CN107790133A - 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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- CN107790133A CN107790133A CN201711083424.9A CN201711083424A CN107790133A CN 107790133 A CN107790133 A CN 107790133A CN 201711083424 A CN201711083424 A CN 201711083424A CN 107790133 A CN107790133 A CN 107790133A
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- cobalt
- ferro
- based photocatalyst
- cobalt based
- iron
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title abstract description 13
- FQMNUIZEFUVPNU-UHFFFAOYSA-N cobalt iron Chemical compound [Fe].[Co].[Co] FQMNUIZEFUVPNU-UHFFFAOYSA-N 0.000 title 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 64
- RIVZIMVWRDTIOQ-UHFFFAOYSA-N cobalt iron Chemical compound [Fe].[Co].[Co].[Co] RIVZIMVWRDTIOQ-UHFFFAOYSA-N 0.000 claims abstract description 61
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 39
- 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 33
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 30
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 30
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 15
- QVYYOKWPCQYKEY-UHFFFAOYSA-N [Fe].[Co] Chemical compound [Fe].[Co] QVYYOKWPCQYKEY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 230000009467 reduction Effects 0.000 claims abstract description 13
- 239000002105 nanoparticle Substances 0.000 claims abstract description 10
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 4
- 239000006185 dispersion Substances 0.000 claims abstract description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 61
- 239000003054 catalyst Substances 0.000 claims description 38
- 239000000047 product Substances 0.000 claims description 27
- 230000003287 optical effect Effects 0.000 claims description 26
- 239000000463 material Substances 0.000 claims description 17
- 239000007789 gas Substances 0.000 claims description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 14
- 229910052593 corundum Inorganic materials 0.000 claims description 14
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 14
- 239000000956 alloy Substances 0.000 claims description 13
- 229910045601 alloy Inorganic materials 0.000 claims description 13
- 238000005286 illumination Methods 0.000 claims description 13
- 229910003321 CoFe Inorganic materials 0.000 claims description 12
- 229910002451 CoOx Inorganic materials 0.000 claims description 9
- 239000003153 chemical reaction reagent Substances 0.000 claims description 9
- 239000012043 crude product Substances 0.000 claims description 9
- 230000001376 precipitating effect Effects 0.000 claims description 9
- 229910015189 FeOx Inorganic materials 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- 239000004202 carbamide Substances 0.000 claims description 7
- 238000002425 crystallisation Methods 0.000 claims description 7
- 230000008025 crystallization Effects 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 159000000013 aluminium salts Chemical class 0.000 claims description 6
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- 150000001868 cobalt Chemical class 0.000 claims description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229910002515 CoAl Inorganic materials 0.000 claims description 4
- 239000003245 coal Substances 0.000 claims description 4
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 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
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 4
- 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 4
- 229910003455 mixed metal oxide Inorganic materials 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 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
- 239000012298 atmosphere Substances 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical group O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 1
- 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 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims 1
- 229910017604 nitric acid Inorganic materials 0.000 claims 1
- 238000009738 saturating Methods 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 abstract description 20
- 229930195733 hydrocarbon Natural products 0.000 abstract description 16
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 15
- -1 carbon hydrocarbon Chemical class 0.000 abstract description 11
- 230000008569 process Effects 0.000 abstract description 9
- 229910021645 metal ion Inorganic materials 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 4
- 239000002243 precursor Substances 0.000 abstract description 4
- 239000011943 nanocatalyst Substances 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 239000002086 nanomaterial Substances 0.000 abstract 1
- 239000002135 nanosheet Substances 0.000 abstract 1
- 230000005540 biological transmission Effects 0.000 description 28
- 238000002441 X-ray diffraction Methods 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 238000002834 transmittance Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000012495 reaction gas Substances 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 239000012266 salt solution Substances 0.000 description 5
- 239000003643 water by type Substances 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000004134 energy conservation Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 150000002823 nitrates Chemical class 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical class [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 2
- 239000003102 growth factor Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000002905 metal composite material Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 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 description 1
- 208000000058 Anaplasia Diseases 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 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
- 238000010276 construction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 230000003993 interaction Effects 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
- MVZXTUSAYBWAAM-UHFFFAOYSA-N iron;sulfuric acid Chemical compound [Fe].OS(O)(=O)=O MVZXTUSAYBWAAM-UHFFFAOYSA-N 0.000 description 1
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical class O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Classifications
-
- 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
- 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
- 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 & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- 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 present invention relates to photocatalysis technology field, more particularly to a kind of ferro-cobalt based photocatalyst and its preparation and application.
Background technology
It is increasing to the demand of fossil fuel with the increase of population and the quickening of global industry process, and then lead
Cause CO2Discharge capacity it is increasing.CO2A large amount of discharges had resulted in serious greenhouse effects and global warming issue.At present
Suppress CO2The method of amount includes：CO2Trapping close storage, CO2Direct chemical conversion.And CO2Direct chemical conversion undoubtedly
It is the method for a kind of " double gain ", CO in air can be reduced2Content, while can also be CO2It is converted into available chemistry
Product.CO at present2Conversion, be concentrated mainly on CO2Hydrogenation, is what is realized on Ni, Ru, Fe, Co base catalyst, Ni, Co and
Ru can be only generated low value methane due to its serious hydrogenation capability, so also referred to as methanation catalyst.Fe has due to it
Coal gas variation characteristic and good fischer-tropsch reaction are active against the current for catalysis, so may generally serve to realize the generation of advanced carbon hydrocarbon.
