CN110756193B - Carbon dioxide electrochemical reduction copper-indium bimetal co-doped organic framework catalyst and preparation method and application thereof - Google Patents
Carbon dioxide electrochemical reduction copper-indium bimetal co-doped organic framework catalyst and preparation method and application thereof Download PDFInfo
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- CN110756193B CN110756193B CN201911009245.XA CN201911009245A CN110756193B CN 110756193 B CN110756193 B CN 110756193B CN 201911009245 A CN201911009245 A CN 201911009245A CN 110756193 B CN110756193 B CN 110756193B
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 123
- 239000003054 catalyst Substances 0.000 title claims abstract description 80
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 62
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- HVMJUDPAXRRVQO-UHFFFAOYSA-N copper indium Chemical compound [Cu].[In] HVMJUDPAXRRVQO-UHFFFAOYSA-N 0.000 title description 12
- 239000013384 organic framework Substances 0.000 title description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 60
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 239000002243 precursor Substances 0.000 claims abstract description 36
- 238000001354 calcination Methods 0.000 claims abstract description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 21
- 238000001816 cooling Methods 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 11
- UJMDYLWCYJJYMO-UHFFFAOYSA-N benzene-1,2,3-tricarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1C(O)=O UJMDYLWCYJJYMO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000001879 copper Chemical class 0.000 claims abstract description 7
- 150000002471 indium Chemical class 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 12
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 claims description 10
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical group O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims description 10
- 229910000337 indium(III) sulfate Inorganic materials 0.000 claims description 10
- XGCKLPDYTQRDTR-UHFFFAOYSA-H indium(iii) sulfate Chemical compound [In+3].[In+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O XGCKLPDYTQRDTR-UHFFFAOYSA-H 0.000 claims description 10
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical group CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 claims description 9
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 8
- LLPKQRMDOFYSGZ-UHFFFAOYSA-N 2,5-dimethyl-1h-imidazole Chemical compound CC1=CN=C(C)N1 LLPKQRMDOFYSGZ-UHFFFAOYSA-N 0.000 claims description 4
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 3
- FTXJFNVGIDRLEM-UHFFFAOYSA-N copper;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O FTXJFNVGIDRLEM-UHFFFAOYSA-N 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 238000009792 diffusion process Methods 0.000 claims description 2
- YZZFBYAKINKKFM-UHFFFAOYSA-N dinitrooxyindiganyl nitrate;hydrate Chemical class O.[In+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YZZFBYAKINKKFM-UHFFFAOYSA-N 0.000 claims description 2
- XUVCWJBXGHOWID-UHFFFAOYSA-H indium(3+);trisulfate;hydrate Chemical class O.[In+3].[In+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O XUVCWJBXGHOWID-UHFFFAOYSA-H 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 abstract description 10
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract description 6
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 abstract description 5
- 235000019253 formic acid Nutrition 0.000 abstract description 5
- 229910052738 indium Inorganic materials 0.000 abstract description 5
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 abstract description 5
- 150000001450 anions Chemical class 0.000 abstract description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 3
- 230000001276 controlling effect Effects 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract description 3
- 239000010949 copper Substances 0.000 description 19
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 229910052802 copper Inorganic materials 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 229910002651 NO3 Inorganic materials 0.000 description 9
- -1 polytetrafluoroethylene Polymers 0.000 description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 description 9
- 229910001220 stainless steel Inorganic materials 0.000 description 9
- 239000010935 stainless steel Substances 0.000 description 9
- 239000011259 mixed solution Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 239000012621 metal-organic framework Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/825—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with gallium, indium or thallium
-
- B01J35/33—
-
- B01J35/61—
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a carbon dioxide electrochemical reduction catalyst, a preparation method and application thereof, wherein the method comprises the following steps: dissolving copper salt and indium salt in a solvent simultaneously, adding dimethyl imidazole and benzenetricarboxylic acid simultaneously, mixing uniformly to form a precursor solution, transferring the precursor solution to a reaction kettle for hydrothermal reaction, naturally cooling, centrifuging, washing with methanol, and drying to obtain a precursor; and placing the prepared precursor in a tubular furnace, introducing nitrogen for 1-3 h for calcination, wherein the calcination temperature is 250-450 ℃, and the calcination time is 4-24 h, so as to obtain the carbon dioxide electrochemical reduction catalyst. The invention obviously improves the specific surface area of the catalyst, increases the electrochemical reduction catalytic activity of the catalyst on carbon dioxide reduction, and effectively inhibits hydrogen evolution reaction. Particularly, the catalytic activity and selectivity of the electrocatalytic reduction of carbon dioxide into formic acid and carbon monoxide and the current density can be effectively improved by effectively regulating and controlling the anion species and the doping concentration of different indium doping precursors.
