CN117385404A - Electrode loaded with in-situ reconstruction copper-carbon composite catalyst and preparation method and application thereof - Google Patents
Electrode loaded with in-situ reconstruction copper-carbon composite catalyst and preparation method and application thereof Download PDFInfo
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- CN117385404A CN117385404A CN202311133507.XA CN202311133507A CN117385404A CN 117385404 A CN117385404 A CN 117385404A CN 202311133507 A CN202311133507 A CN 202311133507A CN 117385404 A CN117385404 A CN 117385404A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 47
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 46
- 239000002131 composite material Substances 0.000 title claims abstract description 36
- AHADSRNLHOHMQK-UHFFFAOYSA-N methylidenecopper Chemical compound [Cu].[C] AHADSRNLHOHMQK-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title abstract description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 71
- 239000000243 solution Substances 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229920000557 Nafion® Polymers 0.000 claims abstract description 25
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 24
- 239000008055 phosphate buffer solution Substances 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 239000003960 organic solvent Substances 0.000 claims abstract description 14
- 150000001879 copper Chemical class 0.000 claims abstract description 13
- 238000011068 loading method Methods 0.000 claims abstract description 7
- 239000011159 matrix material Substances 0.000 claims abstract description 5
- 230000001681 protective effect Effects 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 34
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 31
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 31
- 239000007789 gas Substances 0.000 claims description 30
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 22
- 230000009467 reduction Effects 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 15
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 229910052786 argon Inorganic materials 0.000 claims description 11
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 claims description 10
- 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 9
- 230000008569 process Effects 0.000 claims description 9
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 8
- 239000008363 phosphate buffer Substances 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 8
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 6
- 238000010304 firing Methods 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 4
- 239000002041 carbon nanotube Substances 0.000 claims description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 4
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 4
- 229910021389 graphene Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 3
- 235000011009 potassium phosphates Nutrition 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 6
- 239000001569 carbon dioxide Substances 0.000 abstract description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 3
- 230000010757 Reduction Activity Effects 0.000 abstract description 2
- 239000013043 chemical agent Substances 0.000 abstract 1
- 238000011946 reduction process Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 50
- 238000006722 reduction reaction Methods 0.000 description 29
- 229910052799 carbon Inorganic materials 0.000 description 26
- 239000010949 copper Substances 0.000 description 25
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 21
- 229910052802 copper Inorganic materials 0.000 description 20
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 19
- 230000010355 oscillation Effects 0.000 description 18
- 238000010438 heat treatment Methods 0.000 description 16
- 239000008367 deionised water Substances 0.000 description 15
- 229910021641 deionized water Inorganic materials 0.000 description 15
- 238000003756 stirring Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- 238000001514 detection method Methods 0.000 description 4
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 4
- 235000019799 monosodium phosphate Nutrition 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000012691 Cu precursor Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- TVZRAEYQIKYCPH-UHFFFAOYSA-N 3-(trimethylsilyl)propane-1-sulfonic acid Chemical compound C[Si](C)(C)CCCS(O)(=O)=O TVZRAEYQIKYCPH-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- RAOSIAYCXKBGFE-UHFFFAOYSA-K [Cu+3].[O-]P([O-])([O-])=O Chemical compound [Cu+3].[O-]P([O-])([O-])=O RAOSIAYCXKBGFE-UHFFFAOYSA-K 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 230000005311 nuclear magnetism Effects 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 241000208340 Araliaceae Species 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N Heavy water Chemical group [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 238000003988 headspace gas chromatography Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002060 nanoflake Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 238000000079 presaturation Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- HWEXKRHYVOGVDA-UHFFFAOYSA-M sodium;3-trimethylsilylpropane-1-sulfonate Chemical compound [Na+].C[Si](C)(C)CCCS([O-])(=O)=O HWEXKRHYVOGVDA-UHFFFAOYSA-M 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000005556 structure-activity relationship Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- 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
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
-
- 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
- C25B1/23—Carbon monoxide or syngas
-
- 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
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/065—Carbon
-
- 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
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/25—Reduction
- C25B3/26—Reduction of carbon dioxide
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the field of carbon dioxide resource utilization, and discloses a method for preparing an electrode loaded with an in-situ reconstructed copper-carbon composite catalyst, which comprises the following steps: (1) Copper salt, carbon material, organic solvent and water are mixed and then baked in the presence of protective gas; (2) Mixing the roasting product obtained in the step (1) with a phosphate buffer solution, and then drying; (3) Mixing the dried product obtained in the step (2) with Nafion ethanol solution, then loading the obtained mixture on a conductive matrix, and carrying out in-situ electroreduction to obtain the electrode loaded with the in-situ reconstructed copper-carbon composite catalyst. The loaded in-situ reconstructed copper-carbon composite catalyst prepared by adopting the methodElectrode of the chemical agent in CO 2 The catalyst has stable morphology, higher reduction activity, good product selectivity, low preparation cost and simple preparation in the electro-reduction process.
Description
Technical Field
The invention relates to the field of carbon dioxide resource utilization, in particular to an electrode loaded with an in-situ reconstruction copper-carbon composite catalyst, and a preparation method and application thereof.
Background
With CO in the atmosphere 2 The continuous increase of the content promotes various CO 2 Development of emission reduction conversion technologies, including thermochemical, photochemical and electrochemical, have contemplated conversion of carbon dioxide to valuable chemical products and fuels, and maintaining a dynamic balance of carbon circulation. Electrochemical CO 2 Reduction is one of the most attractive strategies because it has a number of advantages, including mild reaction conditions operating at room temperature and pressure, recoverable electrolytes, and environmentally friendly driving forces generated by potential synergy with renewable electricity.
