CN114032581A - Method for electrochemically reconstructing metal surface by ionic liquid medium to electro-catalytically reduce carbon dioxide - Google Patents
Method for electrochemically reconstructing metal surface by ionic liquid medium to electro-catalytically reduce carbon dioxide Download PDFInfo
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Abstract
The invention provides a method for electrochemically reconstructing a metal surface by an ionic liquid medium to be used for electrocatalytic reduction of carbon dioxide, which is characterized by comprising the following steps: putting the three-electrode system in an H-shaped electrolytic cell for electrocatalytic reduction of carbon dioxide; the three-electrode system comprises a counter electrode, a reference electrode and a working electrode, wherein a platinum mesh is used as the counter electrode, a silver/silver ion electrode is used as the reference electrode, and the electrochemical reconstruction metal is used as the working electrode. The method for preparing the carbon dioxide by the electro-catalysis reduction of the metal surface through the ionic liquid medium electrochemical reconstruction for the first time has the advantages of high formic acid/carbon monoxide selectivity, large current density, good stability and the like, and can provide an effective way for the resource utilization of the carbon dioxide.
Description
Technical Field
The invention relates to the field of electroreduction, in particular to a method for electrochemically reconstructing a metal surface by an ionic liquid medium to be used for electrocatalytic reduction of carbon dioxide.
Background
With the rapid development of human society and economy, human beings consume a large amount of non-renewable fossil energy, resulting in serious energy crisis and environmental problems. Meanwhile, carbon dioxide is a natural, rich and renewable cheap carbon source, and is converted into products with high added values, such as carbon monoxide, formic acid, methanol, acetic acid, ethanol and the like, so that the method is an important way for fundamentally slowing down the greenhouse effect and reducing the consumption of fossil fuels, and has great significance. The current routes for carbon dioxide conversion are numerous, and among them, electrocatalytic reduction of carbon dioxide is of great interest because of its availability of renewable energy sources and the variety of products. However, there are still many problems to realize the high-efficiency conversion and utilization of carbon dioxide: carbon dioxide molecules are stable in thermodynamic property and inert in kinetics, so that activation and conversion are difficult to achieve, multi-electron and multi-proton transfer is involved in the steps, the problems of poor product selectivity, low current density and the like are solved, and an economical, stable and efficient carbon dioxide electrocatalytic reduction system is urgently needed to be developed.
The electrocatalytic reduction of carbon dioxide to produce high value-added products (formic acid/carbon monoxide and the like) is a method with great industrial application prospect, and can carry out reaction under mild reaction conditions. The most important design of the catalytic system for preparing chemicals by electrocatalytic reduction of carbon dioxide is mainly the modification preparation of the metal catalyst (CN202011202530.6) and the carbon-based non-metal catalyst (CN201911109432.5), but the conventional modification preparation process of the metal catalyst is complex and is not beneficial to industrial scale-up production, and the activity and the stability of the carbon-based non-metal catalyst (CN109161922B) need to be further improved. As a novel solvent, the ionic liquid has the advantages of wide electrochemical window, low reaction temperature and the like, provides an important reaction environment for electrocatalytic reduction of carbon dioxide as an electrolyte, and forms a closed circuit as a conductive medium. Meanwhile, the overpotential of the reaction can be obviously reduced, the hydrogen evolution reaction is inhibited, the selectivity and the current density of the product are improved, and the method has a huge application prospect in the field of electrocatalytic reduction of carbon dioxide.
Disclosure of Invention
The invention provides a method for preparing chemicals by electrocatalytic reduction of carbon dioxide on the surface of electrochemically reconstructed metal of an ionic liquid medium, which combines the metal with high specific area obtained after electrochemical reconstruction with an ionic liquid electrolyte and efficiently electrocatalytic reduces the carbon dioxide. The method has the advantages of high selectivity of formic acid/carbon monoxide, large current density, good stability and the like. At present, no metal source is added in an ionic liquid system, a certain current is applied in a three-electrode system to dissolve metal in electrolyte, then a certain current is applied, relevant researches on electrochemically reconstructed metal surfaces are not reported, and relevant researches on electrocatalytic reduction of carbon dioxide by combining the ionic liquid electrolyte are deficient.