But traditional CO2Hydrogenation is required to HTHP, and thus undoubtedly accelerating the formation of carbon distribution and sintering of catalyst causes
The inactivation of catalyst；All extremely wasted from energy and efficiency simultaneously.So compared with driving CO under temperate condition2Hydrogenation
Reaction, it is catalysis and the problem of chemical field forefront and great challenge all the time, in recent years, tradition is substituted using solar energy
Heat energy drive CO2Hydrogenation has proven to very promising new approaches for hydro carbons and utilizes solar energy photocatalytic technology
Chemical energy is converted solar energy into, one of optimal path for having been considered as solving following regenerative resource.
Hydrotalcite is a kind of two-dimensional layer compound, and its main layer board structure is similar to shepardite Mg (OH)2, laminate eight
Face body MO6Seamed edge, metal ion occupy octahedra center altogether, and because the metal ion composition of laminate is adjustable, ratio is adjustable, assigns
It is widely applied.Simultaneously using hydrotalcite as rigid presoma, by high temperature, the cheap gold that confinement forms high dispersive can induce
Belong to nanocatalyst.It can control the spilling order of metal ion in hydrotalcite by controlling reduction temperature, further may be used simultaneously
Abundant nanostructured is formed, due to the catalyst being formed in situ, traditional infusion process etc. can be avoided to be formed weak in catalyst
Catalyst component-carrier interaction.The abundant nanostructured is expected to have wide practical use in catalytic field.
The content of the invention
Based on above technical background, the present invention provides a kind of ferro-cobalt based photocatalyst and its preparation and application.Base of the present invention
In the layer structure and laminate divalence of hydrotalcite and the ratio Modulatory character of trivalent metal ion, by controlling high-temp in-situ to reduce
Temperature, a kind of ferro-cobalt based photocatalyst, specially three kinds of loaded photocatalysts, respectively FeO can be formedxIt is carried on CoAl
In mixed-metal oxides nanometer sheet, FeOx-CoOxIt is carried on unformed Al2O3In nanometer sheet, and CoFe alloy is carried on without fixed
Type Al2O3In nanometer sheet, and optical drive carbon dioxide hydrogenation is used it for first, three kinds of photochemical catalysts can be respectively by CO2It is high
Effect is converted into CO, CH4With high added value carbon hydrocarbon compound.
To achieve the above object, the present invention uses following technical proposals：
One aspect of the invention provides a kind of ferro-cobalt based photocatalyst, including tri- kinds of metallic elements of Co, Fe and Al, passes through control
The reduction temperature of ternary metal CoFeAl-LDH nanometer sheets processed, the spilling order of accuracy controlling metal, obtains, includes one of which
Or the uniform high-dispersion load of nano particle of two kinds of metallic elements is in the nanometer sheet for including residual metallic element.
Preferably, the ferro-cobalt based photocatalyst is：FeOxIt is carried in CoAl mixed-metal oxides nanometer sheets, FeOx-
CoOxIt is carried on unformed Al2O3In nanometer sheet, or CoFe alloy is carried on unformed Al2O3In nanometer sheet.Wherein FeOxRepresent
Fe2O3And Fe3O4One of which or mixture, CoOxRepresent CoO and Co3O4One of which or mixture.
Another aspect of the invention also provides the preparation method of above-mentioned ferro-cobalt based photocatalyst, comprises the following steps：
1) cobalt salt, molysite and aluminium salt are dissolved in deionized water, precipitating reagent are added, fully after dissolving, at 50~120 DEG C
Under the conditions of crystallization flow back 12~36h, obtain crude product；
2) crude product for obtaining step 1) is washed, dried, after grinding, that is, obtains CoFeAl ternary hydrotalcite materials；
3) the CoFeAl ternary hydrotalcite materials that step 2) obtains are warming up to 300-700 DEG C in hydrogen-argon-mixed, protected
Hold 2~5h to be reduced, be down to room temperature in inertia protects gas atmosphere afterwards, that is, obtain ferro-cobalt based photocatalyst.
Preferably, the concentration of the cobalt salt is 0.005~0.1molL-1；The concentration of the molysite be 0.05~
0.002mol·L-1；The aluminium salt concentration is 0.002~0.05molL-1。
Preferably, the cobalt salt is cobalt nitrate, cobalt chloride or cobaltous sulfate；The molysite is ferric nitrate, iron chloride or sulfuric acid
Iron；The aluminium salt is aluminum nitrate, aluminium chloride or aluminum sulfate.
Preferably, the precipitating reagent is urea, and concentration is 0.05~0.8molL after dissolving-1。
Preferably, the speed of heating is 2~5 DEG C of min in step 3)-1。
Preferably, the inertia protection gas is nitrogen.
Preferably, the reduction temperature is 650 DEG C.
Third aspect of the present invention also provides above-mentioned iron cobalt-based photochemical catalyst in optical drive carbon dioxide hydrogenation reaction
Using.
Preferably, above-mentioned application specifically includes following steps：Ferro-cobalt based photocatalyst is added in closed reactor, is passed through
Gas CO2, H2, and Ar (internal standard gas) progress ultraviolet-visible illumination, monitor product.Wherein CO2And H2For reaction gas, Ar is
Internal standard gas, used for gas-chromatography quantitative amount of product.
