WO2022121575A1 - 通过能量辐射产生氢分子的方法 - Google Patents

通过能量辐射产生氢分子的方法 Download PDF

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WO2022121575A1
WO2022121575A1 PCT/CN2021/128724 CN2021128724W WO2022121575A1 WO 2022121575 A1 WO2022121575 A1 WO 2022121575A1 CN 2021128724 W CN2021128724 W CN 2021128724W WO 2022121575 A1 WO2022121575 A1 WO 2022121575A1
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nano
hydrogen
base structure
atomic
reaction
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PCT/CN2021/128724
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English (en)
French (fr)
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王琮
霍海滨
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北京光合氢能科技有限公司
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Priority to EP21902282.9A priority Critical patent/EP4261183A1/en
Priority to US18/266,553 priority patent/US20240043267A1/en
Priority to AU2021398031A priority patent/AU2021398031A1/en
Priority to CN202180082710.1A priority patent/CN116600890A/zh
Publication of WO2022121575A1 publication Critical patent/WO2022121575A1/zh

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8913—Cobalt and noble metals
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
    • C01B3/042—Decomposition of water
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/462—Ruthenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/48—Silver or gold
    • B01J23/52—Gold
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/66—Silver or gold
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/009—Preparation by separation, e.g. by filtration, decantation, screening
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • B01J37/035—Precipitation on carriers
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
    • B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • C01B2203/1064—Platinum group metal catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Definitions

  • the invention relates to a method for catalyzing hydrogen production by energy radiation, in particular to a composite catalyst and its application in energy radiation catalyzing hydrogen production.
  • Hydrogen is the most abundant element in nature and is widely present in water, fossil fuels and various carbohydrates. Hydrogen is also the main industrial raw material and the most important industrial gas and special gas. It is used as an important raw material for the synthesis of ammonia, methanol, and hydrochloric acid. It is also used as a reducing agent for metallurgy and a hydrodesulfurizing agent for petroleum refining.
  • plasmonic metal catalysts Due to the plasmonic effect, plasmonic metal catalysts can achieve great enhancement of local energy on nanostructured surfaces. Therefore, in the case of mild overall reaction conditions, the catalytic reaction is efficiently promoted, making it possible to achieve reactions that cannot be achieved under normal temperature and pressure.
  • the splitting of water into hydrogen and oxygen has been achieved in recent years, but so far there is still a need to develop more efficient, stable and cost-effective catalysts.
  • single-atom catalysis 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 have been used to clarify the structure-activity relationship of catalysts from the atomic and molecular levels, and to connect heterogeneous catalysis and homogeneous catalysis. Catalysis offers the possibility. Due to their special structure, single-atom catalysts exhibit different activity, selectivity and stability than conventional nanocatalysts.
  • the present invention clarifies a novel plasmonic catalyst technology
  • the plasmonic catalyst includes atomic sites, such as single-atom sites and/or atomic clusters containing 2-25 atoms , provides a unique method for the production of hydrogen by decomposing a hydrogen-containing source, preferably water, by light radiation and/or thermal radiation in the presence of a cost-effective catalyst.
  • One aspect of the invention is a method of producing hydrogen by energy radiation, comprising:
  • the composite catalyst comprises at least one nano-base structure and at least one atomic site, the atomic site comprises one or more chemical elements in Ru, Rh, Ag, Au, Pt, Pd, Os, Ir , preferably one or both of Ru and Au.
  • the atomic site further comprises one or more chemical elements selected from Mn, Co, Fe, Al, Cu, Ni, Zn, Ti, and La, preferably Co, Fe, Mn one or more of them.
  • the energy radiation is selected from at least one of optical radiation and thermal radiation, preferably optical radiation.
  • 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.
  • the atomic sites are bound to the nanosubstrate structure, for example, physically or chemically.
  • the mass percentage of the atomic sites to the nano-base structure is less than or equal to 50%, preferably 0.01% to 30%, preferably 0.01% to 5%, more preferably 0.1% to 2%, most preferably 0.1% to 1%.
  • the spacing between atomic sites is 0.2-500 nm, preferably 1-50 nm, more preferably 1-20 nm.
  • the nano-base 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
  • the composite catalyst is a Ru and Co supported or bound to TiO 2 (RuCo-TiO 2 ) catalyst, a Ru supported or bound Al 2 O 3 (Ru-Al 2 O 3 ) catalyst, Au supported or bound to Al 2 O 3 (Au-Al 2 O 3 ) catalyst or Au supported or bound to CeO 2 (Au-CeO 2 ) catalyst.
  • At least one dimension of 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.
  • the nano-base structures are each independently about 1 nm to about 3000 nm long, wide and high, preferably, about 100 nm to about 3000 nm long, about 500 nm to about 2500 nm long, or about 1000 nm to about 2000 nm long, and/or from about 1 nm to about 1000 nm in width or height, 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, or
  • the nanobase 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.
  • the shape of the nano-base structure is spherical, spiked, flake, needle, blade of grass, cylinder, polyhedron, three-dimensional pyramid, cube, sheet, hemispherical, irregular three-dimensional shape , porous structures, or any combination thereof.
  • a plurality of said atomic sites are arranged in a patterned arrangement on said nano-base structure, preferably in a multilayer arrangement, or
  • a plurality of the atomic sites are randomly dispersed in and/or on the nano-base structure.
  • the energy radiation causes the reaction to proceed at a temperature between about 20°C to 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 specific catalyst activity for hydrogen production is greater than 2 ⁇ mol g ⁇ 1 h ⁇ 1 , preferably greater than 3 ⁇ mol g ⁇ 1 h ⁇ 1 , more preferably greater than 7 ⁇ mol g ⁇ 1 h ⁇ 1 .
  • the reaction is initiated using optical radiation or thermal radiation, and the reaction is continued using optical or thermal radiation, 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 .
  • the optical radiation increases the temperature of the composite catalyst and the hydrogen-containing source, preferably the sole source of temperature increase.
  • the hydrogen-containing source is selected from the group consisting of water, saturated alcohols, carboxylic acids and phenols, and any combination thereof, preferably water.
  • the two or more elements may be arranged at intervals or randomly.
  • each atomic cluster 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 the number of atoms.
  • Figure 1 shows the gas chromatogram of the gas-phase product after the Ru-Al 2 O 3 composite catalyst and thermal radiation are used to react with liquid water as a raw material.
  • FIG. 2 shows the gas chromatogram of the gas phase product after the reaction using the Au-Al 2 O 3 composite catalyst and thermal radiation with liquid water as the raw material.
  • Figure 3 shows a transmission electron microscope (TEM) image of the CoRu-TiO 2 composite catalyst.
  • the present invention demonstrates that, unexpectedly, a hydrogen-containing source, preferably water, can be converted into hydrogen molecules in the presence of a composite catalyst with plasmonic action, with optical radiation and/or thermal radiation as energy input.
  • a hydrogen-containing source preferably water
  • catalyst refers to a substance that exhibits the effect of increasing the rate of a chemical reaction by reducing the activation energy of the reaction. The rate-increasing effect is referred to as "catalysis”. Catalysts are not consumed in catalytic reactions, so they can continue to catalyze further reactions of reactants with small amounts.
  • Plasmonic donor refers to a conductor whose real part of the dielectric constant is negative. Plasmonic donors can provide surface plasmons when excited by electromagnetic radiation.
  • temperature dependence refers to a property that can change when temperature changes by a given level.
  • the temperature difference that changes the properties can be any number of degrees, such as 0.1°C, 1°C, 5°C, 10°C, 100°C, or 1000°C.
