CN110938836B - Improve CO2Method for stabilizing electrode for electrochemical reduction - Google Patents

Improve CO2Method for stabilizing electrode for electrochemical reduction Download PDF

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CN110938836B
CN110938836B CN201811108842.3A CN201811108842A CN110938836B CN 110938836 B CN110938836 B CN 110938836B CN 201811108842 A CN201811108842 A CN 201811108842A CN 110938836 B CN110938836 B CN 110938836B
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邱艳玲
李先锋
张华民
张桃桃
姚鹏飞
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Dalian Institute of Chemical Physics of CAS
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Abstract

The invention relates to a method for improving the stability of an electrode for electrochemical reduction of carbon dioxide, which comprises a supporting electrolyte containing impurity metal ions, wherein the supporting electrolyte is a bicarbonate aqueous solution containing alkali metal, and when the impurity metal ions M in the supporting electrolyte comprise Fe2+、Zn2+、Ca2+、Pb2+When the total molar concentration of impurity metal ions is 0.01-0.5 mu M, organic additives are introduced into the supporting electrolyte, and the method obviously improves the stability of the electrode for electrochemical reduction of carbon dioxide.

Description

Improve CO2Method for stabilizing electrode for electrochemical reduction
Technical Field
The invention belongs to the technical field of electrochemical reduction of carbon dioxide, and particularly relates to a method for improving electrode stability.
Background
Electrochemical reduction of CO2(ERC) technique involving the use of electric energy to convert CO2Reducing to a target product to realize CO2A technique for transformation and efficient utilization. Because the ERC technology can utilize water as the protonation hydrogen source, the CO can be realized at normal temperature and normal pressure2The method has the advantages of simple operation and low cost.
Currently, the main factors that slow the development of ERC technology include: (1) the reaction overpotential is high; (2) low catalytic activity and slow reaction rate; (3) the target product has poor selectivity; (4) the stability of the electrode is low. In ERC reaction systems that use aqueous solutions as supporting electrolytes, flat (e.g., sheet, foil, and bulk) metals are typically used to catalyze the electrode reaction process. Among them, the Cu electrode is the most used metal that catalyzes the most abundant species of ERC reaction products, and the hydrocarbon is the characteristic product of the Cu electrode that catalyzes the ERC reaction. Since the overpotential for the reaction of hydrocarbons usually exceeds 1V, hydrogen evolution side reactions are violent in the potential window interval of the generation of the hydrocarbonsStrongly supporting the trace impurity metal ions (e.g., Zn) in the electrolyte2+，Pb2+，Fe2+Etc.) on the surface of the Cu electrode, the occurrence of hydrogen evolution side reactions is exacerbated, resulting in a copper electrode having a very low lifetime, typically no more than 2 hours.
To improve the stability of the electrode for ERC reaction, y.hori et al use a method of pre-electrolysis at negative potential to remove KHCO of different concentrations3The impurity metal ions in the solution (electrochimica acta 50, 2005, 5354-5369) keep the catalytic activity and product selectivity of the Cu electrode substantially stable within 2 hours, but the pre-electrolysis method takes more than 16 hours and needs large area of Pt black as the working electrode, thus the practicability is very low. Wuttig et al reported a supported imido ion exchange resin, chelax-100(ACS Catal.2015,5, 4479-.
The invention content is as follows:
in order to solve the technical problem, the invention adds an organic additive into the supporting electrolyte containing the impurity metal ions, and eliminates the attenuation of the impurity metal ions to the catalytic activity of the electrode through the in-situ complexing action of coordination atoms in the organic additive and the impurity ions in the electrolyte.