Preferably, the gas volume fraction ratio is CO2/H2/ Ar=15/60/25, gas is passed through to closed reactor
Pressure is 0.18MPa.
Preferably, addition of the ferro-cobalt based photocatalyst in 50mL reactors is 100mg.
Preferably, the closed reactor is the closed reactor of top light-permeable.
Beneficial effects of the present invention
The ferro-cobalt based photocatalyst of the present invention can induce confinement using hydrotalcite as rigid presoma, by high temperature and form high score
Scattered cheap metal nanocatalyst.By controlling reduction temperature the spilling of metal ion in hydrotalcite can be controlled suitable simultaneously
Sequence, abundant nanostructured can be further formed, be hydrogenated in optical drive carbon dioxide and prepare CO, CH4Have very with terms of high-carbon hydrocarbon
High selectivity.In the case where optimizing catalyst preparation conditions, the selectivity of high-carbon hydrocarbon may be up to 35.26%.The present invention realizes first
In optical drive carbon dioxide Hydrogenation for high added value carbon hydrocarbon compound, and prepared by the iron cobalt-based photochemical catalyst of the present invention
Cost is cheap, easy to operate, and technique is simple, is easy to mass produce, and is expected to be applied to commercial Application side instead of traditional thermocatalytic
Face.
Brief description of the drawings
Fig. 1 shows the XRD spectra of ferro-cobalt based photocatalyst and its presoma that 1-5 of the embodiment of the present invention is obtained；
Wherein curve a is the XRD spectra of the Co2Fe1Al-LDH presomas obtained in embodiment 1-3；Curve b is embodiment
4 obtained Co1Fe1The XRD spectra of Al-LDH presomas；Curve c is the Co that embodiment 4 obtains3Fe1The XRD of Al-LDH presomas
Spectrogram；Curve d is the XRD spectra of the ferro-cobalt based photocatalyst (Co2Fe1-300) obtained in embodiment 1；Curve e is embodiment 2
In the obtained XRD spectra of ferro-cobalt based photocatalyst (Co2Fe1-550)；Curve f is that the ferro-cobalt base light obtained in embodiment 3 is urged
The XRD spectra of agent (Co2Fe1-650)；Curve g is the ferro-cobalt based photocatalyst (Co obtained in embodiment 41Fe1- 650)
XRD spectra；Curve h is the ferro-cobalt based photocatalyst (Co obtained in embodiment 53Fe1- 650) XRD spectra.
Fig. 2 shows the transmission electron microscope picture for the CoFeAl-LDH presomas that the embodiment of the present invention is obtained；
Wherein, the Co that a is obtained by embodiment 12Fe1The transmission electron microscope picture of Al-LDH presomas；B is obtained by embodiment 4
Co1Fe1The transmission electron microscope picture of Al-LDH presomas；The Co that c is obtained by embodiment 53Fe1The transmission electricity of Al-LDH presomas
Mirror figure.
Fig. 3 shows the ferro-cobalt based photocatalyst (Co that the embodiment of the present invention 1 is obtained2Fe1- 300) transmission electron microscope picture；
Wherein a is low resolved transmittance electron microscope, and b and c are respectively the high-resolution-ration transmission electric-lens figure of zone1 and zone2 in a.
Fig. 4 shows the ferro-cobalt based photocatalyst (Co that the embodiment of the present invention 2 is obtained2Fe1- 550) transmission electron microscope picture；
Wherein a is low resolved transmittance electron microscope, and b is high-resolution-ration transmission electric-lens figure.
Fig. 5 shows the ferro-cobalt based photocatalyst (Co that the embodiment of the present invention 3 is obtained2Fe1- 650) transmission electron microscope picture；
Wherein a is low resolved transmittance electron microscope, and b is high-resolution-ration transmission electric-lens figure.
Fig. 6 shows the ferro-cobalt based photocatalyst (Co that the embodiment of the present invention 4 is obtained1Fe1- 650) transmission electron microscope picture；
Wherein a is low resolved transmittance electron microscope, and b is high-resolution-ration transmission electric-lens figure.
Fig. 7 shows the ferro-cobalt based photocatalyst (Co that the embodiment of the present invention 5 is obtained3Fe1- 700) transmission electron microscope picture；
Wherein a is low resolved transmittance electron microscope, and b is high-resolution-ration transmission electric-lens figure.
Fig. 8 shows the ferro-cobalt based photocatalyst Co after the reduction of the embodiment of the present invention 32Fe1- 650 catalyst optical drive CO2Hydrogen
Change transfer capability and selectivity of product versus time curve.
Embodiment
In order to illustrate more clearly of the present invention, the present invention is done further with reference to preferred embodiments and drawings
It is bright.Similar part is indicated with identical reference in accompanying drawing.It will be appreciated by those skilled in the art that institute is specific below
The content of description is illustrative and be not restrictive, and should not be limited the scope of the invention with this.
