CN107790133B - Cobalt-iron-based photocatalyst and preparation and application thereof - Google Patents
Cobalt-iron-based photocatalyst and preparation and application thereof Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- FQMNUIZEFUVPNU-UHFFFAOYSA-N cobalt iron Chemical compound [Fe].[Co].[Co] FQMNUIZEFUVPNU-UHFFFAOYSA-N 0.000 title 1
- RIVZIMVWRDTIOQ-UHFFFAOYSA-N cobalt iron Chemical compound [Fe].[Co].[Co].[Co] RIVZIMVWRDTIOQ-UHFFFAOYSA-N 0.000 claims abstract description 48
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 40
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 37
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 37
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 20
- 230000009467 reduction Effects 0.000 claims abstract description 20
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 16
- 239000002135 nanosheet Substances 0.000 claims abstract description 12
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 34
- 239000000047 product Substances 0.000 claims description 26
- 239000000463 material Substances 0.000 claims description 22
- 239000007789 gas Substances 0.000 claims description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 15
- 229910052593 corundum Inorganic materials 0.000 claims description 15
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 15
- 239000000956 alloy Substances 0.000 claims description 13
- 229910045601 alloy Inorganic materials 0.000 claims description 13
- 229910003321 CoFe Inorganic materials 0.000 claims description 12
- 229910002451 CoOx Inorganic materials 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 9
- 239000004202 carbamide Substances 0.000 claims description 9
- 239000012043 crude product Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 9
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 8
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical group [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 8
- 239000012716 precipitator Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000002425 crystallisation Methods 0.000 claims description 7
- 230000008025 crystallization Effects 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 6
- 150000001868 cobalt Chemical class 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical group [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical group [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000005286 illumination Methods 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 150000002505 iron Chemical class 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- 230000001376 precipitating effect Effects 0.000 claims 1
- 229910021653 sulphate ion Inorganic materials 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 70
- 239000002243 precursor Substances 0.000 abstract description 27
- 229910052751 metal Inorganic materials 0.000 abstract description 16
- 229930195733 hydrocarbon Natural products 0.000 abstract description 15
- QVYYOKWPCQYKEY-UHFFFAOYSA-N [Fe].[Co] Chemical compound [Fe].[Co] QVYYOKWPCQYKEY-UHFFFAOYSA-N 0.000 abstract description 13
- 239000002105 nanoparticle Substances 0.000 abstract description 11
- 239000002184 metal Substances 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 10
- 229910052799 carbon Inorganic materials 0.000 abstract description 9
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 8
- 229910021645 metal ion Inorganic materials 0.000 abstract description 6
- -1 carbon hydrocarbon Chemical class 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 239000011943 nanocatalyst Substances 0.000 abstract description 4
- 239000002086 nanomaterial Substances 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract description 3
- 229910052742 iron Inorganic materials 0.000 abstract description 3
- 229910052782 aluminium Inorganic materials 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 description 24
- 239000000203 mixture Substances 0.000 description 17
- 238000001228 spectrum Methods 0.000 description 17
- 230000005540 biological transmission Effects 0.000 description 13
- 238000001000 micrograph Methods 0.000 description 13
- 150000002430 hydrocarbons Chemical class 0.000 description 12
- 229910020598 Co Fe Inorganic materials 0.000 description 11
- 229910002519 Co-Fe Inorganic materials 0.000 description 11
- 238000003917 TEM image Methods 0.000 description 10
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 8
- 229910015189 FeOx Inorganic materials 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000001276 controlling effect Effects 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 5
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 239000012495 reaction gas Substances 0.000 description 5
- 239000012266 salt solution Substances 0.000 description 5
- 238000004627 transmission electron microscopy Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910002515 CoAl Inorganic materials 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 3
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- 229910017061 Fe Co Inorganic materials 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003102 growth factor Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910052599 brucite Inorganic materials 0.000 description 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/12—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon dioxide with hydrogen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/50—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon dioxide with hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/74—Iron group metals
- C07C2523/75—Cobalt
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- Chemical Kinetics & Catalysis (AREA)
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- Oil, Petroleum & Natural Gas (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a cobalt-iron-based photocatalyst and preparation and application thereof. The ferrocobalt-based photocatalyst includes three metal elements of Co, Fe and Al, and nanoparticles containing one or two of the metal elements are uniformly and highly dispersed and supported on nanosheets containing the remaining metal elements. The cobalt-iron-based photocatalyst takes hydrotalcite as a rigid precursor, and can be induced to limit the domain through high temperature to form a high-dispersion cheap metal nano catalyst. Meanwhile, the overflow sequence of metal ions in the hydrotalcite can be controlled by controlling the reduction temperature, so that rich nano-structures can be further formed, and CO and CH can be prepared by hydrogenation of light-driven carbon dioxide4And high selectivity in high carbon hydrocarbon. The iron-cobalt-based photocatalyst has low preparation cost, simple and convenient operation and simple process, is easy for large-scale production, and is expected to replace the traditional thermal catalysis to be applied to the industrial application.