Description
Technical Field
The invention belongs to the technical field of carbon dioxide electrochemical reduction catalysts, and particularly relates to a co-doped bimetallic organic framework carbon dioxide electrochemical reduction catalyst, and a preparation method and application thereof.
Background
Since the industrial revolution, the rapid expansion of the population and the massive combustion of fossil fuels has led to higher and higher atmospheric carbon dioxide concentrations, currently reaching 411 ppm. Excessive carbon dioxide accumulation causes numerous environmental problems such as greenhouse effect and sea level rise. Therefore, how to control and reduce the carbon dioxide content in the atmosphere has become the focus of research and attention. One of the effective means is to convert carbon dioxide into usable energy fuels and chemicals by electrochemical reaction. However, since the carbon dioxide molecule has extremely stable C ═ O double bond, and its inert characteristic is difficult to make it proceed under normal temperature and pressure, it is the biggest problem in the process of carbon dioxide conversion, and finding a suitable novel catalyst material becomes the focus of current scientific research [ chem. Copper is a widespread concern because of its high conductivity, as well as the diversity of products. However, in aqueous systems, the catalytic activity of copper on carbon dioxide is deactivated relatively quickly and the selectivity is poor. In addition, in order to increase the energy efficiency of the entire reaction process, higher demands are also made on the current density.
The metal organic framework structure of copper has good electrochemical performance, and the metal copper has abundant reserves in nature, and the cost of raw materials is low. In addition, copper metal organic framework materials have high specific surface area and special morphological structure, thus providing more catalytic active sites than metal copper [ Chemical Engineering journal.313,1623(2017) ]. The catalyst is applied to electrochemical devices such as lithium ion batteries and the like [ J.Mater.chem.A.1,11126(2013) ] and electrochemical conversion of carbon dioxide [ nanoscale.11,4911(2019) ], however, the catalytic activity and selectivity achieved at present are poor, the obtained current density is low, and the final energy efficiency is low. In order to solve the above problems, a copper-based catalyst doped with other metals may be used, however, a multi-metal co-doped metal organic framework carbon dioxide electrocatalytic material having better electrochemical properties than a single metal organic framework has not been reported.
Disclosure of Invention
The invention aims to provide a carbon dioxide electrochemical reduction catalyst which can obviously improve the selectivity of the catalyst and increase the electrochemical reduction catalytic activity of the catalyst on carbon dioxide reduction, and a preparation method and application thereof.
In order to solve the technical problem, the invention provides a preparation method of a carbon dioxide electrochemical reduction catalyst, which is characterized by comprising the following steps:
step 1: dissolving copper salt and indium salt in a solvent simultaneously, adding dimethyl imidazole and benzenetricarboxylic acid simultaneously, mixing uniformly to form a precursor solution, transferring the precursor solution to a reaction kettle for hydrothermal reaction, naturally cooling, centrifuging, washing with methanol, and drying to obtain a precursor;
step 2: and (3) placing the precursor prepared in the step (1) in a tubular furnace, introducing nitrogen for 1-3 h for calcination, wherein the calcination temperature is 250-450 ℃, and the calcination time is 4-24 h, so as to obtain the carbon dioxide electrochemical reduction catalyst.
Preferably, the copper salt in step 1 is copper nitrate, and the copper nitrate is copper nitrate trihydrate and/or copper nitrate hexahydrate.
Preferably, in the precursor solution in the step 1, the concentration of the copper salt is 0.01-0.05M, and the concentration of the indium salt is 0.01-0.05M.
Preferably, the indium salt in step 1 is indium nitrate or indium sulfate, the indium nitrate is one of indium nitrate hydrates, and the indium sulfate is one of indium sulfate hydrates.
Preferably, the solvent in step 1 is deionized water or methanol.