The technical scheme for realizing the invention is as follows:
in the electrolytic cell which is divided into an anode chamber and a cathode chamber by a proton exchange membrane, a metal working electrode and a silver/silver ion electrode are taken as reference electrodes and put into the cathode chamber, a platinum mesh is taken as a counter electrode and put into the anode chamber, ionic liquid electrolyte is filled into the cathode chamber, and sulfuric acid electrolyte is filled into the anode chamber. Inert gas or carbon dioxide is introduced into the electrolyte of the cathode chamber until the electrolyte is saturated, then Linear Scanning (LSV) is respectively carried out under corresponding atmosphere, and the activity of the catalyst is preliminarily evaluated. Further, constant potential electrolysis is carried out under the condition that carbon dioxide is continuously introduced into the cathode electrolyte, and product analysis and stability test of a reduction system are carried out. The working electrode is metal lead, silver and the like obtained by electrochemical reconstruction in ionic liquid electrolyte.
A method for electrochemically reconstructing a metal surface by an ionic liquid medium for electrocatalytic reduction of carbon dioxide comprises the following steps:
(1) taking metals such as lead, silver and the like as a working electrode, electrochemically reconstructing the metal surface in ionic liquid, washing with acetonitrile, and then airing at room temperature to obtain the working electrode; the preparation method comprises the following steps:
in an electrolytic cell partitioned into an anode chamber and a cathode chamber by a proton exchange membrane, metals polished by sandpaper, such as lead, silver and the like, and a silver/silver ion electrode as a reference electrode are put into the cathode chamber, a platinum mesh as a counter electrode is put into the anode chamber, an ionic liquid electrolyte is charged into the cathode chamber, and a sulfuric acid electrolyte is charged into the anode chamber. Under the condition of no additional metal source, a positive current is firstly applied to the three-electrode body system to dissolve the metal in the electrolyte, then a negative current is applied to the three-electrode body system, and the metal is re-deposited, so that the working electrode on the surface of the electrochemically reconstructed metal can be obtained.
(2) And (2) placing the working electrode obtained in the step (1) in an ionic liquid electrolyte, and continuously introducing carbon dioxide to perform constant-potential electro-catalytic reduction.
The range of the cyclic voltammetry curve of the electrochemical reconstruction metal surface of the ionic liquid medium is-0.1 to-2.9V (vs+)。
The constant current deposition current range of the ionic liquid medium electrochemical reconstruction metal surface is-0.1A, and the time is 0-360 min.
The constant voltage electrolysis range in the step (2) is-1.6 to-2.9V (vs. Ag/Ag)+) The reduction time is 1 h.
And (3) electrochemically reconstructing the metal surface by using an ionic liquid medium in the step (1) and the step (2), wherein the ionic liquid is imidazole, quaternary ammonium, quaternary phosphine and the like.
In the step (1) and the step (2), the ionic liquid/acetonitrile solution of which the ionic liquid concentration is 0.1-2M is [ Emim][PF6]、[Bmim][PF6]、[Bmim][BF4]、[Bmim][OTF]、[Bmim][TFA]、[Bmim][NTF2]、[BZmim][PF6]、 [BMmim][PF6]、[Bmim][Cl]、[N4444][BF4]、[P4444][BF4]And the acetonitrile contains 0-20% of water by mass fraction.
The structural formula of the ionic liquid is as follows:
the electrochemical active surface area of the electrochemically reconstructed metal surface of the ionic liquid medium is increased by 1.2-6 times compared with the electrochemical active surface area of untreated metal.