Description
Technical Field
The invention relates to the technical field of photocatalysis, in particular to a cobalt-iron-based photocatalyst and preparation and application thereof.
Background
With the increasing population and the accelerated global industrialization process, the demand for fossil fuels is increasing, which in turn leads to CO2The discharge amount of (a) becomes larger and larger. CO22Has caused serious greenhouse effect and global warming problems. Current CO suppression2The method of measuring comprises: CO22Capture and storage of CO2Direct chemical conversion of (2). And CO2The direct chemical conversion is undoubtedly a 'one-arrow double-carving' method, which can reduce CO in the atmosphere2In combination with CO2Converted to a useful chemical. At present, CO2Mainly concentrated on CO2The hydrogenation reaction is realized on Ni, Ru, Fe and Co based catalysts, and Ni, Co and Ru can only generate low-value methane due to the severe hydrogenation capability, so the catalyst is also called as a methanation catalyst. Fe can be used for generating higher hydrocarbons generally due to the catalytic reverse water gas change characteristic and good Fischer-Tropsch reaction activity. However, conventional CO2The hydrogenation reaction requires high temperature and high pressure, thereby undoubtedly accelerating the formation of carbon deposit and the deactivation of the catalyst caused by the sintering of the catalyst; and is extremely wasteful in terms of both energy and efficiency. Therefore, CO is driven under milder conditions2Hydrogenation has been the leading and challenging topic in catalysis and chemistry, and in recent years, solar energy has been used to drive CO instead of traditional thermal energy2The preparation of hydrocarbons by hydrogenation has proven to be a promising new approach to convert solar energy into chemical energy by means of solar photocatalytic technology, and has been considered as one of the best approaches to solve future renewable energy sources.
Hydrotalcite is a two-dimensional layered compound with a bulk layer structure similar to brucite Mg (OH)2The laminate is octahedral MO6The edges are shared, metal ions occupy the center of an octahedron, and the metal ions of the laminate are adjustable in composition and proportion, so that the laminate is widely applied. Meanwhile, hydrotalcite is used as a rigid precursor, and a high-dispersion cheap metal nano catalyst can be formed in an induced confinement mode through high temperature. Meanwhile, the overflow sequence of metal ions in the hydrotalcite can be controlled by controlling the reduction temperature, so that rich nano-structures can be further formed, and weak catalytic component-carrier interaction in the catalyst formed by the traditional impregnation method and the like can be avoided due to the in-situ formed catalyst. The abundant nanostructure is expected to have wide application prospect in the field of catalysis.
Disclosure of Invention
Based on the technical background, the invention provides a cobalt-iron-based photocatalyst and preparation and application thereof. The invention is based on the layered structure of hydrotalcite and the controllable proportion of the divalent and trivalent metal ions of the laminate, and can form a cobalt-iron-based photocatalyst by controlling the high-temperature in-situ reduction temperature, in particular three supported photocatalysts which are respectively FeOxFeO supported on CoAl mixed metal oxide nanosheetsx-CoOxSupported on amorphous Al2O3Nano-sized sheet, and CoFe alloy supported on amorphous Al2O3The three photocatalysts can respectively react CO on the nano-chip and are used for the photo-driven carbon dioxide hydrogenation reaction for the first time2High efficiency of converting into CO and CH4And high value-added hydrocarbon compounds.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a cobalt-iron-based photocatalyst, which comprises three metal elements of Co, Fe and Al, and is obtained by controlling the reduction temperature of a ternary metal CoFeAl-LDH nanosheet and accurately regulating and controlling the overflow sequence of the metals, wherein nanoparticles containing one or two metal elements are uniformly and highly dispersed and loaded on the nanosheet containing the remaining metal elements.
Preferably, the cobalt-iron based photocatalyst is: FeOxFeO supported on CoAl mixed metal oxide nanosheetsx-CoOxSupported on amorphous Al2O3Nano-scale or CoFe alloy supported on amorphous Al2O3And (4) nano-chips. In which FeO is presentxRepresents Fe2O3And Fe3O4One or a mixture thereof, CoOxRepresent CoO and Co3O4One or a mixture thereof.