Preferably, the dimethylimidazole in step 1 is 1, 2-dimethylimidazole and/or 2, 4-dimethylimidazole.
Preferably, the benzene tricarboxylic acid in the step 1 is 1,3, 5-benzene tricarboxylic acid and/or 1,2, 4-benzene tricarboxylic acid.
Preferably, in the precursor solution in the step 1, the concentration of the dimethyl imidazole is 0.001 to 0.005M, and the concentration of the trimesic acid is 0.001 to 0.005M.
Preferably, the reaction kettle in the step 1 is a hydrothermal reaction kettle with a polytetrafluoroethylene inner container and a stainless steel outer sleeve.
The invention also provides the carbon dioxide electrochemical reduction catalyst prepared by the method. The catalyst comprises a copper-indium bimetal co-doped organic framework, and the selectivity and the current density of the electrochemical reduction of carbon dioxide are obviously improved by regulating and controlling the anion species and the metal doping concentration in the indium-doped metal precursor.
The invention also provides application of the carbon dioxide electrochemical reduction catalyst prepared by the method in preparation of a gas diffusion electrode.
Compared with the prior art, the invention has the beneficial effects that:
1. the catalyst is a nano catalyst, is synthesized by a hydrothermal method, forms a catalytic material with a unique morphology structure, remarkably improves the specific surface area of the catalyst, increases the electrochemical reduction catalytic activity of the catalyst on carbon dioxide reduction, and effectively inhibits hydrogen evolution reaction;
2. the preparation method of the catalyst is simple, easy to operate and low in cost, and greatly reduces the hydrogen evolution reaction of the electrode and the catalyst deactivation during the electrochemical reduction of the carbon dioxide in the aqueous solution.
Drawings
FIG. 1 shows 0.5M KHCO saturated with carbon dioxide for the carbon dioxide electrochemical reduction catalysts of examples 1-43Polarization graph of (1);
FIG. 2 shows the electrochemical reduction of carbon dioxide catalysts of examples 5-6 at 0.5M KHCO saturated with carbon dioxide3Polarization graph of (1);
FIG. 3 is a graph showing Faraday efficiencies of carbon dioxide electrochemically reduced to formic acid in examples 1 to 8;
FIG. 4 is a graph showing Faraday efficiencies of carbon monoxide produced by electrochemical reduction of carbon dioxide in examples 1 to 8.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
The embodiment provides a preparation method of a carbon dioxide electrochemical reduction catalyst, which comprises the following specific steps:
step 1: 0.453g of copper nitrate trihydrate and 0.188g of InN3O9Dissolving in 50mL of methanol solution at the same time to prepare a mixed solution of 0.0019M copper nitrate and 0.0006M indium nitrate, adding 0.2053g of 1, 2-dimethylimidazole and 0.5253g of 1,3, 5-trimesic acid, stirring for 30min, uniformly mixing, transferring to a 100mL reaction kettle, putting the reaction kettle into an oven for hydrothermal reaction at 160 ℃ for 12h, naturally cooling, centrifuging, cleaning with methanol, and drying to obtain a precursor; the reaction kettle is provided with a polytetrafluoroethylene inner container and a stainless steel outer sleeveThe hydrothermal reaction kettle;
step 2: placing the precursor prepared in the step 1 in a tubular furnace, introducing nitrogen for 1h for calcination at the calcination temperature of 350 ℃ for 4h to obtain black powder, namely the carbon dioxide electrochemical reduction catalyst (copper-indium bimetallic co-doped organic framework catalyst) named as Cu3In1-MOF-NO3Catalyst 1.
Example 2
The embodiment provides a preparation method of a carbon dioxide electrochemical reduction catalyst, which comprises the following specific steps:
step 1: 0.4010g of copper nitrate trihydrate and 0.2497g of InN3O9Dissolving in 50mL of methanol solution at the same time to prepare a mixed solution of 0.0017M copper nitrate and 0.0008M indium nitrate, adding 0.2053g of 1, 2-dimethylimidazole and 0.5253g of 1,3, 5-trimesic acid, stirring for 30min, uniformly mixing, transferring to a 100mL reaction kettle, putting the reaction kettle into an oven for hydrothermal reaction at 160 ℃ for 12h, naturally cooling, centrifuging, cleaning with methanol, and drying to obtain a precursor; the reaction kettle is a hydrothermal reaction kettle with a polytetrafluoroethylene inner container and a stainless steel outer sleeve;
step 2: placing the precursor prepared in the step 1 in a tubular furnace, introducing nitrogen for 1h for calcination at the calcination temperature of 350 ℃ for 4h to obtain black powder, namely the carbon dioxide electrochemical reduction catalyst (copper-indium bimetallic co-doped organic framework catalyst) named as Cu2In1-MOF-NO3Catalyst 1.