In order to achieve the purpose of the invention, the invention adopts the following specific technical scheme:
a method for improving the stability of an electrode for electrochemical reduction of carbon dioxide, wherein the electrochemical reduction reaction of the carbon dioxide comprises a supporting electrolyte containing impurity metal ions, and the supporting electrolyte is a bicarbonate aqueous solution containing alkali metal, and the concentration of the supporting electrolyte is 0.1-0.5M. When the impurity metal ions M in the supporting electrolyte comprise Fe2+、Zn2+、Ca2+、Pb2+When the total molar concentration of impurity metal ions is 0.01-0.5 mu M, introducing an organic additive into the supporting electrolyte, wherein the molecular structure of the organic additive at least contains 3 coordination atomsThe coordinating atoms comprise one or two of N, O and P;
wherein the organic additive: the molar ratio of the total molar concentration of the impurity metals is 10-1000, and the preferred molar ratio is 200-800.
The solubility of the organic additive in water at room temperature is not less than 0.5g L-1. The alkali metal is one of K and Na. The stable complexation constant of the additive and the impurity metal ions at room temperature is not lower than 8.0. Comprises one or more than two of ethylene diamine tetraacetic acid, ethylene diamine tetra methylene phosphoric acid and iminodiacetic acid; one or two of ethylene diamine tetraacetic acid and ethylene diamine tetramethylene phosphoric acid are preferred.
The proportion of the additive to the total molar concentration of the impurity metal is 10-1000, and the preferable proportion is 200-800.
The complex generated by the additive molecules and the impurity metal ions has stable structure in a potential window of carbon dioxide electrochemical reduction.
The potential window of the electrochemical reduction of the carbon dioxide is-0.6V to-4.0V (relative to a saturated calomel electrode).
The electrode is a copper electrode
The invention has the advantages and beneficial effects that:
the method for improving the stability of the copper electrode has the characteristics of simplicity and practicability. The method utilizes the in-situ complexing principle to stabilize impurity metal ions in a liquid phase in a complex form, and because the stable complexing constant of the complex is higher, the complex can still stably exist even under the negative potential of ERC reaction and can not be deposited on the surface of a copper electrode, so that the surface of the copper electrode is ensured to be clean and the active sites are fully exposed; in addition, due to Fe2+、Zn2+The impurity ions can not be deposited on the surface of the copper electrode, and the competing hydrogen evolution side reaction can not obtain the catalytic action of impurity metal under a more negative electrolytic potential.
The invention provides a method for improving the stability of a copper electrode for electrochemical reduction of carbon dioxide, which utilizes the principle that a complexing agent and impurity metal ions in a supporting electrolyte are in-situ complexed, increases the stability of the impurity metal ions, prevents the impurity metal ions from depositing on the surface of the Cu electrode in a potential window interval of ERC reaction, and ensures that the copper electrode keeps the catalytic activity and the product selectivity in a longer reaction time.
Drawings
FIG. 1 shows the method provided in example 1 to improve the stability of the Cu electrode, and then CO is added2The electrochemical reduction reaction was continued for 6 hours with the change of the reaction current with time, and compared with comparative example 1.
FIG. 2 shows the method of example 1, after improving the stability of the Cu electrode, CO2The selectivity of the reaction product was varied with time for the electrochemical reduction reaction lasting 6 hours and compared with comparative example 1.
Detailed Description
Example 1
1. Pretreatment of electrode materials: the copper content is more than or equal to 99.5 percent, the thickness is 100 micrometers, and the area is 10cm2The copper sheet is used as an electrode material, and is firstly soaked in concentrated hydrochloric acid with the volume fraction of 36-38% for treatment for 20min at room temperature to remove surface impurities, then is washed to be neutral by a large amount of deionized water, and is dried by high-purity nitrogen;
2. preparing an organic additive solution: a1 mM solution was prepared with analytically pure ethylenediaminetetraacetic acid (EDTA) as a solute and ultrapure water having a resistivity of 18.2 M.OMEGA.for use.
3. Supporting the determination of impurity metal ions and the concentration thereof in the electrolyte: KHCO with purity of 99.7%3200ml of 0.1M KHCO prepared from ultrapure water having a resistivity of 18.2 M.OMEGA. (manufactured by Sigma-Aldrich) as a solvent3An aqueous solution. After 1ml of the solution is diluted by 100 times, the species and the concentration of impurity metal ions in the electrolyte are tested by ICP-MS. The test results are: fe2+、Zn2+、Ca2+、Pb2+The concentrations of (A) were 0.03. mu.M, 0.04. mu.M, 0.015. mu.M and 0.035. mu.M, respectively, and the total concentration was 0.12. mu.M.