Copper-based composite materialThe material is the only material reported at present and can convert CO 2 The metal catalyst is high-efficiency and can be converted into multi-carbon products, and the metal catalyst is rich in content, low in cost and easy to obtain. However, the problems of poor selectivity, low activity, insufficient stability and the like still exist at present. On the one hand, the slow carbon-carbon coupling kinetics of copper surfaces limits the efficient production of multi-carbon products. On the other hand, mass transfer limitations at the electrode interface have a large impact on the reactivity of the reaction, generally limiting the increase in current density. Therefore, research is conducted on improving the CO content of copper-based composite materials 2 The activity and selectivity in the electroreduction to the multi-carbon product is of great importance.
Morphology structure of copper nano catalytic material for electrocatalytic CO 2 The product selectivity of the reduction reaction has a significant effect. The method has been reported in the literature, and copper catalysts with different morphologies are synthesized by annealing, film chemical treatment, colloid synthesis, solution electrodeposition and other methods, and the results show that the morphology difference can indeed bring about electrocatalytic CO 2 Variation in reduction reaction performance. Copper catalyst for CO at negative potential 2 During the electro-reduction reaction, the morphology structure of the catalyst may be changed, and the electrochemical in-situ reconstruction processes such as crushing, agglomeration and the like are generated, so that the particle size and morphology are changed, and the performance of the catalyst is influenced finally. For example, team Yang Peidong reports that closely packed spherical copper particles, upon application of a certain potential, will reform into cubic nanostructures, resulting in a multi-carbon product (Copper Nanoparticle Ensembles for Selective Electroreduction of CO 2 to C 2 -C 3 Products.proceedings of the National Academy of Sciences of the United States of America,2017,114 (40): 10560). Sargent et al adopts a surface reconstruction process to adjust the morphology of copper catalyst and improve the CO yield 2 Product selectivity and bias current density in the electro-reduction reaction (ASurface Reconstruction Route to High Productivity and Selectivity in CO) 2 Electroreduction toward C 2+ Advanced Materials,2018,30 (49): 1804867). However, the prior researches focus on the research on the structure-activity relationship of the catalyst, and the knowledge on the dynamic change of the catalyst structure is insufficient; meanwhile, the preparation method is complex, and the ginseng needs to be controlledAnd a large number. In addition, the morphology and structure of the catalyst are changed in the early stage of the electrocatalytic reaction, which is not common.
Disclosure of Invention
The invention aims to overcome the defects of CO existing in the prior art 2 The electrode of the in-situ-reconstructed copper-carbon composite catalyst is loaded, and the preparation method and application thereof are provided.
To achieve the above object, a first aspect of the present invention provides a method of preparing an electrode supporting an in-situ reconstituted copper-carbon composite catalyst, the method comprising the steps of:
(1) Copper salt, carbon material, organic solvent and water are mixed and then baked in the presence of protective gas;
(2) Mixing the roasting product obtained in the step (1) with a phosphate buffer solution, and then drying;
(3) Mixing the dried product obtained in the step (2) with Nafion ethanol solution, then loading the obtained mixture on a conductive matrix, and carrying out in-situ electroreduction to obtain the electrode loaded with the in-situ reconstructed copper-carbon composite catalyst.
Preferably, in the step (1), the copper salt is one or more selected from copper nitrate, copper chloride, copper acetate and copper sulfate.
Preferably, the solid to liquid ratio of the copper salt to the water is 1-10mg:1mL.
Preferably, in the step (1), the carbon material is one or more selected from activated carbon, carbon black, carbon nanotubes and graphene.
Preferably, the carbon material and water are used in a solid-to-liquid ratio of 5 to 50mg:1mL.
Preferably, in step (1), the organic solvent is selected from ethanol and/or propanol.
Preferably, the volume ratio of the organic solvent to the water is 0.01-0.1:1.
preferably, in step (1), the shielding gas is at least one selected from nitrogen, argon and helium.
Preferably, the shielding gas has a gas flow rate of 10-300mL/min, preferably 50-100mL/min.
Preferably, in step (1), the calcination temperature is 200-600 ℃, preferably 250-500 ℃; the calcination time is 1 to 10 hours, preferably 1 to 5 hours.
Preferably, in step (2), the amount of the calcination product and the phosphate buffer is used in a solid-to-liquid ratio of 0.5 to 10g:1L.
Preferably, in the step (2), the phosphate buffer solution is selected from two or more of potassium phosphate, potassium phosphate monobasic, sodium phosphate monobasic.
Preferably, in step (2), the mixing time is 1-13h.
Preferably, in the step (3), the solid-to-liquid ratio of the calcined product to the Nafion ethanol solution is 5-50mg:1mL.
Preferably, in step (2), the Nafion concentration of the Nafion ethanol solution is 0.1-3 wt%, preferably 0.5-1 wt%.
Preferably, in step (3), the pre-reduction potential applied by in situ electroreduction is from-0.6 to-1.6 v vs. rhe, preferably from-0.8 to-1.4 v vs. rhe.
In a second aspect the invention provides an electrode loaded with an in situ reconstituted copper-carbon composite catalyst prepared by the method described hereinbefore.
In a third aspect, the invention provides the electrode carrying the in situ reconstituted copper-carbon composite catalyst as described above for the electroreduction of CO 2 Is used in the field of applications.
