CN111676482B - Electrode for electrochemical reduction of carbon dioxide and application thereof - Google Patents
Electrode for electrochemical reduction of carbon dioxide and application thereof Download PDFInfo
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- CN111676482B CN111676482B CN202010540150.7A CN202010540150A CN111676482B CN 111676482 B CN111676482 B CN 111676482B CN 202010540150 A CN202010540150 A CN 202010540150A CN 111676482 B CN111676482 B CN 111676482B
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 65
- 230000009467 reduction Effects 0.000 title claims abstract description 40
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 120
- 239000010949 copper Substances 0.000 claims abstract description 109
- 238000001035 drying Methods 0.000 claims abstract description 67
- 239000003054 catalyst Substances 0.000 claims abstract description 55
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 53
- 238000005406 washing Methods 0.000 claims abstract description 50
- 229910052802 copper Inorganic materials 0.000 claims abstract description 46
- 150000001879 copper Chemical class 0.000 claims abstract description 45
- 230000008021 deposition Effects 0.000 claims abstract description 43
- 239000000758 substrate Substances 0.000 claims abstract description 39
- 238000009792 diffusion process Methods 0.000 claims abstract description 37
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000002070 nanowire Substances 0.000 claims abstract description 27
- 239000003792 electrolyte Substances 0.000 claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 239000011258 core-shell material Substances 0.000 claims abstract description 17
- 238000002791 soaking Methods 0.000 claims abstract description 16
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 13
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 8
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 7
- 230000003647 oxidation Effects 0.000 claims abstract description 5
- 238000000151 deposition Methods 0.000 claims description 77
- 238000006722 reduction reaction Methods 0.000 claims description 45
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 38
- 238000004140 cleaning Methods 0.000 claims description 36
- 239000007800 oxidant agent Substances 0.000 claims description 36
- 239000007789 gas Substances 0.000 claims description 35
- 230000001590 oxidative effect Effects 0.000 claims description 30
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000012266 salt solution Substances 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 21
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 19
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 19
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 16
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 16
- 229910016553 CuOx Inorganic materials 0.000 claims description 15
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 239000011261 inert gas Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 10
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 10
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 10
- 239000003381 stabilizer Substances 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 9
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 9
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 9
- 239000001509 sodium citrate Substances 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 239000011889 copper foil Substances 0.000 claims description 8
- 238000004070 electrodeposition Methods 0.000 claims description 8
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims description 8
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 239000011736 potassium bicarbonate Substances 0.000 claims description 6
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 6
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 4
- 229910001431 copper ion Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 3
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 3
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 3
- 239000001103 potassium chloride Substances 0.000 claims description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical group [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 3
- 235000019263 trisodium citrate Nutrition 0.000 claims description 3
- 229940038773 trisodium citrate Drugs 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 2
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 9
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 7
- 229930195733 hydrocarbon Natural products 0.000 abstract description 7
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 7
- 230000008878 coupling Effects 0.000 abstract description 5
- 238000010168 coupling process Methods 0.000 abstract description 5
- 238000005859 coupling reaction Methods 0.000 abstract description 5
- 230000007547 defect Effects 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 230000006872 improvement Effects 0.000 abstract description 2
- 238000011946 reduction process Methods 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 239000000654 additive Substances 0.000 abstract 1
- 230000000996 additive effect Effects 0.000 abstract 1
- 239000003638 chemical reducing agent Substances 0.000 abstract 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical class [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 abstract 1
- 229910001948 sodium oxide Inorganic materials 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 43
- 239000000047 product Substances 0.000 description 34
- OVBJJZOQPCKUOR-UHFFFAOYSA-L EDTA disodium salt dihydrate Chemical compound O.O.[Na+].[Na+].[O-]C(=O)C[NH+](CC([O-])=O)CC[NH+](CC([O-])=O)CC([O-])=O OVBJJZOQPCKUOR-UHFFFAOYSA-L 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 18
- 229910021642 ultra pure water Inorganic materials 0.000 description 14
- 239000012498 ultrapure water Substances 0.000 description 14
- 239000007864 aqueous solution Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000009826 distribution Methods 0.000 description 9
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 7
- 238000010531 catalytic reduction reaction Methods 0.000 description 7
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 7
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 6
- 235000011083 sodium citrates Nutrition 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910052927 chalcanthite Inorganic materials 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 235000011007 phosphoric acid Nutrition 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000012546 transfer Methods 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
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229940075397 calomel Drugs 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- RCTYPNKXASFOBE-UHFFFAOYSA-M chloromercury Chemical compound [Hg]Cl RCTYPNKXASFOBE-UHFFFAOYSA-M 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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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
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
-
- 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
- B01J23/72—Copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/18—Electroplating using modulated, pulsed or reversing current
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
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- Chemical Kinetics & Catalysis (AREA)
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- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
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Abstract
The invention relates to an electrode for electrochemical reduction of carbon dioxide and application thereof, wherein the catalyst is an ordered core-shell catalyst; the preparation method of the electrode comprises the following steps: pretreating a substrate, immersing the substrate in a certain amount of mixture of sodium hydroxide and oxide, and preparing CuO by chemical oxidation methodxA nanowire/Cu substrate; adding a reducing agent and an additive into copper salt, mixing in a certain proportion, carrying out Cu deposition by using variable current density, washing, drying, and placing into CO2Reducing, washing and drying the saturated electrolyte at constant potential; and soaking the prepared gas diffusion electrode in a concentrated hydrochloric acid solution with the concentration of 36-38% to prepare the electrode. The invention utilizes vacancy copper with more active area, defect sites and coupling synergistic effect among components to improve the selectivity and activity of hydrocarbon; using Cu+Interacts with each metal to convert CO2The electro-reduction is limited in the functional structure domain, and the catalyst is prevented from being in CO2Loss in the reduction process and improvement of the stability of the catalyst.
Description
Technical Field
The invention belongs to the technical field of carbon dioxide electrochemical reduction, and particularly relates to an electrode for carbon dioxide electrochemical reduction and application thereof.
