CN114808002B - Electrode for carbon dioxide electroreduction and preparation method thereof - Google Patents
Electrode for carbon dioxide electroreduction and preparation method thereof Download PDFInfo
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- CN114808002B CN114808002B CN202210328401.4A CN202210328401A CN114808002B CN 114808002 B CN114808002 B CN 114808002B CN 202210328401 A CN202210328401 A CN 202210328401A CN 114808002 B CN114808002 B CN 114808002B
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 28
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 118
- 239000000758 substrate Substances 0.000 claims abstract description 81
- 238000000151 deposition Methods 0.000 claims abstract description 58
- 239000001913 cellulose Substances 0.000 claims abstract description 53
- 229920002678 cellulose Polymers 0.000 claims abstract description 53
- 230000007704 transition Effects 0.000 claims abstract description 51
- 238000001035 drying Methods 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000004140 cleaning Methods 0.000 claims abstract description 41
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 36
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052802 copper Inorganic materials 0.000 claims abstract description 30
- 239000010949 copper Substances 0.000 claims abstract description 30
- 230000003197 catalytic effect Effects 0.000 claims abstract description 26
- 230000001590 oxidative effect Effects 0.000 claims abstract description 24
- 230000000694 effects Effects 0.000 claims abstract description 12
- 238000011065 in-situ storage Methods 0.000 claims abstract description 7
- 230000003647 oxidation Effects 0.000 claims abstract description 5
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 5
- 239000011889 copper foil Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 72
- 239000003054 catalyst Substances 0.000 claims description 64
- 238000005507 spraying Methods 0.000 claims description 50
- 238000011068 loading method Methods 0.000 claims description 26
- 239000006259 organic additive Substances 0.000 claims description 23
- 239000007864 aqueous solution Substances 0.000 claims description 22
- 238000009713 electroplating Methods 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 22
- 239000001509 sodium citrate Substances 0.000 claims description 22
- 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 claims description 22
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 15
- 230000009467 reduction Effects 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- 238000004070 electrodeposition Methods 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 9
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 230000008021 deposition Effects 0.000 claims description 5
- 230000004048 modification Effects 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 5
- -1 p-aminobenzyl Chemical group 0.000 claims description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 claims description 2
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000003381 stabilizer Substances 0.000 claims description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 2
- 230000009466 transformation Effects 0.000 claims description 2
- 239000000203 mixture Substances 0.000 description 38
- 239000008151 electrolyte solution Substances 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 22
- 238000006722 reduction reaction Methods 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000005868 electrolysis reaction Methods 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 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 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 235000019253 formic acid Nutrition 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- VWCFCFOIUSKKSC-UHFFFAOYSA-N ethane-1,2-diamine;2-hydroxy-1,3,2$l^{5}-dioxaphosphepane 2-oxide Chemical compound NCCN.OP1(=O)OCCCCO1 VWCFCFOIUSKKSC-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000002159 nanocrystal Substances 0.000 description 2
- 239000002073 nanorod Substances 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- MIQWEMDDUPSLRW-UHFFFAOYSA-N [O].O=C=O Chemical compound [O].O=C=O MIQWEMDDUPSLRW-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000005363 electrowinning Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 231100000783 metal toxicity Toxicity 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000012430 stability testing Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 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
- C25B11/055—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
- C25B11/061—Metal or alloy
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention relates to an electrode for carbon dioxide electroreduction and a preparation method thereof, wherein the electrode comprises three layers of a basal layer, a transition layer and a catalytic layer, and the preparation steps are as follows: taking a copper net, a copper sheet, a copper plate or a copper foil with the thickness of 100-500 mu m as a substrate, treating the substrate cleanly by using acetone and hydrochloric acid, and then placing the substrate in an oxidizing solution for oxidation to obtain an electrode substrate layer with oxide or hydroxide on the surface; preparing an amino cellulose modified transition layer on the surface of the treated basal layer; under the protection of inert atmosphere, depositing a catalytic layer in situ in a gradient manner, cleaning the deposited catalytic layer with ethanol and water, drying, and then placing the catalytic layer in a vacuum oven for drying at 100-200 ℃ to obtain an electrode; the electrode has excellent carbon dioxide electroreduction activity, selectivity and stability.
Description
Technical Field
The invention belongs to the technical field of preparation and application of an electrode for electrochemical reduction of carbon dioxide, and particularly relates to an electrode for electrochemical reduction of carbon dioxide and a preparation method thereof.
Background
Electrochemical reduction of carbon dioxide (ERC) is the utilization of electrical energy, especially renewable energy, to convert CO 2 Reducing into chemicals with high added value such as CO, formic acid, hydrocarbon and the like, and effectively realizing the greenhouse gas CO 2 A technology for recycling and storing renewable energy. ERC technology is also one of the important ways to achieve the goal of carbon peaking, carbon neutralization, and "two carbon". Thus, the ERC technology has potential economic and environmental benefits.
The catalyst is one of key materials for Electrochemical Reduction (ERC) of carbon dioxide, and its performance directly affects the conversion efficiency, selectivity and life of ERC reaction. The Sn-based catalyst is a catalyst for catalyzing CO 2 One of the effective catalysts for electrochemical reduction. Since the Sn metal storage amount is relatively large, the price is relatively low,is suitable for being used as a catalyst material for large-scale use. In addition, with other processes for reduction of CO 2 The catalyst for preparing organic acid (Pb, cd, hg, etc.) has relatively low Sn metal toxicity, so that the catalyst is an environment-friendly metal catalyst. However, the existing Sn electrocatalyst has relatively low selectivity, and the activity and stability still do not meet the requirements of commercial application. At present, many people synthesize catalysts such as tin oxide, tin and the like by using a chemical method, in the practical application process, the prepared powder catalyst needs to be coated on the surface of a substrate through a binder, so that the electrode manufacturing process is complicated, and the activity of the prepared catalyst is reduced due to the coating of the binder, so that the activity is reduced. In addition, the performance of the electrode is low (faradaic efficiency is below 60%). In addition, the Sn-based catalyst is easy to decompose and poison in the long-term electrolysis process, so that the performance of the electrode is reduced.
