CN114622236A - Oxide-derived densely-arranged copper array material and preparation method and application thereof - Google Patents

Oxide-derived densely-arranged copper array material and preparation method and application thereof Download PDF

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CN114622236A
CN114622236A CN202210284619.4A CN202210284619A CN114622236A CN 114622236 A CN114622236 A CN 114622236A CN 202210284619 A CN202210284619 A CN 202210284619A CN 114622236 A CN114622236 A CN 114622236A
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CN114622236B (en
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宫勇吉
刘伟
翟朋博
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Beihang University
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    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
    • 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
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    • C—CHEMISTRY; METALLURGY
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    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
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Abstract

The invention relates to the technical field of catalysts, in particular to a densely arranged copper array material derived from an oxide and a preparation method and application thereof. According to the preparation method of the copper array material, the copper array material which is derived from the oxide and is densely arranged can keep the shape stability in the carbon dioxide reduction process and simultaneously keep Cu2The O/Cu interface is stable, has a large number of reaction active sites, has good adsorption effect on an intermediate in the ethylene generation process, is beneficial to formation and stability of the ethylene intermediate, and further improves the activity and selectivity of producing ethylene by reducing carbon dioxide.

Description

Oxide-derived densely-arranged copper array material and preparation method and application thereof
Technical Field
The invention relates to the technical field of catalysts, in particular to a densely arranged copper array material derived from an oxide and a preparation method and application thereof.
Background
Depletion of fossil fuels and their non-renewable nature continues to emphasize the use of renewable energy sources to supply carbon dioxide (CO)2) The importance of conversion to fuels and chemical feedstocks. The artificial conversion of carbon dioxide is crucial to reduce carbon dioxide emissions and to achieve human sustainability. Electrochemical carbon dioxide reductionThe reaction is among the most attractive methods because of its mild reaction conditions and its ability to exploit reproducible ionization. Of the products of the reduction of carbon dioxide, carbon monoxide (CO) and formate (HCOO)-) Equal low added value C1The products are most common due to the slow kinetics of the C-C coupling reaction. As shown in previous studies, the C-C coupling reaction is C2+The critical step of speciation. Theoretical calculations indicate that either too strong or too weak binding of CO (indicating adsorption sites) intermediates on the catalyst is detrimental to C2+Generation of species. Copper-based materials have moderate adsorption energy to CO intermediates, are the most effective catalysts for converting carbon dioxide to C with considerable activity2+Hydrocarbons and oxygenates. Among these products, ethylene has been highly industrially valuable, and reduction of carbon dioxide to ethylene (C) at high current density and Faraday Efficiency (FE) has been induced2H4) The present inventors made intensive studies. However, since the formation process of ethylene involves multiple electron and proton transfer steps, hydrogen (H) is inevitably generated during the electrolysis process2) And other by-products, e.g. methane (CH)4). Thus, the ethylene generation activity and selectivity of copper-based catalysts remain limited.
Disclosure of Invention
The invention aims to provide an oxide-derived densely-arranged copper array material and a preparation method and application thereof. The oxide-derived densely-arranged copper array material has high catalytic activity and selectivity for reducing carbon dioxide to produce ethylene.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of an oxide-derived densely-arranged copper array material, which comprises the following steps:
performing constant-current electrolysis by taking a copper material as an anode and a copper bar as a cathode to obtain the copper material with a black copper oxide array on the surface;
taking the copper material with the black copper oxide array on the surface as a working electrode, introducing carbon dioxide into a three-electrode system, and electrolyzing to obtain the copper array material which is derived from the oxide and is densely arranged;
the current of the constant current electrolysis is 0.22-0.28 mA/cm2。
Preferably, the electrolyte adopted by the constant current electrolysis is a sodium hydroxide solution;
the concentration of the sodium hydroxide solution is 0.5 mol/L.
Preferably, the constant current electrolysis time is 2-4 h.
Preferably, the reference electrode in the three-electrode system is a silver/silver chloride electrode, the counter electrode is a platinum sheet electrode, and the electrolyte adopted for electrolysis is a potassium chloride solution; the potassium chloride solution comprises saturated carbon dioxide;
the carbon dioxide is introduced at a rate of 20-50 sccm.