Example 3
The embodiment provides a preparation method of a carbon dioxide electrochemical reduction catalyst, which comprises the following specific steps:
step 1: 0.302g of copper nitrate trihydrate and 0.3760g of InN3O9Dissolving in 50mL of methanol solution simultaneously to prepare a mixed solution of 0.0013M copper nitrate and 0.0013M indium nitrate, adding 0.2053g of 1, 2-dimethylimidazole and 0.5253g of 1,3, 5-trimesic acid, stirring for 30min, uniformly mixing, transferring to a 100mL reaction kettle, putting the reaction kettle into an oven for hydrothermal reaction at 160 ℃ for 12h, naturally cooling, centrifuging, and using a catalyst ACleaning with alcohol, and drying to obtain a precursor; the reaction kettle is a hydrothermal reaction kettle with a polytetrafluoroethylene inner container and a stainless steel outer sleeve;
step 2: placing the precursor prepared in the step 1 in a tubular furnace, introducing nitrogen for 1h for calcination at the calcination temperature of 350 ℃ for 4h to obtain black powder, namely the carbon dioxide electrochemical reduction catalyst (copper-indium bimetallic co-doped organic framework catalyst) named as Cu1In1-MOF-NO3Catalyst 1.
Example 4
The embodiment provides a preparation method of a carbon dioxide electrochemical reduction catalyst, which comprises the following specific steps:
step 1: 0.1510g of copper nitrate trihydrate and 0.5640g of InN3O9Dissolving in 50mL of methanol solution at the same time to prepare a mixed solution of 0.0006M copper nitrate and 0.0019M indium nitrate, adding 0.2053g of 1, 2-dimethylimidazole and 0.5253g of 1,3, 5-trimesic acid, stirring for 30min, uniformly mixing, transferring to a 100mL reaction kettle, putting the reaction kettle into an oven for hydrothermal reaction at 160 ℃ for 12h, naturally cooling, centrifuging, cleaning with methanol, and drying to obtain a precursor; the reaction kettle is a hydrothermal reaction kettle with a polytetrafluoroethylene inner container and a stainless steel outer sleeve;
step 2: placing the precursor prepared in the step 1 in a tubular furnace, introducing nitrogen for 1h for calcination at the calcination temperature of 350 ℃ for 4h to obtain black powder, namely the carbon dioxide electrochemical reduction catalyst (copper-indium bimetallic co-doped organic framework catalyst) named as Cu1In3-MOF-NO3Catalyst 1.
Example 5
The embodiment provides a preparation method of a carbon dioxide electrochemical reduction catalyst, which comprises the following specific steps:
step 1: 0.453g of copper nitrate trihydrate and 0.1620g of In2S3O12Dissolving in 50mL methanol solution to obtain a mixed solution of 0.0019M copper nitrate and 0.0006M indium sulfate, adding 0.2053g1, 2-dimethylimidazole and 0.5253g1,3, 5-trimesic acid, stirring for 30min, mixing, and transferringMoving the mixture into a 100mL reaction kettle, putting the reaction kettle into an oven for hydrothermal reaction for 12 hours at 160 ℃, naturally cooling, centrifuging, washing with methanol, and drying to obtain a precursor; the reaction kettle is a hydrothermal reaction kettle with a polytetrafluoroethylene inner container and a stainless steel outer sleeve;
step 2: placing the precursor prepared in the step 1 in a tubular furnace, introducing nitrogen for 1h for calcination at the calcination temperature of 350 ℃ for 4h to obtain black powder, namely the carbon dioxide electrochemical reduction catalyst (copper-indium bimetallic co-doped organic framework catalyst) named as Cu3In1-MOF-NO3Catalyst 2.