Background
With the increasing energy consumption and environmental pollution, CO is added2The amount of emissions is increasing year by year, and the resulting rise in air temperature and sea level has become a focus of global attention. CO22Is one of the main ways to reduce the carbon dioxide emission, mainlyThe desired techniques include catalytic hydrogenation, catalytic reforming, electrochemical or photoelectrochemical reduction, and the like. CO22The Electrochemical Reduction (ERC) of (A) is the utilization of electrical energy, in particular renewable energy, to convert CO2The new technology for reducing the carbon dioxide into high value-added chemicals such as synthesis gas, formic acid, hydrocarbon, ethanol and the like is a green way for coupling energy storage and carbon element recycling, and has important significance for sustainable development of human beings.
CO2The valence state of the middle C is +4, the highest valence state of carbon, the molecular configuration of the middle C is linear, and from the chemical perspective, molecules are in a stable state, similar to inert gases, electrons can not be lost any more to generate oxidation reaction, electrons can be obtained to generate reduction reaction, but the reduction of CO2 is relatively difficult to realize because the molecules are relatively stable. In electrocatalytic reduction of CO2The first reaction in the process is that CO2 gets an electron to generate a negatively charged CO2The standard electrode potential of the half reaction is-1.90V (vs RHE), the overpotential is higher, the process is regarded as the speed-determining step of electrocatalytic reduction, the basis for accelerating the reaction rate and improving the catalytic efficiency is to reduce the overpotential and reduce the activation energy, the addition of a catalyst is inevitably needed, and the high energy barrier can be overcome after the catalyst is added, so the activation energy of the reaction is reduced, and the overpotential is also reduced.
Conventional metal electrode materials are classified according to reduction products as follows: (1) the main product is material of HCOOH: cd, In, Sn, Hg, Tl, Pb, etc.; (2) material whose main product is CO: ag. Au, Zn, etc.; (3) the main product is material of H2: ni, Fe, Pd, Pt, Ti, etc.; (4) to date, the hydrocarbon product catalysts have been essentially Cu-based catalysts. Many researchers achieve the orientation of hydrocarbon products by regulating the composition and microstructure of the Cu catalyst, constructing special morphology, regulating the species of active sites, and the like. The study shows that Cu2O is beneficial to the generation of products such as ethylene, ethanol and the like, but the selectivity and the activity action mechanism of the Cu oxide content on the products are still unclear; how to ensure the conductivity and high defect active site of the catalyst by adjusting the parameters in the preparation process to realize the orientation and shape control of the product is yet to be deeply researchedAnd (5) discussing.
The invention takes a copper net and a copper foil as substrates, and utilizes the combination of chemical oxidation, hydrothermal synthesis and electrochemical reduction to grow crystalline phase heterogeneous Cu-vacancy copper (shell)/Cu on the surface in situ2And O, preparing the obtained electrode, and improving the selectivity of the electrode to hydrocarbon by improving the active specific surface area and edge and corner active sites of copper (Cu).
Disclosure of Invention
In order to solve the technical problems, the invention provides an electrode for electrochemical reduction of carbon dioxide and application thereof2O, wherein Cu-vacancy copper is the shell, Cu2O is a nucleus body, and the catalyst comprises the following components: 50-90 wt% of Cu, 5-30 wt% of vacancy copper and Cu2O5-20 wt%, and the preparation method of the electrode for electrochemical reduction of carbon dioxide comprises the following steps:
s1: cleaning the copper net, the foamed nickel and the copper foil basal layer with water, ethanol or acetone, and then adding H with the mass concentration of 50-95%3PO4Leveling for 5-1200 s under the condition that the voltage of the constant potential is 3-5V, and then washing and drying for later use;
s2: immersing the substrate layer into a certain amount of mixture of sodium hydroxide and an oxidant, carrying out chemical oxidation reaction for 30 s-120 min, cleaning, and drying at 40-150 ℃ to obtain CuOxA nanowire/Cu base layer;
s3: mixing copper salt, sulfuric acid and a stabilizer, magnetically stirring for 30-120 min to form a precursor copper salt solution, and under the protection of inert atmosphere, changing the current density to CuO at normal temperaturexAnd electrodepositing a catalyst on the surface of the nanowire/Cu base layer to prepare the electrode.
S4: placing the prepared electrode in CO2Reducing the saturated electrolyte for 20-10000 s at constant current density, washing, and drying by using inert gas to prepare a gas diffusion electrode;
s5: and soaking the prepared gas diffusion electrode in a concentrated hydrochloric acid solution with the concentration of 36-38% for 10-30 min, cleaning and drying to obtain the copper electrode.
Preferably, the oxidant is one or two of ammonium persulfate, potassium persulfate, sodium persulfate, hydrogen peroxide and potassium dichromate, the concentration of the oxidant is 0.01-0.2M, the preferred concentration is 0.015-0.12M, and the concentration of the sodium hydroxide is 0.5-4M, the preferred concentration is 0.5-2M; the ratio of the sodium hydroxide to the oxidant is 5-80: 1, and the preferable ratio is 10-40: 1.
Preferably, the precursor copper salt solution is Cu (NO)3)2·3H2O、CuCl2·2H2O、CuSO4·5H2O, wherein the concentration of copper ions is 1 mM-1.4M, preferably 300 mM-1.0M, the pH of a copper salt solution is adjusted to 0.5-2.0 by using sulfuric acid, the stabilizer is one of polyvinylpyrrolidone, trisodium citrate and disodium ethylene diamine tetraacetate, and the concentration ratio of the stabilizer to Cu in the copper salt is 20: 1-1: 30, preferably 10: 1-1: 15;
preferably, in the variable-current electrodeposition, the deposition current density of the first step is-100 to-200 mAcm-2The time of electrodeposition is 5 to 120s, and the preferred condition is-100 to-150 mAcm-2Depositing for 20-60 s; the second step is to deposit a current with a density of-5 to-100 mAcm-2The deposition time is 60-2000 s; the preferable condition is-30 to-70 mAcm-2Depositing for 300-1000 s;
preferably, the CO is2The saturated electrolyte is KHCO3、NaHCO3One or more of NaOH, KOH, NaCl, KCl, KBr and NaBr, and the CO2The concentration of the saturated electrolyte is 0.02-2M, the preferable concentration is 0.1-0.5M, and the current density of the constant current is-5 mAcm-2～-150mAcm-2Preferably, the constant current has a current density of-40 mAcm-2～-80mAcm-2The reduction time is 10-5000 s, and the preferable time is 120-2400 s.