Preferably, the reduction voltage of the electrolysis is-0.6 to-1.2V, and the time is 1 to 3 min.
Preferably, the copper material is pretreated before the constant current electrolysis;
the pretreatment is to carry out annealing treatment on the copper material in a protective atmosphere;
the protective atmosphere is a mixed atmosphere of argon and hydrogen.
Preferably, the temperature of the annealing treatment is 900-1100 ℃, and the time is 1-3 h.
Preferably, the temperature rise rate of the temperature rise to the annealing treatment temperature is 30 to 50 ℃/min.
The invention also provides a copper array material which is derived from the oxide and is densely arranged, and the copper array material comprises copper and cuprous oxide; the cuprous oxide is positioned on the surface of the copper;
the mass percentage of the cuprous oxide in the densely arranged copper array material derived from the oxide is 1-3%.
The invention also provides application of the oxide-derived densely-arranged copper array material in electrochemical carbon dioxide reduction catalysis.
The invention providesA preparation method of a compactly arranged copper array material derived from oxides comprises the steps of carrying out constant-current electrolysis by taking a copper material as an anode and a copper bar as a cathode to obtain the copper material with a black copper oxide array on the surface; taking the copper material with the black copper oxide array on the surface as a working electrode, introducing carbon dioxide into a three-electrode system, and electrolyzing to obtain the oxide-derived copper array material in compact arrangement; the current of the constant current electrolysis is 0.22-0.28 mA/cm2. In the process of constant current electrolysis (anodic oxidation), the black copper oxide array is uniformly grown on the surface of the copper material by controlling the current of the constant current electrolysis, and the constant current electrolysis mode is simple and convenient to operate, rapid in reaction, small in energy input and easy for large-scale preparation; and then carrying out electrolysis in a three-electrode system to generate electrochemical in-situ reduction reaction, so that the copper oxide array is transposed into a copper array material which is derived from oxides and is densely arranged, the adsorption capacity of the copper oxide array material on an ethylene intermediate generated in the reduction process of carbon dioxide is improved, and the generation of ethylene has lower free energy barrier compared with other products, thereby being beneficial to the generation of ethylene. Meanwhile, the nano array generated in situ has good charge transfer capacity and firm connection with the substrate, so that the resistance of carbon dioxide reduction reaction is reduced, and the structure migration in the reaction process is prevented. The flaky nano-structure array has a larger electrochemical active area, can effectively disperse the current density on the surface of an electrode, greatly slows down the dissolution/redeposition process on the surface of a catalyst, enables the nano-structure to be stable without agglomeration, and can improve the stability of the reduction reaction of carbon dioxide.
The invention also provides a copper array material which is derived from the oxide and is densely arranged, and the copper array material comprises copper and cuprous oxide; the mass percentage of the cuprous oxide in the densely arranged copper array material derived from the oxide is 1-3%. The densely arranged array structure can keep the morphological stability of the array structure in the carbon dioxide reduction process and simultaneously keep Cu2The O/Cu interface is stable and has a large amount of Cu2The O/Cu interface forms a reactive site and is used for ethylene generationThe intermediate has good adsorption effect, is beneficial to the formation and the stability of an ethylene intermediate, and further improves the activity and the selectivity of producing ethylene by reducing carbon dioxide.
Drawings
FIG. 1 is an SEM photograph of a black copper foil prepared in example 1;
FIG. 2 is an EDS chart of a black copper foil prepared in example 1;
FIG. 3 is an SEM image of an oxide-derived densely packed copper array material prepared in example 1;
FIG. 4 is an XRD pattern of an oxide-derived, densely packed copper array material prepared in example 1;
FIG. 5 is an SEM image of an oxide-derived densely packed copper array material prepared in example 2;
fig. 6 is a graph comparing the electrocatalytic carbon dioxide reduction performance of the oxide-derived densely packed copper array material and the polycrystalline copper material prepared in example 1.
Detailed Description
The invention provides a preparation method of a densely arranged copper array material derived from oxides, which comprises the following steps:
performing constant-current electrolysis by taking a copper material as an anode and a copper bar as a cathode to obtain the copper material with a black copper oxide array on the surface;
and (3) taking the copper material with the black copper oxide array on the surface as a working electrode, introducing carbon dioxide into a three-electrode system, and electrolyzing to obtain the oxide-derived densely-arranged copper array material.