  • chemical element refers to a chemical substance consisting of atoms in the nucleus that have the same number of protons. Specifically, chemical elements are those recorded in the periodic table of chemical elements. Chemical elements include natural and synthetic elements. Chemical elements also include elements with more than 118 protons in their nuclei that have yet to be discovered.
  • bound or “supported” as used herein refer to physically or chemically bound or supported on a surface, internal channel or internal lattice, where physical means include van der Waals forces, metal bonds, and other conventional physical binding means, chemical Methods include ionic bonds, covalent bonds, coordinate bonds, and other conventional chemical bonding methods.
  • alloy refers to a mixture of metals or a mixture of metals and other elements. Alloys are defined by metallic bonding properties.
  • the alloy can be a solid solution of a metal element (single phase) or a mixture of metal phases (two or more solutions).
  • 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, preferably forming a metal bond or a coordinate bond.
  • saturated alcohol refers to a saturated hydrocarbon compound substituted with an -OH group, such as a C1 - C15 saturated alcohol, preferably a C1 - C8 saturated alcohol, more preferably a C1 - C4 saturated alcohol, such as methanol , ethanol, propanol, isopropanol, butanol, isobutanol.
  • carboxylic acid refers to a saturated hydrocarbon compound substituted with a -COOH group, such as a C1 - C15 carboxylic acid, preferably a C1 - C8 carboxylic acid, more preferably a C1 - C4 carboxylic acid, such as formic acid , acetic acid, propionic acid, isopropionic acid, butyric acid, isobutyric acid.
  • phenolic refers to compounds comprising -OH attached directly to an aromatic ring, wherein the aromatic ring is 5-25 carbon atoms, preferably 5-20 carbon atoms, most preferably 5-15 carbon atoms carbon atoms, more preferably a monocyclic, bicyclic or tricyclic ring of 6-12 carbon atoms, and the aromatic ring is, for example, benzene, naphthalene.
  • MOF metal organic framework
  • the term "metal organic framework (MOF)" as used herein refers to an organic-inorganic hybrid material with intramolecular pores or a metal-organic framework with periodic network structure formed by self-assembly of organic ligands and metal ions or clusters .
  • the MOF may contain transition metals, rare earth metals, main group metals such as alkali metals and alkaline earth metals, etc. as metal elements, such as Cu, Zn, Cd, Fe, Ti, Mn, Al and Co, preferably Ti, and also O, N , S, P, halogen (such as F, Cl, Br, I) and other non-metallic elements.
  • MOFs can be prepared by methods known in the art such as evaporative solvent methods, diffusion methods, hydrothermal or solvothermal methods, ultrasonic and microwave methods, and the like.
  • One aspect of the present invention is a plasmonic composite catalyst that generates hydrogen molecules by light radiation and/or thermal radiation.
  • the plasmonic composite catalysts of the present invention interact with the starting materials in the reaction to reduce the activation energy of the reaction, thereby enabling the reaction to be initiated by optical and/or thermal radiation, and increasing the reaction rate.
  • the plasmonic composite catalyst of the present invention includes two structures: atomic sites and nano-substrate structures, wherein the atomic sites and nano-substrate structures are in contact with each other.
  • the mass percentage of the atomic sites and the nano-base 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%, most preferably 0.1% to 1%.
  • atomic site 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, said metal single atoms and/or all
  • the atomic clusters are stably bound or supported on the surface of the nano-base structure and/or in the internal channels and/or in the internal lattice, preferably uniformly distributed on the nano-base structure, more preferably evenly distributed on the surface of the nano-base structure.
  • the atoms in the metal single atom or the atomic cluster exist in a valence state between 0 and the highest valence usually present in the metal, the average valence of the metal atom being, for example, 0 to +4, or 0 to +3 valence, or 0 to +2 valence, or 0 to +1 valence, preferably 0 valence.
  • the atomic spacing in the atomic cluster is less than 1 nm, preferably 0.1-0.5 nm.
  • the atoms in the atomic sites are physically or chemically bonded to the atoms in the nanosubstrate structure, such as by van der Waals forces, metallic bonds, and other conventional physical bonding methods, or ionic bonds, covalent bonds, coordinate bonds, and other conventional chemical bonding, such as metal bonding to form alloys, or coordinate bonding to form complexes.
  • the interaction between the metal single atoms and the atoms in the nano-base structure can prevent the metal single atoms from agglomerating and make them more stable.
  • all catalytic metals exist in the form of isolated atoms, that is, the dispersion of catalytic metal atoms is 100%, which can maximize the utilization of catalytic metal atoms; preferably All the catalytic metal atoms are directly fixed on the surface of the nano-substrate structure, and the catalytic metal atoms form 100% of the interface atoms, which can maximize the use of the metal-substrate interface interaction to optimize the catalytic performance.
  • the metal atom clusters are physically or chemically combined with atoms in the nano-base structure.
  • the metal atomic clusters are stably dispersed on and/or in the nano-base structure.
  • the single metal element acts as both a plasmon donor and a catalytic property donor, and the nano-base structure provides physical support; In other embodiments, the single metal element acts as a plasmon donor, the nano-base structure provides physical support, and acts as a catalytic property donor.
  • the atomic sites are metal atomic clusters
  • some atomic clusters containing specific elements serve as plasmon donors
  • some atomic clusters containing specific elements serve as catalytic property donors
  • the nanometer The base structure provides physical support; in other embodiments, the atomic clusters serve as plasmon donors
  • the nano-base structure provides physical support and serves as a donor of catalytic properties.
  • the atomic sites and the nano-substrate structure act together as both a donor of plasmons and a donor of catalytic properties, and the nano-substrate structure provides physical support.
  • nanosubstrate structure refers to a structure having a size range on the nanometer scale, ie, at least one dimension of length, width, high and middle is about 1 nm to about 1000 nm, preferably about 70 nm to about 1000 nm, about 100 nm to about 800 nm, about 200nm to about 500nm.
  • Nanosubstrate structures can have dimensions in excess of 1000 nm, eg, have lengths in the micrometer scale range, such as 1 ⁇ m to 5 ⁇ m. In some cases, tubes and fibers with only two dimensions in the nanometer range are also considered nanobasal structures. Materials with nano-based structures can exhibit size-dependent properties that are significantly different from those observed in bulk materials.
  • the nano-base structures of the present invention are each independently about 1 nm to about 3000 nm in length, width and height.
  • the length thereof is preferably about 100 nm to about 3000 nm, more preferably about 500 nm to about 2500 nm, still more preferably about 1000 nm to about 2000 nm.
  • Its width or height is preferably about 1 nm to about 1000 nm, preferably about 70 nm to about 1000 nm, more preferably about 100 nm to about 800 nm, still more preferably about 200 nm to about 500 nm.
  • the nanosubstrate structures of the present invention each independently have an aspect ratio (ie, 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 Compare.
  • the nanosubstrate structures of the present invention can also have relatively low aspect ratios, such as about 1 to about 2.
  • the nano-substrate structures of the present invention each independently have the following shapes: spheres, spikes, flakes, needles, blades of grass, cylinders, polyhedrons, three-dimensional pyramids, cubes, sheets, hemispherical, irregular three-dimensional shapes , porous structures, or any combination thereof.
  • the nano-base structure is selected from 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.
  • base structure contains more than 25 atoms, preferably more than 30 atoms.
  • a plurality of the nano-base structures of the present invention can be arranged in a pattern on the substrate, preferably a multilayer arrangement, or a plurality of the nano-base structures can be randomly dispersed in a medium.
  • the nano-base structure can be bound to a matrix.
  • the nano-base structures are generally not aggregated with each other, but are arranged or stacked in a regular pattern.
  • a plurality of nanosubstrate structures can be dispersed in a liquid medium, wherein each nanosubstrate structure can move freely relative to other nanosubstrate structures.