Example 6
The embodiment provides a preparation method of a carbon dioxide electrochemical reduction catalyst, which comprises the following specific steps:
step 1: 0.4010g of copper nitrate trihydrate and 0.2149g of In2S3O12Dissolving in 50mL of methanol solution at the same time to prepare a mixed solution of 0.0017M copper nitrate and 0.0008M indium sulfate, adding 0.2053g of 1, 2-dimethylimidazole and 0.5253g of 1,3, 5-trimesic acid, stirring for 30min, uniformly mixing, transferring to a 100mL reaction kettle, putting the reaction kettle into an oven for hydrothermal reaction at 160 ℃ for 12h, naturally cooling, centrifuging, cleaning with methanol, and drying to obtain a precursor; the reaction kettle is a hydrothermal reaction kettle with a polytetrafluoroethylene inner container and a stainless steel outer sleeve;
step 2: placing the precursor prepared in the step 1 in a tubular furnace, introducing nitrogen for 1h for calcination at the calcination temperature of 350 ℃ for 4h to obtain black powder, namely the carbon dioxide electrochemical reduction catalyst (copper-indium bimetallic co-doped organic framework catalyst) named as Cu2In1-MOF-NO3Catalyst 2.
Example 7
The embodiment provides a preparation method of a carbon dioxide electrochemical reduction catalyst, which comprises the following specific steps:
step 1: 0.3020g of copper nitrate trihydrate and 0.3236g of In2S3O12Dissolving in 50mL methanol solution to obtain 0.0013M copper nitrate and 0.0M copper nitrate013M indium sulfate mixed solution is added with 0.2053g of 1, 2-dimethylimidazole and 0.5253g of 1,3, 5-trimesic acid, stirred for 30min, mixed uniformly and transferred to a 100mL reaction kettle, the reaction kettle is placed in an oven for hydrothermal reaction for 12h at 160 ℃, and the precursor is obtained after natural cooling, centrifugation, washing with methanol and drying; the reaction kettle is a hydrothermal reaction kettle with a polytetrafluoroethylene inner container and a stainless steel outer sleeve;
step 2: placing the precursor prepared in the step 1 in a tubular furnace, introducing nitrogen for 1h for calcination at the calcination temperature of 350 ℃ for 4h to obtain black powder, namely the carbon dioxide electrochemical reduction catalyst (copper-indium bimetallic co-doped organic framework catalyst) named as Cu1In1-MOF-NO3Catalyst 2.
Example 8
The embodiment provides a preparation method of a carbon dioxide electrochemical reduction catalyst, which comprises the following specific steps:
step 1: 0.1510g of copper nitrate trihydrate and 0.4855g of In2S3O12Dissolving in 50mL of methanol solution at the same time to prepare a mixed solution of 0.00069M copper nitrate and 0.0019M indium sulfate, adding 0.2053g of 1, 2-dimethylimidazole and 0.5253g of 1,3, 5-trimesic acid, stirring for 30min, uniformly mixing, transferring to a 100mL reaction kettle, putting the reaction kettle into an oven for hydrothermal reaction at 160 ℃ for 12h, naturally cooling, centrifuging, cleaning with methanol, and drying to obtain a precursor; the reaction kettle is a hydrothermal reaction kettle with a polytetrafluoroethylene inner container and a stainless steel outer sleeve;
step 2: placing the precursor prepared in the step 1 in a tubular furnace, introducing nitrogen for 1h for calcination at the calcination temperature of 350 ℃ for 4h to obtain black powder, namely the carbon dioxide electrochemical reduction catalyst (copper-indium bimetallic co-doped organic framework catalyst) named as Cu1In3-MOF-NO3Catalyst 2.
FIGS. 1-2 show linear scanning polarization curves, the apparatus used being an electrochemical workstation manufactured by Shanghai Chenghua, Inc. and having model number CHI600 e. FIG. 1 shows examples 1,2, 3 and 4And indium nitrate is used as a carbon dioxide electrochemical reduction catalyst of the In-doped metal. FIG. 1 illustrates that of the 4 catalysts, example 3 exhibited the best catalytic performance, i.e., the maximum current density and the minimum peak overpotential at a copper to indium ratio of 1: 1. FIG. 2 shows the catalysts for electrochemical reduction of carbon dioxide using indium sulfate as In-doped metal In examples 5, 6, 7 and 8, respectively, and FIG. 2 shows the best performance of the catalysts In example 5 among the four catalysts, i.e., -0.42V vs. RHE at a copper to indium ratio of 3:1, and a current density of 90mA/cm was obtained2The electrode potential was then-1.16V.