In the present invention, all the starting materials for the preparation are commercially available products known to those skilled in the art unless otherwise specified.
The invention takes copper material as anode and copper bar as cathode to carry out constant current electrolysis, thus obtaining the copper material with black copper oxide array on the surface.
In the invention, the copper material is preferably copper foil or a material with a copper layer sputtered on the surface of a substrate; in the embodiment of the invention, the copper material is specifically copper foil or carbon paper with a copper layer sputtered on the surface(ii) a The carbon paper with the copper layer sputtered on the surface is preferably prepared by the following steps: placing carbon paper on a substrate of an electron beam evaporation instrument, and evaporating a 500nm copper layer to the surface of the carbon paper at a speed of 0.2nm/s (the vacuum degree during evaporation is 5 multiplied by 10)- 5Pa), the surface of the carbon paper is reddish brown, and the carbon paper with the copper foil on the surface is obtained.
In the present invention, when the copper material is a copper foil, the copper foil is preferably subjected to a pretreatment, and the pretreatment is preferably performed by annealing the copper foil in a protective atmosphere.
In the present invention, the protective atmosphere is preferably a mixed atmosphere of argon and hydrogen; the volume ratio of the argon to the hydrogen in the mixed atmosphere is preferably (9-19): 1, more preferably 9: 1.
in the invention, the annealing temperature is preferably 900-1100 ℃, and more preferably 950-1050 ℃; the time is preferably 1 to 3 hours, and more preferably 2 hours. In the present invention, the rate of temperature increase to the temperature of the annealing treatment is preferably 30 to 50 ℃/min, and more preferably 40 to 50 ℃/min.
After the annealing treatment, the invention also preferably comprises cooling, and the cooling mode is preferably furnace cooling.
In the present invention, it is preferable that the copper material is sandwiched between platinum and carbon electrodes, and the platinum and carbon electrodes obtained by sandwiching the copper material are used as an anode.
In the invention, the electrolyte adopted by the constant current electrolysis is preferably sodium hydroxide solution; the concentration of the sodium hydroxide solution is preferably 0.5 mol/L.
In the invention, the current of the constant current electrolysis is preferably 0.22-0.28 mA/cm2More preferably 0.26mA/cm2(ii) a The time is preferably 2-4 h, and more preferably 3 h.
In the invention, the constant-current electrolysis condition can better ensure that the speed of in-situ growth of copper hydroxide and the speed of dehydration of the generated copper hydroxide are balanced, so that the copper hydroxide generated in the alkaline solution can be completely converted into copper oxide, and a densely arranged copper oxide array structure is formed.
After the constant-current electrolysis is finished, the method also preferably comprises the step of cleaning the obtained copper material with the black copper oxide array on the surface, wherein the cleaning agent adopted for cleaning is preferably deionized water; the number of washing is preferably 3. In the invention, the purpose of the cleaning is to remove sodium hydroxide on the surface of the copper material with the black copper oxide array on the surface.
After the copper material with the black copper oxide array on the surface is obtained, the copper material with the black copper oxide array on the surface is taken as a working electrode, carbon dioxide is introduced into a three-electrode system, and electrolysis is carried out to obtain the copper array material which is derived from the oxide and is densely arranged.
In the invention, the reference electrode in the three-electrode system is preferably a silver/silver chloride electrode, the counter electrode is preferably a platinum sheet electrode, and the electrolyte used for electrolysis is preferably a potassium chloride solution; the concentration of the potassium chloride solution is preferably 0.1-1 mol/L, and more preferably 0.5 mol/L; the potassium chloride solution comprises saturated carbon dioxide. In the present invention, the saturated carbon dioxide is preferably achieved by introducing high purity carbon dioxide gas into the electrolyte at a rate of 500 sccm. In a specific embodiment of the present invention, the process of achieving the saturation state of carbon dioxide in the potassium chloride solution is as follows: 50mL of potassium chloride solution with the concentration of 0.5mol/L is respectively added to two sides of a 100mL H-shaped electrolytic cell, and high-purity carbon dioxide gas of 500sccm is respectively introduced into the two sides for 30min, so that air in the solution is completely removed and carbon dioxide is saturated in the solution.