Preferably, the electrode can be used as a cathode for the electrochemical reduction reaction of carbon dioxide.
The invention has the beneficial effects that:
1. by oxidationThe agent directly oxidizes the surface of the substrate, metal hydroxide nanowires can grow on the surface of the substrate in situ under the condition of no template agent, and CuO is obtained by dryingxA nanowire/Cu base layer; the size of the nanowire can be regulated and controlled by regulating and controlling the concentration of the solution; the preparation process is simple and easy to control, and avoids the application of a template agent or a surfactant, so that the preparation cost is reduced;
2. compared with the traditional current deposition technology, the method of variable current deposition is adopted, the gradient catalyst layer can be obtained through deposition, the catalyst layer with the gradient distribution structure is prepared, not only can active centers be provided as much as possible, but also a 'gas-liquid-solid' three-phase reaction interface is favorably constructed, meanwhile, the characteristics of a smooth proton channel and a product/reactant mass transfer channel are achieved, the utilization rate and the electrochemical circulation stability of the catalytic active centers are improved, and the diffusion of reaction raw materials and products is promoted.
3. The oxygen vacancy of the present invention is CO2Provide a large amount of electrons, is beneficial to the adsorption of-CO, -COH intermediate products and-CH2To promote the coupling of C-C, thereby improving the C-C coupling of the Cu catalystxHySelectivity of (a); vacancy copper has more active area, defect sites and coupling synergistic effect among components, so that the selectivity and activity of hydrocarbon products are improved;
4. the invention utilizes Cu+Interacts with each metal to convert CO2The electro-reduction is limited in a 'functional domain', so that the catalyst is prevented from being in CO2Loss in the reduction process and improvement of the stability of the catalyst.
5. According to the invention, the Cu nano structure with a special morphology is grown on the substrate layer, so that the specific surface area, the edge active sites and the corner active sites of the copper electrode are obviously increased, the activity of the copper electrode on the electrocatalytic reduction reaction of carbon dioxide is improved, and the selectivity on hydrocarbon is also improved.
6. The preparation method is simple and easy to operate, the production equipment is conventional, and the prepared electrode has large active specific surface area and higher carbon dioxide catalytic activity.
Drawings
FIG. 1 shows the present inventionDescription of the electrode in example 1 at CO2Saturated NaHCO3The reduction product profile in (1);
FIG. 2 shows the electrode in CO in example 2 of the present invention2Saturated NaHCO3The reduction product profile in (1);
FIG. 3 shows the electrode of comparative example 1 of the present invention in CO2Saturated NaHCO3The reduction product profile in (1);
FIG. 4 shows the electrode of comparative example 2 of the present invention in CO2Saturated NaHCO3Distribution of reduction products in (1).
FIG. 5 shows the electrodes in the examples of the present invention and comparative examples in CO2Saturated NaHCO3Distribution of reduction products in (1).
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings of the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention is further described below:
an electrode for electrochemical reduction of carbon dioxide and application thereof comprise a catalyst, wherein the catalyst is an ordered core-shell catalyst, and the catalyst is Cu-vacancy copper/Cu2O, wherein Cu-vacancy copper is the shell, Cu2O is a nucleus body, and the catalyst comprises the following components: 50-90 wt% of Cu, 5-30 wt% of vacancy copper and Cu2O5-20 wt%, and the preparation method of the electrode for electrochemical reduction of carbon dioxide comprises the following steps:
s1: cleaning the copper net, the foamed nickel and the copper foil basal layer with water, ethanol or acetone, and then adding H with the mass concentration of 50-95%3PO4Leveling for 5-1200 s under the condition that the voltage of the constant potential is 3-5V, and then washing and drying for later use;
s2: immersing the substrate layer in a quantity of sodium hydroxide and an oxidizing agentThe mixture of (1) and (2) is characterized in that the oxidant is one or two of ammonium persulfate, potassium persulfate, sodium persulfate, hydrogen peroxide and potassium dichromate, the concentration of the oxidant is 0.01-0.2M, the preferable concentration is 0.015-0.12M, and the concentration of the sodium hydroxide is 0.5-4M, the preferable concentration is 0.5-2M; the ratio of sodium hydroxide to oxidant is 5-80: 1, the preferred ratio is 10-40: 1, the reaction is continued for 30 s-120 min, and CuO is obtained after cleaningxA nanowire/Cu base layer;
s3: mixing copper salt, sulfuric acid and a stabilizer, and magnetically stirring for 30-120 min to form a precursor copper salt solution, wherein the precursor copper salt solution is Cu (NO)3)2·3H2O、CuCl2·2H2O、CuSO4·5H2O, wherein the concentration of copper ions is 1 mM-1.4M, preferably 300 mM-1.0M, the pH of a copper salt solution is adjusted to 0.5-2.0 by using sulfuric acid, the stabilizer is one of polyvinylpyrrolidone, trisodium citrate and disodium ethylene diamine tetraacetate, and the concentration ratio of the stabilizer to Cu in the copper salt is 20: 1-1: 30, preferably 10: 1-1: 15; under the protection of inert atmosphere and at normal temperature, the current density is changed to be CuOxThe catalyst is electrodeposited on the surface of the nanowire/Cu substrate layer, and in the variable-current electrodeposition, the deposition current density of the first step is-100 to-200 mAcm-2The time of electrodeposition is 5 to 120s, and the preferred condition is-100 to-150 mAcm-2Depositing for 20-60 s; the second step is to deposit a current with a density of-5 to-100 mAcm-2The deposition time is 60-2000 s; the preferable condition is-30 to-70 mAcm-2Depositing for 300-1000 s;
s4: placing the prepared electrode in CO2Reducing for 20-10000 s in saturated electrolyte at constant current density, washing, drying with inert gas, and preparing to obtain gas diffusion electrode, wherein the CO is2The saturated electrolyte is KHCO3、NaHCO3One or more of NaOH, KOH, NaCl, KCl, KBr and NaBr, and the CO2The concentration of the saturated electrolyte is 0.02-2M, the preferable concentration is 0.1-0.5M, and the current density of the constant current is-5 mAcm-2～-150mAcm-2Preferably constant currentThe current density of (A) was-40 mAcm-2～-80mAcm-2The reduction time is 10-5000 s, and the preferable time is 120-2400 s;
s5: and soaking the prepared gas diffusion electrode in a concentrated hydrochloric acid solution with the concentration of 36-38% for 10-30 min, cleaning and drying to obtain the copper electrode.