In a fourth aspect the invention provides an electroreduction of CO 2 The method comprising: the three-electrode system is adopted, and the electrode of the supported in-situ reconstructed copper-carbon composite catalyst is used as the electric reduction CO 2 The working electrode of (2), ag/AgCl electrode as reference electrode, platinum net as counter electrode, soluble bicarbonate solution as electrolyte, sealed H-type double-cell electrolytic tank as reactor, introducing CO 2 Connected with voltage, for CO 2 In situ electroreduction is performed.
Preferably, CO 2 The gas flow rate of (2) is 5-100mL/min.
Preferably, the reaction temperature is 10-60 ℃.
Preferably, the voltage is-1.0 to-2.0V vs. RHE.
Compared with the prior art, the technical mode of the invention has the following advantages:
(1) The preparation method is simple, and the parameters to be controlled are few.
(2) The electrode of the supported in-situ reconstructed copper-carbon composite catalyst obtained by the invention has stable morphology, better electrocatalytic performance and higher reduction activity.
Drawings
FIG. 1 is an SEM image of a sample prepared according to example 1;
fig. 2 is a TEM image of the sample prepared in example 1.
Detailed Description
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
In the description of the present application, the terms "first", "second" are used for descriptive purposes only and are not to be construed as indicating relative importance or implicitly indicating the number of technical features indicated. Thus, unless otherwise indicated, features defining "first", "second" may include one or more such features either explicitly or implicitly; the meaning of "plurality" is two or more. The terms "comprises," "comprising," and any variations thereof, are intended to cover a non-exclusive inclusion, such that one or more other features, integers, steps, operations, elements, components, and/or groups thereof may be present or added.
In one aspect, the present invention provides a method of preparing an electrode supporting an in situ reconstituted copper-carbon composite catalyst, the method comprising the steps of:
(1) Copper salt, carbon material, organic solvent and water are mixed and then baked in the presence of protective gas;
(2) Mixing the roasting product obtained in the step (1) with a phosphate buffer solution, and then drying;
(3) Mixing the dried product obtained in the step (2) with Nafion ethanol solution, then loading the obtained mixture on a conductive matrix, and carrying out in-situ electroreduction to obtain the electrode loaded with the in-situ reconstructed copper-carbon composite catalyst.
In the method of the invention, the step (1) obtains the carbon material loaded with CuO x And (3) obtaining the composite material with the carbon material and Cu nano particles loaded on the conductive matrix.
In a preferred embodiment, the specific process of step (1) comprises: copper salt, carbon material, organic solvent and water are mixed, stirred and evaporated to dryness, and then baked in the presence of protective gas.
In a preferred embodiment, in step (1), the copper salt is a water-soluble copper salt, and specifically, the copper salt may be one or more of copper nitrate, copper chloride, copper acetate and copper sulfate.
Further preferably, in step (1), the solid-to-liquid ratio of the copper salt to the water is 1 to 10mg:1mL; specifically, it may be 1mg:1mL, 2mg:1mL, 3mg:1mL, 4mg:1mL, 5mg:1mL, 6mg:1mL, 7mg:1mL, 8mg:1mL, 9mg:1mL or 10mg:1mL.
In a preferred embodiment, in step (1), the carbon material is selected from one or more of activated carbon, carbon black, carbon nanotubes or graphene.
Further preferably, in step (1), the carbon material and water are used in an amount such that the solid-to-liquid ratio is 5 to 50mg:1mL; specifically, it may be 5mg:1mL, 10mg:1mL, 15mg:1mL, 20mg:1mL, 25mg:1mL, 30mg:1mL, 35mg:1mL, 40mg:1mL, 45mg:1mL or 50mg:1mL.
In a preferred embodiment, in step (1), the organic solvent is a hydrophilic organic solvent, in particular the organic solvent is selected from ethanol and/or propanol.
Further preferably, in step (1), the volume ratio of the amount of ethanol and water used is 0.01 to 0.1, and in particular, may be 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, or 0.1.
In the invention, the hydrophilic organic solvent promotes the carbon material to be better dispersed in the solution, and is beneficial to the copper loading process.
In a preferred embodiment, in step (1), the mixing is by ultrasonic agitation.
Further preferably, the time of the ultrasonic oscillation is 5 to 60min, more preferably, the time of the ultrasonic oscillation is 10 to 30min, and specifically, may be 10min, 15min, 20min, 25min, 30min or 50min.
In a preferred embodiment, in step (1), the temperature of the stirred and evaporated to dryness is 10-60 ℃, in particular, may be 10 ℃,20 ℃, 25 ℃,30 ℃, 40 ℃, 45 ℃, 50 ℃ or 60 ℃.
The stirring and evaporating treatment in the invention mainly comprises water and a small amount of organic solvent, and the low-temperature stirring and evaporating can keep the evaporating process slow, so that the copper precursor is more uniformly dispersed and loaded in the carbon material.
In a preferred embodiment, in the step (1), the shielding gas is one or more selected from nitrogen, argon and helium.
In a preferred embodiment, in step (1), the shielding gas has a gas flow rate of 10-300mL/min, preferably 50-100mL/min; specifically, it may be 50mL/min, 60mL/min, 70mL/min, 80mL/min, 90mL/min, 100mL/min or 200mL/min.