The invention also provides a preparation method of the cobalt-iron-based photocatalyst, which comprises the following steps:
1) dissolving cobalt salt, iron salt and aluminum salt in deionized water, adding a precipitator, fully dissolving, and performing crystallization reflux for 12-36 hours at 50-120 ℃ to obtain a crude product;
2) washing, drying and grinding the crude product obtained in the step 1) to obtain a CoFeAl ternary hydrotalcite material;
3) heating the CoFeAl ternary hydrotalcite material obtained in the step 2) to 300-700 ℃ in a hydrogen-argon mixed gas, keeping the temperature for 2-5 h for reduction, and then cooling to room temperature in an inert protective gas atmosphere to obtain the cobalt-iron-based photocatalyst.
Preferably, the concentration of the cobalt salt is 0.005-0.1 mol.L-1(ii) a The concentration of the ferric salt is 0.05-0.002 mol.L-1(ii) a The concentration of the aluminum salt is 0.002-0.05 mol.L-1。
Preferably, the cobalt salt is cobalt nitrate, cobalt chloride or cobalt sulfate; the ferric salt is ferric nitrate, ferric chloride or ferric sulfate; the aluminum salt is aluminum nitrate, aluminum chloride or aluminum sulfate.
Preferably, the precipitator is urea, and the concentration of the urea after dissolution is 0.05-0.8 mol.L-1。
Preferably, the temperature rising rate in the step 3) is 2-5 ℃ min-1。
Preferably, the inert shielding gas is nitrogen.
Preferably, the reduction temperature is 650 ℃.
The third aspect of the invention also provides the application of the iron-cobalt-based photocatalyst in the light-driven carbon dioxide hydrogenation reaction.
Preferably, the above application specifically comprises the following steps: in a closed reactionAdding cobalt-iron base photocatalyst into the kettle, and introducing gas CO2,H2And Ar (internal standard gas) is subjected to ultraviolet visible light illumination, and the product is monitored. Wherein CO is2And H2Ar is internal standard gas used for gas chromatography quantitative product.
Preferably, the gas volume fraction ratio is CO2/H2And (3) introducing a gas to the closed reaction kettle under the pressure of 0.18MPa, wherein the Ar is 15/60/25.
Preferably, the adding amount of the cobalt-iron-based photocatalyst in a 50mL reaction kettle is 100 mg.
Preferably, the closed reaction kettle is a closed reaction kettle with a light-permeable top.
The invention has the advantages of
The cobalt-iron-based photocatalyst takes hydrotalcite as a rigid precursor, and can be induced to limit the domain through high temperature to form a high-dispersion cheap metal nano catalyst. Meanwhile, the overflow sequence of metal ions in the hydrotalcite can be controlled by controlling the reduction temperature, so that rich nano-structures can be further formed, and CO and CH can be prepared by hydrogenation of light-driven carbon dioxide4And high selectivity in high carbon hydrocarbon. Under the optimized catalyst preparation conditions, the selectivity of the high-carbon hydrocarbon can reach 35.26 percent. The invention realizes the preparation of the high value-added carbon hydrocarbon compound by carbon dioxide hydrogenation under the drive of light for the first time, and the iron-cobalt-based photocatalyst has low preparation cost, simple and convenient operation and simple process, is easy for large-scale production, and is expected to replace the traditional thermal catalysis to be applied to the aspect of industrial application.
Drawings
Fig. 1 shows XRD patterns of the cobalt-iron based photocatalysts and their precursors obtained in examples 1-5 of the present invention;
wherein curve a is the XRD spectrum of the Co2Fe1Al-LDH precursor obtained in examples 1-3; curve b represents the Co yield in example 41Fe1XRD spectrogram of the Al-LDH precursor; curve c represents the Co obtained in example 43Fe1XRD spectrogram of the Al-LDH precursor; curve d is the XRD spectrum of the coferro-based photocatalyst (Co2Fe1-300) obtained in example 1; curve e shows the ferrocobalt photocatalysis obtained in example 2XRD spectrum of agent (Co2Fe 1-550); curve f is the XRD spectrum of the coferro-based photocatalyst (Co2Fe1-650) obtained in example 3; curve g shows the ferrocobalt-based photocatalyst (Co) obtained in example 41Fe1-650) XRD spectrum; curve h shows the ferrocobalt-based photocatalyst (Co) obtained in example 53Fe1-650) XRD spectrum.
FIG. 2 shows a transmission electron microscope image of a CoFeAl-LDH precursor obtained in the example of the invention;
wherein a is Co obtained in example 12Fe1Transmission electron micrograph of Al-LDH precursor; b is Co obtained in example 41Fe1Transmission electron micrograph of Al-LDH precursor; c is Co obtained in example 53Fe1Transmission electron micrograph of Al-LDH precursor.
FIG. 3 shows a cobalt-iron based photocatalyst (Co) obtained in example 1 of the present invention2Fe1-300) transmission electron microscopy;
wherein a is a low-resolution transmission electron microscope image, and b and c are high-resolution transmission electron microscope images of zone1 and zone2 in a respectively.