In particular, the electrode can be used as a cathode for the electrochemical reduction reaction of carbon dioxide.
Example 1
Ultrasonic washing copper mesh as substrate in ultrapure water and ethanol for 10min, respectively, and treating with 95% H3PO4Leveling for 900s under the condition that the constant potential voltage is 4V, washing and drying for later use; immersing the substrate layer into a mixture of 2M sodium hydroxide aqueous solution and 0.05M ammonium persulfate, wherein the ratio of sodium hydroxide to oxidant is 15: 1, continuously reacting for 30min, and drying at 100 ℃ to obtain CuOxA nanowire/Cu base layer; 0.4M CuCl with the molar concentration ratio of disodium ethylene diamine tetraacetate dihydrate to Cu in the copper salt being 1:12·2H2O is mixed with disodium edetate dihydrate and H is used2SO4Adjusting the pH of the copper salt solution to 1.0 as an electrolyte, and adopting a deposition current density of-150 mAcm-2Depositing for 60s, and then adopting the deposition current density of-60 mAcm-2Depositing for 1200s, and cleaning, and placing the prepared electrode in CO2Saturated 0.5M NaHCO3Medium constant current density-80 mAcm-2Reducing for 2000s, washing and drying to prepare the gas diffusion electrode; soaking the prepared gas diffusion electrode in 37.5% concentrated hydrochloric acid solution for 15min, cleaning, and drying to obtain 70% Cu-10% vacancy copper/20% Cu2O, and an ordered core-shell catalyst.
Example 2
Ultrasonic washing copper mesh as substrate in ultrapure water and ethanol for 10min, respectively, and treating with 95% H3PO4Leveling for 900s under the condition that the voltage of the constant potential is 4V, washing and drying for later use; immersing the substrate layer in a 1.5M aqueous solution of sodium hydroxideIn the mixture of the solution and 0.05M potassium persulfate, the ratio of sodium hydroxide to oxidant is 10:1, the reaction is continued for 40min, and CuO is obtained by drying at 100 DEG CxA nanowire/Cu base layer; 0.2M of Cu (NO) is added according to the molar concentration ratio of the disodium ethylene diamine tetraacetate dihydrate to the Cu in the copper salt of 1:13)2·3H2O is mixed with disodium edetate dihydrate and H is used2SO4Adjusting the pH of the copper salt solution to 1.0 as an electrolyte, and adopting a deposition current density of-120 mAcm-2Depositing for 80s, and then adopting a deposition current density of-60 mAcm-2Depositing for 1500s, cleaning, and placing the prepared electrode in CO2Saturated 0.2M KHCO3Medium constant current density-60 mAcm-2Reducing for 2000s, washing, and drying with inert gas to prepare a gas diffusion electrode; soaking the prepared gas diffusion electrode in a concentrated hydrochloric acid solution with the concentration of 37.5% for 15min, cleaning and drying to obtain 60% Cu-30% vacancy copper/10% Cu2O, and an ordered core-shell catalyst.
Example 3
Ultrasonically washing copper foil serving as a substrate in ultrapure water and ethanol for 10min respectively, then leveling for 900s in H3PO4 with the mass concentration of 95% under the condition that the voltage of a constant potential is 3V, and washing and drying for later use; immersing the substrate layer in a mixture of 1.0M sodium hydroxide aqueous solution and 0.02M potassium dichromate at a ratio of sodium hydroxide to oxidant of 12: 1, reacting for 40min, and drying at 80 deg.C to obtain CuOxA nanowire/Cu base layer; 0.3M of Cu (NO) with the molar concentration ratio of sodium citrate to Cu in copper salt being 2: 13)2·3H2Mixing O with sodium citrate, and using H2SO4Adjusting the pH of the copper salt solution to 1.0 as an electrolyte, and adopting a deposition current density of-150 mAcm-2Depositing for 60s, and then adopting the deposition current density of-60 mAcm-2Depositing for 1000s, cleaning, placing the prepared electrode in 0.5M KBr saturated with CO2 and constant current density of-60 mAcm-2Reducing for 1500s, washing, and drying with inert gas to prepare a gas diffusion electrode; prepared by the above methodSoaking the gas diffusion electrode in 37.5% concentrated hydrochloric acid solution for 20min, cleaning, and drying to obtain Cu-5% vacancy copper/10% Cu2O, and an ordered core-shell catalyst.
Example 4
Ultrasonic washing copper mesh as substrate in ultrapure water and ethanol for 10min, respectively, and treating with 95% H3PO4Leveling for 700s under the condition that the voltage of the constant potential is 4V, washing and drying for later use; immersing the substrate layer into a mixture of 1.5M sodium hydroxide aqueous solution and 0.05M potassium persulfate, wherein the ratio of sodium hydroxide to oxidant is 10:1, continuously reacting for 40min, and drying at 100 deg.C to obtain CuOxA nanowire/Cu base layer; 0.3M of Cu (NO) with the molar concentration ratio of sodium citrate to Cu in copper salt being 2: 13)2·3H2Mixing O with sodium citrate, and using H2SO4Adjusting the pH of the copper salt solution to 1.0 as an electrolyte, and adopting a deposition current density of-120 mAcm-2Depositing for 80s, and then depositing at a current density of-40 mAcm-2Depositing for 1000s, cleaning, and placing the prepared electrode in CO2Saturated 0.5M KBr medium constant current density-60 mAcm-2Reducing for 1500s, washing, and drying with inert gas to prepare a gas diffusion electrode; soaking the prepared gas diffusion electrode in a concentrated hydrochloric acid solution with the concentration of 37.5% for 20min, cleaning and drying to obtain the copper based on 85% Cu-5% vacancy/10% Cu2O, and an ordered core-shell catalyst.