In the present invention, the carbon dioxide is preferably introduced at a rate of 20 to 50sccm, more preferably 20 sccm.
In the present invention, the reduction voltage of the electrolysis is preferably-0.6 to-1.2V, more preferably-0.8V; the time is preferably 1-3 min, and more preferably 2 min. In the present invention, the reduction voltage is preferably set to a value based on a standard voltage of the reversible hydrogen electrode.
The invention also provides a copper array material which is derived from the oxide and is densely arranged, and the copper array material comprises copper and cuprous oxide;
the mass percentage of the cuprous oxide in the densely arranged copper array material derived from the oxide is 1-3%.
In the present invention, the cuprous oxide is preferably located on the surface of the copper, and the content of the cuprous oxide in the oxide-derived densely arranged copper array material is preferably 1.57% by mass.
The invention also provides application of the oxide-derived densely-arranged copper array material in electrochemical carbon dioxide reduction catalysis. The method of the present invention is not particularly limited, and the method may be performed by a method known to those skilled in the art.
The oxide-derived densely arranged copper matrix material and the preparation method and application thereof provided by the present invention will be described in detail with reference to the following examples, which should not be construed as limiting the scope of the present invention.
Example 1
Cutting the copper foil into a rectangle of 1.5 x 3cm, then placing the rectangle into a quartz tube, heating the furnace to 1050 ℃ in a mixed atmosphere of argon and hydrogen (the volume ratio of argon to hydrogen is 9: 1) at a heating rate of 50 ℃/min, preserving heat for 3h, and cooling the furnace to room temperature to obtain the annealed copper foil;
clamping the annealed copper foil on a platinum-carbon electrode as an anode, taking a copper bar as a cathode, and performing constant current electrolysis in 200mL of 0.5mol/L sodium hydroxide solution, wherein the current of the constant current electrolysis is 0.26mA/cm2After the time is 2 hours, the surface of the copper foil is converted into uniform black copper oxide, the surface of the copper foil is washed by deionized water for 3 times, and the sodium hydroxide solution remained on the surface is washed off to obtain black copper foil (a surface densely arranged copper oxide array);
respectively adding 50mL of potassium chloride solution with the concentration of 0.5mol/L into two sides of a 100mL H-shaped electrolytic cell, introducing 500sccm high-purity carbon dioxide gas into the two sides of the H-shaped electrolytic cell for 30min, completely removing air in the solution, enabling the carbon dioxide to be saturated in the solution, adjusting the flow rate of the carbon dioxide to 20sccm, carrying out constant-potential electrolysis by using a black copper foil as a working electrode, a silver/silver chloride electrode as a reference electrode and a platinum sheet electrode as a counter electrode, setting the voltage to be-0.8V (relative to a reversible hydrogen electrode), and after 2min of electrolysis, converting the black color of the surface of the copper foil into red color to obtain the oxide-derived copper array material in dense arrangement.
Performing SEM test on the black copper foil, wherein the test result is shown in figure 1, and as can be seen from figure 1, the copper foil forms a densely-arranged copper oxide array material which is formed by densely-arranged nanosheets;
EDS (electronic discharge machining) is carried out on the black copper foil, the test result is shown in figure 2, as can be seen from figure 2, the atomic ratio of copper element to oxygen element in the black copper foil is 1:1, and the black copper foil is proved to be copper oxide;
performing SEM test on the oxide-derived densely arranged copper array material, wherein the test result is shown in FIG. 3, and as can be seen from FIG. 3, the oxide-derived densely arranged copper array material is a densely arranged array structure formed by nanosheets;
the XRD test of the oxide-derived densely arranged copper array material showed that the main component of the oxide-derived densely arranged copper array material was copper and a trace amount of cuprous oxide (cuprous oxide content: 1.57% by mass) was contained, as shown in fig. 4.