In order to solve the problem, many researchers directly prepare the electrode by growing the Sn-based catalyst on the substrate in situ, so that the problem of the reduction of the specific surface caused by the doctor-blading process is avoided. SnO and SnO were prepared by electrodeposition from YIhong Chen et al, stanford university 2 Is deposited on the surface of the Ti electrode to form a thin film, thereby preparing a catalyst in which Sn is mixed with an oxide. The current density of ERC is increased to 8 times that of the normal Sn electrode, and the Faraday Efficiency (FE) is increased to 4 times that of the normal Sn electrode. However, the Sn-based catalyst deposited on the Ti surface is not uniform, the particle size is large, and the hydrogen evolution side reaction is serious. The ERC faraday efficiency is approximately 58%. For example, an electrode for electrochemical reduction of carbon dioxide with the publication number of CN201510924130.9, a preparation method and application thereof are disclosed, an Sn nano rod catalyst is deposited on a substrate in situ by an electrochemical method, and an organic aid is dispersed on the surface of the Sn nano rod catalyst to prepare a porous gas diffusion electrode of the Sn catalyst, a stable gas/liquid/solid three-phase interface is established, a gas diffusion path is shortened, and the electrode reaction rate is improved, so that the preparation process of the catalyst is simplified, the dominant crystal face and morphology of the catalyst can be effectively controlled, and the performance of the electrode is regulated and controlled. However, the catalyst particles prepared by the patent are relatively large, so that the current density of the catalyst is relatively low, and the actual application cannot be satisfiedIn addition, because the binding force between the surfaces of the carbon substrate and the metal catalytic layer is smaller, the in-situ deposited surface catalytic layer is not stable enough, and particularly in the long-term electrolysis process, the catalytic layer is very easy to separate from the substrate layer, so that the catalyst is lost. Therefore, we propose an electrode for carbon dioxide electroreduction and a method for preparing the same.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides an electrode for carbon dioxide electroreduction and a preparation method thereof, wherein oxides or hydroxides prepared through chemical oxidation can be used as active components and stabilizers, so that the activity of a catalyst and the binding force with a transition layer can be improved; the transition layer is introduced with an amino cellulose thin layer as an interface modification layer, so that the hydrophobicity of the surface of the basal layer can be reduced, uniform metal nano crystal nucleation points are formed, the surface of the substance contains amino and hydroxyl, the substance can interact with metal, and the binding force between the catalyst and the basal layer can be improved; the space structure of the transition layer provides sufficient space for fixing the catalyst, so that a continuous, uniform and fully-covered metal catalytic layer is formed; the porous network structure of the catalyst does not influence the conductivity of the catalyst. And then growing a Sn catalyst layer on the surface of the transition layer to prepare the electrode with high specific surface and high stability. Gradient electrowinning may result in graded catalyst layers. The electrode has excellent carbon dioxide electroreduction activity, selectivity and stability.
In order to solve the technical problems, the invention provides the following technical scheme: an electrode for carbon dioxide electroreduction is characterized by comprising a basal layer, a transition layer and a catalytic layer.
The invention also provides the following technical scheme: the preparation method of the electrode for carbon dioxide electroreduction comprises the following steps:
s1: taking a copper mesh, a copper sheet, a copper plate or a copper foil with the thickness of 100-500 mu m as a substrate, cleaning by using acetone and hydrochloric acid, placing the substrate in an oxidizing solution, treating for 2-8min, and taking the substrate as a substrate layer after cleaning;
s2: the prepared amino cellulose solution is adoptedImpregnating for 1-20min to impregnate the surface of the substrate with the amino cellulose solution, or spraying the amino cellulose solution onto the surface of the substrate layer by spraying method, wherein the loading amount of the transition layer is 0.05mg/cm 2 ～1.0mg/cm 2 Preferably, the loading is 0.1mg/cm 2 ～0.4mg/cm 2 And (5) placing the sprayed electrode in a vacuum oven and drying at 60-180 ℃ for 6-12 h.
S3: snCl is added 2 Mixing with hydrochloric acid and water to obtain SnCl with concentration of 0.1-0.3mol/L 2 Mixing the aqueous solution with NaF 0.500-1.00 mol/L and organic additive 0.01-0.10mol/L, adding sodium citrate 0.07-0.15mol/L to obtain electroplating solution, regulating pH to 4-5 with hydrochloric acid, and preferably selecting tin salt concentration of 0.12-0.20mol/L SnCl 2 The preferable concentration of NaF in the aqueous solution is 0.500-1.00 mol/L NaF, and the preferable concentration of additive is 0.01-0.04mol/L NaF; the preferable concentration of sodium citrate is 0.09-0.12 mol/L; wherein the mol ratio of Sn to the organic additive is 1:1-30:1, and the preferable ratio is 4:1-10:1; the molar ratio of NaF to Sn is 1:20-40:1, and the preferable ratio is 1:5-20:1.
S4: at N 2 And (3) in-situ gradient power transformation deposition of the catalytic layer in the electroplating solution, cleaning and drying the deposited catalytic layer by using ethanol and water, and then placing the catalytic layer in a vacuum oven for drying for 30 min-2 h at the temperature of 100-200 ℃ to prepare the electrode.
Preferably, the oxidizing solution is NH 3 ·H 2 O and 0.5mol/L (NH) 4 ) 2 S 2 O 8 Ammonium persulfate mixed solution, wherein NH 3 ·H 2 O and (NH) 4 ) 2 S 2 O 8 The molar ratio of (2) is 30:1-1:10; the preferred molar ratio is 10:1 to 1:2;
preferably, the amino cellulose is one or more of aminoethyl cellulose, diethylamino cellulose, triethylamino cellulose, p-aminobenzyl cellulose and vinylsulfonyl anilino cellulose, and the solvent of the cellulose is one or more of water, alcohols and DMSO, DMF, DMAC, and the mixture is stirred at a temperature of 25-50 ℃ until the amino cellulose is completely dissolved, so that a solution with a mass concentration of 0.05-0.3% is formed.
Preferably, the additive is one or more than two of ethylenediamine tetraacetic acid, ethylenediamine tetramethylene phosphoric acid, iminodiacetic acid and triethanolamine; preferably one or two of ethylenediamine tetraacetic acid and iminodiacetic acid.
Preferably, the electrodeposition process is a gradient variable-potential deposition method, wherein the constant voltage is deposited at-6.0V to-8.0V for 50-900 s, and the constant voltage is preferably between-6.0V to-7.0V; then depositing 120-600 s under constant voltage of-3.0V to-6.0V, preferably constant voltage of-3.0V to-4.5V; finally, depositing 180s to 600s under the constant voltage of-1.5V to-3.0V, and preferably setting the constant voltage to be-2.0V to-2.8V.
Preferably, the electrode may serve as a cathode for the electrochemical reduction of carbon dioxide. The beneficial effects of the invention are as follows:
1. the invention provides a preparation method of an electrode, which comprises a basal layer, a transition layer and an Sn catalyst layer.