  • nanosubstrate structures can have spike-like or blade-like geometries.
  • the nanosubstrate structures are flake-like geometries with relatively thin thicknesses.
  • the nano-base structure has a nano-jungle, nano-grass, and/or nano-snowflake configuration.
  • the nano-base structure can have a relatively large aspect ratio, and such a nano-base structure can adopt the configuration of nano-spikes, nano-snow flakes 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.
  • the length of the nano-base structure may 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 may 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.
  • the nano-base structure can be bound to a matrix. Therefore, the nanosubstrate structures are generally not clustered together, but arranged in an ordered manner.
  • the matrix may be formed from metallic or polymeric materials (eg, polyimide, PTFE, polyester, polyethylene, polypropylene, polystyrene, polyacrylonitrile, etc.).
  • the nanosubstrate structure has the shape of a sphere, a cylinder, a polyhedron, a three-dimensional pyramid, a cube, a sheet, a hemisphere, an irregular three-dimensional shape, a porous structure, or any combination thereof.
  • Such nanosubstrate 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.
  • the plasmonic atomic catalysts of the present invention are capable of functioning in various states, such as dispersed, aggregated or attached/grown on other material surfaces.
  • the plasmonic atomic catalyst is dispersed in a medium, which is preferably a reactant for the reaction, such as water.
  • Another aspect of the present invention is a method for generating hydrogen molecules by optical radiation and/or thermal radiation, comprising the steps of:
  • the plasmonic composite catalyst, the hydrogen-containing source, are irradiated with light and/or heat to generate hydrogen molecules.
  • plasmonic composite catalyst Under the catalytic action of the plasmonic composite catalyst, energy radiation, ie, light radiation and/or thermal radiation, initiates the reaction of the hydrogen-containing source.
  • the decomposition of a hydrogen-containing source, preferably water, to produce hydrogen molecules is an endothermic reaction.
  • plasmonic composite catalysts are capable of converting and transferring the energy of light radiation and thermal radiation, thereby allowing the reactions of the present invention to continue. Within a certain temperature range, increasing the temperature can result in a higher energy conversion rate for the production of hydrogen molecules.
  • the light irradiation and/or thermal irradiation step is at about 20°C to about 800°C, about 20°C to about 500°C, 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, etc.
  • the specific catalyst activity for hydrogen production is greater than 2 ⁇ mol g -1 h -1 , preferably greater than 3 ⁇ mol g -1 h -1 , more preferably greater than 7 ⁇ mol g -1 h -1 .
  • heat refers to thermal energy transferred from one system to another as a result of heat exchange. Heat 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, the reaction components that carry thermal energy prior to the reaction are also referred to as internal heat sources. In certain embodiments, thermal radiation increases the temperature of the plasmonic composite catalyst and the hydrogen-containing source in the reactions of the present invention.
  • the optical radiation simulates the wavelength composition and intensity of sunlight, so it increases the temperature of the irradiated catalyst and reactants.
  • the radiation intensity reaches a certain level, the temperature of the plasmonic composite catalyst, the hydrogen-containing source, is increased by optical radiation.
  • optical radiation is the only source of elevated temperature.
  • the reaction of the present invention In the reaction of the present invention, after the reaction is started, the reaction is continued under light irradiation.
  • the term "light” as used herein refers to electromagnetic waves having wavelengths between about 250 nm and about 2000 nm. In other words, light refers to the radiation of visible light.
  • the optical radiation power is lower than the solar radiation power (ie, the solar constant).
  • the optical radiation power is 200-1500 W/m 2 , preferably 200-1000 W/m 2 , most preferably 500-1000 W/m 2 .
  • the optical radiation may be sunlight or light emitted by an artificial light source, the optical radiation having a wavelength between about 250 nm and about 2000 nm.
  • the reaction time varies depending on the size of the reaction, radiation intensity, temperature, and other factors, and the reaction is continued using a well-established apparatus with continuous addition of a hydrogen-containing source.
  • the reaction time may be more than 0.1 hour, preferably 0.1 hour to 1000 hours, preferably 0.1 hour to 500 hours, preferably 0.5 hour to 100 hours, preferably 1 hour to 50 hours, preferably 2 hours to 30 hours, most preferably 4 hours to 20 hours .
  • the reaction can be carried out under 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, preferably 1 bar to 20 bar, more preferably 1.5 bar to 5 bar.
  • the reaction raw materials include hydrogen-containing sources, such as water, saturated alcohols, carboxylic acids and phenols, preferably water, such as pure water or hard water, and the water can be gaseous or liquid.
  • the reactions of the present invention are capable of producing hydrogen molecules.
  • the reaction mechanism of the present invention may involve the decomposition and reorganization of various reaction feedstock molecules on the atomic sites and nanosubstrate structures of the plasmonic composite catalyst.
  • Ru-Al 2 O 3 (Ru supported or bound to Al 2 O 3 ) composite catalyst and Au-Al 2 O 3 (Au supported Or combined with Al 2 O 3 ) composite catalyst is prepared by the following method:
  • RuCl 3 ruthenium trichloride
  • the Ru- Al2O3 precursor was obtained by washing with deionized water five times.
  • the solution obtained by mixing 20 mL of sodium hydroxide pre-adjusted to pH 12.0 and 0.4 g of solid sodium borohydride (NaBH 4 ) was slowly added to the precursor, stirred evenly, and then filtered with suction.
  • the Ru-Al 2 O 3 composite catalyst can be obtained by drying under nitrogen atmosphere.
  • the Au-Al 2 O 3 composite catalyst can be obtained by replacing RuCl 3 in the above process with 3.4 mg of chloroauric acid (HAuCl 4 ).
  • RuCo-TiO 2 (Ru and Co supported or bound to TiO 2 ) composite catalyst
  • the composite catalyst is composed of Prepared as follows:
  • TiO 2 titanium dioxide
  • anatase 5-10nm, hydrophilic type
  • a mixed solution containing 0.0020 g of hydrated ruthenium trichloride (RuCl 3 .xH 2 O) and 0.0014 g of cobalt nitrate hexahydrate (Co(NO 3 ) 2 .6H 2 O) was dissolved in 100 mL of deionized water and sonicated for 10 min. It was slowly added dropwise to the above A solution. After the formed suspension was aged at room temperature for 2.5 hours, the formed precipitate was centrifuged and washed three times with deionized water at 12500 rpm, and then dried in an oven at 60°C for 12 hours to obtain the RuCo-TiO 2 composite catalyst.
  • the high-resolution electron microscopy (HRTEM) image of the RuCo- TiO composite catalyst is shown in Figure 3.
  • Au-CeO 2 (Au supported or bound to CeO 2 ) composite catalyst The composite catalyst was prepared by the following method preparation:
  • the catalyst used is the Ru-Al 2 O 3 composite catalyst prepared according to Example 1, and the Al 2 O 3 is a nano-base structure, which is characterized by SEM and is an irregular shape spherical particle with a diameter of 500-1000 nm; isolated Ru metal single The atoms are uniformly distributed on the surface of Al2O3 , and the metal single-atom spacing is 5-20nm.
  • the hydrogen content in the gas in the reaction tube was characterized by thermal conductivity detector (TCD) gas chromatography.
  • TCD thermal conductivity detector
  • the gas chromatogram of the product obtained after the thermal catalytic reaction using the Ru-Al 2 O 3 composite catalyst is shown in Figure 1.
  • the calculated hydrogen content is 2053 ppm, and the unit catalyst activity for hydrogen production is about 6.44 ⁇ mol g -1 h -1 .
  • the catalytic activity of the catalyst for catalyzing hydrogen production did not decrease.