4. Supporting the in-situ complexation of impurity metal ions in the electrolyte to react with ERC: in an H-type electrolytic cell, 50ml of 0.1M KHCO was added to the anode chamber3Aqueous solution, adding 0 prepared in 3 into a cathode cavity.1M KHCO3140ml of solution and a calculated volume of 1mM EDTA solution, the concentration of EDTA being controlled at 10. mu.M. NF115 manufactured by DuPont was used as a separator of the cathode and anode chambers. Before testing, high-purity N is firstly introduced into the cathode cavity21h, then introducing CO with the purity of 99.995 percent2Gas, CO2The flow rate of (2) was controlled to 60 sccm. And after 30min, taking a Cu sheet as a working electrode, a Pt sheet as a counter electrode and a saturated calomel electrode as a reference electrode. Under the electrolytic voltage of-3.0V, CO is continuously carried out2And performing electrochemical reduction reaction for 6 hours. And introducing the reaction tail gas into a gas chromatograph for quantitative detection of gas products, wherein the detection time interval is 20 min.
FIG. 1 shows the CO in this example2The electrochemical reduction reaction was continued for 6 hours with the change of the reaction current with time, and compared with the comparative example. It can be found that within 6 hours of reaction time, the reaction current is very stable, and the current change rate is less than 4%, which indicates that the catalytic activity of the surface of the copper electrode is stable, i.e. the total amount of active sites on the surface of the copper electrode is basically unchanged before and after the stability test, while the current density of the comparative example without EDTA in the supporting liquid is increased by 35% within 6 hours. FIG. 2 shows CO in the present example2Total Faraday efficiency of electrochemically reduced product and by-product H2And compared with comparative example 1. In comparative example 1, H after 6 hours of reaction of ERC2The Faraday efficiency is increased by 137 percent, and CO2The total Faraday efficiency of the electrochemical reduction product is reduced by 34 percent, and H is added into an EDTA in-situ complexing system2And CO2The change rates of the total faradaic efficiencies of the electrochemical reduction products are-36% and 10.8%, respectively, which are far lower than the corresponding test results of the comparative examples, and the beneficial complexing effect of EDTA as an additive is verified.
Example 2
1. Pretreatment of electrode materials: the copper content is more than or equal to 99.5 percent, the thickness is 100 micrometers, and the area is 10cm2The copper sheet is used as an electrode material, and is firstly soaked in concentrated hydrochloric acid with the volume fraction of 36-38% for treatment for 20min at room temperature to remove surface impurities, then is washed to be neutral by a large amount of deionized water, and is dried by high-purity nitrogen;
2. preparing an organic additive solution: a1 mM solution was prepared from 30% ethylenediamine tetramethylene phosphate (EDTMPS) as a raw material and ultrapure water having a resistivity of 18.2 M.OMEGA.for use.
3. Supporting the determination of impurity metal ions and the concentration thereof in the electrolyte: KHCO with purity of 99.99%3(manufactured by Aladdin Co., Ltd.) as a raw material, ultrapure water having a resistivity of 18.2 M.OMEGA.as a solvent, 200ml of 0.1M KHCO was prepared3An aqueous solution. After 1ml of the solution is diluted by 100 times, the species and the concentration of impurity metal ions in the electrolyte are tested by ICP-MS. The test results are: fe2+、Zn2+、Ca2+、Pb2+The concentrations of (A) were 0.0035. mu.M, 0.003. mu.M, 0.001M and 0.0025. mu.M, respectively, and the total concentration was 0.01. mu.M.
