalytically active single atoms, the unit catalytic activity was about 84.38 μmol / g / h.

[0135] Infrared radiation catalytic reaction for generating hydrocarbon molecules in Example 4

[0136] The catalyst used was the Fe-Al2O3 composite catalyst prepared according to Example 1. Al2O3 was a nano-substrate structure. Characterized by SEM, its morphology was irregular-shaped particles with a diameter of 500 - 1000 nm; isolated Fe metal single atoms were distributed on the surface and pores of Al2O3, and the metal atom spacing was 1 - 5 nm, as Figure 2 shown.

[0137] Using the catalyst, reaction conditions and process in Example 2, the halogen lamp in Example 2 was changed to an infrared light source with a radiation intensity of 1000 W / m 2The temperature of the glass tube was controlled at 135 °C ± 5 °C, and continuous light irradiation was carried out for 18 h to conduct the infrared radiation catalytic reaction. After the reaction, through measurement and analysis, the concentration of C1-C3 hydrocarbon products in the product after stable reaction was observed to be about 506.3 ppm. It can be calculated that corresponding to the loading amount of the active single atoms of the catalyst, the unit catalyst activity was about 40.53 μmol / g / h. The concentrations and selectivities of various products are shown in Table 1.

[0138] Table 1

[0139] Product type Product concentration (ppm) Product selectivity % Methane 369.0 72.9 Ethane 102.4 20.2 Propane 34.9 6.9

[0140] Infrared radiation catalytic reaction for generating hydrocarbon molecules under ultrasonic field in Example 5

[0141] The same Fe-Al2O3 composite catalyst as in Example 4 was used, and the ultrasonic field-assisted photocatalytic reaction was carried out in the same manner as in Example 4 and on this basis, a sieve frame sheet metal connection was connected to the reactor surface to conduct ultrasonic waves. The vibration frequency of the ultrasonic wave was about 250 kHz, the ultrasonic power density was 300 W / L, the temperature of the glass tube was controlled at 135 °C ± 5 °C, and continuous light irradiation was carried out for 18 h to conduct the infrared radiation catalytic reaction. The reaction system diagram is as Figure 4 shown. After the reaction, product analysis was carried out in the same manner as in Example 4. Through measurement and analysis, the concentration of C1-C3 hydrocarbon products in the product after stable reaction was observed to be about 1023.7 ppm. It can be calculated that corresponding to the loading amount of the active single atoms of the catalyst, the unit catalyst activity was about 58.24 μmol / g / h. The concentrations and selectivities of various products are shown in Table 2.

[0142] Table 2

[0143] Product type Product concentration (ppm) Product selectivity % Methane 523.9 51.1 Ethane 303.4 29.6 Propane 197.2 19.3

[0144] From the above experimental results, it can be seen that under the ultrasonic field, the selectivities of C2 and C3 in the hydrocarbon molecules produced in the photocatalytic reaction increased.

[0145] Thermal catalytic reaction for generating hydrocarbon molecules in Example 6

[0146] The catalyst used was the FeCo-TiO2 composite catalyst prepared according to Example 1. TiO2 was a nanoscale substrate structure. After being characterized by SEM, its morphology was irregular-shaped particles with a diameter of 150-200 nm; the Fe and Co metal single atoms were distributed on the surface and pores of TiO2, and the metal atom spacing was 2-5 nm.

[0147] 1.5 g of FeCo- was added to a 30 mL sealed and pressure-bearing stainless steel reaction tube TiO2The composite catalyst and 2 mL of pure water were used to exhaust the air inside the tube with CO2 and filled with 4 bar CO2. The reaction tube was tightly wrapped with a heating tape and laid flat on glass wool to evenly spread the catalyst and water. The temperature of the heating tape was controlled at 135°C ± 5°C. After the reaction was carried out for 18 hours, the outlet of the reaction tube was connected to GC-FID and GC-TCD for product analysis.