  • the catalyst used is the Au-Al 2 O 3 composite catalyst prepared according to Example 1, and the Al 2 O 3 is a nano-base structure, which is characterized by SEM and is an irregular shape spherical particle with a diameter of 500-1000 nm; isolated Au metal single The atoms are uniformly distributed on the Al2O3 surface, and the metal atoms are separated by 5-20 nm.
  • thermocatalytic reaction was carried out in the same manner as in Example 2 using 0.1 g of the Au-Al 2 O 3 composite catalyst.
  • the temperature in the oven was controlled to be 130°C ⁇ 10°C, and the reaction was continued for 18 hours.
  • the reacted gas was characterized by gas chromatography in the same manner as in Example 2.
  • the gas chromatogram of the product obtained after the thermal catalytic reaction using the Au-Al 2 O 3 composite catalyst is shown in Figure 2.
  • the calculated hydrogen content is 2890 ppm, and the unit catalyst activity for hydrogen production is about 9.073 ⁇ mol g -1 h -1 .
  • the catalytic activity of the catalyst for catalyzing hydrogen production did not decrease.
  • the catalyst used is the Au-CeO 2 composite catalyst prepared according to Example 1, and CeO 2 is a nano-base structure, which is characterized by SEM and is an irregular shape spherical particle with a diameter of 400-1500 nm; isolated Au metal single atoms are uniformly distributed in CeO 2 surface, the metal single atom spacing is 5-20nm.
  • thermocatalytic reaction was carried out in the same manner as in Example 2.
  • the temperature in the oven was controlled to be 130°C ⁇ 10°C, and the reaction was continued for 18 hours.
  • the reacted gas was characterized by gas chromatography in the same manner as in Example 2.
  • the hydrogen content was calculated to be 1862 ppm, and the unit catalyst activity for hydrogen production was about 5.845 ⁇ mol g -1 h -1 .
  • the catalytic activity of the catalyst for catalyzing the generation of hydrogen did not decrease.
  • the catalyst used is a RuCo-TiO 2 composite catalyst, and TiO 2 is a nano-base structure. It is characterized by SEM and is irregular spherical particles with a diameter of 600-1500 nm; isolated Ru, Co metal single atoms or atomic clusters are uniformly distributed in the TiO. 2 surface, metal single atom or metal atom cluster spacing is 5-20nm.
  • thermocatalytic reaction was carried out in the same manner as in Example 2 using 0.2 g of the RuCo-TiO 2 composite catalyst.
  • the temperature in the oven was controlled to be 130°C ⁇ 10°C, and the reaction was continued for 18 hours.
  • the reacted gas was characterized by gas chromatography in the same manner as in Example 2.
  • the hydrogen content was calculated to be 6863 ppm, and the unit catalyst activity for hydrogen production was about 10.77 ⁇ mol g -1 h -1 .
  • the catalytic activity of the catalyst to catalyze the generation of hydrogen did not decrease.
  • the catalyst used was the RuCo-TiO 2 composite catalyst described in Example 5.
  • the reacted gas was characterized by gas chromatography in the same manner as in Example 2, and it was found that the hydrogen content was 1848 ppm. It can be calculated that the unit catalyst activity for hydrogen production is about 2.901 ⁇ mol g -1 h -1 . After the above reaction was continuously carried out for 10 cycles (180 h), the catalytic activity of the catalyst for catalyzing the generation of hydrogen did not decrease.