In the electrocatalytic reduction process of carbon dioxide, the potential range of linear scanning is-0.4 to-2.9V (vs+) The potential range of constant voltage electrolysis is-1.6 to-2.9V (vs. Ag/Ag)+). A large number of experiments prove that the ionic liquid medium electrochemically reconstructed lead metal is taken as the working electrode, the faradaic efficiency of formic acid is close to 90 percent and the formic acid current density is 48.7mA cm when the electrolytic potential is-2.2V-2The generation rate of the formic acid can reach 851.9 mu mol h-1cm-2。
In the electrocatalytic reduction process of carbon dioxide, the potential range of linear scanning is-0.4 to-2.9V (vs+) The potential range of constant voltage electrolysis is-1.6 to-2.9V (vs. Ag/Ag)+). A large number of experiments prove that the ionic liquid medium electrochemically reconstructed silver metal is taken as the working electrode, the Faraday efficiency of carbon monoxide is close to 99.0% and the current density of the carbon monoxide is 60.8mA cm at an electrolytic potential of-2.2V-2The generation rate of the carbon monoxide can reach 1914.5 mu mol h-1cm-2。
The stability of the electrochemically reconstructed lead/silver metal is proved that the current density and the selectivity of the catalyst are not obviously changed within 24h through a constant potential reduction experiment under-2.2V for 24h continuously, which shows that the used electrochemically reconstructed lead/silver catalyst has good stability.
The invention has the beneficial effects that:
(1) the invention firstly uses the ionic liquid medium to electrochemically reconstruct the surface of the lead metal and combines the electrocatalytic reduction of carbon dioxide to produce chemicals, when the potential is-2.2V, the Faraday efficiency of formic acid is close to 90 percent, and the current density of formic acid is 48.7mA cm-2The generation rate of formic acid is as high as 851.9 mu mol h-1cm-2。
(2) The invention firstly uses the ionic liquid medium to electrochemically reconstruct the silver metal surface and the combination of electrocatalytic reduction and carbon dioxide to produce chemicals, when the potential is-2.2V, the Faraday efficiency of the carbon monoxide is close to 99.0 percent, and the current density of the carbon monoxide is 60.8mA cm-2Of carbon monoxideThe generation rate can reach 1914.5 mu mol h-1cm-2。
(3) The electrocatalytic reduction system for carbon dioxide can ensure high current density and maintain high selectivity, and effectively solves the problem that the high current density and the high selectivity are incompatible.
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In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a scanning electron microscope image of electrochemically reconstituted lead metal of the present invention.
Fig. 2 is a linear scan of electrochemically reconstituted lead metal of the present invention under carbon dioxide and nitrogen atmosphere.
Figure 3 is a graph comparing the formic acid faradaic efficiency and current density of electrochemically reconstituted lead metal of the present invention versus untreated lead.
Figure 4 is an XRD pattern of electrochemically reconstituted lead metal of the present invention versus untreated lead.
Fig. 5 is a graph comparing the electrochemically active area of electrochemically reconstituted lead metal of the present invention with untreated lead.
Figure 6 is a graph of carbon monoxide faradaic efficiency and current density of electrochemically reconstituted silver metal of the present invention compared to untreated silver.
Detailed Description
The technical solution of the present invention will be clearly and completely described below with reference to the following embodiments. It is to be understood that the embodiments described are only some of the embodiments of the invention, and not all of them. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the invention without inventive step, belong to the invention.
Example 1
A method for electrochemically reconstructing a metal surface by an ionic liquid medium for electrocatalytic reduction of carbon dioxide, comprising the steps of:
1) electrochemical reconstruction of lead metal surfaces in ionic liquid media
In an electrolytic cell divided into an anode chamber and a cathode chamber by a proton exchange membrane, lead metal polished by abrasive paper and a silver/silver ion electrode as a reference electrode are placed in the cathode chamber, a platinum mesh as a counter electrode is placed in the anode chamber, [ Bmim ] [ TFA ] ionic liquid/acetonitrile electrolyte is filled in the cathode chamber, and 0.1M sulfuric acid electrolyte is filled in the anode chamber. And applying a current of 0.1A in a three-electrode system for 900s to dissolve the metal in the electrolyte, adjusting the current to-0.1A, and performing deposition for 900s to obtain the electrochemically reconstructed lead metal.