In a preferred embodiment, in step (1), the firing temperature is 200-600 ℃, the firing time is 1-10 hours, more preferably 250-500 ℃, and the firing time is 1-5 hours; specifically, the baking temperature is 200 ℃, 250 ℃, 300 ℃, 380 ℃, 450 ℃, 500 ℃, 550 ℃ or 600 ℃; the time may be 1h, 2h, 3h, 4h or 5h.
In a preferred embodiment, in step (2), the initial temperature of calcination is from 20 to 30 ℃; specifically, it may be 20 ℃, 21 ℃, 22 ℃, 23 ℃, 24 ℃, 25 ℃, 26 ℃, 27 ℃, 28 ℃, 29 ℃ or 30 ℃.
In a preferred embodiment, in step (1), the temperature increase rate of the firing is 1 to 20 ℃/min, more preferably, the temperature increase rate of the annealing treatment is 1 to 10 ℃/min. Specifically, it may be 1℃per minute, 2℃per minute, 3℃per minute, 5℃per minute, 8℃per minute or 10℃per minute.
The roasting in the invention can promote the decomposition of Cu precursor, thereby obtaining the CuO loaded by the carbon material x (x= 0,0.5,1). Because of the reducibility of the carbon material in the high-temperature inert atmosphere, cu and Cu can be obtained respectively by decomposing the Cu precursor according to different roasting temperatures 2 O and CuO, i.e. Cu species of different valence.
In a preferred embodiment, the specific process of step (2) comprises: and (3) carrying out first mixing on the roasting product obtained in the step (1) and a phosphate buffer solution, then carrying out second mixing by shaking on a shaking table, and then drying.
In a preferred embodiment, in step (2), the amount of calcination product and phosphate buffer used in a solid to liquid ratio of 0.5 to 10g:1L, in particular, may be 0.5g:1L, 1g:1L, 2g:1L, 3g:1L, 4g:1L, 5g:1L, 6g:1L, 7g:1L, 8g:1L, 9g:1L or 10g:1L.
In a preferred embodiment, in step (2), the phosphate buffer solution is formulated from two or more selected from potassium phosphate, potassium phosphate monobasic, sodium phosphate monobasic, or sodium phosphate monobasic.
In a preferred embodiment, in step (2), the phosphate buffer is formulated with a molar ratio of dihydrogen phosphate to monohydrogen phosphate of 1.58, ph=7.
Further preferably, the concentration of the phosphate buffer solution is 0.01 to 0.5mol/L, and specifically, may be 0.01mol/L, 0.05mol/L, 0.1mol/L, 0.2mol/L, 0.3mol/L, 0.4mol/L, or 0.5mol/L.
In the present invention, cuO supported on a carbon material can be obtained by using a phosphate buffer x Cu converted into nano-flake 3 (PO 4 ) 2 。
In a preferred embodiment, in step (2), the first mixing means is stirring and/or ultrasonic vibration.
Further preferably, in step (2), the first mixing is for a time of 5-60min, more preferably for a time of 30-60min, in particular, 30min, 35min, 40min, 45min, 50min, 55min or 60min.
In a preferred embodiment, in step (2), the second mixing is carried out by shaking on a shaker for a period of time of 1 to 12 hours, in particular 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 and 12 hours
In a preferred embodiment, in step (2), the temperature of the drying is 60-100 ℃, in particular, 60 ℃, 70 ℃, 80 ℃, 90 ℃ or 100 ℃.
In a preferred embodiment, in step (2), the drying is performed in an oven for a period of 8-24 hours, in particular, 12, 15, 18, 20, 22 or 24 hours.
Preferably, in the step (3), the solid-to-liquid ratio of the calcined product to the Nafion ethanol solution is 5-50mg:1mL, specifically, may be 5mg:1mL, 10mg:1mL, 15mg:1mL, 20mg:1mL, 25mg:1mL, 30mg:1mL, 35mg:1mL, 40mg:1mL, 45mg:1mL or 50mg:1mL.
In a preferred embodiment, in the step (3), the Nafion ethanol solution is an ethanol solution of a perfluorosulfonic acid polymer, and is purchased from dupont in the united states and used as a 5 wt% solution of Nafion in ethanol diluted with ethanol.
In a preferred embodiment, in step (3), the Nafion ethanol solution has a Nafion concentration of 0.1 to 3 wt.%, more preferably a concentration of 0.5 to 1 wt.%, and in particular may be 0.5 wt.%, 0.6 wt.%, 0.7 wt.%, 0.8 wt.%, 0.9 wt.%, or 1 wt.%.
In step (3), the conductive substrate is a conventional choice in the art, and in a preferred embodiment, the conductive substrate is porous carbon paper purchased from HCP020, inc. of Shanghon electric Co.
In a preferred embodiment, in step (3), the pre-reduction potential is-0.6 to-1.6 v vs. rhe, more preferably the pre-reduction potential is-0.8 to-1.4 v vs. rhe, in particular it may be-0.8 v vs. rhe, -0.9v vs. rhe, -1.0v vs. rhe, -1.1v vs. rhe, -1.2v vs. rhe, -1.3v vs. rhe, -1.4v vs. rhe or-1.6 v vs. rhe.
In the present invention, the vs. RHE is a relatively reversible hydrogen electrode potential, and the applied potential is converted to a reversible hydrogen electrode by the following formula with respect to an Ag/AgCl reference electrode (saturated KCl solution)
E(vs.RHE)＝E(vs.Ag/AgCl)+0.197V+0.0591V×pH
In the formula E (vs. Ag/AgCl) is the applied potential compared with the Ag/AgCl reference electrode, the pH value is the electrolyte KHCO measured by a pH meter 3 When the pH is in the range of 6-8.