Embodiment 1
A kind of preparation method of ferro-cobalt based photocatalyst and its application in optical drive carbon dioxide hydrogenation, including
Following steps：
1) mixed salt solution is prepared：0.01mol cobalt nitrates, 0.005mol ferric nitrates, 0.005mol aluminum nitrates is molten
Solution adds precipitating reagent urea 0.06mol in 100mL deionized waters, fully dissolving, is transferred in 200mL three-necked flasks,
110 DEG C of oil baths, crystallization backflow 24h.
2) crude product for obtaining step 1) is washed, dried, after grinding, that is, obtains CoFeAl ternary hydrotalcite materials, is remembered
For Co2Fe1Al-LDH。
3) the CoFeAl ternary hydrotalcites (Co for obtaining step 2)2Fe1Al-LDH) material is in 10% (volume fraction) hydrogen argon
With with 5 DEG C of min in gaseous mixture-1Heating rate be warming up to 300 DEG C, keep 5h, after switch to nitrogen atmosphere, drop naturally
Temperature arrives room temperature, that is, obtains ferro-cobalt based photocatalyst, be designated as Co2Fe1-300。
4) Co being prepared according to the above method2Fe1- 300 apply in optical drive carbon dioxide hydrogenation, can
(50mL) adds iron cobalt-based photochemical catalyst 100mg in the closed reactor of printing opacity, is filled with reaction gas (CO2/H2/ Ar=15/60/
25, v/v) to 0.18MPa, ultraviolet-visible illumination is carried out, is changed over time using gas chromatographic detection product, to determine catalysis
The selectivity of agent reactivity and each product.
Curve a is Co in Fig. 12Fe1The XRD spectra of Al-LDH presomas, curve d are the ferro-cobalt base after being reduced in embodiment 1
Photochemical catalyst Co2Fe1- 300 XRD spectra.A figures are the Co obtained in embodiment 1 in Fig. 22Fe1The transmission of Al-LDH presomas
Electron microscope, a is the ferro-cobalt based photocatalyst Co after being reduced in embodiment 1 in Fig. 32Fe1- 300 low resolved transmittance electron microscope, Fig. 3
Middle b and c are the ferro-cobalt based photocatalyst Co after being reduced in embodiment 12Fe1- 300 high-resolution-ration transmission electric-lens figure.Table 1- I is real
Apply Co in example 12Fe1- 300 catalyst are in optical drive CO2Performance in hydrogenation.
From the curve a in Fig. 1, on this condition, the presoma hydrotalcite Co of synthesis2Fe1Al-LDH can form perfection
Hydrotalcite structure, its (003), (006) and (009) characteristic peak is apparent.As shown in Figure 2, the presoma hydrotalcite of synthesis by
100nm or so nanometer sheet composition, its thickness is about 7nm.In hydrogen-argon-mixed after 300 DEG C of reduction, hydrotalcite structure occurs
Topology conversion, is changed into FeOx, CoOxAnd Al2O3The metal composite oxide of (amorphous state).Further by Fig. 3 transmission electron microscope
Figure and high-resolution-ration transmission electric-lens figure can be seen that FeOxNano particle is dispersed in CoAl mixed-metal oxides nanometer sheets
On.The catalyst directly applies to optical drive CO2In hydrogenation, it be can be seen that from table 1-I after two hours of illumination, CO2
Conversion ratio be 6.1%, product is all CO substantially.In the process, due to the FeO preferentially overflowed in reduction processxSpecies
It is CO2CO active specy is generated in hydrogenation process, therefore without the generation of carbon hydrocarbon.It follows that the catalyst can efficiently by
CO2Optical drive has been converted into value-added product CO, CO and has been further used for other reactions, such as F- T synthesis.
Embodiment 2
A kind of preparation method of iron cobalt-based photochemical catalyst and the application in optical drive carbon dioxide hydrogenation, including with
Lower step：
1) mixed salt solution is prepared：By 0.01mol cabaltous nitrate hexahydrates, the water ferric nitrates of 0.005mol nine,
0.005mol ANN aluminium nitrate nonahydrates are dissolved in 100mL deionized waters, add precipitating reagent urea 0.06mol, fully dissolving, transfer
Into 200mL three-necked flasks, 110 DEG C of oil baths, crystallization backflow 24h.
2) crude product for obtaining step 1) is washed, dried, after grinding, that is, obtains CoFeAl ternary hydrotalcite materials, is remembered
For Co2Fe1Al-LDH。
3) the CoFeAl ternary hydrotalcite materials (Co for obtaining step 2)2Fe1Al-LDH) in 10% (volume fraction) hydrogen argon
With with 5 DEG C of min in gaseous mixture-1Heating rate be warming up to 550 DEG C, keep 5h, after switch to nitrogen atmosphere, drop naturally
Temperature arrives room temperature, that is, obtains ferro-cobalt based photocatalyst, be designated as Co2Fe1-550。
4) Co being prepared according to the above method2Fe1- 550 apply in optical drive carbon dioxide hydrogenation, can
(50mL) adds iron cobalt-based photochemical catalyst 100mg in the closed reactor of printing opacity, is filled with reaction gas (CO2/H2/ Ar=15/60/
25, v/v) to 0.18MPa, ultraviolet-visible illumination is carried out, is changed over time using gas chromatographic detection product, to determine catalysis
Each selectivity of product of agent reactivity.
Curve a is the Co that embodiment 2 obtains in Fig. 12Fe1The XRD spectra of Al-LDH presomas, curve e are in embodiment 2
Ferro-cobalt based photocatalyst Co after reduction2Fe1- 550 XRD spectra.A figures are the Co obtained in embodiment 2 in Fig. 22Fe1Al-
The transmission electron microscope picture of LDH presomas, a is the ferro-cobalt based photocatalyst Co after being reduced in embodiment 2 in Fig. 42Fe1- 300 transmission
Electron microscope, b is the ferro-cobalt based photocatalyst Co after being reduced in embodiment 2 in Fig. 42Fe1- 300 high-resolution-ration transmission electric-lens figure.Table
1- II is Co in embodiment 22Fe1- 300 catalyst are in optical drive CO2Performance in hydrogenation.