FIG. 1 is a scanning electron microscope image of electrochemically reconstituted lead metal prepared in accordance with the present invention.
2) Preparation of working electrode
And (2) washing the electrochemically reconstructed metal obtained in the step 1) with acetonitrile, and airing at room temperature to obtain the working electrode.
3) Electrocatalytic reduction carbon dioxide performance test
Putting the working electrode prepared in the step 2) into electrolyte, wherein the electrolyte used by the cathode is 1mol/L of [ Bmim ]][PF6]Wherein the acetonitrile contains 5 wt% of water. A three-electrode system is utilized, the potential is selected to be-0.4 to-2.9V, linear scanning is carried out in electrolyte saturated by carbon dioxide or inert gas, further-1.6 to-2.9V is selected, a constant potential electrocatalytic reduction experiment is carried out under the condition of continuously introducing carbon dioxide, the time is fixed to be 1h, the potential interval is 0.1V, gas obtained from a cathode chamber of an electrolytic cell within 1h is collected in a gas bag, after the electrocatalytic reduction is completed, a gas phase product is detected in a gas phase chromatogram, the detection result shows that the main gas products of the electrocatalytic reduction carbon dioxide are carbon monoxide and hydrogen, no other carbon-containing products exist, 150 mu L of the electrolyte after the electrocatalytic reduction is subjected to nuclear magnetic detection by taking phenol as an internal standard and deuterium-substituted dimethyl sulfoxide as a solvent, and a liquid phase product is mainly formic acid. When the potential is-2.2V, the Faraday efficiency of formic acid is close to 90%, and the current density of formic acid is 48.7mA cm-2The generation rate of formic acid can reach 851.9 mu mol h-1cm-2。
Fig. 2 is a linear scan of the electrochemically reconstructed lead metal in the carbon dioxide and nitrogen atmosphere, and it can be seen from the graph that the response of the electrochemically reconstructed lead metal to carbon dioxide is larger, specifically, the electrochemically reconstructed lead metal has a larger initial potential and current density than the electrolyte saturated with nitrogen in the ionic liquid electrolyte saturated with carbon dioxide.
Figure 3 is a graph comparing the formic acid faradaic efficiency and current density of electrochemically reconstituted lead metal of the present invention to the product faradaic efficiency and current density of untreated lead, and it can be seen that electrochemically reconstituted lead metal exhibits higher product activity than untreated lead.
In order to research the reason that the synthesized electrochemically reconstructed lead shows excellent electrocatalytic reduction carbon dioxide activity, a series of condition experiments are carried out, firstly, the composition of the electrochemically reconstructed lead metal is analyzed through XRD characterization, and FIG. 4 is an XRD (X-ray diffraction) diagram of the electrochemically reconstructed lead metal and untreated lead, and it can be seen from the diagram that the main components of the electrochemically reconstructed material are still lead and are not changed; meanwhile, the electrochemical active areas of the two catalysts are obtained by comparing the lead metal subjected to electrochemical reconstruction with untreated lead by using cyclic voltammetry. Fig. 5 is a comparison of the electrochemical active areas of the electrochemically reconstituted lead metal and untreated lead of the present invention, which shows that the electrochemically reconstituted lead metal has an increased electrochemical active area, and is beneficial to mass transfer and electron transfer during the electrocatalytic reduction process, thereby resulting in an improved electrocatalytic performance.