FIG. 4 shows the cobalt-iron based photocatalyst (Co) obtained in example 2 of the present invention2Fe1-550) transmission electron microscopy;
wherein a is a low-resolution transmission electron microscope image, and b is a high-resolution transmission electron microscope image.
FIG. 5 shows the cobalt-iron based photocatalyst (Co) obtained in example 3 of the present invention2Fe1-650) transmission electron microscopy;
wherein a is a low-resolution transmission electron microscope image, and b is a high-resolution transmission electron microscope image.
FIG. 6 shows the cobalt-iron based photocatalyst (Co) obtained in example 4 of the present invention1Fe1-650) transmission electron microscopy;
wherein a is a low-resolution transmission electron microscope image, and b is a high-resolution transmission electron microscope image.
FIG. 7 shows a cobalt-iron based photocatalyst (Co) obtained in example 5 of the present invention3Fe1-700) transmission electron micrographs;
wherein a is a low-resolution transmission electron microscope image, and b is a high-resolution transmission electron microscope image.
FIG. 8 shows the reduced Co-Fe-based photocatalyst Co of example 3 of the present invention2Fe1-650 catalyst light driven CO2The hydroconversion capacity and the product selectivity as a function of time.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below with reference to preferred embodiments and the accompanying drawings. Similar parts in the figures are denoted by the same reference numerals. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
Example 1
A preparation method of a cobalt-iron-based photocatalyst and application of the cobalt-iron-based photocatalyst in a light-driven carbon dioxide hydrogenation reaction comprise the following steps:
1) preparing mixed metal salt solution: dissolving 0.01mol of cobalt nitrate, 0.005mol of ferric nitrate and 0.005mol of aluminum nitrate in 100mL of deionized water, adding 0.06mol of precipitator urea, fully dissolving, transferring to a 200mL three-neck flask, carrying out oil bath at 110 ℃, and carrying out crystallization reflux for 24 h.
2) Washing, drying and grinding the crude product obtained in the step 1) to obtain a CoFeAl ternary hydrotalcite material, and recording the CoFeAl ternary hydrotalcite material as Co2Fe1Al-LDH。
3) CoFeAl ternary hydrotalcite (Co) obtained in step 2)2Fe1Al-LDH) material in 10% (volume fraction) hydrogen-argon mixture at 5 deg.C/min-1Heating to 300 ℃ at a heating rate, keeping the temperature for 5 hours, switching to a nitrogen atmosphere after the heating is finished, and naturally cooling to room temperature to obtain the cobalt-iron based photocatalyst which is marked as Co2Fe1-300。
4) Co prepared according to the above method2Fe1-300 is applied to the light-driven carbon dioxide hydrogenation reaction, 100mg of Fe-Co based photocatalyst is added into a light-permeable closed reaction kettle (50mL), and reaction gas (CO) is filled in the reaction kettle2/H215/60/25, v/v) to 0.18MPa, ultraviolet and visible light illumination, and detecting the change of the product with time by gas chromatographyThe catalytic activity and the selectivity of each product are determined.
Curve a in fig. 1 is Co2Fe1XRD spectrum of Al-LDH precursor, curve d is Co-Fe-based photocatalyst after reduction in example 12Fe1-300 XRD spectrum. FIG. 2, panel a shows Co obtained in example 12Fe1Transmission electron microscope picture of Al-LDH precursor, wherein a in figure 3 is cobalt-iron-based photocatalyst Co reduced in example 12Fe1300, B and c in FIG. 3 are reduced Co-Fe-based photocatalyst Co in example 12Fe1-300 high resolution transmission electron microscopy images. TABLE 1-I is Co in example 12Fe1-300 catalyst in light driven CO2Performance in hydrogenation reactions.
From the curve a in FIG. 1, the hydrotalcite Co precursor synthesized under these conditions2Fe1Al-LDH can form a perfect hydrotalcite structure, and characteristic peaks of (003), (006) and (009) are obvious. As can be seen from FIG. 2, the synthesized precursor hydrotalcite is composed of nanosheets of about 100nm, and the thickness thereof is about 7 nm. After the hydrotalcite is reduced in hydrogen-argon mixed gas at 300 ℃, the hydrotalcite structure is subjected to topological transformation and is changed into FeOx,CoOxAnd Al2O3(amorphous state) composite metal oxide. As can be further seen from the transmission electron microscope image and the high resolution transmission electron microscope image of FIG. 3, FeO is presentxThe nano particles are uniformly dispersed on the CoAl mixed metal oxide nano sheets. The catalyst is directly applied to light-driven CO2In the hydrogenation, as can be seen from Table 1-I, after two hours of light irradiation, CO2The conversion of (a) was 6.1% and the product was essentially all CO. In this process, FeO is preferentially overflowed during the reductionxThe species being CO2The hydrogenation process produces active species of CO so no carbon hydrocarbons are produced. It is understood from the above that the catalyst can efficiently convert CO2The light is driven to convert into value added product CO, and the CO is further used for other reactions, such as Fischer-Tropsch synthesis.