3. Supporting the in-situ complexation of impurity metal ions in the electrolyte to react with ERC: in an H-type electrolytic cell, 50ml of 0.1M KHCO was added to the anode chamber3Aqueous solution, 0.1M KHCO prepared in 3 is added into a cathode cavity3Solution 140ml and calculated volume of 1mM EDTMPS solution, controlling the concentration of EDTMPS to 0.2. mu.M. NF115 manufactured by DuPont was used as a separator of the cathode and anode chambers. Before testing, high-purity N is firstly introduced into the cathode cavity21h, then introducing CO with the purity of 99.995 percent2Gas, CO2The flow rate of (2) was controlled to 60 sccm. And after 30min, taking a Cu sheet as a working electrode, a Pt sheet as a counter electrode and a saturated calomel electrode as a reference electrode. Under the electrolytic voltage of-3.0V, CO is continuously carried out2And performing electrochemical reduction reaction for 6 hours. And introducing the reaction tail gas into a gas chromatograph for quantitative detection of gas products, wherein the detection time interval is 20 min.
Within 6 hours of reaction time, the reaction current is very stable, the current change rate is less than 7%, which indicates that the catalytic activity of the surface of the copper electrode is relatively stable, namely, the total amount of the surface active sites of the copper electrode is basically unchanged before and after the stability test; h2And CO2The total faradaic efficiency change rates of the electrochemical reduction products are-18% and 20.5%, respectively, which are far lower than the corresponding test results of the comparative example, and the beneficial complexing effect of EDTMPS as an additive is verified.
Example 3
1. Pretreatment of electrode materials: the copper content is more than or equal to 99.5 percent100 μm thick and 10cm area2The copper sheet is used as an electrode material, and is firstly soaked in concentrated hydrochloric acid with the volume fraction of 36-38% for treatment for 20min at room temperature to remove surface impurities, then is washed to be neutral by a large amount of deionized water, and is dried by high-purity nitrogen;
2. preparing an organic additive solution: a1 mM solution was prepared from analytically pure iminodiacetic acid as the starting material and ultrapure water having a resistivity of 18.2 M.OMEGA.for use.
3. Supporting the determination of impurity metal ions and the concentration thereof in the electrolyte: KHCO with purity of 99.99%3(manufactured by Shanghai national drug group) as a raw material, and ultrapure water having a resistivity of 18.2 M.OMEGA.as a solvent, 200ml of 0.1M KHCO was prepared3An aqueous solution. After 1ml of the solution is diluted by 100 times, the species and the concentration of impurity metal ions in the electrolyte are tested by ICP-MS. The test results are: fe2+、Zn2+、Ca2+、Pb2+The concentrations of (A) were 0.06. mu.M, 0.07. mu.M, 0.06M and 0.03. mu.M, respectively, and the total concentration was 0.22. mu.M. And 4, supporting the in-situ complexation of impurity metal ions in the electrolyte to react with ERC: in an H-type electrolytic cell, 50ml of 0.1M KHCO was added to the anode chamber3Aqueous solution, 0.1M KHCO prepared in 3 is added into a cathode cavity3140ml of solution and a calculated volume of 1mM iminodiacetic acid solution, with the concentration of iminodiacetic acid controlled at 45. mu.M. NF115, manufactured by DuPont, was used as the diaphragm for the cathode and anode chambers. Before testing, high-purity N is firstly introduced into the cathode cavity21h, then introducing CO with the purity of 99.995 percent2Gas, CO2The flow rate of (2) was controlled to 60 sccm. And after 30min, taking a Cu sheet as a working electrode, a Pt sheet as a counter electrode and a saturated calomel electrode as a reference electrode. Under the electrolytic voltage of-3.0V, CO is continuously carried out2And performing electrochemical reduction reaction for 6 hours. And introducing the reaction tail gas into a gas chromatograph for quantitative detection of gas products, wherein the detection time interval is 20 min.
Within 6 hours of reaction time, the reaction current is very stable, the current change rate is less than 7%, which indicates that the catalytic activity of the surface of the copper electrode is relatively stable, namely, the total amount of the surface active sites of the copper electrode is basically unchanged before and after the stability test; h2And CO2Electrochemical reduction ofThe change rates of the total Faraday efficiencies of the compounds are respectively 41 percent and-18 percent, which are lower than the corresponding test results of the comparative example, and the result shows that the iminodiacetic acid has the beneficial complexing effect and can improve the stability of the copper electrode.