Example 2
Placing carbon paper on a substrate of an electron beam evaporation instrument, and evaporating 500nm copper layer to the surface of the carbon paper at a speed of 0.2nm/s (vacuum degree during evaporation is 5 × 10)-5Pa), the surface of the carbon paper is reddish brown, and the carbon paper with the copper foil on the surface is obtained;
clamping the carbon paper with the copper foil on the surface on a platinum carbon electrode as an anode, taking a copper bar as a cathode, and performing constant current electrolysis in 200mL of 0.5mol/L sodium hydroxide solution, wherein the current of the constant current electrolysis is 0.26mA/cm2And after the time is 2 hours, the surface of the carbon paper is converted into uniform black copper oxide, the surface of the copper foil is washed for 3 times by deionized water, and the residual sodium hydroxide solution on the surface is washed off to obtain the carbon paper (the surface of which is densely provided with oxygen) with the black copper foil on the surfaceCopper arrays);
respectively adding 50mL of potassium chloride solution with the concentration of 0.5mol/L into two sides of a 100mL H-shaped electrolytic cell, introducing 500sccm of high-purity carbon dioxide gas into the two sides of the H-shaped electrolytic cell for 30min, completely removing air in the solution, enabling the carbon dioxide to be saturated in the solution, adjusting the flow rate of the carbon dioxide to 20sccm, taking carbon paper with a black copper foil surface as a working electrode, a silver/silver chloride electrode as a reference electrode and a platinum sheet electrode as a counter electrode, performing constant potential electrolysis with the voltage set to-0.8V (relative to a reversible hydrogen electrode), and after 2min of electrolysis, converting the black color of the surface of the carbon paper into red color to obtain the oxide-derived densely-arranged copper array material.
The oxide-derived densely-arranged copper array material is subjected to SEM test, the test result is shown in FIG. 5, and as can be seen from FIG. 5, the oxide-derived densely-arranged copper array material is a densely-arranged array structure formed by nanosheets, which indicates that the preparation method is not only suitable for copper foils, but also suitable for copper layers attached to other substrates, and shows the application potential of the preparation method.
Comparative example 1
The oxide-derived densely packed copper array material described in example 1 was annealed in an argon-hydrogen atmosphere at an argon-hydrogen ratio of 9: 1, the temperature is 450 ℃, the heating rate is 50 ℃/min, and the heat preservation time at 450 ℃ is 3 hours, so that the polycrystalline copper is obtained.
Test example
The oxide-derived densely-arranged copper array material prepared in example 1 was used as a working electrode, silver/silver chloride was used as a reference electrode, a platinum sheet was used as a counter electrode, the working electrode and the reference electrode were placed on one side of an H-type electrolytic cell, the counter electrode was placed on the other side, the electrolytic cells on both sides were separated by a Nafion-117 membrane, 50mL of a 0.5mol/L potassium chloride solution was added to each of both sides, 500sccm of high purity carbon dioxide was introduced to each of both sides to saturate the carbon dioxide in the solution, the flow rate was changed to 20sccm, and the gas introduced to one side of the working electrode flowed out of the electrolytic cell and into a six-way valve of a gas chromatograph. Electrolyzing the electrolytic cell by using an electrochemical workstation, setting a constant voltage for electrolysis for 30 minutes, pumping the gas in the six-way valve into a gas chromatograph, and analyzing the components of the gas flowing out of the electrolytic cell and the current recorded in the electrochemical workstation by using the gas chromatograph to calculate the Faraday efficiency of a gas product;
1mL of electrolyzed electrolyte was added to 0.2mL of D2O, 0.2mL of DMSO dispersion (prepared by adding 0.1mL of DMSO to 500mL of water) was added to the reaction mixture, and the mixture was used1HNMR analysis of the concentration of the liquid product in the electrolyte combined with the recorded current in the electrochemical workstation calculated the faradaic efficiency of the liquid product. Electrolyzing the system under the constant voltage of-0.8V, recording the current magnitude, and simultaneously testing the Faraday efficiency of the gas-phase product.
The test results are shown in fig. 6, where a is the electrocatalytic carbon dioxide reduction product faradaic efficiency of the oxide-derived densely arranged copper array material described in example 1, b is the electrocatalytic carbon dioxide reduction product faradaic efficiency of the polycrystalline copper prepared in comparative example 1, and c is a long cycle test under the condition of-0.8V; as can be seen from FIG. 6, the oxide-derived densely arranged copper array material as a carbon dioxide reduction catalyst has a faradaic efficiency of ethylene of 73.6% at a potential of-0.9V, and C is added2+The product has Faraday efficiency as high as 82.6%, can maintain stable electrolysis current for 50h and average Faraday efficiency as high as 62.2% at-0.8V, has ethylene Faraday efficiency, stability and other performance indexes superior to those of the polycrystalline copper catalyst in the comparative example 1 (the Faraday efficiency is lower than 50% and the stabilization time is less than 5h) and most of catalysts reported at present, and shows great potential and prospect of the material as an electrochemical carbon dioxide reduction catalyst.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and amendments can be made without departing from the principle of the present invention, and these modifications and amendments should also be considered as the protection scope of the present invention.