Example 2
A preparation method of an iron-cobalt-based photocatalyst and application of the iron-cobalt-based photocatalyst in light-driven carbon dioxide hydrogenation reaction comprise the following steps:
1) preparing mixed metal salt solution: 0.01mol of cobalt nitrate hexahydrate, 0.005mol of ferric nitrate nonahydrate and 0.005mol of aluminum nitrate nonahydrate are dissolved in 100mL of deionized water, 0.06mol of precipitator urea is added, the mixture is fully dissolved and transferred into a 200mL three-neck flask, and the mixture is subjected to oil bath at 110 ℃ and crystallization reflux for 24 hours.
2) Washing, drying and grinding the crude product obtained in the step 1) to obtain a CoFeAl ternary hydrotalcite material, and recording the CoFeAl ternary hydrotalcite material as Co2Fe1Al-LDH。
3) The CoFeAl ternary hydrotalcite material (Co) obtained in the step 2)2Fe1Al-LDH) in a 10% (volume fraction) hydrogen-argon mixture at 5 ℃ min-1Heating to 550 ℃ at the heating rate, keeping the temperature for 5 hours, switching to a nitrogen atmosphere after the heating is finished, and naturally cooling to room temperature to obtain the cobalt-iron based photocatalyst which is marked as Co2Fe1-550。
4) Co prepared according to the above method2Fe1-550 is applied to the light-driven carbon dioxide hydrogenation reaction, 100mg of iron-cobalt-based photocatalyst is added into a light-permeable closed reaction kettle (50mL), and reaction gas (CO) is filled in the reaction kettle2/H215/60/25, v/v) to 0.18MPa, and detecting the change of the products with time by gas chromatography to determine the selectivity of each product of the catalyst reaction activity.
Curve a in FIG. 1 shows Co obtained in example 22Fe1XRD spectrum of Al-LDH precursor, curve e is Co-Fe-based photocatalyst after reduction in example 22Fe1-XRD spectrum of 550. FIG. 2, panel a shows Co obtained in example 22Fe1Transmission electron microscope picture of Al-LDH precursor, wherein a in figure 4 is cobalt-iron-based photocatalyst Co reduced in example 22Fe1300 in the sample, and b in FIG. 4 is the Co-Fe-based photocatalyst after reduction in example 22Fe1-300 high resolution transmission electron microscopy images. TABLE 1-II is Co in example 22Fe1-300 catalyst in light driven CO2Performance in hydrogenation reactions.
From curve e in fig. 1, it can be seen thatAfter reduction at 550 ℃ in a hydrogen-argon mixed gas, the hydrotalcite structure undergoes topological transformation and becomes FeOx,CoOxAnd Al2O3(amorphous state) composite metal oxide. Further as can be seen from the transmission electron micrograph and the high-resolution transmission electron micrograph of FIG. 4, the comparison is made with Co in example 12Fe1-300,Co2Fe1Co species in-550 further overflow from the hydrotalcite laminate to finally form FeOx,CoOxThe bimetallic oxide is uniformly dispersed in amorphous Al2O3And (4) nano-chips. TABLE 1-II shows the use of CoFe-550 catalyst in light-driven CO of example 22Performance in hydrogenation reactions. It can be seen that after two hours of light exposure, CO2The conversion of (3) was 68.2%, the selectivity of CO in the product was 6.42%, CH4The selectivity of (A) is as high as 90.89%, and the selectivity of the higher hydrocarbon is only 2.69%. The reactivity is due to CoOxAnd FeOxSpecies in CO2Parallel relationship in hydrogenation, and CO2Is more preferred to the CoOxMethane is formed on the surface. It is thus understood that under this reduction condition, CO is driven by light2Hydrogenation can be carried out to methane with high efficiency and high selectivity.
Example 3
A preparation method of an iron-cobalt-based photocatalyst and application of the iron-cobalt-based photocatalyst in light-driven carbon dioxide hydrogenation reaction comprise the following steps:
1) preparing mixed metal salt solution: dissolving 0.01mol of cobalt nitrate, 0.005mol of ferric nitrate and 0.005mol of aluminum nitrate in 100mL of deionized water, adding 0.06mol of precipitator urea, fully dissolving, transferring to a 200mL three-neck flask, carrying out oil bath at 110 ℃, and carrying out crystallization reflux for 24 h.