Example 5
Ultrasonic washing nickel screen as substrate in ultrapure water and ethanol for 20min, respectively, and treating with 95% H3PO4Leveling for 500s under the condition that the voltage of the constant potential is 5V, washing and drying for later use; immersing the substrate layer into a mixture of 1.5M sodium hydroxide aqueous solution and 0.05M potassium persulfate, wherein the ratio of sodium hydroxide to oxidant is 10:1, continuously reacting for 40min, and drying at 100 deg.C to obtain CuOxA nanowire/Cu base layer; 0.2M of Cu (NO) with the molar concentration ratio of sodium citrate to Cu in copper salt being 1: 23)2·3H2Mixing O with sodium citrate, and using H2SO4Adjusting the pH of the copper salt solution to 1.0 as an electrolyte, and adopting a deposition current density of-150 mAcm-2Depositing for 30s, and then adopting a deposition current density of-80 mAcm-2Depositing for 1200s, cleaning, and placing the prepared electrode in CO2Saturated 0.5M KHCO3Medium constant current density-80 mAcm-2Reducing for 1500s, washing, and drying with inert gas to prepare a gas diffusion electrode; soaking the prepared gas diffusion electrode in 37.5% concentrated hydrochloric acid solution for 15min, cleaning, and drying to obtain 70% Cu-20% vacancy copper/10% Cu2O, and an ordered core-shell catalyst.
Example 6
Ultrasonic washing copper foil as substrate in ultrapure water and ethanol for 30min, respectively, and treating with 95% H3PO4Leveling for 600s under the condition that the voltage of the constant potential is 4V, washing and drying for later use; immersing the substrate layer into a mixture of 1.5M sodium hydroxide aqueous solution and 0.05M potassium persulfate, wherein the ratio of sodium hydroxide to oxidant is 12: 1, continuously reacting for 60min, and drying at 100 ℃ to obtain CuOxA nanowire/Cu base layer; 0.2M Cu (NO) with molar concentration ratio of polyvinylpyrrolidone to Cu in copper salt of 0.001: 13)2·3H2O is mixed with polyvinylpyrrolidone and H is used2SO4Adjusting the pH of the copper salt solution to 1.0 as an electrolyte, and adopting a deposition current density of-180 mAcm-2Depositing for 30s, and then adopting a deposition current density of-70 mAcm-2Depositing for 1000s, cleaning, and placing the prepared electrode in CO2Saturated 0.5M KHCO3Medium constant current density-60 mAcm-2Reducing for 1200s, washing, and drying with inert gas to prepare a gas diffusion electrode; soaking the prepared gas diffusion electrode in a concentrated hydrochloric acid solution with the concentration of 37.5% for 15min, cleaning and drying to obtain the copper/5% Cu based on 90% Cu-5% vacancy2O, and an ordered core-shell catalyst.
Example 7
Ultrasonically washing copper foil serving as a substrate in ultrapure water and ethanol for 30min respectively, then leveling for 600s in H3PO4 with the mass concentration of 95% under the constant potential voltage of 4V, washing, and drying for later use; immersing the substrate layer into a mixture of 1.8M sodium hydroxide aqueous solution and 0.05M ammonium persulfate, wherein the ratio of sodium hydroxide to oxidant is 10:1, continuously reacting for 40min, and drying at 100 ℃ to obtain CuOxA nanowire/Cu base layer; 0.2M Cu (NO) with molar concentration ratio of polyvinylpyrrolidone to Cu in copper salt of 5: 13)2·3H2O is mixed with polyvinylpyrrolidone and H is used2SO4Adjusting the pH of the copper salt solution to 1.0 as an electrolyte, and adopting a deposition current density of-180 mAcm-2Depositing for 30s, and then adopting a deposition current density of-60 mAcm-2Depositing for 1000s, cleaning, and placing the prepared electrode in 0.5M KHCO saturated with CO23Medium constant current density-60 mA cm-2Reducing for 1200s, washing, and drying with inert gas to prepare a gas diffusion electrode; the gas diffusion electrode prepared above was immersed in a concentrated hydrochloric acid solution of 37.5% concentration for 15min, washed and dried to prepare an electrode based on a 90% Cu-5% vacancy copper (Cu-V) (shell)/5% Cu2O (core) ordered "core-shell" catalyst.
Example 8
Ultrasonic washing copper foil as substrate in ultrapure water and ethanol for 30min, respectively, and treating with 95% H3PO4Leveling for 600s under the condition that the voltage of the constant potential is 4V, washing and drying for later use; immersing the substrate layer into a mixture of 1.5M sodium hydroxide aqueous solution and 0.05M potassium persulfate, wherein the ratio of sodium hydroxide to oxidant is 10:1, continuously reacting for 40min, and drying at 100 deg.C to obtain CuOxA nanowire/Cu base layer; mixing 0.2M CuSO4 & 5H2O and polyvinylpyrrolidone at molar concentration ratio of polyvinylpyrrolidone to Cu in copper salt of 1: 10, and adding H2SO4Adjusting the pH of the copper salt solution to 1.0 as an electrolyte, and adopting a deposition current density of-120 mAcm-2Depositing for 90s, and then adopting a deposition current density of-70 mAcm-2Depositing for 300s, cleaning, and placing the prepared electrode onCO2Saturated 0.5M NaCl constant current density-60 mAcm-2Reducing for 1200s, washing, and drying with inert gas to prepare a gas diffusion electrode; soaking the prepared gas diffusion electrode in 37.5% concentrated hydrochloric acid solution for 15min, cleaning, and drying to obtain 70% Cu-20% vacancy copper/10% Cu2O, and an ordered core-shell catalyst.