Example 2
1) Electrochemical reconstitution of lead metal in ionic liquid media
In an electrolytic cell divided into an anode chamber and a cathode chamber by a proton exchange membrane, lead polished by abrasive paper and a silver/silver ion electrode as a reference electrode are placed in the cathode chamber, a platinum mesh as a counter electrode is placed in the anode chamber, [ Bmim ] [ TFA ] ionic liquid/acetonitrile electrolyte is filled in the cathode chamber, and 0.1M sulfuric acid electrolyte is filled in the anode chamber. And applying a current of 0.1A in a three-electrode system for 900s to dissolve the metal in the electrolyte, adjusting the current to-0.05A, and obtaining the electrochemically reconstructed lead metal after the deposition time is 1800 s.
2) Preparation of working electrode
And (3) washing the electrochemically reconstructed lead metal in the step 1) with acetonitrile, and airing at room temperature to obtain the working electrode.
3) Electrocatalytic reduction carbon dioxide activity test
Putting the working electrode prepared in the step 2) into electrolyte, wherein the electrolyte is 1mol/L of ionic liquid [ Bmim ]][PF6]The water content of the acetonitrile is 5 wt%, a three-electrode system is utilized, a constant potential electrocatalysis reduction experiment is carried out in carbon dioxide or inert gas saturated electrolyte at a potential of-0.8-3.0V, further-2.0-2.4V is carried out, the constant potential electrocatalysis reduction experiment is carried out under the condition of continuously introducing carbon dioxide, the time is fixed to be 1h, the potential interval is 0.1V, gas obtained from a cathode chamber of an electrolytic cell within 1h is collected in a gas bag, after the electrocatalysis reduction is completed, a gas phase product is detected in a gas chromatography, a detection result shows that the electroreduction gas mainly comprises carbon monoxide and hydrogen, no other carbon-containing product exists, 150 mu L of electrolyte after the electrocatalysis obtained, phenol is used as an internal standard, deuterated dimethyl sulfoxide is used as a solvent, nuclear magnetic detection is carried out, and a liquid phase product mainly comprises formic acid. The Faraday efficiency of formic acid was 86% and the formic acid current density was 43.4mA cm at a potential of-2.2V-2The generation rate of the formic acid can reach 785.2 mu mol h-1cm-2。
Example 3
1) Electrochemical reconstitution of lead metal in ionic liquid media
In an electrolytic cell divided into an anode chamber and a cathode chamber by a proton exchange membrane, lead metal polished by abrasive paper and a silver/silver ion electrode as a reference electrode are placed in the cathode chamber, a platinum mesh as a counter electrode is placed in the anode chamber, and [ Bmim ] is placed in the cathode chamber][PF6]Ionic liquid/acetonitrile electrolyte, 0.1M sulfuric acid electrolyte was charged to the anode compartment. And applying a current of 0.1A in a three-electrode system for 900s to dissolve the metal in the electrolyte, adjusting the current to-0.1A, and performing deposition for 900s to obtain the electrochemically reconstructed lead metal.
2) Preparation of working electrode
And (3) washing the electrochemically reconstructed lead metal in the step 1) with acetonitrile, and airing at room temperature to obtain the working electrode.