2. The basal layer is oxidized in a short time by an oxidant, and metal oxide or hydroxide can be grown on the surface of the basal layer, so that the basal layer can be used as an active component and a stabilizing layer, and the activity of a catalyst and the binding force with a transition layer can be improved;
3. the transition layer is introduced with an amino cellulose thin layer as an interface modification layer, so that the hydrophobicity of the surface of the basal layer can be reduced, uniform metal nano crystal nucleation points can be formed, and the possibility of successful metal deposition is provided; the surfaces of the substances contain amino and hydroxyl groups, so that the substances can interact with metal, and the binding force between the catalyst and the substrate layer can be improved; and the space structure of the transition layer provides sufficient space for fixing the catalyst, so that a continuous, uniform and fully-covered metal catalytic layer is formed.
4. Cellulose is the most abundant biological renewable resource on earth, and has the characteristics of low price, easy modification, biodegradability and the like. The lateral group of the molecular chain on the cellulose contains hydrophilic hydroxyl and ammonia (quaternary ammonium) groups, so that the cellulose has basically hydrophilic property, is favorable for reaction, and the transition layer is a bio-based material, is environment-friendly and has low cost.
5. The invention effectively improves the current density of the catalyst for the reduction reaction of carbon dioxide and the Faraday efficiency, and the electrode structure does not need to be pressed, so that the problems that the structure, the morphology and the activity specific surface of the catalyst are changed due to the pressed electrolysis in the traditional electrode manufacturing process, and the performance of the catalyst is influenced are avoided; by depositing the catalyst by a variable voltage, it is possible to have gradient electrodes of different particle size distribution and further increase the active area of the electrodes, thereby further increasing the activity of the catalyst.
6. The preparation method is simple, easy to operate and conventional in production equipment, is suitable for large-scale production, and the prepared electrode has large specific surface area and high carbon dioxide oxygen reduction catalytic performance.
Drawings
FIG. 1 is a graph of Faraday efficiency versus which electrodes of the present invention are prepared;
FIG. 2 is a graph of Faraday efficiency of electrodes prepared in examples 1-10 of the present invention;
FIG. 3 is a graph of Faraday efficiencies at various electrolysis times during stability testing in ERC reactions of the invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention is further described below:
examples:
as shown in fig. 1-3, an electrode for electrochemical reduction of carbon dioxide and a preparation method thereof are characterized by comprising a basal layer, a transition layer and a catalytic layer, wherein the preparation process of the electrode for electrochemical reduction of carbon dioxide is as follows:
s1: at 10Cleaning copper mesh, copper sheet, copper plate or copper foil with thickness of 0-500 μm with acetone and hydrochloric acid, placing in oxidation solution, and treating for 2-8min. Preparation of electrode and application thereof in electrochemical reduction of carbon dioxide, wherein the oxidant solution is NH 3 ·H 2 O and 0.5mol/L (NH) 4 ) 2 S 2 O 8 Ammonium persulfate mixed solution, wherein NH 3 ·H 2 O and (NH) 4 ) 2 S 2 O 8 The molar ratio of (2) is 30:1-1:10; the preferred molar ratio is 10:1 to 1:2. Taking the substrate as a basal layer after the substrate is cleaned;
s2, dipping the prepared amino cellulose solution for 1-20min to dip the amino cellulose solution on the surface of the substrate, or spraying the amino cellulose solution on the surface of the substrate layer by using a spraying method, wherein the loading capacity of the transition layer is 0.05mg/cm 2 ～1.0mg/cm 2 . Preferably, the loading is 0.1mg/cm 2 ～0.4mg/cm 2 . And (5) placing the electrode after spraying in a vacuum oven, and drying at 60-180 ℃ for 6-12 h.
S3: snCl is added 2 Mixing with hydrochloric acid and water to obtain SnCl with concentration of 0.1-0.3mol/L 2 The aqueous solution is evenly mixed with NaF of 0.500-1.00 mol/L and organic additive of 0.01-0.10mol/L, then sodium citrate of 0.07-0.15mol/L is added to obtain electroplating solution, and the PH value is adjusted between 4 and 5 by hydrochloric acid. The preferable concentration of the tin salt is 0.12-0.20mol/L SnCl 2 The preferable concentration of NaF in the aqueous solution is 0.500-1.00 mol/L NaF, and the preferable concentration of additive is 0.01-0.04mol/L NaF; the preferable concentration of sodium citrate is 0.09-0.12 mol/L; wherein the mol ratio of Sn to the organic additive is 1:1-30:1, and the preferable ratio is 4:1-10:1; the molar ratio of NaF to Sn is 1:20-40:1, and the preferable ratio is 1:5-20:1.
S4: at N 2 And (3) in-situ electrotransformation deposition of the catalytic layer in the atmosphere, cleaning and drying the deposited catalytic layer by using ethanol and water, and then placing the catalytic layer in a vacuum oven for drying for 30min-1h at the temperature of 100-200 ℃ to prepare the electrode.
Example 1
Using 200 μm copper mesh as substrate, cleaning with acetone and hydrochloric acid, and concentratingIt is placed in NH 3 ·H 2 O and (NH) 4 ) 2 S 2 O 8 Is treated for 8min in an oxidizing solution with the mol ratio of 8:1. Taking the substrate as a basal layer after the substrate is cleaned; preparing 0.2% concentration amino cellulose solution, spraying diethylaminocellulose onto the surface of basal layer by spraying method, and loading the transition layer at 0.3mg/cm 2 . The electrode after spraying was dried in a vacuum oven at 100℃for 6 hours. SnCl is added 2 Mixing with hydrochloric acid and water to obtain SnCl with concentration of 0.2mol/L 2 The aqueous solution is evenly mixed with 0.6mol/L NaF and 0.10mol/L ethylenediamine tetraacetic acid, then 0.09mol/L sodium citrate is added to obtain the electroplating solution, and the PH value is adjusted to be 4 by hydrochloric acid. Wherein the molar ratio of Sn to ethylenediamine tetraacetic acid is 8:1 and the molar ratio of NaF to Sn is 15:1. Depositing electrolyte solution under the protection of inert atmosphere at constant voltage of-6.0V for 300s, and then depositing electrolyte solution at constant voltage of-4.0V for 200; and finally, depositing 300s to 600s at constant voltage of-2.1V. And cleaning and drying the electrodeposited Sn catalyst layer by using ethanol and water. Then placing the mixture in a vacuum oven at 150 ℃ and drying the mixture for 30 minutes to prepare the electrode.