Claims (10)

1. A method for preparing an oxide-derived densely-arranged copper array material, comprising the steps of:
performing constant-current electrolysis by taking a copper material as an anode and a copper bar as a cathode to obtain the copper material with a black copper oxide array on the surface;
taking the copper material with the black copper oxide array on the surface as a working electrode, introducing carbon dioxide into a three-electrode system, and electrolyzing to obtain the copper array material which is derived from the oxide and is densely arranged;
the current of the constant current electrolysis is 0.22-0.28 mA/cm2。
2. The preparation method according to claim 1, wherein the electrolyte used for the constant current electrolysis is a sodium hydroxide solution;
the concentration of the sodium hydroxide solution is 0.5 mol/L.
3. The preparation method according to claim 1 or 2, wherein the constant current electrolysis time is 2-4 h.
4. The preparation method of claim 1, wherein the reference electrode in the three-electrode system is a silver/silver chloride electrode, the counter electrode is a platinum sheet electrode, and the electrolyte used for electrolysis is a potassium chloride solution; the potassium chloride solution comprises saturated carbon dioxide;
the introduction rate of the carbon dioxide is 20-50 sccm.
5. The method of claim 1, wherein the reduction voltage of the electrolysis is-0.6 to-1.2V and the time is 1 to 3 min.
6. The method of claim 1, wherein the copper material is pretreated prior to the constant current electrolysis;
the pretreatment is to carry out annealing treatment on the copper material in a protective atmosphere;
the protective atmosphere is a mixed atmosphere of argon and hydrogen.
7. The method according to claim 6, wherein the annealing is performed at 900 to 1100 ℃ for 1 to 3 hours.
8. The method according to claim 7, wherein a temperature increase rate of increasing the temperature to the annealing temperature is 30 to 50 ℃/min.
9. The oxide-derived densely-arranged copper array material prepared by the preparation method of any one of claims 1 to 8, which is characterized by comprising copper and cuprous oxide; the cuprous oxide is positioned on the surface of the copper;
the mass percentage of the cuprous oxide in the densely arranged copper array material derived from the oxide is 1-3%.
10. Use of the oxide-derivatized densely packed copper array material of claim 9 in electrochemical catalytic carbon dioxide reduction.
CN202210284619.4A 2022-03-22 2022-03-22 Oxide-derived densely arranged copper array material and preparation method and application thereof Active CN114622236B (en)

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JP2018024895A (en) * 2016-08-08 2018-02-15 古河電気工業株式会社 Catalyst, electrode catalyst, and manufacturing method of electrode catalyst
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CN112899709A (en) * 2021-01-19 2021-06-04 北京化工大学 Copper-based compound/copper nano electrode with interface synergistic effect and preparation and application thereof
US20220042198A1 (en) * 2020-08-03 2022-02-10 Brown University Copper Catalysts for Electrochemical CO2 Reduction to C2+ Products

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Publication number Priority date Publication date Assignee Title
JP2018024895A (en) * 2016-08-08 2018-02-15 古河電気工業株式会社 Catalyst, electrode catalyst, and manufacturing method of electrode catalyst
KR102187859B1 (en) * 2019-06-12 2020-12-08 한국과학기술연구원 Basic electrocatalyst for producing ethylene through electrochemically reduction of carbon dioxide, electrode and device including the same, and a method for producing the electrode
US20220042198A1 (en) * 2020-08-03 2022-02-10 Brown University Copper Catalysts for Electrochemical CO2 Reduction to C2+ Products
CN112899709A (en) * 2021-01-19 2021-06-04 北京化工大学 Copper-based compound/copper nano electrode with interface synergistic effect and preparation and application thereof

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Title
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