  • Example 2 to Example 6 show that the method of the present invention can efficiently directly convert the oligosaccharide using a cost-effective catalyst under mild overall reaction conditions, such as when the optical radiation power is lower than the solar radiation power.
  • the resulting feedstock is converted into hydrogen.

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Abstract

一种通过能量辐射产生氢的方法，包括：使复合催化剂与至少一种含氢源相接触，并且能量辐射复合催化剂和含氢源，以产生氢分子，其中复合催化剂包含至少一种纳米基底结构和至少一种原子位点，原子位点包含Ru、Rh、Ag、Au、Pt、Pd、Os、Ir中的一种或两种以上化学元素。

Description

通过能量辐射产生氢分子的方法 技术领域
本发明涉及通过能量辐射催化制氢的方法，具体涉及一种复合催化剂及其在能量辐射催化制氢中的应用。
背景技术
在新能源领域中，氢能已普遍被认为是一种最理想、无污染的新世纪绿色能源，这是因为氢燃烧后的唯一产物是水。氢是自然界中最丰富的元素，广泛地存在于水、矿物燃料和各类碳水化合物中。氢也是主要的工业原料，是最重要的工业气体和特种气体，用作合成氨、合成甲醇、合成盐酸的重要原料，还用作冶金用还原剂、石油炼制用加氢脱硫剂等。
然而，传统的制氢方法需要消耗巨大的常规能源，使氢能成本太高，大大限制了氢能的推广应用。于是科学家们想到利用取之不尽、廉价的太阳能作为氢能形成过程中的一次能源，使氢能开发展现出更加广阔的前景。科学家们发现了以光催化材料为“媒介”，能利用太阳能把水裂解为燃料电池所必需的氧和氢，科学家们将这种仅用阳光和水生产出氢和氧的技术称为“人类的理想技术之一”。
由于等离激元效应，等离激元金属催化剂可以在纳米结构表面上实现局域能量的极大增强。从而，在整体反应条件温和的情况下，高效地促进催化反应，使得常温常压下无法达到的反应成为可能。近年已可实现将水分解为氢气和氧气，但目前为止，仍需要研发更高效、更稳定和成本有效的催化剂。
单原子催化的概念自近年提出以来，受到了广泛的关注和研究，随着先进表征技术的发展，单原子催化剂为从原子和分子层面阐明催化剂的构效关系，以及连接多相催化和均相催化提供了可能。单原子催化剂由于具有特殊的结构，因而呈现出不同于常规纳米催化剂的活性、选择 性和稳定性。
因此，结合等离激元效应与单原子催化的优势，有可能开发出效率、稳定性和成本都能够满足商业化要求的制氢催化剂。
发明内容
基于背景技术存在的技术问题，本发明阐明了一种新型等离激元催化技术，该等离激元催化剂包括原子位点，例如单原子位点和/或含2-25个原子的原子团簇，提供了一种在成本有效的催化剂的存在下，通过光辐射和/或热辐射分解含氢源，优选水，制备氢气的独特方法。
本发明的一方面是通过能量辐射产生氢的方法，包括：
使复合催化剂与至少一种含氢源相接触，并且
能量辐射所述复合催化剂和所述含氢源，以产生氢分子，其中
所述复合催化剂包含至少一种纳米基底结构和至少一种原子位点，所述原子位点包含Ru、Rh、Ag、Au、Pt、Pd、Os、Ir中的一种或两种以上化学元素，优选Ru和Au中的一种或两种。
在某些实施例中，所述原子位点还包含Mn、Co、Fe、Al、Cu、Ni、Zn、Ti、La中的一种或两种以上化学元素，优选包含Co、Fe、Mn中的一种或两种以上。
在某些实施例中，所述能量辐射选自光辐射和热辐射中的至少一种，优选为光辐射。
在某些实施例中，所述纳米基底结构和所述原子位点之间的距离小于等于5nm，优选小于等于1nm，更优选小于0.1nm，最优选两者紧密接触。
在某些实施例中，所述原子位点与所述纳米基底结构结合，例如以 物理方式或化学方式结合。
在某些实施例中，所述原子位点与所述纳米基底结构的质量百分比小于等于50％，优选0.01％至30％，优选0.01％至5％，更优选0.1％至2％，最优选0.1％至1％。
在某些实施例中，所述原子位点负载于所述纳米基底结构表面、内部孔道，或分布于所述纳米基底结构的内部晶格中，优选各原子位点均匀分布，并且
各原子位点之间间隔0.2-500nm，优选1-50nm，更优选1-20nm。
在某些实施例中，所述纳米基底结构选自由Mn、Co、Ce、Fe、Al、Ca、Ce、Cu、Ni、Ti、Zn、Si、Mo、Bi、V、C、N及其氧化物、氮化物、硫化物、碳化物、氢氧化物、氯化物以及金属有机框架(MOF)所组成的组，优选为金属有机框架、TiO 2、Al 2O 3、或CeO 2。
在某些实施例中，所述复合催化剂为Ru和Co负载或结合于TiO 2的(RuCo-TiO 2)催化剂、Ru负载或结合于Al 2O 3的(Ru-Al 2O 3)催化剂、Au负载或结合于Al 2O 3的(Au-Al 2O 3)催化剂或Au负载或结合于CeO 2的(Au-CeO 2)催化剂。
在优选实施例中，所述纳米基底结构的长、宽、高中的至少一个维度为约1nm至约1000nm，优选为约70nm至约1000nm，约100nm至约800nm，约200nm至约500nm。
在优选实施例中，所述纳米基底结构各自独立地长、宽、高为约1nm至约3000nm，优选地，长为约100nm至约3000nm，约500nm至约2500nm，或约1000nm至约2000nm，并且/或者宽或高为约1nm至约1000nm，约70nm至约1000nm，约100nm至约800nm，或约200nm至约500nm，或者
所述纳米基底结构各自独立地具有约1至约20的长径比，优选约1至约10，或约2至约8的长径比。
在某些实施例中，所述纳米基底结构的形状为球形、尖刺、薄片、针状、草叶、柱形、多面体、三维锥体、立方形、片状、半球形、不规则三维形状、多孔结构或其任意组合。
在某些实施例中，多个所述原子位点在所述纳米基底结构上呈有图案地配置排列，优选地多层排列，或者
多个所述原子位点随机分散在所述纳米基底结构中和/或表面。
在某些实施例中，所述能量辐射使得反应在约20℃至约500℃之间的温度下进行，优选约50℃至约300℃、约70℃至约250℃、约90℃至约200℃、约100℃至约200℃、约100℃至约180℃、约110℃至约160℃、约120℃至约150℃、约130℃至约150℃，并且
生产氢的单位催化剂活性大于2μmol g -1h -1，优选大于3μmol g -1h -1，更优选大于7μmol g -1h -1。
在某些实施例中，使用光辐射或热辐射引发反应，并使用光辐射或热辐射使得反应继续进行，其中
所述光辐射的光辐射功率为200-1500W/m 2，优选为200-1000W/m 2，最优选为500-1000W/m 2。
在某些实施例中，所述光辐射提高了所述复合催化剂和所述含氢源的温度，优选为提高温度的唯一来源。
在某些实施例中，所述含氢源选自由水、饱和醇、羧酸和酚类及其任意组合所组成的组，优选为水。
在某些实施例中，在所述原子位点包含两种以上化学元素且为单原 子时，所述两种以上元素可以是间隔排布，也可以是随机排布。
在某些实施例中，在所述原子位点为原子团簇时，各原子团簇的组成可以是相同的，也可以是不同的，例如各原子团簇可能包含不同的元素组成，和/或包含不同的原子数。
附图说明
图1示出利用Ru-Al 2O 3复合催化剂和热辐射以液态水为原料反应后，气相产物的气相色谱图。
图2示出利用Au-Al 2O 3复合催化剂和热辐射以液态水为原料反应后，气相产物的气相色谱图。
图3示出CoRu-TiO 2复合催化剂的透射电镜(TEM)图。
具体实施方式
本发明阐明，出乎意料地，能够在具有等离激元作用的复合催化剂的存在下，以光辐射和/或热辐射作为能量输入，将含氢源、优选水转化为氢分子。
在进一步描述本发明之前，下面的章节中收集了说明书、实施例、和附加的权利要求中使用的某些术语。本文所列定义应被本领域技术人员根据本发明的其余部分来阅读并理解。除非另外定义，否则本文使用的所有技术和科学术语均具有本发明所属领域普通技术人员通常理解相同的含义。
定义