2) Washing, drying and grinding the crude product obtained in the step 1) to obtain a CoFeAl ternary hydrotalcite material, and recording the CoFeAl ternary hydrotalcite material as Co2Fe1Al-LDH。
3) The CoFeAl ternary hydrotalcite material (Co) obtained in the step 2)2Fe1Al-LDH) in a 10% (volume fraction) hydrogen-argon mixture at 5 ℃ min-1The temperature is raised to 650 ℃ at the heating rate, the temperature is kept for 5 hours, the nitrogen atmosphere is switched after the temperature is raised, the temperature is naturally reduced to the room temperature,obtaining the cobalt-iron base photocatalyst marked as Co2Fe1-650。
4) The cobalt-iron-based photocatalyst Co prepared by the method2Fe1-650 application in light-driven carbon dioxide hydrogenation, adding 100mg of Fe-Co based photocatalyst into a light-permeable closed reaction kettle (50mL), and filling reaction gas (CO)2/H215/60/25, v/v) to 0.18MPa, and detecting the change of the products with time by gas chromatography to determine the selectivity of each product of the catalyst reaction activity.
Curve a in FIG. 1 shows Co obtained in example 32Fe1XRD spectrum of Al-LDH precursor, curve f is Co-Fe-based photocatalyst after reduction in example 32Fe1-XRD spectrum of 650. In FIG. 5, a is the reduced Co-Fe-based photocatalyst Co in example 32Fe1Low resolution transmission electron micrograph of 650, b in FIG. 5 is Co photocatalyst Co reduced in example 32Fe1-650 high resolution transmission electron microscopy. FIG. 8 shows the reduced Co-Fe-based photocatalyst Co of example 32Fe1-650 catalyst light driven CO2The hydroconversion capacity and the product selectivity as a function of time.
As can be seen from the curve f in FIG. 1, the precursor hydrotalcite material Co2Fe1The Al-LDH is reduced at 650 ℃ to become a CoFe alloy and amorphous Al2O3A mixture of (a). As shown in FIG. 5, the reduced cobalt-iron-based photocatalyst at the temperature is formed by loading CoFe alloy nanoparticles on amorphous Al2O3On the nano-sheet, the size of the nano-particles is about 30 nm. The catalyst can be used for preparing CO under full-spectrum irradiation along with the prolonging of illumination time2The conversion of (a) is gradually increased, and C2+The selectivity of (A) can be maintained at a high level. As shown in tables 1 to III, it can be seen that CO was present after two hours of light irradiation2Has a conversion of 78.6%, a CO selectivity of 4.97% in the product, CH4The selectivity of (A) is 59.77%, the selectivity of the high-carbon hydrocarbon can be as high as 35.26%, and the growth factor of the carbon chain in the high-carbon hydrocarbon is 0.345. It can be seen that in thisCoFe-650 catalyst obtained by reduction at temperature, CoFe alloy as catalytic active center, and CO can be extracted2High efficiency conversion into high value-added hydrocarbon compounds. Compared with the traditional thermal catalysis, the process can convert CO by utilizing clean solar energy2Is a high value-added product, and the process is energy-saving and environment-friendly.
Example 4
A preparation method of an iron-cobalt-based photocatalyst and application of the iron-cobalt-based photocatalyst in light-driven carbon dioxide hydrogenation reaction comprise the following steps:
1) preparing mixed metal salt solution: dissolving 0.0075mol of cobalt chloride, 0.0075mol of ferric chloride and 0.005mol of aluminum chloride in 100mL of deionized water, adding 0.06mol of precipitator urea, fully dissolving, transferring into a 200mL three-neck flask, carrying out oil bath at 110 ℃, and carrying out crystallization reflux for 24 hours.
2) Washing, drying and grinding the crude product obtained in the step 1) to obtain a CoFeAl ternary hydrotalcite material, and recording the CoFeAl ternary hydrotalcite material as Co1Fe1Al-LDH。
3) The CoFeAl ternary hydrotalcite material (Co) obtained in the step 2)1Fe1Al-LDH) in a 10% (volume fraction) hydrogen-argon mixture at 5 ℃ min-1The temperature rise rate is increased to 650 ℃, the temperature is kept for 5 hours, the mixture is switched to nitrogen atmosphere after the temperature rise is finished, and the mixture is naturally cooled to room temperature, thus obtaining the cobalt-iron based photocatalyst which is marked as Co1Fe1-650。
4) The cobalt-iron based photocatalyst prepared by the method is applied to the light-driven carbon dioxide hydrogenation reaction, 100mg of the cobalt-iron based photocatalyst is added into a light-permeable closed reaction kettle (50mL), and reaction gas (CO) is filled in the reaction kettle2/H215/60/25, v/v) to 0.18MPa, and detecting the change of the products with time by gas chromatography to determine the selectivity of each product of the catalyst reaction activity.