Comparative example 1 (without transition layer)
Using 200 μm copper mesh as substrate, cleaning with acetone and hydrochloric acid, and placing in NH 3 ·H 2 O and (NH) 4 ) 2 S 2 O 8 Is treated for 8min in an oxidizing solution with the mol ratio of 8:1. Taking the substrate as a basal layer after the substrate is cleaned; snCl is added 2 Mixing with hydrochloric acid and water to obtain SnCl with concentration of 0.2mol/L 2 The aqueous solution is evenly mixed with 0.6mol/L NaF and 0.10mol/L organic additive, then 0.09mol/L sodium citrate is added to obtain the electroplating solution, and the PH value is adjusted to be 4 by hydrochloric acid. Wherein the mol ratio of Sn to ethylenediamine tetraacetic acid is 8:1, and the mol ratio of NaF to Sn is 15:1. Depositing electrolyte solution under the protection of inert atmosphere at constant voltage of-6.0V for 300s, and then depositing electrolyte solution at constant voltage of-4.0V for 200; and finally, depositing 300s to 600s at constant voltage of-2.1V. And cleaning and drying the electrodeposited Sn catalyst layer by using ethanol and water. Then placed in a vacuum oven 1Drying at 50deg.C for 30min to obtain the electrode.
Comparative example 2 (non-oxidizing substrate Process)
Using a copper mesh with the thickness of 200 mu m as a substrate, and using acetone and hydrochloric acid to clean the copper mesh as a substrate layer; preparing 0.2% concentration amino cellulose solution, spraying diethylaminocellulose onto the surface of basal layer by spraying method, and loading the transition layer at 0.3mg/cm 2 . The electrode after spraying was dried in a vacuum oven at 100℃for 6 hours. SnCl is added 2 Mixing with hydrochloric acid and water to obtain SnCl with concentration of 0.2mol/L 2 The aqueous solution is evenly mixed with 0.6mol/L NaF and 0.10mol/L organic additive, then 0.09mol/L sodium citrate is added to obtain the electroplating solution, and the PH value is adjusted to be 4 by hydrochloric acid. Wherein the mol ratio of Sn to ethylenediamine tetraacetic acid is 8:1, and the mol ratio of NaF to Sn is 15:1. Depositing electrolyte solution under the protection of inert atmosphere at constant voltage of-6.0V for 300s, and then depositing at constant voltage of-4.0V for 200s; and finally, depositing 300s to 600s at constant voltage of-2.1V. And cleaning and drying the electrodeposited Sn catalyst layer by using ethanol and water. Then placing the mixture in a vacuum oven at 150 ℃ and drying the mixture for 30 minutes to prepare the electrode.
Comparative example 3 (no organic additive)
Using 200 μm copper mesh as substrate, cleaning with acetone and hydrochloric acid, and placing in NH 3 ·H 2 O and (NH) 4 ) 2 S 2 O 8 Is treated for 8min in an oxidizing solution with the mol ratio of 8:1. Taking the substrate as a basal layer after the substrate is cleaned; preparing 0.2% concentration amino cellulose solution, spraying diethylaminocellulose onto the surface of basal layer by spraying method, and loading the transition layer at 0.3mg/cm 2 . The electrode after spraying was dried in a vacuum oven at 100℃for 6 hours. SnCl is added 2 Mixing with hydrochloric acid and water to obtain SnCl with concentration of 0.2mol/L 2 The aqueous solution is uniformly mixed with NaF of 0.6mol/L, then sodium citrate of 0.09mol/L is added to obtain electroplating solution, and the PH value is regulated to be 4 by hydrochloric acid. The molar ratio of NaF to Sn was 15:1. Depositing electrolyte solution under the protection of inert atmosphere at constant voltage of-6.0V300s, then depositing 200 at constant voltage-4.0V; and finally, depositing 300s to 600s at constant voltage of-2.1V. And cleaning and drying the electrodeposited Sn catalyst layer by using ethanol and water. Then placing the mixture in a vacuum oven at 150 ℃ and drying the mixture for 30 minutes to prepare the electrode.
Comparative example 4 (potentiostatic deposition)
Using 200 μm copper mesh as substrate, cleaning with acetone and hydrochloric acid, and placing in NH 3 ·H 2 O and (NH) 4 ) 2 S 2 O 8 Is treated for 8min in an oxidizing solution with the mol ratio of 8:1. Taking the substrate as a basal layer after the substrate is cleaned; preparing 0.2% concentration amino cellulose solution, spraying diethylaminocellulose onto the surface of basal layer by spraying method, and loading the transition layer at 0.3mg/cm 2 . The electrode after spraying was dried in a vacuum oven at 100℃for 6 hours. SnCl is added 2 Mixing with hydrochloric acid and water to obtain SnCl with concentration of 0.2mol/L 2 The aqueous solution is evenly mixed with 0.6mol/L NaF and 0.10mol/L organic additive, then 0.09mol/L sodium citrate is added to obtain the electroplating solution, and the PH value is adjusted to be 4 by hydrochloric acid. Wherein the molar ratio of Sn to ethylenediamine tetraacetic acid is 8:1 and the molar ratio of NaF to Sn is 15:1. And (3) depositing the electrolyte solution for 900s under the protection of inert atmosphere and constant voltage of-4.0V, and cleaning and drying the electrodeposited Sn catalyst layer by using ethanol and water. Then placing the mixture in a vacuum oven at 150 ℃ and drying the mixture for 30 minutes to prepare the electrode.
Comparative example 5 (transition layer thickness exceeding upper limit)
Using 200 μm copper mesh as substrate, cleaning with acetone and hydrochloric acid, and placing in NH 3 ·H 2 O and (NH) 4 ) 2 S 2 O 8 Is treated for 8min in an oxidizing solution with the mol ratio of 8:1. Taking the substrate as a basal layer after the substrate is cleaned; preparing 0.2% concentration amino cellulose solution, spraying diethylaminocellulose onto the surface of basal layer by spraying method, and loading the transition layer at 1.2mg/cm 2 . The electrode after spraying was dried in a vacuum oven at 100℃for 6 hours. SnCl is added 2 Mixing with hydrochloric acid and water to obtainSnCl with concentration of 0.2mol/L 2 The aqueous solution is evenly mixed with 0.6mol/L NaF and 0.10mol/L diethylamino cellulose, then 0.09mol/L sodium citrate is added to obtain the electroplating solution, and the PH value is adjusted to be 4 by hydrochloric acid. Wherein the mol ratio of Sn to ethylenediamine tetraacetic acid is 8:1, and the mol ratio of NaF to Sn is 15:1. Depositing electrolyte solution under the protection of inert atmosphere at constant voltage of-6.0V for 300s, and then depositing electrolyte solution at constant voltage of-4.0V for 200; and finally, depositing 300s to 600s at constant voltage of-2.1V. And cleaning and drying the electrodeposited Sn catalyst layer by using ethanol and water. Then placing the mixture in a vacuum oven at 150 ℃ and drying the mixture for 30 minutes to prepare the electrode.