In a second aspect the invention provides an electrode loaded with an in situ reconstituted copper-carbon composite catalyst prepared by the method described hereinbefore.
In a preferred case, the electrode loading of the in-situ reconfiguration copper-carbon composite catalyst prepared by the method is 0.1-5mg/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the Specifically, the loading may be 0.1mg/cm 2 、0.5mg/cm 2 、1mg/cm 2 、2mg/cm 2 、3mg/cm 2 、4mg/cm 2 、5mg/cm 2 、6mg/cm 2 、7mg/cm 2 、8mg/cm 2 、9mg/cm 2 Or 10mg/cm 2 . The load is 1cm of in-situ reconstructed copper/carbon composite catalyst 2 Amount on the conductive substrate.
In a third aspect, the invention provides the electrode carrying the in situ reconstituted copper-carbon composite catalyst as described above for the electroreduction of CO 2 Is used in the field of applications.
In a fourth aspect the invention provides an electroreduction of CO 2 The method comprising: using a three-electrode system, as described hereinbeforeElectrode loaded with in-situ reconstructed copper-carbon composite catalyst as electric reduction CO 2 The working electrode of (2), ag/AgCl electrode as reference electrode, platinum net as counter electrode, soluble bicarbonate solution as electrolyte, sealed H-type double-cell electrolytic tank as reactor, introducing CO 2 Is connected with a power supply and is used for CO 2 Electrolysis is performed.
In a preferred embodiment, the soluble bicarbonate solution is potassium bicarbonate at a concentration of 0.1 to 0.5mol/L.
In a preferred embodiment, the CO is reduced electrically 2 CO in applications of (2) 2 The flow is 5-100mL/min; specifically, it may be 5mL/min, 10mL/min, 15mL/min, 20mL/min, 30mL/min, 40mL/min, 50mL/min, 60mL/min, 80mL/min, 90mL/min or 100mL/min.
In a preferred embodiment, the CO is reduced electrically 2 The reaction temperature is 10-60 ℃ in the application; specifically, it may be 10 ℃, 15 ℃,20 ℃, 25 ℃,30 ℃, 40 ℃, 50 ℃ or 60 ℃.
In a preferred embodiment, the CO is reduced electrically 2 The voltage is-1.0 to-2.0 Vvs. RHE; in particular, -1.2V vs. RHE, -1.3V vs. RHE, -1.4V vs. RHE, -1.5V vs. RHE or-1.6V vs. RHE.
The electrode carrying the in-situ reconstructed copper-carbon composite catalyst, the preparation method and the application thereof are further described by the following examples. The embodiment is implemented on the premise of the technical scheme of the invention, and detailed implementation modes and specific operation processes are given, but the protection scope of the invention is not limited to the following embodiment.
The experimental methods in the following examples, unless otherwise specified, are all conventional in the art. The experimental materials used in the examples described below are commercially available unless otherwise specified.
Example 1
(1) Adding 70mg of copper nitrate, 200mg of active carbon and 0.5mL of ethanol into 10mL of deionized water, and performing ultrasonic oscillation for 20min; stirring the obtained solution at 25 ℃ until the water is evaporated, then heating to 400 ℃ at a heating rate of 2 ℃/min, and roasting for 4 hours by taking argon with a flow rate of 100mL/min as a shielding gas;
(2) Adding 0.2g of the roasting product into 200mL of phosphate buffer solution prepared by 0.05mol/L potassium dihydrogen phosphate and monopotassium phosphate (pH=7, specifically the preparation method is that 0.83g of potassium dihydrogen phosphate, 0.41g of potassium dihydrogen phosphate and 200mL of deionized water are mixed), carrying out ultrasonic oscillation for 60min, shaking for 4h on a shaking table, and drying for 12h at 80 ℃ by using an oven;
(3) After dispersing 10mg of the dried product in 0.6mL of 0.5% Nafion ethanol solution, 30. Mu.L of the solution was dropped on 1cm 2 applying-1.2V vs. RHE pre-reduction potential on porous carbon paper (1 cm×1 cm), and performing in-situ electroreduction to obtain the final product with load of 0.5mg/cm 2 Copper-based CO of (a) 2 An electro-reduction catalyst.
Example 2
(1) 50mg of copper chloride, 300mg of active carbon and 0.5mL of ethanol are added into 20mL of deionized water, and ultrasonic oscillation is carried out for 25min; stirring the obtained solution at 30 ℃ until the water is evaporated, then heating to 250 ℃ at a heating rate of 2 ℃/min, and roasting for 4 hours by taking argon with a flow rate of 100mL/min as a shielding gas;
(2) Adding 0.3g of the roasting product into 300mL of phosphate buffer solution prepared by 0.1mol/L potassium dihydrogen phosphate and monopotassium phosphate (pH=7, specifically the preparation method is that 2.5g of potassium dihydrogen phosphate, 1.24g of potassium dihydrogen phosphate and 300mL of deionized water are mixed), carrying out ultrasonic oscillation for 40min, shaking for 6h on a shaking table, and drying for 18h at 90 ℃ by using an oven;
(3) 30mg of the dried product was dispersed in 0.6mL of 0.5% Nafion ethanol solution, and 30. Mu.L was dropped onto 1cm 2 applying-1.0V vs. RHE pre-reduction potential on porous carbon paper (1 cm×1 cm) for in-situ electroreduction to obtain 1.5mg/cm of load 2 Copper-based CO of (a) 2 An electro-reduction catalyst.