本文所用术语“催化剂”是指呈现通过降低反应活化能量以增加化学反应速率的作用的物质。速率增加效果被称为“催化”。催化剂在催化反应中不会被消耗，因此他们可以用少量继续催化反应物的进一步反应。
本文所用术语“等离激元供体”是指其介电常数的实部为负数的导 体。当被电磁辐射激发时，等离激元供体可提供表面等离激元。
本文所用术语“温度依赖性”是指当温度改变给定水平时可以变化的特性。改变特性的温度差异可以是任意度数的，如0.1℃、1℃、5℃、10℃、100℃、或1000℃。
本文所用术语“化学元素”是指由原子核中拥有相同质子数的原子所组成的化学物质。具体而言，化学元素是化学元素周期表中记录的元素。化学元素包括天然元素和合成元素。化学元素还包括尚未被发现的原子核中有超过118个质子的元素。
本文所用术语“结合”或“负载”是指以物理方式或化学方式结合或负载在表面、内部孔道或内部晶格中，其中物理方式包括范德华力、金属键以及其他常规的物理结合方式，化学方式包括离子键、共价键、配位键以及其他常规的化学结合方式。
本文所用术语“合金”是指金属混合物或金属和其他元素的混合物。合金是由金属键合(metallic bonding)特性定义的。合金可以是金属元素(单相)或金属相的混合物(两种以上的溶液)的固溶体。
本文所用术语“单位催化剂活性”是指在一定反应条件下，单位质量活性催化剂在单位时间内产生的产物摩尔数量。具体地，单位催化剂活性＝反应产物摩尔数/活性催化剂质量/反应时间。
本文所用术语“紧密接触”是指两者之间基本没有间隙，例如两者之间的距离小于等于1nm，小于等于0.1nm，或者基本为0nm，优选形成金属键或配位键。
本文所用术语“饱和醇”是指被-OH基团取代的饱和烃化合物，例如C 1-C 15饱和醇、优选C 1-C 8饱和醇、更优选C 1-C 4饱和醇，例如甲醇、乙 醇、丙醇、异丙醇、丁醇、异丁醇。
本文所用术语“羧酸”是指被-COOH基团取代的饱和烃化合物，例如C 1-C 15羧酸、优选C 1-C 8羧酸、更优选C 1-C 4羧酸，例如甲酸、乙酸、丙酸、异丙酸、丁酸、异丁酸。
本文所用术语“酚类”是指包含直接与芳族环相连的-OH的化合物，其中所述芳族环为包含5-25个碳原子、优选5-20个碳原子、最优选5-15个碳原子，更优选6-12个碳原子的单环、双环或三环，所述芳族环例如为苯、萘。
本文所用术语“金属有机框架(MOF)”是指有机配体和金属离子或团簇通过自组装形成的具有分子内孔隙的有机-无机杂化材料或具有周期性网络结构的金属-有机骨架结构。MOF可包含过渡金属，稀土金属，主族金属例如碱金属和碱土金属等作为金属元素，例如包含Cu、Zn、Cd、Fe、Ti、Mn、Al和Co，优选包含Ti，还包含O、N、S、P、卤素(例如F、Cl、Br、I)等非金属元素。MOF可通过现有技术已知的方法例如蒸发溶剂法、扩散法、水热或溶剂热法、超声和微波法等制得。
等离激元复合催化剂
本发明一方面是通过光辐射和/或热辐射产生氢分子的等离激元复合催化剂。
不期望受缚于理论，本发明的等离激元复合催化剂与反应中的原料相互作用以降低反应的活化能，从而使得反应能够通过光辐射和/或热辐射引发，并且增加反应速率。
本发明的等离激元复合催化剂包括两种结构：原子位点和纳米基底结构，其中原子位点和纳米基底结构相互接触。在优选实施例中，等离激元复合催化剂中所述原子位点与所述纳米基底结构的质量百分比为小 于等于50％，优选0.01％至30％，优选0.01％至5％，更优选0.1％至2％，最优选0.1％至1％。
原子位点
本发明所用术语“原子位点”是指相互独立的金属单原子和/或相互独立的包括2-25个、优选包括2-20个金属原子的原子团簇，所述金属单原子和/或所述原子团簇稳定结合或负载于纳米基底结构表面上和/或内部孔道和/或内部晶格中，优选均匀分布于纳米基底结构，更优选均匀分布于纳米基底结构的表面上。所述金属单原子或所述原子团簇中的原子以0价态和金属通常存在的最高价态之间的价态存在，所述金属原子的平均价态例如为0至+4价，或者0至+3价，或者0至+2价，或者0至+1价，优选0价。所述原子团簇中原子间距小于1nm，优选0.1-0.5nm。
原子位点中的原子与纳米基底结构中的原子通过物理方式或化学方式结合，例如通过范德华力、金属键以及其他常规的物理结合方式，或离子键、共价键、配位键以及其他常规的化学结合方式，例如通过金属键形成合金，或通过配位键形成配合物。
当所述原子位点是相互独立的金属单原子时，金属单原子与所述纳米基底结构中的原子之间的相互作用，可以阻止所述金属单原子团聚，使其更加稳定。在一些实施方式中，在催化金属单原子位点中，所有的催化金属都以孤立原子的形式存在，即，催化金属原子的分散度为100％，这样可以最大限度地利用催化金属原子；优选地，所有催化金属原子均直接固定于所述纳米基底结构表面，催化金属原子形成了100％的界面原子，可以最大限度利用金属-基底界面相互作用优化催化性能。
当所述原子位点是相互独立的金属原子团簇时，所述金属原子团簇与所述纳米基底结构中的原子通过物理方式或化学方式结合。所述金属原子团簇稳定分散于所述纳米基底结构上和/或中。
当所述原子位点是单一金属元素的单原子时，在一些实施方式中，所述单一金属元素同时作为等离激元供体和催化特性供体，所述纳米基底结构提供物理支撑作用；在另一些实施方式中，所述单一金属元素作为等离激元供体，所述纳米基底结构提供物理支撑作用，且作为催化特性供体。
当所述原子位点是金属原子团簇时，在一些实施方式中，一些含有特定元素的原子团簇作为等离激元供体，另一些含有特定元素的原子团簇作为催化特性供体，所述纳米基底结构提供物理支撑作用；在另一些实施方式中，所述原子团簇作为等离激元供体，所述纳米基底结构提供物理支撑作用，且作为催化特性供体。
在另一些实施方式中，所述原子位点和所述纳米基底结构共同作用，同时作为等离激元供体和催化特性供体，所述纳米基底结构提供物理支撑作用。
纳米基底结构
本文所用术语“纳米基底结构”是指具有纳米尺度的尺寸范围的结构，即长、宽、高中至少一个维度为约1nm至约1000nm，优选为约70nm至约1000nm，约100nm至约800nm，约200nm至约500nm。纳米基底结构能够具有超过1000nm的维度，例如，具有微米尺度范围内的长度，如1μm至5μm。在某些情况下，只有两个维度在纳米范围内的管状物和纤维也视为纳米基底结构。具有纳米基底结构的材料可呈现与块体材料中观察到的显著不同的尺寸相关特性。
本发明的所述纳米基底结构各自独立地长、宽、高为约1nm至约3000nm。其长度优选为约100nm至约3000nm，更优选为约500nm至约2500nm，还更优选为约1000nm至约2000nm。其宽度或高度优选为约1nm至约1000nm，优选为约70nm至约1000nm，更优选为约100nm至约800nm，还更优选为约200nm至约500nm。
本发明的所述纳米基底结构各自独立地具有约1至约20的长径比(即，长度与宽度/高度的比例)，优选为约1至约10，或约2至约8的长径比。本发明的所述纳米基底结构也能够具有相对低的长径比，例如约1至约2。
本发明的所述纳米基底结构各自独立地具有以下形状：球形、尖刺、薄片、针状、草叶、柱形、多面体、三维锥体、立方形、片状、半球形、不规则三维形状、多孔结构或其任意组合。
所述纳米基底结构选自由Mn、Co、Ce、Fe、Al、Ca、Ce、Cu、Ni、Ti、Zn、Si、Mo、Bi、V、C、N及其氧化物、氮化物、硫化物、碳化物、氢氧化物、氯化物以及金属有机框架所组成的组。
本文所用术语“纳米基底结构”包含高于25个、优选高于30个原子。
本发明的多个所述纳米基底结构能够在基质上呈有图案地配置排列，优选地为多层排列，或者多个所述纳米基底结构能够随机分散在介质中。例如，所述纳米基底结构可以结合于基质。在这种情况下，所述纳米基底结构大体上不相互聚集，而是以规则的形式排列或堆积。或者，多个纳米基底结构能够分散在液体介质中，其中各个纳米基底结构能够相对于其他纳米基底结构自由地移动。
例如，纳米基底结构可以具有尖刺状或草叶状的几何构造。可任选地，纳米基底结构为具有相对薄的厚度的薄片状几何构造。优选地，纳米基底结构具有纳米丛林、纳米草、和/或纳米雪片构造。纳米基底结构可以具有相对大的长径比，这样的纳米基底结构可以采用纳米尖刺、纳米雪片或纳米针的构造。长径比可以为约1至约20，约1至约10，或约2至约8。优选地，纳米基底结构的长度可以为约100nm至约3000nm，约500nm至约2500nm，或约1000nm至约2000nm；宽度或高度可以 为约1nm至约1000nm，约70nm至约1000nm，约100nm至约800nm，或约200nm至约500nm。