Example 4
1. Pretreatment of electrode materials: the copper content is more than or equal to 99.5 percent, the thickness is 100 micrometers, and the area is 10cm2The copper sheet is used as an electrode material, and is firstly soaked in concentrated hydrochloric acid with the volume fraction of 36-38% for treatment for 20min at room temperature to remove surface impurities, then is washed to be neutral by a large amount of deionized water, and is dried by high-purity nitrogen;
2. preparing an organic additive solution: a1 mM solution was prepared with analytically pure ethylenediaminetetraacetic acid (EDTA) as a solute and ultrapure water having a resistivity of 18.2 M.OMEGA.for use.
3. Supporting the determination of impurity metal ions and the concentration thereof in the electrolyte: KHCO with purity of 99.5%3(produced by Tianjin Damao chemical reagent factory) as raw material, ultrapure water with resistivity of 18.2M omega as solvent, 200ml of 0.1M NaHCO is prepared3An aqueous solution. After 1ml of the solution is diluted by 100 times, the species and the concentration of impurity metal ions in the electrolyte are tested by ICP-MS. The test results are: fe2+、Zn2+、Ca2+、 Pb2+The concentrations of (A) were 0.18. mu.M, 0.12M and 0.08. mu.M, respectively, and the total concentration was 0.5. mu.M.
4. Supporting the in-situ complexation of impurity metal ions in the electrolyte to react with ERC: in an H-type electrolytic cell, 50ml of 0.1M NaHCO was added to the anode chamber3Aqueous solution, adding 0.1M NaHCO prepared in 3 into a cathode cavity3140ml of the solution and a calculated volume of 1mM EDTA solution, then 200ml of solution was prepared by adding 18.2 M.OMEGA.ultra pure water to control KHCO3The concentration of (2) was 0.1M and the concentration of EDTA was 100. mu.M. NF115, manufactured by DuPont, was used as the diaphragm for the cathode and anode chambers. Before testing, high-purity N is firstly introduced into the cathode cavity21h, then introducing CO with the purity of 99.995 percent2Gas, CO2The flow rate of (2) was controlled to 60 sccm. And after 30min, taking a Cu sheet as a working electrode, a Pt sheet as a counter electrode and a saturated calomel electrode as a reference electrode. Under the electrolytic voltage of-3.0V, the process is continuously carried outCO2And performing electrochemical reduction reaction for 6 hours. And introducing the reaction tail gas into a gas chromatograph for quantitative detection of gas products, wherein the detection time interval is 20 min.
Within 6 hours of reaction time, the reaction current is very stable, the current change rate is less than 3%, which indicates that the catalytic activity of the surface of the copper electrode is stable, namely, the total amount of the surface active sites of the copper electrode is basically unchanged before and after the stability test; h2And CO2The change rates of the total faradaic efficiencies of the electrochemical reduction products are respectively-10% and 8%, which are far lower than the corresponding test results of the comparative example, and the beneficial complexing effect of EDTA as an additive for improving the stability of the Cu electrode is verified.
Example 5
1. Pretreatment of electrode materials: the copper content is more than or equal to 99.5 percent, the thickness is 100 micrometers, and the area is 10cm2The copper sheet is used as an electrode material, and is firstly soaked in concentrated hydrochloric acid with the volume fraction of 36-38% for treatment for 20min at room temperature to remove surface impurities, then is washed to be neutral by a large amount of deionized water, and is dried by high-purity nitrogen;
2. preparing an organic additive solution: a1 mM solution was prepared from analytically pure iminodiacetic acid as the starting material and ultrapure water having a resistivity of 18.2 M.OMEGA.for use.