Example 3
(1) Adding 300mg of copper sulfate, 600mg of active carbon and 0.5mL of ethanol into 50mL of deionized water, and carrying out ultrasonic oscillation for 50min; stirring the obtained solution at 50 ℃ until the water is evaporated, then heating to 600 ℃ at a heating rate of 5 ℃/min, and roasting for 4 hours by taking argon with a flow rate of 100mL/min as a shielding gas;
(2) Adding 0.6g of the roasting product into 100mL of phosphate buffer solution prepared by 0.3mol/L potassium dihydrogen phosphate and monopotassium phosphate (pH=7, specifically the preparation method is that 2.5g of potassium dihydrogen phosphate, 1.24g of potassium dihydrogen phosphate and 100mL of deionized water are mixed), carrying out ultrasonic oscillation for 50min, shaking for 8h on a shaking table, and drying for 10h at 80 ℃ by using an oven;
(3) After dispersing 20mg of the dried product in 1.2mL of 0.5% Nafion ethanol solution, 30. Mu.L of the solution was dropped on 1cm 2 (1 cm. Times.1 cm) porous carbon paper, applying-1.4V vs. RHE pre-reduction potential to perform in-situ electroreduction to obtain 0.5mg/cm load 2 Copper-based CO of (a) 2 An electro-reduction catalyst.
Example 4
(1) Adding 100mg of copper acetate, 200mg of activated carbon and 0.5mL of ethanol into 30mL of deionized water, and performing ultrasonic oscillation for 30min; stirring the obtained solution at 45 ℃ until the water is evaporated, then heating to 450 ℃ at a heating rate of 5 ℃/min, and roasting for 6 hours by taking argon with a flow rate of 200mL/min as a shielding gas;
(2) Adding 0.5g of the roasting product into 500mL of phosphate buffer solution prepared from 0.1mol/L sodium dihydrogen phosphate and sodium dihydrogen phosphate (pH=7, the specific preparation method is that 3.7g of sodium dihydrogen phosphate is mixed with 1.7g of sodium dihydrogen phosphate and 500mL of water), carrying out ultrasonic oscillation for 30min, shaking for 4h on a shaking table, and drying for 10h at 90 ℃ by using an oven;
(3) 30mg of the dried product was dispersed in 1.8mL of 0.5% Nafion ethanol solution, and 30. Mu.L was dropped onto 1cm 2 (1 cm. Times.1 cm) porous carbon paper, applying-1.6V vs. RHE pre-reduction potential to perform in-situ electroreduction to obtain the product with load of 0.5mg/cm 2 Copper-based CO of (a) 2 An electro-reduction catalyst.
Example 5
(1) 80mg of copper nitrate, 200mg of graphene and 0.5mL of ethanol are added into 20mL of deionized water, and ultrasonic oscillation is carried out for 30min; stirring the obtained solution at 60 ℃ until the water is evaporated, then heating to 380 ℃ at a heating rate of 2 ℃/min, and roasting for 4 hours by taking argon with a flow rate of 100mL/min as a shielding gas;
(2) Adding 0.4g of the roasting product into 100mL of phosphate buffer solution prepared by 0.05mol/L potassium dihydrogen phosphate and monopotassium phosphate (pH=7, specifically the preparation method is that 0.42g of potassium dihydrogen phosphate, 0.21g of potassium dihydrogen phosphate and 100mL of deionized water are mixed), carrying out ultrasonic oscillation for 60min, shaking for 4h on a shaking table, and drying for 12h at 80 ℃ by using an oven;
(3) After dispersing 10mg of the dried product in 0.6mL of 0.5% Nafion ethanol solution, 30. Mu.L of the solution was dropped on 1cm 2 applying-1.2V vs. RHE pre-reduction potential on porous carbon paper (1 cm×1 cm) for in-situ electroreduction to obtain 0.5mg/cm of load 2 Copper-based CO of (a) 2 An electro-reduction catalyst.
Example 6
(1) 60mg of copper nitrate, 300mg of active carbon and 0.5mL of ethanol are added into 30mL of deionized water, and ultrasonic oscillation is carried out for 30min; stirring the obtained solution at 40 ℃ until the water is evaporated, then heating to 250 ℃ at a heating rate of 2 ℃/min, and roasting for 4 hours by taking argon with a flow rate of 100mL/min as a shielding gas;
(2) Adding 0.6g of the roasting product into 200mL of phosphate buffer solution prepared by 0.1mol/L potassium dihydrogen phosphate and monopotassium phosphate (pH=7, specifically the preparation method is that 1.67g of potassium dihydrogen phosphate, 0.83g of potassium dihydrogen phosphate and 200mL of deionized water are mixed), carrying out ultrasonic oscillation for 60min, shaking for 4h on a shaking table, and drying for 12h at 80 ℃ by using an oven;
(3) After dispersing 10mg of the dried product in 0.6mL of 0.5% Nafion ethanol solution, 30. Mu.L of the solution was dropped on 1cm 2 applying-1.2V vs. RHE pre-reduction potential on porous carbon paper (1 cm×1 cm) for in-situ electroreduction to obtain 0.5mg/cm of load 2 Copper-based CO of (a) 2 An electro-reduction catalyst.