Curve e can be seen that in hydrogen-argon-mixed after 550 DEG C of reduction from Fig. 1, and hydrotalcite structure occurs topology and turned
Change, be changed into FeOx, CoOxAnd Al2O3The metal composite oxide of (amorphous state).Further by Fig. 4 transmission electron microscope pictures and high score
Distinguish that transmission electron microscope picture can be seen that compared to the Co in embodiment 12Fe1- 300, Co2Fe1Co species are further from water in -550
Overflowed in talcum laminate and ultimately form FeOx, CoOxBimetallic oxide is dispersed in unformed Al2O3In nanometer sheet.Table 1-
II be embodiment 2 in CoFe-550 catalyst in optical drive CO2Performance in hydrogenation.It is as can be seen that two small in illumination
Shi Hou, CO2Conversion ratio be 68.2%, CO selectivity is 6.42%, CH in product4Selectivity be up to 90.89%, high-carbon
The selectivity of hydrocarbon is only 2.69%.The reactivity worth is due to CoOxAnd FeOxSpecies are in CO2It is parallel relation in hydrogenation, and
CO2More preferably in CoOxSurface forms methane.It follows that under condition reduction, optical drive CO2Hydrogenation can efficient Gao Xuan
Selecting property is converted into methane.
Embodiment 3
A kind of preparation method of iron cobalt-based photochemical catalyst and the application in optical drive carbon dioxide hydrogenation, including with
Lower step：
1) mixed salt solution is prepared：0.01mol cobalt nitrates, 0.005mol ferric nitrates, 0.005mol aluminum nitrates is molten
Solution adds precipitating reagent urea 0.06mol in 100mL deionized waters, fully dissolving, is transferred in 200mL three-necked flasks,
110 DEG C of oil baths, crystallization backflow 24h.
2) crude product for obtaining step 1) is washed, dried, after grinding, that is, obtains CoFeAl ternary hydrotalcite materials, is remembered
For Co2Fe1Al-LDH。
3) the CoFeAl ternary hydrotalcite materials (Co for obtaining step 2)2Fe1Al-LDH) in 10% (volume fraction) hydrogen argon
With with 5 DEG C of min in gaseous mixture-1Heating rate be warming up to 650 DEG C, keep 5h, after switch to nitrogen atmosphere, drop naturally
Temperature arrives room temperature, that is, obtains ferro-cobalt based photocatalyst, be designated as Co2Fe1-650。
4) the ferro-cobalt based photocatalyst Co being prepared according to the above method2Fe1- 650 apply it is hydrocarbon in optical drive titanium dioxide
Change in reaction, (50mL) adds iron cobalt-based photochemical catalyst 100mg in the closed reactor of light-permeable, is filled with reaction gas (CO2/
H2/ Ar=15/60/25, v/v) to 0.18MPa, ultraviolet-visible illumination is carried out, using gas chromatographic detection product anaplasia at any time
Change, to determine each selectivity of product of catalyst reaction activity.
Curve a is the Co obtained in embodiment 3 in accompanying drawing 12Fe1The XRD spectra of Al-LDH presomas, curve f are embodiment
Ferro-cobalt based photocatalyst Co after being reduced in 32Fe1- 650 XRD spectra.A is the ferro-cobalt base light after being reduced in embodiment 3 in Fig. 5
Catalyst Co2Fe1- 650 low resolved transmittance electron microscope, b is the ferro-cobalt based photocatalyst after being reduced in embodiment 3 in Fig. 5
Co2Fe1- 650 high-resolution-ration transmission electric-lens figure.Fig. 8 is the ferro-cobalt based photocatalyst Co after being reduced in embodiment 32Fe1- 650 urge
Agent optical drive CO2Hydrogenate transfer capability and selectivity of product versus time curve.
F curves can be seen that precursor hydrotalcite material Co from Fig. 12Fe1Al-LDH is changed into after 650 DEG C of reduction
CoFe alloy and with amorphous state Al2O3Mixture.From the point of view of Fig. 5, the ferro-cobalt based photocatalyst after reducing at this temperature is
CoFe alloy nano particle is supported on unformed Al2O3In nanometer sheet, the size of nano particle is about 30nm.This catalyst is complete
Under spectral illumination, with the extension of light application time, CO2Conversion ratio gradually step up, and C2+Selectivity can maintain one
Individual very high level.As shown in table 1- III, it can be seen that after two hours of illumination, CO2Conversion ratio be 78.6.%, product
Middle CO selectivity is 4.97%, CH4Selectivity be 59.77%, the selectivity of high-carbon hydrocarbon may be up to 35.26%, in carbon hydrocarbon
The growth factor of carbochain is 0.345.As can be seen that reducing obtained CoFe-650 catalyst at such a temperature, CoFe alloy is
Catalytic active center, can be by CO2Efficient Conversion is high added value carbon hydrocarbon compound.Compared to traditional thermocatalytic, process profit
CO can be converted with the solar energy of cleaning2For high value added product, process energy conservation environmental protection.