3. Supporting the determination of impurity metal ions and the concentration thereof in the electrolyte: with NaHCO of 99.5% purity3200ml of 0.1M NaHCO was prepared using as a raw material ultrapure water having a resistivity of 18.2 M.OMEGA. (manufactured by Sigma-Aldrich Co.) as a solvent3An aqueous solution. After 1ml of the solution is diluted by 100 times, the species and the concentration of impurity metal ions in the electrolyte are tested by ICP-MS. The test results are: fe2+、Zn2+、Ca2+、 Pb2+The concentrations of (A) were 0.08. mu.M, 0.06M and 0.03. mu.M, respectively, and the total concentration was 0.23. mu.M.
4. Supporting the in-situ complexation of impurity metal ions in the electrolyte to react with ERC: in an H-type electrolytic cell, 50ml of 0.1M NaHCO was added to the anode chamber3Aqueous solution, adding 0.1M NaHCO prepared in 3 into a cathode cavity3140ml of solution and a calculated volume of 1mM iminodiacetic acid solution, with the concentration of iminodiacetic acid controlled at 200. mu.M. Using DuPont corporationNF115 is manufactured as a diaphragm for the cathode and anode chambers. Before testing, high-purity N is firstly introduced into the cathode cavity21h, then introducing CO with the purity of 99.995 percent2Gas, CO2The flow rate of (2) was controlled to 60 sccm. And after 30min, taking a Cu sheet as a working electrode, a Pt sheet as a counter electrode and a saturated calomel electrode as a reference electrode. Under the electrolytic voltage of-3.0V, CO is continuously carried out2And performing electrochemical reduction reaction for 6 hours. And introducing the reaction tail gas into a gas chromatograph for quantitative detection of gas products, wherein the detection time interval is 20 min.
Within 6 hours of reaction time, the reaction current is very stable, the current change rate is less than 5%, which indicates that the catalytic activity of the surface of the copper electrode is relatively stable, namely, the total amount of the surface active sites of the copper electrode is basically unchanged before and after the stability test; h2And CO2The change rates of the total Faraday efficiencies of the electrochemical reduction products are respectively-15% and 8%, which are far lower than the corresponding test results of the comparative example, and the result shows that the iminodiacetic acid has a beneficial complexing effect and can improve the stability of the copper electrode.
Comparative example 1
1. Pretreatment of electrode materials: the copper content is more than or equal to 99.5 percent, the thickness is 100 micrometers, and the area is 10cm2The copper sheet is used as an electrode material, and is firstly soaked in concentrated hydrochloric acid with the volume fraction of 36-38% for treatment for 20min at room temperature to remove surface impurities, then is washed to be neutral by a large amount of deionized water, and is dried by high-purity nitrogen;
2. supporting the determination of impurity metal ions and the concentration thereof in the electrolyte: KHCO with purity of 99.7%3200ml of 0.1M KHCO prepared from ultrapure water having a resistivity of 18.2 M.OMEGA. (manufactured by Sigma-Aldrich) as a solvent3An aqueous solution. After 1ml of the solution is diluted by 100 times, the species and the concentration of impurity metal ions in the electrolyte are tested by ICP-MS. The test results are: fe2+、Zn2+、Ca2+、Pb2+The concentrations of (A) were 0.03. mu.M, 0.04. mu.M, 0.015. mu.M and 0.035. mu.M, respectively, and the total concentration was 0.12. mu.M.
ERC reaction: in an H-type electrolytic cell, 0.1M KHCO prepared in 2 is respectively added into a cathode cavity and an anode cavity3140ml and 50ml of aqueous solution. Manufactured by DuPont corporationNF115 acts as a diaphragm for the cathode and anode chambers. Before testing, high-purity N is firstly introduced into the cathode cavity21h, then introducing CO with the purity of 99.995 percent2Gas, CO2The flow rate of (2) was controlled to 60 sccm. And after 30min, taking a Cu sheet as a working electrode, a Pt sheet as a counter electrode and a saturated calomel electrode as a reference electrode. Under the electrolytic voltage of-3.0V, CO is continuously carried out2And performing electrochemical reduction reaction for 6 hours. And introducing the reaction tail gas into a gas chromatograph for quantitative detection of gas products, wherein the detection time interval is 20 min.