Example 7
(1) Adding 100mg of copper nitrate, 250mg of carbon nano tubes and 0.5mL of ethanol into 20mL of deionized water, and performing ultrasonic oscillation for 20min; stirring the obtained solution at 25 ℃ until the water is evaporated, then heating to 450 ℃ at a heating rate of 2 ℃/min, and roasting for 4 hours by taking argon with a flow rate of 100mL/min as a shielding gas;
(2) Adding 0.8g of the roasting product into 300mL of phosphate buffer solution prepared by 0.2mol/L potassium dihydrogen phosphate and monopotassium phosphate (pH=7, specifically the preparation method is that 5g of potassium dihydrogen phosphate, 2.48g of potassium dihydrogen phosphate and 300mL of deionized water are mixed), carrying out ultrasonic oscillation for 60min, shaking for 4h on a shaking table, and drying for 12h at 80 ℃ by using an oven;
(3) After dispersing 10mg of the dried product in 0.6mL of 0.5% Nafion ethanol solution, 30. Mu.L of the solution was dropped on 1cm 2 applying-1.2V vs. RHE pre-reduction potential on porous carbon paper (1 cm×1 cm) for in-situ electroreduction to obtain 0.5mg/cm of load 2 Copper-based CO of (a) 2 An electro-reduction catalyst.
Example 8
(1) 200mg of copper nitrate, 600mg of conductive carbon black and 3mL of ethanol are added into 50mL of deionized water, and ultrasonic oscillation is carried out for 20min; stirring the obtained solution at 30 ℃ until the water is evaporated, then heating to 600 ℃ at a heating rate of 2 ℃/min, and roasting for 4 hours by taking argon with a flow rate of 100mL/min as a shielding gas;
(2) Adding 0.2g of the roasting product into 200mL of phosphate buffer solution prepared by 0.05mol/L potassium dihydrogen phosphate and monopotassium phosphate (pH=7, specifically the preparation method is that 0.83g of potassium dihydrogen phosphate, 0.41g of potassium dihydrogen phosphate and 200mL of deionized water are mixed), carrying out ultrasonic oscillation for 60min, shaking for 4h on a shaking table, and drying for 12h at 80 ℃ by using an oven;
(3) After dispersing 10mg of the dried product in 0.6mL of 0.5% Nafion ethanol solution, 30. Mu.L of the solution was dropped on 1cm 2 applying-1.2V vs. RHE pre-reduction potential on porous carbon paper (1 cm×1 cm) for in-situ electroreduction to obtain 0.5mg/cm of load 2 Copper-based CO of (a) 2 An electro-reduction catalyst.
Comparative example 1
The procedure described in example 1 was followed, except that copper nitrate was not added in step (1).
Comparative example 2
The procedure described in example 1 was followed, except that in step (1), calcination was not carried out in the presence of a shielding gas.
Comparative example 3
The procedure described in example 1 was followed, except that no phosphate buffer was added in step (2).
Comparative example 4
The procedure described in example 1 was followed, except that in step (3) no in situ electroreduction was performed.
Test example 1
The sample obtained during the preparation of example 1 was characterized by SEM and the results are shown in fig. 1.
As can be seen from the figure, in the preparation process of example 1, the carbon material loaded with CuO is obtained by calcination x The composite material of the particles is obtained by treating the composite material of the particles with Phosphate Buffer (PBS) and then is obtained by carrying copper phosphate nano-sheets on the carbon material, and then is obtained by carrying out in-situ electroreduction on the composite material of the porous carbon paper and carrying the carbon material and Cu nano-particles.
Test example 2
The samples obtained during the preparation of example 1 were characterized by TEM and the results are shown in fig. 2.
As can be seen from the figure, the sample obtained in the preparation process of example 1, which is calcined to obtain a carbon material with CuO supported thereon x The composite material of the particles is obtained by treating the composite material of the particles with Phosphate Buffer (PBS) and then is obtained by carrying copper phosphate nano-sheets on the carbon material, and then is obtained by carrying out in-situ electroreduction on the composite material of the porous carbon paper and carrying the carbon material and Cu nano-particles.
Test example 3
CO was performed on the materials prepared in the above examples and comparative examples 2 And (3) electric reduction performance test:
the testing method comprises the following steps: adding 10mg of the prepared product into 0.6mL of 0.5% Nafion ethanol solution, oscillating for 30min with microwave, taking 30 μl of the mixed solution, and dripping onto 1cm 2 (1 cm. Times.1 cm) of carbon paper, and drying for 3 hours to obtain a cathode electrode.
A three-electrode system is adopted, a sealed H-shaped double-cell electrolytic tank is used as a reactor, an Ag/AgCl electrode is used as a reference electrode, and a platinum mesh of 2cm multiplied by 2cm is used as a counter electrode. 30mL KHCO is respectively added into two tanks of the H-type electrolytic tank 3 The solution is used as electrolyte with the concentration of 0.1mol/L, and the cathode and the anode electrolytic tank are separated by adopting a proton exchange membrane nafion 117. After detection ofIn the process, CO is firstly introduced into the reactor for 30min 2 Presaturation is carried out, CO is maintained in the reaction process 2 Is connected with gas chromatograph at the gas outlet for online gas phase product detection, and comprises CO and C 2 H 4 And H 2 . After the reaction is finished, collecting a liquid phase product, detecting an alcohol product by adopting a headspace gas chromatography, and detecting an acid by adopting liquid nuclear magnetism.