Comparative example 6 (transition layer thickness over-run)
Using 200 μm copper mesh as substrate, cleaning with acetone and hydrochloric acid, and placing in NH 3 ·H 2 O and (NH) 4 ) 2 S 2 O 8 Is treated for 8min in an oxidizing solution with the mol ratio of 8:1. Taking the substrate as a basal layer after the substrate is cleaned; preparing 0.2% concentration amino cellulose solution, spraying diethylaminocellulose onto the surface of basal layer by spraying method, and loading the transition layer at 0.02mg/cm 2 . The electrode after spraying was dried in a vacuum oven at 100℃for 6 hours. SnCl is added 2 Mixing with hydrochloric acid and water to obtain SnCl with concentration of 0.2mol/L 2 The aqueous solution is evenly mixed with 0.6mol/L NaF and 0.10mol/L diethylamino cellulose, then 0.09mol/L sodium citrate is added to obtain the electroplating solution, and the PH value is adjusted to be 4 by hydrochloric acid. Wherein the mol ratio of Sn to ethylenediamine tetraacetic acid is 8:1, and the mol ratio of NaF to Sn is 15:1. Depositing electrolyte solution under the protection of inert atmosphere at constant voltage of-6.0V for 300s, and then depositing electrolyte solution at constant voltage of-4.0V for 200; and finally, depositing 300s to 600s at constant voltage of-2.1V. And cleaning and drying the electrodeposited Sn catalyst layer by using ethanol and water. Then placing the mixture in a vacuum oven at 150 ℃ and drying the mixture for 30 minutes to prepare the electrode.
Comparative example 7 (organic additive ratio exceeds the lower limit)
Using 200 μm copper mesh as substrate, cleaning with acetone and hydrochloric acidAfter cleaning, it is placed in NH 3 ·H 2 O and (NH) 4 ) 2 S 2 O 8 Is treated for 8min in an oxidizing solution with the mol ratio of 8:1. Taking the substrate as a basal layer after the substrate is cleaned; preparing 0.2% concentration amino cellulose solution, spraying diethylaminocellulose onto the surface of basal layer by spraying method, and loading the transition layer at 0.3mg/cm 2 . The electrode after spraying was dried in a vacuum oven at 100℃for 6 hours. SnCl is added 2 Mixing with hydrochloric acid and water to obtain SnCl with concentration of 0.2mol/L 2 The aqueous solution is evenly mixed with 0.6mol/L NaF and 0.10mol/L organic additive, then 0.09mol/L sodium citrate is added to obtain the electroplating solution, and the PH value is adjusted to be 4 by hydrochloric acid. Wherein the mol ratio of Sn to ethylenediamine tetraacetic acid is 1:2, and the mol ratio of NaF to Sn is 15:1. Depositing electrolyte solution under the protection of inert atmosphere at constant voltage of-6.0V for 300s, and then depositing electrolyte solution at constant voltage of-4.0V for 200; and finally, depositing 300s to 600s at constant voltage of-2.1V. And cleaning and drying the electrodeposited Sn catalyst layer by using ethanol and water. Then placing the mixture in a vacuum oven at 150 ℃ and drying the mixture for 30 minutes to prepare the electrode.
Comparative example 8 (organic additive ratio exceeds the lower limit)
Using 200 μm copper mesh as substrate, cleaning with acetone and hydrochloric acid, and placing in NH 3 ·H 2 O and (NH) 4 ) 2 S 2 O 8 Is treated for 8min in an oxidizing solution with the mol ratio of 8:1. Taking the substrate as a basal layer after the substrate is cleaned; preparing 0.2% concentration amino cellulose solution, spraying diethylaminocellulose onto the surface of basal layer by spraying method, and loading the transition layer at 0.3mg/cm 2 . The electrode after spraying was dried in a vacuum oven at 100℃for 6 hours. SnCl is added 2 Mixing with hydrochloric acid and water to obtain SnCl with concentration of 0.2mol/L 2 The aqueous solution is evenly mixed with 0.6mol/L NaF and 0.10mol/L organic additive, then 0.09mol/L sodium citrate is added to obtain the electroplating solution, and the PH value is adjusted to be 4 by hydrochloric acid. Wherein the mol ratio of Sn to ethylenediamine tetraacetic acid is 40:1, and the mol ratio of NaF to Sn is 15:1. The electrolyte solution is put in inert gasDepositing at constant voltage of-6.0V for 300s under the protection of atmosphere, and then depositing at constant voltage of-4.0V for 200; and finally, depositing 300s to 600s at constant voltage of-2.1V. And cleaning and drying the electrodeposited Sn catalyst layer by using ethanol and water. Then placing the mixture in a vacuum oven at 150 ℃ and drying the mixture for 30 minutes to prepare the electrode.
Example 2
Using 200 μm copper mesh as substrate, cleaning with acetone and hydrochloric acid, and placing in NH 3 ·H 2 O and (NH) 4 ) 2 S 2 O 8 Is treated for 8min in an oxidizing solution with the mol ratio of 8:1. Taking the substrate as a basal layer after the substrate is cleaned; preparing an amino cellulose solution with concentration of 0.2%, spraying p-aminobenzyl cellulose onto the surface of the basal layer, and loading the transition layer at 0.3mg/cm 2 . The electrode after spraying was dried in a vacuum oven at 100℃for 6 hours. SnCl is added 2 Mixing with hydrochloric acid and water to obtain SnCl with concentration of 0.2mol/L 2 The aqueous solution is evenly mixed with 0.6mol/L NaF and 0.10mol/L iminodiacetic acid, then 0.09mol/L sodium citrate is added to obtain the electroplating solution, and the PH value is adjusted to be 4 by hydrochloric acid. Wherein the molar ratio of Sn to iminodiacetic acid is 8:1NaF to Sn is 15:1. Depositing electrolyte solution under the protection of inert atmosphere at constant voltage of-6.0V for 300s, and then depositing electrolyte solution at constant voltage of-4.0V for 200; and finally, depositing 300s to 600s at constant voltage of-2.1V. And cleaning and drying the electrodeposited Sn catalyst layer by using ethanol and water. Then placing the mixture in a vacuum oven at 150 ℃ and drying the mixture for 30 minutes to prepare the electrode.