[0148] The FeCo-TiO2 composite catalyst with a loading of 0.5% was tested after thermal reaction. The concentration of C1-C3 hydrocarbon products in the stable reaction product was about 579ppm, and the propane selectivity was 8.1%. It was calculated that the unit catalyst activity was about 42.3μmol g corresponding to the loading of the catalyst active single atom. -1 h -1 .

[0149] Thermal catalytic reaction for generating hydrocarbon molecules under ultrasonic field in Example 7

[0150] The same FeCo-TiO2 composite catalyst as in Example 6 was used to carry out the thermal catalytic reaction in the same manner as in Example 6, and a screen frame was connected to the reactor surface to conduct ultrasonic waves. The vibration frequency of the ultrasonic waves was 250 kHz, and the ultrasonic power density was 300 W / L. The reaction system was as follows: Figure 4 shown.

[0151] After the reaction, product analysis was performed in the same manner as in Example 6. After measurement and analysis, C1-C3 hydrocarbon products were observed in the product after the stable reaction, with a total concentration of about 1043 ppm and a propane selectivity of 18.3%. It was calculated that the unit catalyst activity was about 57.26 μmol / g / h, corresponding to the loading amount of the catalyst active single atom.

[0152] Energy radiation combined with ultrasonic vibration catalytic reaction for generating hydrocarbon molecules in Example 8

[0153] In this example, while changing the catalyst composition and reaction parameters, a light-combined ultrasonic vibration catalytic reaction or a heat-combined ultrasonic vibration catalytic reaction was carried out in a manner similar to that of Example 3 or 7. The reaction conditions and results are shown in Table 3.

[0154] Table 3

[0155]

[0156] From the above experimental results, it can be seen that under the condition that other reaction conditions remain unchanged, by applying ultrasonic vibration of a certain intensity, the unit catalyst activity of producing hydrocarbon molecules and the propane selectivity in the hydrocarbon products can be improved.

[0157] In summary, the present invention provides a method for improving the reaction yield of hydrocarbon molecules catalytically generated by a plasmonic catalyst using energy radiation by applying an ultrasonic field. In the present invention, the application of the ultrasonic field can improve the reaction yield and the propane selectivity in the product under various reaction conditions, and can also enhance the catalytic activity of various plasmonic catalysts, which is beneficial to the commercial development and application of hydrocarbon production by catalysis.

[0158] Representative examples are intended to help illustrate the invention and are not intended nor should they be construed as limiting the scope of the invention. In fact, various modifications of the invention and many other embodiments thereof will become apparent to those skilled in the art in addition to those shown and described herein, 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 practicing the invention in its various embodiments and equivalents.

Claims

1. A method for generating hydrocarbon molecules by energy radiation, comprising: In the presence of an ultrasonic field, bringing a composite catalyst into contact with at least one hydrogen source and at least one carbon source, and Energy-radiating the composite catalyst, the hydrogen source, and the carbon source to generate hydrocarbon 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 Mn, Co, Fe, Ru, Rh, Al, Ag, Au, Pt, Pd, Cu, Ni, Zn, Ti, Os, Ir, La.

2. The method according to claim 1, wherein The ultrasonic field is emitted by an ultrasonic generator and is preferably conducted to the reactor via a metal bar.

3. The method according to claim 1 or 2, wherein The ultrasonic vibration frequency is from 20 kHz to about 1 MHz, preferably about 100 - 800 kHz, more preferably 200 - 500 kHz, and / or The power density of the ultrasonic vibration is 100 - 800 W / L, preferably 200 - 600 W / L, more preferably 300 - 500 W / L.

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 thermal radiation, preferably light radiation.

5. The method according to claim 4, wherein The thermal radiation is infrared radiation.

6. The method according to 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 5 nm, preferably less than or equal to 1 nm, more preferably less than 0.1 nm, and most preferably they are in close contact.