Embodiment 4
A kind of preparation method of iron cobalt-based photochemical catalyst and the application in optical drive carbon dioxide hydrogenation, including with
Lower step：
1) mixed salt solution is prepared：By 0.0075mol cobalt chlorides, 0.0075mol iron chloride, 0.005mol aluminium chloride
100mL deionized waters are dissolved in, add precipitating reagent urea 0.06mol, fully dissolving, are transferred in 200mL three-necked flasks,
110 DEG C of oil baths, crystallization backflow 24h.
2) crude product for obtaining step 1) is washed, dried, after grinding, that is, obtains CoFeAl ternary hydrotalcite materials, is remembered
For Co1Fe1Al-LDH。
3) the CoFeAl ternary hydrotalcite materials (Co for obtaining step 2)1Fe1Al-LDH) in 10% (volume fraction) hydrogen argon
With with 5 DEG C of min in gaseous mixture-1Heating rate be warming up to 650 DEG C, keep 5h, after switch to nitrogen atmosphere, drop naturally
Temperature arrives room temperature, that is, obtains ferro-cobalt based photocatalyst, be designated as Co1Fe1-650。
4) the ferro-cobalt based photocatalyst being prepared according to the above method is applied in optical drive carbon dioxide hydrogenation,
(50mL) adds iron cobalt-based photochemical catalyst 100mg in the closed reactor of light-permeable, is filled with reaction gas (CO2/H2/ Ar=15/
60/25, v/v) to 0.18MPa, ultraviolet-visible illumination is carried out, is changed over time using gas chromatographic detection product, with measure
Each selectivity of product of catalyst reaction activity.
Curve b is Co in embodiment 4 in accompanying drawing 11Fe1The XRD spectra of Al-LDH presomas, curve g are to be gone back in embodiment 4
Ferro-cobalt based photocatalyst Co after original1Fe1- 650 XRD spectra.B figures are Co in embodiment 4 in Fig. 21Fe1Al-LDH presomas
Transmission electron microscope picture.A is the ferro-cobalt based photocatalyst Co after being reduced in embodiment 4 in Fig. 61Fe1- 650 low resolved transmittance Electronic Speculum
Scheme, b is the ferro-cobalt based photocatalyst Co after being reduced in embodiment 4 in Fig. 61Fe1- 650 high-resolution-ration transmission electric-lens figure.
Curve b can be seen that the ratio (Co/Fe=1/1) for changing precursor salt from Fig. 1, can still synthesize pure
Net hydrotalcite.B schemes from Fig. 2, and nanometer sheet pattern is presented in the hydrotalcite being synthesized.Before g curves can be seen that from Fig. 1
Body hydrotalcite material by 650 DEG C reduction after, be changed into CoFe alloy and with amorphous state Al2O3Mixture.From the point of view of Fig. 6,
Ferro-cobalt based photocatalyst after reducing at this temperature is supported on unformed Al for CoFe alloy nano particle2O3In nanometer sheet, receive
The size of rice grain is about 60nm, compared to Co2Fe1- 650, the alloy nanoparticle has become big., can be with as shown in table 1- IV
Find out, after two hours of illumination, CO2Conversion ratio be 67.3.%, CO selectivity is 16.97%, CH in product4Selection
Property is 60.61%, high-carbon hydrocarbon C2+Only 22.44%.Compared to Co2Fe1- 650 catalyst, in Co1Fe1- 650 catalytic activity
Reduce, this is due to the Co under the ratio1Fe1Al-LDH reduces obtained Co1Fe1- 650 become large-sized big reason.But phase
Than in traditional thermocatalytic, although high annex value product selectivity reduces, the process can be turned using the solar energy of cleaning
Change CO2For high value added product, process energy conservation environmental protection.
Embodiment 5
A kind of preparation method of iron cobalt-based photochemical catalyst and the application in optical drive carbon dioxide hydrogenation, including with
Lower step：
1) mixed salt solution is prepared：By 0.01125mol cobalt chlorides, 0.00375mol iron chloride, 0.005mol chlorinations
Aluminium is dissolved in 100mL deionized waters, adds precipitating reagent urea 0.06mol, fully dissolving, is transferred in 200mL three-necked flasks,
110 DEG C of oil baths, crystallization backflow 24h.
2) crude product for obtaining step 1) is washed, dried, after grinding, that is, obtains CoFeAl ternary hydrotalcite materials, is remembered
For Co3Fe1Al-LDH。
3) the CoFeAl ternary hydrotalcite materials (Co for obtaining step 2)3Fe1Al-LDH) in 10% (volume fraction) hydrogen argon
With with 5 DEG C of min in gaseous mixture-1Heating rate be warming up to 650 DEG C, keep 5h, after switch to nitrogen atmosphere, drop naturally
Temperature arrives room temperature, that is, obtains ferro-cobalt based photocatalyst, be designated as Co3Fe1-650。
4) the ferro-cobalt based photocatalyst being prepared according to the above method is applied in optical drive carbon dioxide hydrogenation,
(50mL) adds iron cobalt-based photochemical catalyst 100mg in the closed reactor of light-permeable, is filled with reaction gas (CO2/H2/ Ar=15/
60/25, v/v) to 0.18MPa, ultraviolet-visible illumination is carried out, is changed over time using gas chromatographic detection product, with measure
Each selectivity of product of catalyst reaction activity.