Example 3
Using 200 μm copper mesh as substrate, cleaning with acetone and hydrochloric acid, and placing in NH 3 ·H 2 O and (NH) 4 ) 2 S 2 O 8 Is treated for 8min in an oxidizing solution with the mol ratio of 8:1. Taking the substrate as a basal layer after the substrate is cleaned; preparing an amino cellulose solution with the concentration of 0.2%, spraying diethylaminocellulose on the surface of the basal layer by adopting a spraying method, wherein the loading capacity of the transition layer is 0.5mg/cm 2 . Placing the sprayed electrode in vacuumThe oven was dried at 100℃for 6h. SnCl is added 2 Mixing with hydrochloric acid and water to obtain SnCl with concentration of 0.2mol/L 2 The aqueous solution is evenly mixed with 0.6mol/L NaF and 0.10mol/L iminodiacetic acid, then 0.09mol/L sodium citrate is added to obtain the electroplating solution, and the PH value is adjusted to be 4 by hydrochloric acid. Wherein the mol ratio of Sn to ethylenediamine tetraacetic acid is 8:1, and the mol ratio of NaF to Sn is 15:1. Depositing electrolyte solution under the protection of inert atmosphere at constant voltage of-6.0V for 300s, and then depositing electrolyte solution at constant voltage of-4.0V for 200; and finally, depositing 300s to 600s at constant voltage of-2.1V. And cleaning and drying the electrodeposited Sn catalyst layer by using ethanol and water. Then placing the mixture in a vacuum oven at 150 ℃ and drying the mixture for 30 minutes to prepare the electrode.
Example 4
Using 200 μm copper mesh as substrate, cleaning with acetone and hydrochloric acid, and placing in NH 3 ·H 2 O and (NH) 4 ) 2 S 2 O 8 Is treated for 8min in an oxidizing solution with the mol ratio of 8:1. Taking the substrate as a basal layer after the substrate is cleaned; preparing an amino cellulose solution with the concentration of 0.3%, spraying diethylaminocellulose on the surface of the basal layer by adopting a spraying method, wherein the loading capacity of the transition layer is 0.3mg/cm 2 . The electrode after spraying was dried in a vacuum oven at 100℃for 6 hours. SnCl is added 2 Mixing with hydrochloric acid and water to obtain SnCl with concentration of 0.2mol/L 2 The aqueous solution is evenly mixed with 0.6mol/L NaF and 0.10mol/L ethylenediamine tetraacetic acid, then 0.09mol/L sodium citrate is added to obtain the electroplating solution, and the PH value is adjusted to be 4 by hydrochloric acid. Wherein the mol ratio of Sn to ethylenediamine tetraacetic acid is 8:1, and the mol ratio of NaF to Sn is 15:1. Depositing electrolyte solution under the protection of inert atmosphere at constant voltage for 300s, and then depositing at constant voltage-5.0V for 100s; and finally, depositing 300s to 600s at constant voltage of-2.1V. And cleaning and drying the electrodeposited Sn catalyst layer by using ethanol and water. Then placing the mixture in a vacuum oven at 150 ℃ and drying the mixture for 30 minutes to prepare the electrode.
Example 5
Using 200 μm copper mesh as substrate, and acetone and saltAfter the acid is cleaned, the mixture is placed in NH 3 ·H 2 O and (NH) 4 ) 2 S 2 O 8 Is treated for 8min in an oxidizing solution with the molar ratio of 20:1. Taking the substrate as a basal layer after the substrate is cleaned; preparing 0.2% concentration amino cellulose solution, spraying diethylaminocellulose onto the surface of basal layer by spraying method, and loading the transition layer at 0.3mg/cm 2 . The electrode after spraying was dried in a vacuum oven at 100℃for 6 hours. SnCl is added 2 Mixing with hydrochloric acid and water to obtain SnCl with concentration of 0.2mol/L 2 The aqueous solution is evenly mixed with 0.6mol/L NaF and 0.10mol/L ethylenediamine tetraacetic acid, then 0.09mol/L sodium citrate is added to obtain the electroplating solution, and the PH value is adjusted to be 4 by hydrochloric acid. Wherein the molar ratio of Sn to ethylenediamine tetraacetic acid is 8:1 and the molar ratio of NaF to Sn is 15:1. Depositing electrolyte solution under the protection of inert atmosphere at constant voltage of-6.0V for 300s, and then depositing electrolyte solution at constant voltage of-4.0V for 200; and finally, depositing 300s to 600s at constant voltage of-2.1V. And cleaning and drying the electrodeposited Sn catalyst layer by using ethanol and water. Then placing the mixture in a vacuum oven at 150 ℃ and drying the mixture for 30 minutes to prepare the electrode.
Example 6
Using 200 μm copper mesh as substrate, cleaning with acetone and hydrochloric acid, and placing in NH 3 ·H 2 O and (NH) 4 ) 2 S 2 O 8 Is treated for 8min in an oxidizing solution with the mol ratio of 8:1. Taking the substrate as a basal layer after the substrate is cleaned; preparing an amino cellulose solution with the concentration of 0.2%, spraying ethylene sulfonamide anilino cellulose on the surface of the basal layer, wherein the loading capacity of the transition layer is 0.4mg/cm 2 . The electrode after spraying was dried in a vacuum oven at 100℃for 6 hours. SnCl is added 2 Mixing with hydrochloric acid and water to obtain SnCl with concentration of 0.2mol/L 2 The aqueous solution is evenly mixed with 0.6mol/L NaF and 0.10mol/L ethylenediamine tetraacetic acid, then 0.09mol/L sodium citrate is added to obtain the electroplating solution, and the PH value is adjusted to be 4 by hydrochloric acid. Wherein the mol ratio of Sn to ethylenediamine tetraacetic acid is 8:1, and the mol ratio of NaF to Sn is 15:1. The electrolyte solution is kept constant under the protection of inert atmosphereDepositing at-6.0V for 300s, and then depositing at-4.0V for 200s; and finally, depositing 300s to 600s at constant voltage of-2.1V. And cleaning and drying the electrodeposited Sn catalyst layer by using ethanol and water. Then placing the mixture in a vacuum oven at 150 ℃ and drying the mixture for 30 minutes to prepare the electrode.