Electrocatalytic CO 2 The total efficiency of (2) is the sum of the efficiencies of the gas phase product and the liquid phase product, the test conditions are shown in Table 1, the test results are shown in Table 2,
gas phase product H 2 ，CO，C 2 H 4 And (3) detecting by using Shimadzu GC-2014 gas chromatography on line. The liquid phase product formic acid adopts nuclear magnetism to carry out off-line detection, and an adopted instrument is a JNM-ECZR nuclear magnetic resonance spectrometer. The nuclear magnetic internal standard used in the product test is heavy water (D 2 O) and 6mmol L -1 Sodium 3- (trimethylsilyl) -1-propanesulfonate (DSS). Taking 500 mu L of reacted liquid, 100 mu L of DSS solution and D respectively 2 O100. Mu.L was placed in a nuclear magnetic tube, and then liquid phase product detection was performed using a frequency of 600Hz and water peak suppression conditions.
The product faraday efficiency calculation formula refers to the following formula:
FE i (gas phase product) ＝α i ×c i ×v×F×t/Q×100％
FE i (liquid phase product) ＝α i ×c i ×V×F/Q×100％
α i Is made by CO 2 The number of electrons transferred when the electrocatalytic reduction reaction produces product i; c i (mol·L -1 ) The concentration of product i detected; v (L.h) -1 ) CO introduced into the reactor 2 A flow rate; v (L) volume of electrode chamber liquid; f is Faraday constant (96485 C.mol) -1 ) The method comprises the steps of carrying out a first treatment on the surface of the t (h) is the length of time the reaction takes place; q (C) is the total amount of charge applied.
TABLE 1
TABLE 2
As can be seen from the results of Table 2, the electrode of the supported in-situ reconstructed copper-carbon composite catalyst prepared by the method of the present invention, CO 2 High electrocatalytic efficiency and high selectivity of products.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (16)
1. A method of preparing an electrode supporting an in situ reconstituted copper-carbon composite catalyst, the method comprising the steps of:
(1) Copper salt, carbon material, organic solvent and water are mixed and then baked in the presence of protective gas;
(2) Mixing the roasting product obtained in the step (1) with a phosphate buffer solution, and then drying;
(3) Mixing the dried product obtained in the step (2) with Nafion ethanol solution, then loading the obtained mixture on a conductive matrix, and carrying out in-situ electroreduction to obtain the electrode loaded with the in-situ reconstructed copper-carbon composite catalyst.
2. The method according to claim 1, wherein in step (1), the copper salt is one or more selected from the group consisting of copper nitrate, copper chloride, copper acetate and copper sulfate;
preferably, the solid to liquid ratio of the copper salt to the water is 1-10mg:1mL.
3. The method according to claim 1 or 2, wherein in step (1), the carbon material is one or more selected from the group consisting of activated carbon, carbon black, carbon nanotubes and graphene;
preferably, the carbon material and water are used in a solid-to-liquid ratio of 5 to 50mg:1mL.
4. A process according to any one of claims 1 to 3, wherein in step (1) the organic solvent is selected from ethanol and/or propanol;
preferably, the volume ratio of the organic solvent to the water is 0.01-0.1:1.
5. the method according to any one of claims 1 to 4, wherein in the step (1), the shielding gas is one or more selected from the group consisting of nitrogen, argon and helium;
preferably, the shielding gas has a gas flow rate of 10-300mL/min, preferably 50-100mL/min.
6. The method according to any one of claims 1 to 5, wherein in step (1), the firing temperature is 200 to 600 ℃, preferably 250 to 500 ℃; the calcination time is 1 to 10 hours, preferably 1 to 5 hours.
7. The method according to any one of claims 1 to 6, wherein in the step (2), the solid-to-liquid ratio of the amount of the calcined product and the phosphate buffer is 0.5 to 10g:1L.
8. The method according to any one of claims 1 to 7, wherein in the step (2), the phosphate buffer solution is selected from two or more of potassium phosphate, potassium phosphate monobasic, sodium phosphate monobasic.
9. The method according to any one of claims 1 to 8, wherein in step (2), the mixing is performed for a period of 1 to 13 hours.
10. The method according to any one of claims 1 to 9, wherein in step (3), the solid-to-liquid ratio of the calcined product to the Nafion ethanol solution is 5 to 50mg:1mL.
11. The method according to claims 1-10, wherein in step (3) the concentration of Nafion in the Nafion ethanol solution is 0.1-3 wt%, preferably 0.5-1 wt%.
12. A method according to any one of claims 1 to 11, wherein in step (3) the pre-reduction potential applied by in situ electroreduction is from-0.6 to-1.6 v vs. rhe, preferably from-0.8 to-1.4 v vs. rhe.
13. An electrode carrying an in situ reconstituted copper-carbon composite catalyst prepared by the method of any one of claims 1 to 12.
14. The electrode on which an in situ reconstituted copper-carbon composite catalyst of claim 13 is supported for the electroreduction of CO 2 Is used in the field of applications.
15. Electric reduction of CO 2 The method comprising: use of a three-electrode system with the electrode of the supported in-situ reconstituted copper-carbon composite catalyst of claim 13 as an electroreducing CO 2 The working electrode of (2), ag/AgCl electrode as reference electrode, platinum net as counter electrode, soluble bicarbonate solution as electrolyte, sealed H-type double-cell electrolytic tank as reactor, introducing CO 2 Is connected with a power supply and is used for CO 2 In situ electroreduction is performed.
16. The method of claim 15, wherein the CO 2 The gas flow rate of the catalyst is 5-100mL/min;
preferably, the temperature of the electroreduction reaction is 10-60 ℃;
preferably, the voltage of the electroreduction reaction is-1.0 to-2.0V vs. RHE.
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