Curve b in FIG. 1 is that of example 41Fe1XRD spectrum of Al-LDH precursor, curve g is Co-Fe-based photocatalyst after reduction in example 41Fe1-XRD spectrum of 650. FIG. 2 b shows Co in example 41Fe1Transmission electron micrograph of Al-LDH precursor. In FIG. 6, a is an implementationReduced ferrocobalt photocatalyst Co of example 41Fe1Low resolution transmission electron micrograph of 650, b in FIG. 6 is Co photocatalyst Co reduced in example 41Fe1-650 high resolution transmission electron microscopy.
As can be seen from curve b in fig. 1, pure hydrotalcite can still be synthesized by changing the ratio of the precursor salt (Co/Fe-1/1). From the b diagram in fig. 2, the synthesized hydrotalcite presents a nanosheet shape. As can be seen from the g curve in FIG. 1, the precursor hydrotalcite material is reduced at 650 ℃ and then becomes CoFe alloy and amorphous Al2O3A mixture of (a). As shown in FIG. 6, the reduced cobalt-iron-based photocatalyst at the temperature is CoFe alloy nanoparticles loaded on amorphous Al2O3On the nano-sheet, the size of the nano-particles is about 60nm compared with Co2Fe1650, the alloy nanoparticles are enlarged. As shown in tables 1 to IV, it can be seen that CO was present after two hours of light irradiation2Has a conversion of 67.3%, a CO selectivity of 16.97% in the product, CH4Has a selectivity of 60.61%, and is a higher hydrocarbon C2+Only 22.44%. Compared with Co2Fe1-650 catalyst in Co1Fe1The catalytic activity of-650 decreases due to Co at this ratio1Fe1Co obtained by Al-LDH reduction1Fe1The size of-650 is enlarged. However, despite the reduced selectivity of high value-added products, the process utilizes clean solar energy to convert CO, as compared to conventional thermocatalysis2Is a high value-added product, and the process is energy-saving and environment-friendly.
Example 5
A preparation method of an iron-cobalt-based photocatalyst and application of the iron-cobalt-based photocatalyst in light-driven carbon dioxide hydrogenation reaction comprise the following steps:
1) preparing mixed metal salt solution: 0.01125mol of cobalt chloride, 0.00375mol of ferric chloride and 0.005mol of aluminum chloride are dissolved in 100mL of deionized water, then 0.06mol of precipitator urea is added and fully dissolved, the solution is transferred into a 200mL three-neck flask, oil bath is carried out at 110 ℃, and crystallization reflux is carried out for 24 h.
2) Crude product obtained in the step 1)Washing, drying and grinding the materials to obtain a CoFeAl ternary hydrotalcite material, which is marked as Co3Fe1Al-LDH。
3) The CoFeAl ternary hydrotalcite material (Co) obtained in the step 2)3Fe1Al-LDH) in a 10% (volume fraction) hydrogen-argon mixture at 5 ℃ min-1The temperature rise rate is increased to 650 ℃, the temperature is kept for 5 hours, the mixture is switched to nitrogen atmosphere after the temperature rise is finished, and the mixture is naturally cooled to room temperature, thus obtaining the cobalt-iron based photocatalyst which is marked as Co3Fe1-650。
4) The cobalt-iron based photocatalyst prepared by the method is applied to the light-driven carbon dioxide hydrogenation reaction, 100mg of the cobalt-iron based photocatalyst is added into a light-permeable closed reaction kettle (50mL), and reaction gas (CO) is filled in the reaction kettle2/H215/60/25, v/v) to 0.18MPa, and detecting the change of the products with time by gas chromatography to determine the selectivity of each product of the catalyst reaction activity.
Curve c in FIG. 1 is that of example 53Fe1XRD spectrum of Al-LDH precursor, curve h is Co-Fe-based photocatalyst after reduction in example 53Fe1-XRD spectrum of 650. FIG. 2 c shows Co in example 53Fe1Transmission electron micrograph of Al-LDH precursor. In FIG. 7, a is the reduced Co-Fe-based photocatalyst Co in example 53Fe1Low resolution transmission electron micrograph of 650, b in FIG. 7 is Co photocatalyst Co reduced in example 53Fe1-650 high resolution transmission electron microscopy.