Example 7
Using 200 μm copper mesh as substrate, cleaning with acetone and hydrochloric acid, and placing in NH 3 ·H 2 O and (NH) 4 ) 2 S 2 O 8 Is treated for 8min in an oxidizing solution with the mol ratio of 8:1. Taking the substrate as a basal layer after the substrate is cleaned; preparing 0.2% concentration amino cellulose solution, spraying diethylaminocellulose onto the surface of basal layer, and loading the transition layer at 0.3mg/cm 2 . The electrode after spraying was dried in a vacuum oven at 100℃for 6 hours. SnCl is added 2 Mixing with hydrochloric acid and water to obtain SnCl with concentration of 0.1mol/L 2 The aqueous solution is evenly mixed with 0.6mol/L NaF and 0.05mol/L ethylenediamine tetraacetic acid, then 0.09mol/L sodium citrate is added to obtain the electroplating solution, and the PH value is adjusted to be 4 by hydrochloric acid. Wherein the mol ratio of Sn to ethylenediamine tetraacetic acid is 8:1, and the mol ratio of NaF to Sn is 15:1. Depositing electrolyte solution under the protection of inert atmosphere at constant voltage of-6.0V for 300s, and then depositing electrolyte solution at constant voltage of-4.0V for 200; and finally, depositing 300s to 600s at constant voltage of-2.1V. And cleaning and drying the electrodeposited Sn catalyst layer by using ethanol and water. Then placing the mixture in a vacuum oven at 150 ℃ and drying the mixture for 30 minutes to prepare the electrode.
Example 8
Using 100 μm copper plate as substrate, cleaning with acetone and hydrochloric acid, placing in NH 3 ·H 2 O and (NH) 4 ) 2 S 2 O 8 Is treated for 8min in an oxidizing solution with the mol ratio of 5:1. Taking the substrate as a basal layer after the substrate is cleaned; preparing 0.2% concentration amino cellulose solution, spraying diethylaminocellulose onto the surface of basal layer by spraying method, and loading the transition layer at 0.3mg/cm 2 . The electrode after being sprayed is placed in a vacuum oven for drying at 100 DEG CAnd 6h. SnCl is added 2 Mixing with hydrochloric acid and water to obtain SnCl with concentration of 0.2mol/L 2 The aqueous solution is evenly mixed with 0.6mol/L NaF and 0.10mol/L ethylenediamine tetramethylene phosphate, then 0.12mol/L sodium citrate is added to obtain the electroplating solution, and the PH value is adjusted to be 4 by hydrochloric acid. Wherein the mol ratio of Sn to ethylenediamine tetramethylene phosphate is 8:1, and the mol ratio of NaF to Sn is 15:1. Depositing electrolyte solution under the protection of inert atmosphere at constant voltage of-6.0V for 300s, and then depositing electrolyte solution at constant voltage of-4.0V for 200; and finally, depositing 300s to 600s at constant voltage of-2.1V. And cleaning and drying the electrodeposited Sn catalyst layer by using ethanol and water. Then placing the mixture in a vacuum oven at 150 ℃ and drying the mixture for 30 minutes to prepare the electrode.
Example 9
Using 200 μm copper mesh as substrate, cleaning with acetone and hydrochloric acid, and placing in NH 3 ·H 2 O and (NH) 4 ) 2 S 2 O 8 Is treated for 8min in an oxidizing solution with the mol ratio of 8:1. Taking the substrate as a basal layer after the substrate is cleaned; preparing an amino cellulose solution with the concentration of 0.2%, spraying p-aminobenzyl cellulose on the surface of the basal layer by adopting a spraying method, wherein the loading amount of the transition layer is 0.3mg/cm 2 . The electrode after spraying was dried in a vacuum oven at 100℃for 6 hours. SnCl is added 2 Mixing with hydrochloric acid and water to obtain SnCl with concentration of 0.2mol/L 2 The aqueous solution is evenly mixed with 0.6mol/L NaF and 0.10mol/L iminodiacetic acid, then 0.09mol/L sodium citrate is added to obtain the electroplating solution, and the PH value is adjusted to be 4 by hydrochloric acid. Wherein the molar ratio of Sn to iminodiacetic acid is 8:1NaF to Sn is 15:1. Depositing electrolyte solution under the protection of inert atmosphere at constant voltage of-6.0V for 300s, and then depositing electrolyte solution at constant voltage of-4.0V for 200; and finally, depositing 300s to 600s at constant voltage of-2.1V. And cleaning and drying the electrodeposited Sn catalyst layer by using ethanol and water. Then placing the mixture in a vacuum oven at 150 ℃ and drying the mixture for 30 minutes to prepare the electrode.
Specifically, the electrode is used as a cathode for preparing formic acid by reducing carbon dioxide, and passes through a three-electrode systemElectrochemical testing was performed: the working electrode is a prepared electrode; the counter electrode is a Pt sheet, and the reference electrode is Hg/Hg 2 Cl 2 The distance between saturated KCl, WE and RE is 0.5cm, and a salt bridge is adopted to reduce the liquid junction potential. NaHCO with 0.5mol/L catholyte 3 The volume of the electrolyte is 100ml, and the volume of the anolyte is 0.1mol/L H 2 SO 4 。
Specifically, as shown in fig. 1, the faraday efficiencies of the electrodes prepared in comparative examples 1, 2, 3, 4, 5, 6, 1, 2 and 3 were compared. The results show that comparative example 1 is an electrode without a transition layer. Compared with comparative example 1, it can be seen that the electrode of example 1 containing the transition layer has higher faraday efficiency and current density, indicating that the electrode has higher selectivity and catalytic activity of formic acid product, which demonstrates that the introduction of the transition layer has a remarkable effect;
comparative example 2 is the same transition layer and electrolyte composition as in example 1, but without the oxide substrate treatment process. It can be seen that the electrode prepared in example 1 using the oxidation treatment process has a higher current density than comparative example 2;
comparative example 3 is the same transition layer and electrochemical deposition voltage as in example 1, but without organic additives during electrodeposition. It can be seen that the catalyst prepared with the organic additive of example 1 has higher selectivity and current density and no significant drop off at 40h of electrolysis, compared to comparative example 4;
comparative example 4 is the same transition layer and electrolyte composition as in example 1, but with a constant voltage density for the electrochemical deposition voltage. It can be seen that the catalyst prepared by depositing Sn with a variable voltage density in example 1 has higher selectivity and current density compared with comparative example 2, which is mainly that gradient electrodes with different particle sizes are formed by different deposition voltage densities, so that ERC reaction is facilitated;
comparative example 5 is an electrode having a transition layer loading exceeding the upper loading limit specified in the present invention during electrode preparation, and the other conditions are the same as in example 1. Compared with example 1, it can be seen that the transition layer content is too high, which significantly reduces the current density and selectivity of the electrode. The transition layer affects the conductivity of the electrode mainly because of the excessive thick film thickness, thereby obviously reducing the current density and the selectivity of the electrode;
comparative example 6 is an electrode having a transition layer loading exceeding the lower loading limit specified in the present invention during electrode preparation, and the other conditions are the same as in example 1. Compared with example 1, the transition layer loading is too low to play a significant role, and the current density and selectivity of the electrode are significantly reduced.