Comparative example 1
Ultrasonic washing copper mesh as substrate in ultrapure water and ethanol for 10min, respectively, and treating with 95% H3PO4Leveling for 900s under the condition that the constant potential voltage is 4V, washing and drying for later use; 0.4M CuCl with the molar concentration ratio of disodium ethylene diamine tetraacetate dihydrate to Cu in the copper salt being 1:12·2H2O is mixed with disodium edetate dihydrate and H is used2SO4Adjusting the pH of the copper salt solution to 1.0 as an electrolyte, and adopting a deposition current density of-150 mAcm-2Depositing for 60s, and then adopting the deposition current density of-60 mAcm-2Depositing for 1200s, and cleaning, and placing the prepared electrode in CO2Saturated 0.5M NaHCO3Medium constant current density-80 mAcm-2Reducing for 2000s, washing and drying to prepare the gas diffusion electrode; soaking the prepared gas diffusion electrode in 37.5% concentrated hydrochloric acid solution for 15min, cleaning, and drying to obtain 70% Cu-10% vacancy copper/20% Cu2O, and an ordered core-shell catalyst.
Comparative example 2
Ultrasonic washing copper mesh as substrate in ultrapure water and ethanol for 10min, respectively, and treating with 95% H3PO4Leveling for 900s under the condition that the constant potential voltage is 4V, washing and drying for later use; immersing the substrate layer into a mixture of 2M sodium hydroxide aqueous solution and 0.05M ammonium persulfate, wherein the ratio of sodium hydroxide to oxidant is 15: 1, continuously reacting for 30min, and drying at 100 ℃ to obtain CuOxA nanowire/Cu base layer; 0.4M CuCl with the molar concentration ratio of disodium ethylene diamine tetraacetate dihydrate to Cu in the copper salt being 1:12·2H2O is mixed with disodium edetate dihydrate and H is used2SO4Adjusting pH of the copper salt solution to 1.0 to obtain electrolyte with a deposition current density of-60 mAcm-2Depositing for 1200s, and cleaning, and placing the prepared electrode in CO2Saturated 0.5M NaHCO3Medium constant current density-80 mAcm-2Reducing for 2000s, washing and drying to prepare the gas diffusion electrode; soaking the prepared gas diffusion electrode in 37.5% concentrated hydrochloric acid solution for 15min, cleaning, and drying to obtain 70% Cu-10% vacancy copper/20% Cu2O, and an ordered core-shell catalyst.
Comparative example 3
Ultrasonic washing copper mesh as substrate in ultrapure water and ethanol for 10min, respectively, and treating with 95% H3PO4Leveling for 900s under the condition that the constant potential voltage is 4V, washing and drying for later use; immersing the substrate layer into a mixture of 2M sodium hydroxide aqueous solution and 0.05M ammonium persulfate, wherein the ratio of sodium hydroxide to oxidant is 15: 1, continuously reacting for 30min, and drying at 100 ℃ to obtain CuOxA nanowire/Cu base layer; 0.4M CuCl with the molar concentration ratio of disodium ethylene diamine tetraacetate dihydrate to Cu in the copper salt being 1:12·2H2O is mixed with disodium edetate dihydrate and H is used2SO4Adjusting the pH of the copper salt solution to 1.0 as an electrolyte, and adopting a deposition current density of-240 mAcm-2Depositing for 60s, and then adopting the deposition current density of-60 mAcm-2Depositing for 1200s, cleaning, and placing the prepared electrode in CO2Saturated 0.5M NaHCO3Medium constant current density-80 mAcm-2Reducing for 2000s, washing and drying to prepare the gas diffusion electrode; soaking the prepared gas diffusion electrode in 37.5% concentrated hydrochloric acid solution for 15min, cleaning, and drying to obtain 70% Cu-10% vacancy copper/20% Cu2O, and an ordered core-shell catalyst.
Comparative example 4
Using copper net as substrate, adding ultrapure water and pure waterUltrasonic washing in alcohol for 10min, respectively, and treating with 95% H3PO4Leveling for 900s under the condition that the constant potential voltage is 4V, washing and drying for later use; immersing the substrate layer in a mixture of 2M sodium hydroxide aqueous solution and 0.005M ammonium persulfate, the ratio of sodium hydroxide to oxidant is 15: 1, continuously reacting for 30min, and drying at 100 deg.C to obtain CuOxA nanowire/Cu base layer; 0.4M CuCl with the molar concentration ratio of disodium ethylene diamine tetraacetate dihydrate to Cu in the copper salt being 1:12·2H2O is mixed with disodium edetate dihydrate and H is used2SO4Adjusting the pH of the copper salt solution to 1.0 as an electrolyte, and adopting a deposition current density of-150 mAcm-2Depositing for 60s, and then adopting the deposition current density of-120 mAcm-2Depositing for 1200s, and cleaning, and placing the prepared electrode in CO2Saturated 0.5M NaHCO3Medium constant current density-80 mAcm-2Reducing for 2000s, washing and drying to prepare the gas diffusion electrode; soaking the prepared gas diffusion electrode in 37.5% concentrated hydrochloric acid solution for 15min, cleaning, and drying to obtain 70% Cu-10% vacancy copper/20% Cu2O, and an ordered core-shell catalyst.