7. The method according to any one of claims 1 to 6, wherein The atomic site is combined with the nano-substrate structure, for example, by physical or chemical means.

8. The method according to any one of claims 1 to 7, wherein The mass percentage of the atomic site to the nano-substrate 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%.

9. The method according to any one of claims 1 to 8, wherein The atomic site is loaded on the surface of the nano-substrate structure, inside the pores, or distributed in the internal lattice of the nano-substrate structure, preferably each atomic site is evenly distributed, and The distance between each atomic site is 0.2 - 500 nm, preferably 1 - 50 nm, more preferably 1 - 10 nm.

10. The method according to any one of claims 1 to 9, wherein The nano-substrate structure is selected from the group consisting of Mn, Co, Ce, Fe, Al, Ca, Cu, Ni, Ti, Zn, Si, Mo, Bi, V, C, N and their oxides, nitrides, sulfides, carbides, hydroxides, chlorides, and metal-organic frameworks (MOF), preferably metal-organic frameworks, TiO2 or Al2O3.

11. The method according to any one of claims 1 to 10, wherein The composite catalyst is a catalyst with Co and Mn loaded on or combined with a metal organic framework, a catalyst with Fe loaded on or combined with Al2O3, a catalyst with Co loaded on or combined with Al2O3, a catalyst with Ru loaded on or combined with Al2O3, a catalyst with Ru and Fe loaded on or combined with Al2O3, or a catalyst with Ru and Co loaded on or combined with Al2O3.

12. The method according to any one of claims 1 to 11, wherein at least one of the length, width, and height of the nano-substrate structure 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.

13. The method according to any one of claims 1 to 12, wherein each of the nano-substrate structures independently has a length, width, and height of about 1 nm to about 3000 nm. Preferably, the length is about 100 nm to about 3000 nm, about 500 nm to about 2500 nm, or about 1000 nm to about 2000 nm, and / or the width or height is 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 each of the nano-substrate structures independently has an aspect ratio of about 1 to about 20, preferably about 1 to about 10, or about 2 to about 8.

14. The method according to any one of claims 1 to 13, wherein the shape of the nano-substrate structure is spherical, spiky, flaky, needle-shaped, grass-leaf-shaped, cylindrical, polyhedral, three-dimensional conical, cubic, sheet-shaped, hemispherical, irregular three-dimensional shape, porous structure, or any combination thereof.

15. The method according to any one of claims 1 to 14, wherein a plurality of the atomic sites are patterned and arranged on the nano-substrate structure, preferably in a multi-layer arrangement, or a plurality of the atomic sites are randomly dispersed in and / or on the surface of the nano-substrate structure.

16. The method according to any one of claims 1 to 15, wherein the energy radiation causes the reaction to proceed 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 100 °C to about 150 °C, about 110 °C to about 140 °C, or about 120 °C to about 140 °C.

17. The method according to any one of claims 4 to 16, wherein an ultrasonic field is used in combination with light radiation or heat radiation to initiate the reaction and an ultrasonic field is used in combination with light radiation or heat radiation to continue the reaction, wherein The optical radiation power of the optical radiation is 200-1500 W / m 2 , preferably 200-1000 W / m 2 , most preferably 500-1000 W / m 2 .

18. The method according to any one of claims 4 to 17, wherein the light radiation raises the temperature of the composite catalyst, the hydrogen source, and the carbon source, preferably being the sole source of raising the temperature.

19. The method according to any one of claims 1 to 18, wherein The carbon source is selected from the group consisting of CO2, CO, C 1-4 hydrocarbons, syngas, bicarbonates, and any combination thereof, or air, industrial flue gas, tail gas, or emissions containing more than one of these carbon sources, preferably CO2 and CO.

20. The method according to any one of claims 1 to 19, wherein The hydrogen source is selected from the group consisting of water, H2, C 1-4 hydrocarbons and any combination thereof, or air, industrial flue gas, tail gas or emissions containing more than one of these hydrogen sources, preferably water.

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