所述纳米基底结构可以结合于基质。因此，纳米基底结构大体上不聚集在一起，而是以有序的方式排列。所述基质可以由金属或聚合物材料(例如聚酰亚胺、PTFE、聚酯、聚乙烯、聚丙烯、聚苯乙烯、聚丙烯腈等)形成。
在其他实例中，所述纳米基底结构具有球形、圆柱形、多面体、三维锥体、立方形、片状、半球形、不规则三维形状、多孔结构或其任意组合的形状。这样的纳米基底结构各自独立地为长、宽、高约1nm至约1000nm，约70nm至约1000nm，约100nm至约800nm，或约200nm至约500nm。
此外，本发明的等离激元原子催化剂能够在各种状态下起作用，诸如分散、聚集或附着/生长在其它材料表面上。在优选的实施方式中，等离激元原子催化剂分散在介质中，该介质优选为反应的反应物，例如水。
产生氢分子的方法
本发明另一方面是一种通过光辐射和/或热辐射产生氢分子的方法，包含下面步骤：
使一种等离激元复合催化剂与至少一种含氢源相接触；以及
光辐射和/或热辐射所述等离激元复合催化剂、所述含氢源，以产生氢分子。
在等离激元复合催化剂的催化作用下，能量辐射，即光辐射和/或热辐射，引发了含氢源的反应。分解含氢源、优选水产生氢分子反应是一个吸热反应。不期望受缚于理论，等离激元复合催化剂能够将光辐射和热辐射的能量进行转化和传递，从而使本发明的反应持续进行。在特定温度范围内，升高温度可导致更高的生产氢分子的能量转化率。
所述光辐射和/或热辐射步骤在约20℃至约800℃、约20℃至约500℃、约50℃至约300℃、约70℃至约250℃、约90℃至约200℃、约100℃至约200℃、约100℃至约180℃、约110℃至约160℃、约120℃至约150℃、约130℃至约150℃等之间的温度下进行。在上述温度时，生产氢的单位催化剂活性大于2μmol g -1h -1，优选大于3μmol g -1h -1，更优选大于7μmol g -1h -1。
本文所用术语“热”是指作为热交换的结果而从一个系统传递至另一个系统的热能。热能可以从外部热源传递至反应系统，也可以由一个反应组分携带而传递至其他反应组分。换言之，在反应前携带热能的反应组分也称为内部热源。在某些实施方式中，热辐射提高了本发明的反应中，等离激元复合催化剂和含氢源的温度。
在本发明的反应中，光辐射模拟了太阳光的波长组成和强度，因此它可提高被辐射的催化剂和反应物的温度。当辐射强度达到某个特定水平，等离激元复合催化剂、含氢源的温度由光辐射提高。优选地，光辐射为提高温度的唯一来源。
在本发明的反应中，反应开始后，反应在光辐射下继续进行。本文所用术语“光”是指波长在约250nm至约2000nm之间电磁波。换言之，光是指可见光的辐射。优选地，在本发明的反应中，光辐射功率低于太阳光辐射功率(即，太阳常数)。例如，光辐射功率为200-1500W/m 2，优选为200-1000W/m 2，最优选为500-1000W/m 2。所述光辐射可以是太阳光或由人造光源发出的光，所述光辐射的波长在约250nm至约2000nm之间。
反应时间根据反应的大小、辐射强度、温度和其他因素而变化，反应在使用一种完善的装置并持续添加含氢源下持续进行。反应时间可以为0.1小时以上，优选0.1小时至1000小时，优选0.1小时至500小时， 优选0.5小时至100小时，优选1小时至50小时，优选2小时至30小时，最优选4小时至20小时。
所述反应可在低压、常压或高压下进行，可以根据反应的大小、辐射强度、温度和其他因素而选择适当的反应压力，例如，反应压力可以为至少1bar，例如1bar至30bar，优选1bar至20bar，更优选1.5bar至5bar。
反应原料
在本发明的反应中，反应原料包括含氢源，例如水、饱和醇、羧酸和酚类，优选为水，例如纯水或硬水，水可为气态或液态。
反应产物
本发明的反应能够产生氢分子。不期望受缚于理论，本发明的反应机理可能包括各种反应原料分子在等离激元复合催化剂的原子位点和纳米基底结构上的分解和重组。
实施例
实施例1 复合催化剂的制备
Ru-Al 2O 3(Ru负载或结合于Al 2O 3)复合催化剂和Au-Al 2O 3(Au负载 或结合于Al 2O 3)复合催化剂由以下方法制备：
将17.6mg三氯化钌(RuCl 3)溶于5mL去离子水中，在室温下超声混合60分钟；其后加入2g活性氧化铝，在40℃下超声混合60分钟，将得到的干燥固体收集，用去离子水洗涤五次得到Ru-Al 2O 3前驱体。将20mL 预调至pH 12.0的氢氧化钠与0.4g硼氢化钠固体(NaBH 4)混合得到的溶液缓慢加入前驱体中，搅拌均匀后进行抽滤，所得固体用去离子水洗涤三次，在80℃氮气气氛下进行烘干，即可得到Ru-Al 2O 3复合催化剂。用3.4mg氯金酸(HAuCl 4)代替上述过程中的RuCl 3即可得到Au-Al 2O 3复合催化剂。
RuCo-TiO 2(Ru和Co负载或结合于TiO 2)复合催化剂复合催化剂由 以下方法制备：
称取0.2g二氧化钛(TiO 2，锐钛矿，5-10nm，亲水型)置于500mL烧杯中，然后向其中加入200mL去离子水，在磁力搅拌15分钟后向其中加入100mL 1mol/L碳酸铵((NH 4) 2CO 3)溶液，继续搅拌5min，标记为溶液A。将含有0.0020g水合三氯化钌(RuCl 3.xH 2O)和0.0014g硝酸钴六水合物(Co(NO 3) 2.6H 2O)的混合溶液溶于100mL去离子水并超声10min，将其缓慢滴加进上述A溶液中。形成的悬浊液在室温下老化2.5h后，将形成的沉淀用去离子水离心洗涤3次，转速12500rpm，然后于烘箱中60℃干燥12h，得到RuCo-TiO 2复合催化剂。RuCo-TiO 2复合催化剂的高分辨电镜图(HRTEM)如图3所示。
Au-CeO 2(Au负载或结合于CeO 2)复合催化剂复合催化剂由以下方法 制备：
将1.73g六水合硝酸铈(CeNO 3·6H 2O)和0.0068g四氯金酸(HAuCl 4·3H 2O)溶于10mL去离子水中，待完全溶解后，将其缓慢滴加进70mL 6mol/L的氢氧化钠(NaOH)溶液中，在室温下持续搅拌30min后，将悬浊液转移至100mL内衬为聚四氟乙烯的不锈钢反应釜中，在120℃下保温12h。反应结束后，自然冷却至室温，离心收集沉淀并用去离子水洗涤沉淀至洗涤液pH＝7，然后于烘箱中60℃干燥12h。将干燥后样品充分研磨后置于管式炉中在空气气氛下5℃/min升温至400℃并保持2h，得到实验所用催化剂Au-CeO 2复合催化剂。
实施例2 产生氢气的热催化反应
使用的催化剂为根据实施例1制备的Ru-Al 2O 3复合催化剂，Al 2O 3为纳米基底结构，经SEM表征，其为直径500-1000nm的不规则外形球状颗粒；孤立的Ru金属单原子均匀分布在Al 2O 3表面，金属单原子间隔为5-20nm。
在35mL容积的可密封承压铁管中加入0.1g Ru-Al 2O 3复合催化剂和6mL超纯水，用Ar排尽管内空气，充入4bar Ar。铁管放置于可控温的烘箱内，加热以进行反应。控制烘箱内温度为130℃±10℃，连续反应18h。
热催化反应后，用热导检测器(TCD)气相色谱表征反应管内气体中的氢气含量。使用Ru-Al 2O 3复合催化剂进行热催化反应后获得的产物 气相色谱图如图1所示，计算得到氢含量为2053ppm，产生氢的单位催化剂活性约为6.44μmol g -1h -1。上述反应进行10次循环(180h)后，所述催化剂催化产氢的催化活性未下降。
实施例3 产生氢气的热催化反应
使用的催化剂为根据实施例1制备的Au-Al 2O 3复合催化剂，Al 2O 3为纳米基底结构，经SEM表征，其为直径500-1000nm的不规则外形球状颗粒；孤立的Au金属单原子均匀分布在Al 2O 3表面，金属原子间隔为5-20nm。
使用0.1g Au-Al 2O 3复合催化剂，以与实施例2相同的方式进行热催化反应。控制烘箱内温度为130℃±10℃，连续反应18h。