Curve c is Co in embodiment 5 in accompanying drawing 13Fe1The XRD spectra of Al-LDH presomas, curve h are to be gone back in embodiment 5
Ferro-cobalt based photocatalyst Co after original3Fe1- 650 XRD spectra.C figures are Co in embodiment 5 in Fig. 23Fe1Al-LDH presomas
Transmission electron microscope picture.A is the ferro-cobalt based photocatalyst Co after being reduced in embodiment 5 in Fig. 73Fe1- 650 low resolved transmittance Electronic Speculum
Scheme, b is the ferro-cobalt based photocatalyst Co after being reduced in embodiment 5 in Fig. 73Fe1- 650 high-resolution-ration transmission electric-lens figure.
Curve c can be seen that the ratio (Co/Fe=3/1) for changing precursor salt from Fig. 1, can still synthesize pure
Net hydrotalcite.C schemes from Fig. 2, and nanometer sheet pattern is presented in the hydrotalcite being synthesized.Before h curves can be seen that from Fig. 1
Body hydrotalcite material by 650 DEG C reduction after, be changed into CoFe alloy and with amorphous state Al2O3Mixture, but there is portion
Divide simple substance Co diffraction maximum.From the point of view of Fig. 7, the ferro-cobalt based photocatalyst after reducing at this temperature is CoFe alloy nano particle
With simple substance Co mixed loads in unformed Al2O3In nanometer sheet.As shown in table 1- V, it can be seen that after two hours of illumination,
CO2Conversion ratio be 82.3.%, CO selectivity is 4.83%, CH in product4Selectivity be 81.30%, high-carbon hydrocarbon C2+Only
Have 13.87%.Compared to Co2Fe1- 650 catalyst, in Co3Fe1- 650 catalytic activity has raised, but the choosing of high-carbon hydrocarbon
Selecting property only has 13.87%.Because the Co under the ratio3Fe1The nano particle that Al-LDH reduces to obtain be CoFe alloy and
Simple substance Co mixture, CO2Preferentially CH is catalytically conveted on Co particles4, and only part CO2In CoFe alloy activity
High-carbon hydrocarbon is converted into the heart.To sum up, CO can be converted using the solar energy of cleaning compared to traditional thermocatalytic, the process2
For high value added product, process energy conservation environmental protection.
In summary, by simple restoring method, the nanometer that CoFeAl-LDH can be converted into different special constructions is urged
Agent, the different cobalt ferrum-based catalysts are in optical drive CO2Different selectivity of product is shown in hydrogenation.Can be by CO2Efficiently
It is converted into CO, CH4, and CO can be realized2It is converted into the carbon hydrocarbon compound of high added value.Compared to existing technical system, that is, pass
For the thermal drivers of system, the present invention uses optical drive CO2It is hydroconverted, not only energy-conservation more more environmentally friendly than prior art system, and first
It is secondary to realize optical drive CO2Hydroconverted is advanced carbon hydrocarbon.The present invention is expected to industrially amplify and do practical application.
The iron cobalt-based photochemical catalyst of table 1. is in optical drive CO2Performance in hydrogenation
Table is noted：
[a] carbochain growth factors；
Percentage of [b] high-carbon hydrocarbon in carbon hydrocarbon compound.
Obviously, the above embodiment of the present invention is only intended to clearly illustrate example of the present invention, and is not pair
The restriction of embodiments of the present invention, for those of ordinary skill in the field, may be used also on the basis of the above description
To make other changes in different forms, all embodiments can not be exhaustive here, it is every to belong to this hair
Row of the obvious changes or variations that bright technical scheme is extended out still in protection scope of the present invention.
Claims (10)
1. a kind of ferro-cobalt based photocatalyst, it is characterised in that including tri- kinds of metallic elements of Co, Fe and Al, also, include wherein one
The uniform high-dispersion load of nano particle of kind or two kinds of metallic elements is in the nanometer sheet for including residual metallic element.
2. ferro-cobalt based photocatalyst according to claim 1, it is characterised in that the ferro-cobalt based photocatalyst is：FeOxIt is negative
It is loaded in CoAl mixed-metal oxides nanometer sheets, FeOx-CoOxIt is carried on unformed Al2O3In nanometer sheet, or CoFe alloy is born
It is loaded in unformed Al2O3In nanometer sheet.
A kind of 3. method of the ferro-cobalt based photocatalyst prepared described in claim 1 or 2, it is characterised in that comprise the following steps：
1) cobalt salt, molysite and aluminium salt are dissolved in deionized water, precipitating reagent are added, fully after dissolving, in 50~120 DEG C of conditions
12~36h of lower crystallization backflow, obtains crude product；
2) crude product for obtaining step 1) is washed, dried, after grinding, that is, obtains CoFeAl ternary hydrotalcite materials；
3) the CoFeAl ternary hydrotalcite materials that step 2) obtains are warming up to 300-700 DEG C in hydrogen-argon-mixed, keep 2~
5h is reduced, and is down to room temperature in inertia protects gas atmosphere afterwards, that is, is obtained ferro-cobalt based photocatalyst.
4. according to the method for claim 3, it is characterised in that the concentration of the cobalt salt is 0.005~0.1molL-1；Institute
The concentration for stating molysite is 0.002~0.05molL-1；The aluminium salt concentration is 0.002~0.05molL-1；Preferably, institute
It is cobalt nitrate, cobalt chloride or cobaltous sulfate to state cobalt salt；The molysite is ferric nitrate, iron chloride or ferric sulfate；The aluminium salt is nitric acid
Aluminium, aluminium chloride or aluminum sulfate.