Comparative example 2
1. Pretreatment of electrode materials: the copper content is more than or equal to 99.5 percent, the thickness is 100 micrometers, and the area is 10cm2The copper sheet is used as an electrode material, and is firstly soaked in concentrated hydrochloric acid with the volume fraction of 36-38% for treatment for 20min at room temperature to remove surface impurities, then is washed to be neutral by a large amount of deionized water, and is dried by high-purity nitrogen;
2. supporting the determination of impurity metal ions and the concentration thereof in the electrolyte: with NaHCO of 99.5% purity3(produced by Tianjin Damao chemical reagent factory) as raw material, ultrapure water with resistivity of 18.2M omega as solvent, 200ml of 0.1M NaHCO is prepared3An aqueous solution. After 1ml of the solution is diluted by 100 times, the species and the concentration of impurity metal ions in the electrolyte are tested by ICP-MS. The test results are: fe2+、Zn2+、Ca2+、 Pb2+The concentrations of (A) were 0.18. mu.M, 0.12M and 0.08. mu.M, respectively, and the total concentration was 0.5. mu.M.
3. Supporting the in-situ complexation of impurity metal ions in the electrolyte to react with ERC: in an H-type electrolytic cell, 0.1M KHCO prepared in 2 is respectively added into an anode cavity3Aqueous solutions 140ml and 50ml were used, NF115 from DuPont as a membrane for the cathode and anode chambers. Before testing, high-purity N is firstly introduced into the cathode cavity21h, then introducing CO with the purity of 99.995 percent2Gas, CO2The flow rate of (2) was controlled to 60 sccm. And after 30min, taking a Cu sheet as a working electrode, a Pt sheet as a counter electrode and a saturated calomel electrode as a reference electrode. Under the electrolytic voltage of-3.0V, CO is continuously carried out2And performing electrochemical reduction reaction for 6 hours. Introducing the reaction tail gas into gas chromatography to obtain a gas productThe detection time interval is 20 min.
Within 6 hours of reaction time, the reaction current always shows an ascending trend, the current change rate is 25 percent, which shows that the catalytic activity of the surface of the copper electrode is very unstable, and H is2And CO2The rate of change of the total faradaic efficiency of the electrochemically reduced product was 60% and-40%, respectively, which is much higher than the corresponding test results of example 5.

Claims (8)

1. A method for improving the stability of an electrode for electrochemical reduction of carbon dioxide, wherein the electrochemical reduction reaction of the carbon dioxide comprises a supporting electrolyte containing impurity metal ions, and the method is characterized in that the supporting electrolyte is an aqueous bicarbonate solution containing alkali metals, and when the impurity metal ions M in the supporting electrolyte comprise Fe2+、Zn2+、Ca2+、Pb2+When the total molar concentration of the impurity metal ions is 0.01-0.5 mu M, introducing an organic additive into the supporting electrolyte, wherein the organic additive is one or more of ethylenediamine tetraacetic acid, ethylenediamine tetramethylene phosphoric acid and iminodiacetic acid;
wherein the organic additive: the molar ratio of the total molar concentration of the impurity metals is 10-1000.
2. The method of claim 1, wherein: wherein the organic additive: the molar ratio of the total molar concentration of the impurity metal is 200-800.
3. The method of claim 1, wherein: the concentration of the supporting electrolyte is 0.1-0.5M.
4. The method of claim 1, wherein: the alkali metal is K or Na.
5. The method of claim 1, wherein: the solubility of the organic additive in water at room temperature is not less than 0.5g L-1。
6. The method according to claim 1 or 5, characterized in that: the organic additive is one or two of ethylenediamine tetraacetic acid and ethylenediamine tetramethylene phosphoric acid.
7. The method of claim 1, wherein: the stable complexation constant of the organic additive and the impurity metal ions at room temperature is not less than 8.0.
8. The method of claim 1, wherein: the electrode is a copper electrode.
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