FIG. 3 is a graph showing the Faraday efficiency of the catalyst of the above example for the electrocatalytic conversion of carbon dioxide to formic acid using an ion chromatograph model IC1280 manufactured by Shimadzu corporation, Japan. It is shown that of the 8 catalysts, example 8 has the best selectivity to formic acid, i.e. when indium sulfate is used as the In-doped metal precursor, the ratio of copper to indium is 1: the selectivity of the catalyst to formic acid is best at 1, and the anion is SO4 2-。
FIG. 4 is a graph of the Faraday efficiency of carbon monoxide using a gas chromatograph manufactured by Shimadzu corporation of Japan and model number GC 1120. The faradaic efficiency of the catalysts of the above examples to electrocatalyze the conversion of carbon dioxide to carbon monoxide is shown in figure 4. Figure 4 illustrates the best carbon monoxide selectivity of example 4 among the 8 catalysts. That is, when indium nitrate is used as an In-doped metal precursor and the ratio of copper to indium is 2:1, the selectivity of the catalyst to carbon monoxide is best, and the anion is NO3 -. The above shows that the catalytic activity and selectivity of the copper-indium co-doped organic frame electrocatalysis carbon dioxide can be effectively improved by effectively regulating and controlling the species and the doping concentration of the In-doped precursor, and meanwhile, the current density of the catalyst can be remarkably improved, and the energy consumption is reduced.
Claims (8)
1. The preparation method of the carbon dioxide electrochemical reduction catalyst is characterized by comprising the following steps:
step 1: dissolving copper salt and indium salt in a solvent simultaneously, adding dimethyl imidazole and benzenetricarboxylic acid simultaneously, mixing uniformly to form a precursor solution, transferring the precursor solution to a reaction kettle, carrying out hydrothermal reaction at 160 ℃ for 12h, naturally cooling, centrifuging, washing with methanol, and drying to obtain a precursor;
step 2: and (3) placing the precursor prepared in the step (1) in a tubular furnace, introducing nitrogen for 1-3 h for calcination, wherein the calcination temperature is 250-450 ℃, and the calcination time is 4-24 h, so as to obtain the carbon dioxide electrochemical reduction catalyst.
2. The method for preparing a catalyst for electrochemical reduction of carbon dioxide according to claim 1, wherein the copper salt in step 1 is copper nitrate, and the copper nitrate is copper nitrate trihydrate and/or copper nitrate hexahydrate.
3. The method for preparing a catalyst for electrochemical reduction of carbon dioxide as claimed in claim 1, wherein the indium salt in step 1 is indium nitrate or indium sulfate, the indium nitrate is one of indium nitrate hydrates, and the indium sulfate is one of indium sulfate hydrates.
4. The method for preparing a catalyst for electrochemical reduction of carbon dioxide according to claim 1, wherein the solvent in step 1 is deionized water or methanol.
5. The method for preparing a catalyst for electrochemical reduction of carbon dioxide according to claim 1, wherein in the step 1, the dimethylimidazole is 1, 2-dimethylimidazole and/or 2, 4-dimethylimidazole, and the benzenetricarboxylic acid is 1,3, 5-benzenetricarboxylic acid and/or 1,2, 4-benzenetricarboxylic acid.
6. The method for preparing a catalyst for electrochemical reduction of carbon dioxide according to claim 1, wherein in the precursor solution in the step 1, the concentration of copper salt is 0.01 to 0.05M, the concentration of indium salt is 0.01 to 0.05M, the concentration of dimethylimidazole is 0.001 to 0.005M, and the concentration of trimesic acid is 0.001 to 0.005M.
7. A catalyst for electrochemical reduction of carbon dioxide prepared by the method of any one of claims 1 to 6.
8. Use of the carbon dioxide electrochemical reduction catalyst prepared by the method of any one of claims 1 to 6 in the preparation of a gas diffusion electrode.
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