5. according to the method for claim 3, it is characterised in that the precipitating reagent be urea, after dissolving concentration for 0.05~
0.8mol·L-1。
6. according to the method for claim 3, it is characterised in that the speed of heating is 2~5 DEG C of min in step 3)-1。
7. according to the method for claim 3, it is characterised in that the inertia protection gas is nitrogen.
8. according to the method for claim 3, it is characterised in that the reduction temperature is 650 DEG C.
9. application of the iron cobalt-based photochemical catalyst according to claim 1 or 2 in optical drive carbon dioxide hydrogenation reaction.
10. application according to claim 9, it is characterised in that specifically include following steps：Added in closed reactor
Ferro-cobalt based photocatalyst, it is passed through gas CO2, H2Ultraviolet-visible illumination is carried out with Ar, monitors product；Preferably, the gas
Volume fraction ratio is CO2/H2/ Ar=15/60/25, it is 0.18MPa to be passed through gas to closed reactor pressure；Preferably, institute
It is 100mg to state addition of the ferro-cobalt based photocatalyst in 50mL reactors；Preferably, the closed reactor is that top can be saturating
The closed reactor of light.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109939683A (en) * | 2019-04-09 | 2019-06-28 | 江苏新沃催化剂有限公司 | A kind of ternary compound oxides type catalyst and preparation method thereof of catalysis burning VOCs |
| CN110433805A (en) * | 2019-08-22 | 2019-11-12 | 华南理工大学 | A kind of anionic clay-hydro-thermal charcoal sustained release photochemical catalytic oxidation material and the preparation method and application thereof |
| CN110433817A (en) * | 2019-08-05 | 2019-11-12 | 盐城工学院 | A kind of Na for photocatalysis fixed nitrogen synthesis ammonia4CrO4-Cu2The preparation method of O-Cu composite material |
| CN111790396A (en) * | 2020-06-15 | 2020-10-20 | 北京化工大学 | Method for preparing p-n type in-situ symbiotic heterojunction material by pyrolysis of nickel-manganese hydrotalcite topological transformation and application |
| CN111939910A (en) * | 2020-09-08 | 2020-11-17 | 福州大学 | Preparation method of iron-doped aluminum oxide material and application of iron-doped aluminum oxide material in selective oxidation of hydrogen sulfide by photocatalysis |
| CN112076770A (en) * | 2020-08-28 | 2020-12-15 | 北京大学 | Application of layered multi-metal hydroxide in photochemical conversion of methane |
| CN112774682A (en) * | 2019-11-11 | 2021-05-11 | 中国科学院城市环境研究所 | Aluminum-cobalt composite catalyst and preparation method and application thereof |
| CN114471612A (en) * | 2022-01-28 | 2022-05-13 | 中国科学技术大学 | Amorphous iron oxide nanosheet composite material, and preparation method and application thereof |
| CN114797932A (en) * | 2022-03-28 | 2022-07-29 | 武汉大学 | Bimetal 3D unique honeycomb-shaped carbon dioxide reduction catalyst and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104368345A (en) * | 2014-11-20 | 2015-02-25 | 北京化工大学 | Preparation method and catalytic application of supported type high-dispersion nickel-based alloy catalyst |
| CN104437504A (en) * | 2014-11-14 | 2015-03-25 | 宁夏大学 | Catalyst for producing low-carbon olefins through efficient conversion of CO2 |
| CN105056952A (en) * | 2015-08-19 | 2015-11-18 | 中国科学院理化技术研究所 | Preparation method and application of nickel-based photocatalyst for preparing high-carbon hydrocarbon above carbon dioxide by photocatalytic carbon monoxide hydrogenation |
-
2017
- 2017-11-07 CN CN201711083424.9A patent/CN107790133B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104437504A (en) * | 2014-11-14 | 2015-03-25 | 宁夏大学 | Catalyst for producing low-carbon olefins through efficient conversion of CO2 |
| CN104368345A (en) * | 2014-11-20 | 2015-02-25 | 北京化工大学 | Preparation method and catalytic application of supported type high-dispersion nickel-based alloy catalyst |
| CN105056952A (en) * | 2015-08-19 | 2015-11-18 | 中国科学院理化技术研究所 | Preparation method and application of nickel-based photocatalyst for preparing high-carbon hydrocarbon above carbon dioxide by photocatalytic carbon monoxide hydrogenation |
| CN105056952B (en) * | 2015-08-19 | 2017-09-05 | 中国科学院理化技术研究所 | Preparation method and application of nickel-based photocatalyst for preparing high-carbon hydrocarbon above carbon dioxide by photocatalytic carbon monoxide hydrogenation |
Non-Patent Citations (3)
| Title |
|---|
| MUTHU KUMARAN GNANAMANI ET AL.: "Hydrogenation of Carbon Dioxide over Co−Fe Bimetallic Catalysts", 《ACS CATALYSIS》 * |
| RATCHPRAPA SATTHAWONG ET AL.: "Comparative Study on CO2 Hydrogenation to Higher Hydrocarbons over Fe-Based Bimetallic Catalysts", 《TOPICS IN CATALYSIS》 * |
| 徐迎节等: "尖晶石CoFe2O4 光催化还原CO2的研究", 《化学工程与装备》 * |
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