Comparative example 5
Ultrasonic washing copper mesh as substrate in ultrapure water and ethanol for 10min, respectively, and treating with 95% H3PO4Leveling for 900s under the condition that the constant potential voltage is 4V, washing and drying for later use; immersing the substrate layer into a mixture of 2M sodium hydroxide aqueous solution and 0.25M ammonium persulfate, wherein the ratio of sodium hydroxide to oxidant is 15: 1, continuously reacting for 30min, and drying at 100 ℃ to obtain CuOxA nanowire/Cu base layer; 0.4M CuCl with the molar concentration ratio of disodium ethylene diamine tetraacetate dihydrate to Cu in the copper salt of 2-10: 12·2H2O is mixed with disodium edetate dihydrate and H is used2SO4Adjusting the pH of the copper salt solution to 1.0 as an electrolyte, and adopting a deposition current density of-150 mAcm-2Depositing for 60s, and then adopting the deposition current density of-60 mAcm-2Depositing for 1200s, and cleaning, and placing the prepared electrode in CO2Saturated 0.5M NaHCO3Medium constant current density-80 mAcm-2Reducing for 2000s, washing and drying to prepare the gas diffusion electrode; soaking the prepared gas diffusion electrode in 37.5% concentrated hydrochloric acid solution for 15min, cleaning, and drying to obtain 70% Cu-10% vacancy copper/20% Cu2O, and an ordered core-shell catalyst.
Comparative example 6
Ultrasonic washing copper mesh as substrate in ultrapure water and ethanol for 10min, respectively, and treating with 95% H3PO4Leveling for 900s under the condition that the constant potential voltage is 4V, washing and drying for later use; immersing the substrate layer into a mixture of 2M sodium hydroxide aqueous solution and 0.03M ammonium persulfate, wherein the ratio of sodium hydroxide to oxidant is 15: 1, continuously reacting for 30min, and drying at 100 ℃ to obtain CuOxA nanowire/Cu base layer; 0.4M CuCl with the molar concentration ratio of disodium ethylene diamine tetraacetate dihydrate to Cu in the copper salt of 2-10: 12·2H2O is mixed with disodium edetate dihydrate and H is used2SO4Adjusting the pH of the copper salt solution to 1.0 as an electrolyte, and adopting a deposition current density of-150 mAcm-2Depositing for 60s, and then adopting the deposition current density of-60 mAcm-2Depositing for 1200s, and cleaning, and placing the prepared electrode in CO2Saturated 0.5M NaHCO3Medium constant current density-80 mAcm-2Reducing for 2000s, washing and drying to prepare the gas diffusion electrode; soaking the prepared gas diffusion electrode in 37.5% concentrated hydrochloric acid solution for 15min, cleaning, and drying to obtain 70% Cu-10% vacancy copper/20% Cu2O, and an ordered core-shell catalyst.
The prepared electrode is used as a cathode of a reaction system for electrochemically catalyzing and reducing carbon dioxide, a three-electrode system is adopted for electrochemical test in the experiment, the prepared copper electrode is 1cm multiplied by 1cm and is used as a working electrode, and Hg/HgCl is used as a working electrode2A calomel electrode of saturated KCl as a reference electrode, 3cm2The platinum sheet electrode as the counter electrode and the cathode chamber 180mL of 0.5M NaHCO3Solution in the anode 100mL of 0.1M H2SO4Electrocatalytic reduction of CO2During the reaction, CO2The flow rate is set as 100 mL/min; the catalytic reduction product was detected every 15 min.
Specifically, fig. 1 and 2 show the difference in the distribution of the reduction products of example 1 and example 2, respectively, in that: different oxidants are added, and when the ammonium persulfate is selected as the oxidant in example 1, CH is generated at-2.3V4The highest Faraday efficiency of 30.2%, C2H4The Faraday efficiency of (2) is 29%; example 2 formation of CH when Potassium persulfate is used as the oxidizing agent4The highest Faraday efficiency of 28%, C2H4The Faraday efficiency of (2) is 23%; and from the whole reduction potential trend, the faradaic efficiency of the reduction products of ammonium persulfate and potassium persulfate which are both increased along with the increase of the potential is increased firstly and then reduced, the faradaic efficiency has a highest point, and a large amount of C is accompanied by the oxidizing agent2H4However, the catalyst performance is better when the oxidant is ammonium persulfate.
In particular, figure 3 is a product profile for comparative example 1, which, compared to the faradaic efficiency of example 1 of figure 3, gives: electrode without chemical oxidation deposition Cu nanowire layer for catalytic reduction of CH in product after carbon dioxide reduction4And C2H4The faradaic efficiency of (a) is reduced, which indicates that the step of preparing nanowires by the chemical oxidation process is crucial to the performance of the catalyst.
Specifically, the product profile of comparative example 2 in FIG. 4, compared to FIG. 1, gives: comparative example 2 constant current deposition was used to prepare an electrode for catalytic reduction of CH in the product4And C2H4Compared with the traditional current deposition technology, the variable current deposition method is adopted, the gradient catalyst layer can be deposited, the catalyst layer with the gradient distribution structure can be prepared, not only can active centers be provided as much as possible, but also the construction of a gas-liquid-solid three-phase reaction interface is facilitated, and meanwhile, the catalyst layer has smooth qualityThe characteristics of the sub-channel and the product/reactant mass transfer channel improve the utilization rate of the catalytic active center and the electrochemical circulation stability, and promote the diffusion of reaction raw materials and products, thereby improving the current density and showing that the catalytic activity is improved.
Specifically, the product distribution diagram of comparative example 3 in fig. 5, compared with fig. 1, can be obtained: comparative example 3 is an electrode prepared by depositing with variable current density and large current exceeding the protection range and used for reducing CH in products after catalytic reduction4And C2H4The faradaic efficiency of (a) is reduced, which indicates that the selectivity and activity of the catalyst are reduced by too much current. This is mainly due to the fact that the current density is too high, which results in too large particle size of the prepared catalyst, and the specific surface area is reduced, thus reducing the activity, and the electrode structure is changed during the preparation process, which results in reduced selectivity.
Specifically, the product distribution diagram of comparative example 4 in fig. 5, compared with fig. 1, can be obtained: comparative example 4 is an electrode prepared by depositing with variable current density and small current exceeding the protection range, and used for reducing CH in products after catalytic reduction4And C2H4The faradaic efficiency of (a) decreases, which indicates that too little current decreases the selectivity and activity of the catalyst. The main current density is too small, so that the particle size of the surface layer of the prepared catalyst is too small, the particle size of the surface layer of the prepared catalyst is greatly different from that of a large-particle catalyst layer, the surface layer of the prepared catalyst is embedded into holes, the structure is damaged, and the selectivity is reduced.