以与实施例2相同的方式对反应后的气体进行气相色谱表征。使用Au-Al 2O 3复合催化剂进行热催化反应后获得的产物气相色谱图如图2所示，计算得到氢含量为2890ppm，产生氢的单位催化剂活性约为9.073μmol g -1h -1。上述反应进行10次循环(180h)后，所述催化剂催化产氢的催化活性未下降。
实施例4 产生氢气的热催化反应
使用的催化剂为根据实施例1制备的Au-CeO 2复合催化剂，CeO 2为纳米基底结构，经SEM表征，其为直径400-1500nm的不规则外形球状颗粒；孤立的Au金属单原子均匀分布在CeO 2表面，金属单原子间隔为5-20nm。
使用0.1g Au-CeO 2复合催化剂，以与实施例2相同的方式进行热催化反应。控制烘箱内温度为130℃±10℃，连续反应18h。
以与实施例2相同的方式对反应后的气体进行气相色谱表征。计算得到氢含量为1862ppm，产生氢的单位催化剂活性约为5.845μmol g -1h -1。上述反应连续进行10个循环(180h)后，所述催化剂催化产生氢的催化活性未下降。
实施例5 产生氢气的热催化反应
使用的催化剂为RuCo-TiO 2复合催化剂，TiO 2为纳米基底结构，经SEM表征，其为直径600-1500nm的不规则外形球状颗粒；孤立的Ru、Co金属单原子或原子团簇均匀分布在TiO 2表面，金属单原子或金属原子团簇间隔为5-20nm。
使用0.2g RuCo-TiO 2复合催化剂，以与实施例2相同的方式进行热催化反应。控制烘箱内温度为130℃±10℃，连续反应18h。
以与实施例2相同的方式对反应后的气体进行气相色谱表征。计算得到氢含量为6863ppm，产生氢的单位催化剂活性约为10.77μmol g -1h -1。上述反应连续进行10次循环(180h)后，所述催化剂催化产生氢的催化活性未下降。
实施例6 产生氢气的光催化反应
使用的催化剂为实施例5中所述的RuCo-TiO 2复合催化剂。
在35mL容积的可密封承压玻璃管中加入0.2g RuCo-TiO 2复合催化剂和6mL超纯水，用Ar排尽管内空气，充入4bar Ar。玻璃管平放于玻璃棉上，使催化剂和水均匀平铺，使用可控电压的卤素灯从上方垂直照射。入射光强度为约1000W/m 2。热电偶被连接到玻璃管的下半部分以监测温度。控制玻璃管温度为50℃±10℃，连续光照18h以进行光催化反应。
光催化反应后，以与实施例2相同的方式对反应后的气体进行气相色谱表征，得到氢气含量为1848ppm。计算可得，产生氢气的单位催化剂活性约为2.901μmol g -1h -1。上述反应连续进行10个循环(180h)后，所述催化剂催化产生氢的催化活性未下降。
实施例2至实施例6的结果显示，本发明的方法能够在整体反应条件温和的情况下，例如在光辐射功率低于太阳光辐射功率的情况下，使用成本有效的催化剂高效地直接将易得的原料转化为氢气。
除非上下文中另外明确指出，本说明书和随附权利要求书中，单数形式“一个(a)”、“一个(an)”和“所述(the)”包括复数形式。除非另外定义，否则本文使用的所有技术和科学术语均具有本领域普通技术人员通常理解相同的含义。除所公开的特定顺序之外，本文所述的方法可以以逻辑上可能的任何顺序进行。
代表性实例旨在帮助说明本发明，并非意在也不应将其解释为限制本发明的范围。事实上，除了本文所示和所述的那些之外，对本领域技术人员而言，本发明的多种修改和其许多其他实施例将变得显而易见，包括实施例和本文引用的科学和专利文献参考。实施例包含可被本发明在其多种实施例和等效物中实践采用的重要的额外信息、例证和指导。

Claims (17)

  1. 一种通过能量辐射产生氢的方法，包括：
    使复合催化剂与至少一种含氢源相接触，并且
    能量辐射所述复合催化剂和所述含氢源，以产生氢分子，其中
    所述复合催化剂包含至少一种纳米基底结构和至少一种原子位点，所述原子位点包含Ru、Rh、Ag、Au、Pt、Pd、Os、Ir中的一种或两种以上化学元素，优选Ru和Au中的一种或两种。
  2. 如权利要求1所述的方法，其中
    所述原子位点还包含Mn、Co、Fe、Al、Cu、Ni、Zn、Ti、La中的一种或两种以上化学元素，优选包含Co、Fe、Mn中的一种或两种以上。
  3. 如权利要求1或2所述的方法，其中
    所述能量辐射选自光辐射和热辐射中的至少一种，优选为光辐射。
  4. 如权利要求1至3任一项所述的方法，其中
    所述纳米基底结构和所述原子位点之间的距离小于等于5nm，优选小于等于1nm，更优选小于0.1nm，最优选两者紧密接触。
  5. 如权利要求1至4任一项所述的方法，其中
    所述原子位点与所述纳米基底结构结合，例如以物理方式或化学方式结合。
  6. 如权利要求1至5任一项所述的方法，其中
    所述原子位点与所述纳米基底结构的质量百分比小于等于 50％，优选0.01％至30％，优选0.01％至5％，更优选0.1％至2％，最优选0.1％至1％。
  7. 如权利要求1至6任一项所述的方法，其中
    所述原子位点负载于所述纳米基底结构表面、内部孔道，或分布于所述纳米基底结构的内部晶格中，优选各原子位点均匀分布，并且
    各原子位点之间间隔0.2-500nm，优选1-50nm，更优选1-10nm。
  8. 如权利要求1至7任一项所述的方法，其中
    所述纳米基底结构选自由Mn、Co、Ce、Fe、Al、Ca、Ce、Cu、Ni、Ti、Zn、Si、Mo、Bi、V、C、N及其氧化物、氮化物、硫化物、碳化物、氢氧化物、氯化物以及金属有机框架(MOF)所组成的组，优选为金属有机框架、TiO 2、Al 2O 3或CeO 2。
  9. 如权利要求1至8任一项所述的方法，其中
    所述复合催化剂为Ru和Co负载或结合于TiO 2的催化剂、Ru负载或结合于Al 2O 3的催化剂、Au负载或结合于Al 2O 3的催化剂或Au负载或结合于CeO 2的催化剂。
  10. 如权利要求1至9任一项所述的方法，其中
    所述纳米基底结构的长、宽、高中的至少一个维度为约1nm至约1000nm，优选为约70nm至约1000nm，约100nm至约800nm，约200nm至约500nm。
  11. 如权利要求1至10任一项所述的方法，其中
    所述纳米基底结构各自独立地长、宽、高为约1nm至约3000nm，优选地，长为约100nm至约3000nm，约500nm至约2500nm，或约1000nm至约2000nm，并且/或者宽或高为约1nm至 约1000nm，约70nm至约1000nm，约100nm至约800nm，或约200nm至约500nm，或者
    所述纳米基底结构各自独立地具有约1至约20的长径比，优选约1至约10，或约2至约8的长径比。
  12. 如权利要求1至11任一项所述的方法，其中
    所述纳米基底结构的形状为球形、尖刺、薄片、针状、草叶、柱形、多面体、三维锥体、立方形、片状、半球形、不规则三维形状、多孔结构或其任意组合。
  13. 如权利要求1至12任一项所述的方法，其中
    多个所述原子位点在所述纳米基底结构上呈有图案地配置排列，优选地多层排列，或者
    多个所述原子位点随机分散在所述纳米基底结构中和/或表面。
  14. 如权利要求1至13任一项所述的方法，其中
    所述能量辐射使得反应在约20℃至约500℃之间的温度下进行，优选约50℃至约300℃、约70℃至约250℃、约90℃至约200℃、约100℃至约200℃、约100℃至约180℃、约110℃至约160℃、约120℃至约150℃、约130℃至约150℃。
  15. 如权利要求3至14任一项所述的方法，其中
    使用光辐射或热辐射引发反应，并使用光辐射或热辐射使得反应继续进行，其中
    所述光辐射的光辐射功率为200-1500W/m 2，优选为200-1000W/m 2，最优选为500-1000W/m 2。
  16. 如权利要求3至15任一项所述的方法，其中
    所述光辐射提高了所述复合催化剂和所述含氢源的温度，优 选为提高温度的唯一来源。
  17. 如权利要求1至16任一项所述的方法，其中
    所述含氢源选自由水、饱和醇、羧酸和酚类及其任意组合所组成的组，优选为水。
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