As can be seen from curve c in fig. 1, pure hydrotalcite can still be synthesized by changing the ratio of the precursor salt (Co/Fe-3/1). From the c diagram in fig. 2, the synthesized hydrotalcite shows the shape of the nanosheet. As can be seen from the h curve in FIG. 1, the precursor hydrotalcite material is reduced at 650 ℃ and then becomes CoFe alloy and amorphous Al2O3But diffraction peaks of a part of elemental Co appeared. As shown in FIG. 7, the reduced ferrocobalt photocatalyst at the temperature is formed by mixing CoFe alloy nanoparticles and simple substance Co loaded on amorphous Al2O3And (4) nano-chips. From tables 1-VAs shown, it can be seen that after two hours of light irradiation, CO2Has a conversion of 82.3%, a CO selectivity of 4.83% in the product, CH4Has a selectivity of 81.30%, and a higher hydrocarbon C2+Only 13.87%. Compared with Co2Fe1-650 catalyst in Co3Fe1The catalytic activity of-650 increased, but the selectivity for higher hydrocarbons was only 13.87%. This is because of Co at this ratio3Fe1The nano particles obtained by Al-LDH reduction are a mixture of CoFe alloy and simple substance Co, CO2Is preferentially catalytically converted to CH on Co particles4And only part of CO2Converted to higher hydrocarbons on the CoFe alloy active center. In summary, the process utilizes clean solar energy for the conversion of CO, as compared to conventional thermocatalysis2Is a high value-added product, and the process is energy-saving and environment-friendly.
In conclusion, CoFeAl-LDH can be converted into nano-catalysts with different special structures by a simple reduction method, and the different cobalt-iron-based catalysts can drive CO under light2Different product selectivities are exhibited in the hydrogenation. Then CO can be mixed2High efficiency of converting into CO and CH4And can realize CO2And converted into high value-added hydrocarbon compounds. Compared with the prior art system, namely the traditional thermal driving, the invention adopts the light to drive the CO2Hydrogenation conversion is more environment-friendly and energy-saving than the prior art system, and light-driven CO is realized for the first time2Hydrogenated to higher carbon hydrocarbons. The invention is expected to be industrially amplified and practically applied.
TABLE 1 iron cobalt based photocatalysts in light driven CO2Performance in hydrogenation reactions
And (4) surface note:
[a] a carbon chain growth factor;
[b] the percentage of higher hydrocarbons in the hydrocarbon compound.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.
Claims (11)
1. The application of a cobalt-iron-based photocatalyst in a photo-driven carbon dioxide hydrogenation reaction is characterized in that the cobalt-iron-based photocatalyst is as follows: FeOx-CoOxSupported on amorphous Al2O3Nano-scale or CoFe alloy supported on amorphous Al2O3Nano-sheets;
the application method specifically comprises the following steps: adding cobalt-iron base photocatalyst into a closed reaction kettle, and introducing gas CO2,H2And Ar is subjected to ultraviolet and visible light illumination, and the product is monitored.
2. Use according to claim 1, wherein the preparation of the ferrocobalt-based photocatalyst comprises the following steps:
1) dissolving cobalt salt, iron salt and aluminum salt in deionized water, adding a precipitator, fully dissolving, and performing crystallization reflux for 12-36 hours at 50-120 ℃ to obtain a crude product;
2) washing, drying and grinding the crude product obtained in the step 1) to obtain a CoFeAl ternary hydrotalcite material;
3) heating the CoFeAl ternary hydrotalcite material obtained in the step 2) to the temperature of 300-700 ℃ in a hydrogen-argon mixed gas, keeping for 2-5 h for reduction, and then cooling to room temperature in an inert protective gas atmosphere to obtain the cobalt-iron-based photocatalyst.
3. Use according to claim 2, wherein the cobalt salt is present in a concentration of 0.005 to 0.1 mol-L-1(ii) a The concentration of the ferric salt is 0.002-0.05 mol.L-1(ii) a The concentration of the aluminum salt is 0.002-0.05 mol.L-1。
4. Use according to claim 2, wherein the cobalt salt is cobalt nitrate, chloride or sulphate; the ferric salt is ferric nitrate, ferric chloride or ferric sulfate; the aluminum salt is aluminum nitrate, aluminum chloride or aluminum sulfate.
5. The use according to claim 2, wherein the precipitating agent is urea, and the concentration of the urea after dissolution is 0.05-0.8 mol-L-1。
6. The use according to claim 2, wherein the rate of temperature increase in step 3) is 2 to 5 ℃/min-1。
7. Use according to claim 2, wherein the inert protective gas is nitrogen.
8. Use according to claim 2, wherein the reduction temperature is 650 ℃.
9. Use according to claim 1, wherein the gas has a volume fraction ratio of CO2/H2and/Ar =15/60/25, and introducing gas until the pressure of the closed reaction kettle is 0.18 MPa.
10. The use according to claim 1, wherein the amount of the cobalt-iron based photocatalyst added to a 50mL reactor is 100 mg.
11. The use of claim 1, wherein the closed reaction vessel is a closed reaction vessel having a light-permeable top.
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