Comparative example 7 is an electrodeposition process in which the amount of the organic additive added exceeds the lower limit of the prescribed organic additive-containing composition of the present invention, and it can be seen that the amount of the organic additive-containing composition is too low, compared with example 1, to significantly reduce the current density and selectivity of the electrode, mainly because too little additive results in a relatively low amount of the electrodeposited catalyst layer, resulting in a decrease in the specific surface area of the electrode activity, and thus in a decrease in the catalytic activity.
Comparative example 8 is an electrode in which the addition amount of the organic additive exceeds the upper limit of the prescribed organic additive of the present invention during electrodeposition in the electrode preparation process. It can be seen that the surface of the Sn catalyst is covered by the excessive content of the organic additive, so that the current density and the selectivity of the electrode are obviously reduced;
specifically, as shown in fig. 2, the electrochemical properties of the electrodes prepared in examples 1-10 in the ERC reaction show that the electrode prepared by the invention has higher current density and better catalytic selectivity.
In particular, as shown in fig. 3, the electrodes prepared in example 1 and comparative example 1 have very high stability as can be seen from faraday efficiencies at different electrolysis times during stability test in ERC reaction.
In the present invention, unless expressly stated or limited otherwise, a first feature "above" or "below" a second feature may include both the first and second features being in direct contact, as well as the first and second features not being in direct contact but being in contact with each other through additional features therebetween. Moreover, a first feature being "above," "over" and "on" a second feature includes the first feature being directly above and obliquely above the second feature, or simply indicating that the first feature is higher in level than the second feature. The first feature being "under", "below" and "beneath" the second feature includes the first feature being directly under and obliquely below the second feature, or simply means that the first feature is less level than the second feature.
The foregoing has shown and described the basic principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited by the foregoing embodiment, and that the foregoing embodiment and description are merely preferred examples of the invention and are not intended to limit the invention, and that various changes and modifications may be made therein without departing from the spirit and scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (6)
1. The preparation method of the electrode for carbon dioxide electroreduction is characterized by comprising the following steps:
s1: taking a copper mesh, a copper sheet, a copper plate or a copper foil with the thickness of 100-500 mu m as a substrate, cleaning by using acetone and hydrochloric acid, placing the substrate in an oxidizing solution, treating for 2-8min, and taking the substrate as a substrate layer after cleaning;
s2: impregnating the prepared amino cellulose solution for 1-20min to impregnate the surface of the substrate with the amino cellulose solution, or spraying the amino cellulose solution onto the surface of the substrate layer by spraying method, wherein the loading amount of the transition layer is 0.05mg/cm 2 ～1.0mg/cm 2 Drying the sprayed electrode in a vacuum oven at 60-180 ℃ for 6-12 h;
s3: snCl is added 2 Mixing with hydrochloric acid and water to obtain SnCl with concentration of 0.1-0.3mol/L 2 Uniformly mixing the aqueous solution with 0.500-1.00 mol/L NaF and 0.01-0.10mol/L organic additive, then adding 0.07-0.15mol/L sodium citrate uniformly to obtain electroplating solution, and regulating the PH value to be 4-5 by using hydrochloric acid; wherein the mol ratio of Sn to the organic additive is 1:1 to the whole30:1, wherein the molar ratio of NaF to Sn is 1:20-40:1, and the organic additive is one or more than two of ethylenediamine tetraacetic acid, ethylenediamine tetramethylene phosphoric acid, iminodiacetic acid and triethanolamine;
s4: at N 2 And (3) in-situ gradient power transformation deposition of the catalytic layer in the electroplating solution, cleaning and drying the deposited catalytic layer by using ethanol and water, and then placing the catalytic layer in a vacuum oven for drying for 30 min-2 h at the temperature of 100-200 ℃ to prepare the electrode.
2. The method for producing an electrode for electro-reduction of carbon dioxide according to claim 1, wherein the oxidizing solution is NH 3 ·H 2 O and 0.5mol/L (NH) 4 ) 2 S 2 O 8 Ammonium persulfate mixed solution, wherein NH 3 ·H 2 O and (NH) 4 ) 2 S 2 O 8 The molar ratio of (2) is 30:1-1:10.
3. The method for producing an electrode for carbon dioxide electroreduction according to claim 1, wherein the amino cellulose is one or more of aminoethyl cellulose, diethylamino cellulose, triethylamino cellulose, p-aminobenzyl cellulose, and vinylsulfonamide-amino cellulose, and the solvent of the cellulose is one or more of water, alcohols, and DMSO, DMF, DMAC, and the solution is stirred at 25 to 50 ℃ until the amino cellulose is completely dissolved, thereby forming a solution with a mass concentration of 0.05 to 0.3%.
4. The method for preparing an electrode for carbon dioxide electroreduction according to claim 1, wherein the electrodeposition process is a gradient-varying electrodeposition method, wherein the electrodeposition is carried out at a constant voltage of-6.0V to-8.0V for 50-900 s, then at a constant voltage of-3.0V to-6.0V for 120-600 s, and finally at a constant voltage of-1.5V to-3.0V for 180 s-600 s.
5. The method for producing an electrode for electrochemical reduction of carbon dioxide according to claim 1, wherein the electrode can be used as a cathode for electrochemical reduction of carbon dioxide.
6. An electrode for carbon dioxide electroreduction, which is prepared by adopting the preparation method of the electrode for carbon dioxide electroreduction according to claim 1, and is characterized by comprising a substrate layer, a transition layer and a catalytic layer, wherein an oxide or hydroxide is prepared by chemical oxidation to serve as an active component and a stabilizer, the activity of a catalyst and the binding force with the transition layer are improved, an amino cellulose thin layer is introduced into the transition layer to serve as an interface modification layer to reduce the hydrophobicity of the surface of the substrate layer, the surface of a substance contains amino and hydroxyl groups and interacts with metal, the binding force between the catalyst and the substrate layer is improved, the space structure of the transition layer provides sufficient space for fixing the catalyst to form a metal catalytic layer, then an Sn catalyst layer grows on the surface of the transition layer, and the electrode with a high specific surface and high stability is prepared.
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