Specifically, the product distribution diagram of comparative example 5 in fig. 5, compared with fig. 1, can be obtained: cu electrode prepared by oxidizing agent beyond the highest value of the specified range of the invention and used for reducing CH in products after catalytic reduction4And C2H4The faradaic efficiency of (a) is reduced mainly because the oxidant component is too high, resulting in the nanowire being oversized, the specific surface area being reduced, the activity being reduced, the proportion of edge active sites being reduced, and the selectivity also being reduced.
Specifically, the product distribution diagram of comparative example 6 in fig. 5, compared with fig. 1, can be obtained: cu electrode prepared with oxidant beyond the lowest value of the specified range for catalytic reduction of CH in product4And C2H4The faradaic efficiency of (a) is reduced mainly because the oxidizing agent component is too low, resulting in too small nanowire size, too low amount of the oxidizing agent, reduced number of active sites, reduced activity, reduced proportion of edge active sites, and reduced selectivity.
It should be noted that, in this document, moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. The electrode for electrochemical reduction of carbon dioxide is characterized by comprising a catalyst, wherein the catalyst is an ordered core-shell catalyst, and the catalyst is Cu-vacancy copper/Cu2O, wherein Cu-vacancy copper is the shell, Cu2O is a nucleus body, and the catalyst comprises the following components: 50-90 wt% of Cu, 5-30 wt% of vacancy copper and Cu2O5-20 wt%, and the preparation method of the electrode for electrochemical reduction of carbon dioxide comprises the following steps:
s1: cleaning the copper net, the foamed nickel and the copper foil basal layer with water, ethanol or acetone, and then adding H with the mass concentration of 50-95%3PO4Leveling for 5-1200 s under the condition that the voltage of a constant potential is 3-5V, and then washing and drying for later use;
s2: immersing a substrate layer into a certain amount of mixture of sodium hydroxide and an oxidant, wherein the concentration of the sodium hydroxide is 0.5-4M, the concentration of the oxidant is 0.01-0.2M, the ratio of the sodium hydroxide to the oxidant is 5-80: 1, chemically oxidizing for 30 s-120 min, cleaning, and then performing chemical oxidation at 40 DEG CDrying at-150 ℃ to obtain CuOxA nanowire/Cu base layer;
s3: mixing copper salt, sulfuric acid and a stabilizer, magnetically stirring for 30-120 min to form a precursor copper salt solution, and under the protection of inert atmosphere, changing the current density to CuO at normal temperaturexElectrodepositing a catalyst on the surface of the nanowire/Cu substrate layer to prepare the electrode, wherein in the variable-current electrodeposition, the deposition current density of the first step is-100 to-200 mA. cm-2The electrodeposition time is 5-120 s; the deposition current density of the second step is-5 to-100 mA. cm-2The deposition time is 60-2000 s;
s4: placing the prepared electrode in CO2Reducing for 20-10000 s in saturated electrolyte at constant current density, washing, and drying by using inert gas to prepare a gas diffusion electrode;
s5: and soaking the prepared gas diffusion electrode in a concentrated hydrochloric acid solution with the concentration of 36-38% for 10-30 min, cleaning and drying to obtain the copper electrode.
2. The electrode for electrochemical reduction of carbon dioxide according to claim 1, wherein the oxidizing agent is one or two of ammonium persulfate, potassium persulfate, sodium persulfate, hydrogen peroxide, and potassium dichromate, and the concentration of the oxidizing agent is 0.015 to 0.12M, and the concentration of the sodium hydroxide is 0.5 to 2M; the ratio of the sodium hydroxide to the oxidant is 10-40: 1.
3. The electrode for electrochemical reduction of carbon dioxide as claimed in claim 2, wherein the precursor copper salt solution is Cu (NO)3)2·3H2O、CuCl2·2H2O、CuSO4·5H2And O, wherein the concentration of copper ions is 1 mM-1.4M, the pH of the copper salt solution is adjusted to 0.5-2.0 by using sulfuric acid, the stabilizer is one of polyvinylpyrrolidone, trisodium citrate and disodium ethylene diamine tetraacetate, and the concentration ratio of the stabilizer to Cu in the copper salt is 20: 1-1: 30.
4. The electrode for electrochemical reduction of carbon dioxide according to claim 3, wherein the concentration of copper ions is 300mM to 1.0M.
5. The electrode for electrochemical reduction of carbon dioxide according to claim 3, wherein the concentration ratio of the stabilizer to Cu in the copper salt is 10:1 to 1: 15.
6. The electrode for electrochemical reduction of carbon dioxide according to claim 1, wherein the deposition current density in the first step of the variable-current electrodeposition is from-100 to-150 mA. cm-2The electrodeposition time is 20 s-60 s; the second step is that the deposition current density is-30 to-70 mA. cm-2The deposition time is 300 s-1000 s.
7. The electrode for electrochemical reduction of carbon dioxide as claimed in claim 1, wherein said CO is present in an amount sufficient to reduce carbon dioxide2The saturated electrolyte is KHCO3、NaHCO3One or more of NaOH, KOH, NaCl, KCl, KBr and NaBr, and the CO2The concentration of the saturated electrolyte is 0.02-2M, and the current density of the constant current is-5 mA. cm-2～-150mA. cm-2The reduction time is 10-5000 s.
8. The electrode for electrochemical reduction of carbon dioxide as claimed in claim 7, wherein said CO is present in an amount sufficient to reduce carbon dioxide2The concentration of the saturated electrolyte is 0.1-0.5M.
9. The electrode for electrochemical reduction of carbon dioxide as claimed in claim 7, wherein the constant current has a current density of-40 mA. cm-2～-80mA. cm-2The reduction time is 120-2400 s.
10. Use of an electrode for electrochemical reduction of carbon dioxide according to claim 1, wherein the electrode is used as a cathode for electrochemical reduction reaction of carbon dioxide.
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| CN114000177A (en) * | 2021-11-12 | 2022-02-01 | 江苏大学 | Ag @ Cu2O core-shell structure nanosphere catalyst and preparation method and application thereof |
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