3) Electrocatalytic reduction carbon dioxide activity test
Putting the working electrode prepared in the step 2) into electrolyte, wherein the electrolyte is 1mol/L of ionic liquid [ Bmim ]][PF6]The water content of the acetonitrile is 5 wt%, a three-electrode system is utilized, a constant potential electrocatalysis reduction experiment is carried out in carbon dioxide or inert gas saturated electrolyte at a potential of-0.8-3.0V, further-2.0-2.4V is carried out, the constant potential electrocatalysis reduction experiment is carried out under the condition of continuously introducing carbon dioxide, the time is fixed to be 1h, the potential interval is 0.1V, gas obtained from a cathode chamber of an electrolytic cell within 1h is collected in a gas bag, after the electrocatalysis reduction is completed, a gas phase product is detected in a gas chromatography, a detection result shows that the electroreduction gas mainly comprises carbon monoxide and hydrogen, no other carbon-containing product exists, 150 mu L of electrolyte after the electrocatalysis obtained, phenol is used as an internal standard, deuterated dimethyl sulfoxide is used as a solvent, nuclear magnetic detection is carried out, and a liquid phase product mainly comprises formic acid. The Faraday efficiency of formic acid was 79.8% and the current density was 44.3mA cm at a potential of-2.2V-2The generation rate of the formic acid can reach 826.1 mu mol h-1cm-2。
Example 4
1) Electrochemical reconstruction of silver metal in ionic liquid media
In an electrolytic cell divided into an anode chamber and a cathode chamber by a proton exchange membrane, a silver block polished by abrasive paper and a silver/silver ion electrode as a reference electrode are placed in the cathode chamber, a platinum mesh as a counter electrode is placed in the anode chamber, [ Bmim ] [ TFA ] ionic liquid/acetonitrile electrolyte is filled in the cathode chamber, and 0.1M sulfuric acid electrolyte is filled in the anode chamber. And applying a current of 0.1A in a three-electrode system for 900s to dissolve the metal in the electrolyte, adjusting the current to-0.05A, and obtaining the electrochemically reconstructed silver metal after 1800s of deposition time.
2) Preparation of working electrode
And (3) washing the electrochemically reconstructed silver metal obtained in the step 1) with acetonitrile, and airing at room temperature to obtain the working electrode.
3) Electrocatalytic reduction carbon dioxide activity test
Putting the working electrode prepared in the step 2) into electrolyte, wherein the electrolyte is 1mol/L of ionic liquid [ Bmim ]][PF6]The water content of the acetonitrile is 5 wt%, a three-electrode system is utilized, a constant potential electrocatalysis reduction experiment is carried out in carbon dioxide or inert gas saturated electrolyte at a potential of-0.8-3.0V, further-2.0-2.4V is carried out, the constant potential electrocatalysis reduction experiment is carried out under the condition of continuously introducing carbon dioxide, the time is fixed to be 1h, the potential interval is 0.1V, gas obtained from a cathode chamber of an electrolytic cell within 1h is collected in a gas bag, after the electrocatalysis reduction is finished, a gas phase product is detected in a gas chromatography, and a detection result shows that the electroreduction gas mainly comprises carbon monoxide and hydrogen and no other carbon-containing products, 150 mu L of the electrolyte after the electrocatalysis reduced, phenol is used as an internal standard, deuterated dimethyl sulfoxide is used as a solvent, nuclear magnetic detection is carried out, and a liquid phase does not contain formic acid product. When the potential is-2.2V, the Faraday efficiency of carbon monoxide is 99.0%, and the current density is 60.8mA cm-2The generation rate of the carbon monoxide can reach 1914.5 mu mol h-1cm-2。
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (7)
1. A method for electrochemically reconstructing a metal surface by an ionic liquid medium for electrocatalytic reduction of carbon dioxide is characterized by comprising the following steps:
(1) taking metals such as lead, silver and the like as working electrodes, electrochemically reconstructing the metal surfaces in an ionic liquid medium, washing with acetonitrile, and then drying at room temperature to obtain the working electrodes;
(2) and (2) placing the working electrode obtained in the step (1) in an ionic liquid electrolyte, and continuously introducing carbon dioxide to perform constant-potential electro-catalytic reduction.
2. The method of claim 1, wherein the step of electrochemically reconfiguring the metal surface in the ionic liquid medium in step (1) is as follows: in an H-type electrolytic cell, ionic liquid/acetonitrile/water is used as a compound electrolyte, metals such as lead, silver and the like are used as a working electrode, a platinum net and silver/silver ions are used as a counter electrode and a reference electrode, under the condition that no metal source is added, a positive current is firstly applied to a three-electrode system to dissolve the metals in the electrolyte, then a negative current is applied, and the metals are deposited again to obtain the electrochemically reconstructed metal surface.
3. The method according to claim 1, wherein the constant current deposition in step (1) is carried out at a current ranging from-0.1 to 0.1A for 0 to 360 min.
4. The method of claim 1, wherein the potential range of the constant voltage electrocatalytic reduction in the step (2) is-1.6 to-2.9V (vs+) The reduction time is 1 h.
5. The method according to claim 1, wherein the ionic liquid in step (1) and step (2) is an ionic liquid such as imidazolium salt, quaternary phosphonium salt or quaternary ammonium salt.
6. The method according to claim 5, wherein the ionic liquid of imidazolium salt, quaternary phosphonium salt or quaternary ammonium salt is an ionic liquid/acetonitrile solution with the concentration of 0.1-2M, and the ionic liquid can be [ Emim [ ]][PF6]、[Bmim][PF6]、[Bmim][BF4]、[Bmim][OTF]、[Bmim][NTF2]、[BZmim][PF6]、[BMmim][PF6]、[Bmim][Cl]、[N4444][BF4]、[P4444][BF4]And the mass fraction of water in the acetonitrile/water mixed solution is 0-20%.
7. The method for electrocatalytic reduction of carbon dioxide on an electrochemically reconstituted metal surface of an ionic liquid medium according to any one of claims 1 to 6, wherein the electrochemically active surface area of the electrochemically reconstituted metal of the ionic liquid medium is increased by 1.2 to 6 times compared with the electrochemically active surface area of the untreated metal.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101629312A (en) * | 2009-08-14 | 2010-01-20 | 昆明理工大学 | Method for electrodepositing lead by ionic liquid system |
| CN102181876A (en) * | 2011-03-30 | 2011-09-14 | 昆明理工大学 | Method and device for preparing carbon monoxide through electrochemical catalytic reduction of carbon dioxide |
| CN103046081A (en) * | 2012-12-22 | 2013-04-17 | 彩虹集团公司 | Method for preparing silver by utilizing ionic liquid through electrodeposition at low temperature |
| CN108118363A (en) * | 2016-11-26 | 2018-06-05 | 中国科学院大连化学物理研究所 | A kind of CO2The preparation of electrochemical reduction electrode and its electrode and application |
| CN111218697A (en) * | 2020-01-09 | 2020-06-02 | 浙江工业大学 | Pb electrode with octahedral crystal face, preparation method and application thereof |
| CN112813480A (en) * | 2021-01-07 | 2021-05-18 | 江苏大学 | In-situ grown silver nanocluster material, preparation method thereof and electro-catalytic reduction of CO2Applications of |
-
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101629312A (en) * | 2009-08-14 | 2010-01-20 | 昆明理工大学 | Method for electrodepositing lead by ionic liquid system |
| CN102181876A (en) * | 2011-03-30 | 2011-09-14 | 昆明理工大学 | Method and device for preparing carbon monoxide through electrochemical catalytic reduction of carbon dioxide |
| CN103046081A (en) * | 2012-12-22 | 2013-04-17 | 彩虹集团公司 | Method for preparing silver by utilizing ionic liquid through electrodeposition at low temperature |
| CN108118363A (en) * | 2016-11-26 | 2018-06-05 | 中国科学院大连化学物理研究所 | A kind of CO2The preparation of electrochemical reduction electrode and its electrode and application |
| CN111218697A (en) * | 2020-01-09 | 2020-06-02 | 浙江工业大学 | Pb electrode with octahedral crystal face, preparation method and application thereof |
| CN112813480A (en) * | 2021-01-07 | 2021-05-18 | 江苏大学 | In-situ grown silver nanocluster material, preparation method thereof and electro-catalytic reduction of CO2Applications of |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114959761A (en) * | 2022-05-05 | 2022-08-30 | 中国科学院上海高等研究院 | Preparation method and application of silver hollow fiber electrode |
| CN114959761B (en) * | 2022-05-05 | 2023-11-03 | 中国科学院上海高等研究院 | Preparation method and application of silver hollow fiber electrode |
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