CN111790371A - Preparation method and application of bimetallic catalyst - Google Patents
Preparation method and application of bimetallic catalyst Download PDFInfo
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- CN111790371A CN111790371A CN202010808555.4A CN202010808555A CN111790371A CN 111790371 A CN111790371 A CN 111790371A CN 202010808555 A CN202010808555 A CN 202010808555A CN 111790371 A CN111790371 A CN 111790371A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/18—Arsenic, antimony or bismuth
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Inert Electrodes (AREA)
Abstract
The invention discloses a preparation method and application of a bimetallic catalyst material, wherein the preparation method comprises the steps of depositing metal tin Sn and another auxiliary metal gallium Ga, germanium Ge, indium In, bismuth Bi, antimony Sb, lead Pb, zinc Zn, cadmium Cd and the like on a conductive substrate or a gas diffusion electrode or an ion exchange membrane substrate by utilizing a physical or chemical method (including thermal evaporation, magnetron sputtering, liquid phase method synthesis, electrodeposition and the like) to prepare the bimetallic material serving as an electrocatalyst, and the prepared electrocatalyst can have different structural characteristics, chemical components and physical and chemical properties. The material prepared by the invention has the advantages of simple preparation method, good repeatability, green and nontoxic raw materials, rich resources, good practical value and good application prospect.
Description
Technical Field
The invention belongs to the technical field of electrocatalytic reduction materials, and particularly relates to a preparation method of a solid film or a micro-nano structure material which is formed by depositing metal tin Sn and another auxiliary metal gallium Ga, germanium Ge, indium In, bismuth Bi, antimony Sb, lead Pb, zinc Zn, cadmium Cd and the like on a conductive substrate or a gas diffusion electrode or an ion exchange membrane and the like by a physical or chemical method (comprising thermal evaporation coating, magnetron sputtering, liquid phase method synthesis, electrodeposition and the like) as an electrocatalyst and an application In the aspect of electrocatalytic reduction of carbon dioxide.
Background
Global climate problems have begun to endanger human life. For over 20 years, China has been highly concerned about dealing with climate change, and has been a major goal of energy conservation, efficiency improvement and energy utilization efficiency improvement. The reduction of carbon dioxide to valuable chemicals (chemicals, fuels, etc.) by electrochemical methods offers the possibility of storing abundant renewable electrical energy on a large scale in the form of carbon bonds. Electrocatalytic conversion of CO2Reduction to fuels or valuable compounds is an emerging research topic because it is capable of mitigating CO2The influence of the discharge on the ecological environment can be released, and the problem of the discharge of carbon dioxide can be relieved from the root.
CO2The products of the reduction typically include gaseous carbon monoxide (CO), methane (CH)4) Ethylene (C)2H4) Liquid phase formic acid (HCOOH), ethanol (C)2H5OH), and the like. Among these products, HCOOH is a basic and demanding chemical raw material, and is widely used in pharmaceutical, electrowinning, leather and other industries. Further, due to their safety, non-toxicity, low volatility, transportability, and high hydrogen content (53g/L), HCOOH is also considered to be directly useful in formic acid fuel cells. Among the many products, HCOOH is a simple and important monocarbon, electrolyzing CO2Formate production is considered to be technically economically feasible. Various strategies explored to improve electrocatalytic carbon dioxide reduction (CO)2R) selectivity of formate preparation, and CO can be regulated and controlled by controlling synthesis of high index surface, grain boundary engineering, bimetallic effect and the like2Adsorption energy and adsorption mode on the surface of the catalyst. However, the current research technology of electrocatalytic reduction of carbon dioxide can not reach the performance index of industrialized application, and the electrocatalytic reduction of CO is realized2(CO2R) to formic acid (i.e., high faradaic efficiency), how to increase the current density of the process of preparing formic acid by electroreduction of carbon dioxide more greatly, and how to obtain higher energy conversion rate and longer-term stability remains a challenge.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method and application of a bimetallic material as an electrocatalyst, wherein a physical or chemical method (comprising thermal evaporation coating, magnetron sputtering, liquid phase method synthesis, electrodeposition and the like) is used for depositing metal tin Sn and another auxiliary metal comprising gallium Ga, germanium Ge, indium In, bismuth Bi, antimony Sb, lead Pb, zinc Zn, cadmium Cd and the like on a conductive substrate or a gas diffusion electrode or an ion exchange membrane and the like to synthesize the bimetallic material which has high-efficiency electrocatalytic activity and can be applied to preparing formic acid by electrocatalytic reduction of carbon dioxide, including realizing the electrocatalytic reduction of CO2(CO2R) high selectivity to formic acid, high current density, high energy conversion rate, long stability, and the like.
In order to solve the problems, the technical scheme adopted by the invention is as follows:
a preparation method of a bimetallic catalyst comprises the following steps:
through physical or chemical methods (including thermal evaporation coating, magnetron sputtering, liquid phase synthesis, electrodeposition and the like), the metal tin Sn and the other auxiliary metal gallium Ga, germanium Ge, indium In, bismuth Bi, antimony Sb, lead Pb, zinc Zn and cadmium Cd are deposited on a conductive substrate or a gas diffusion electrode or an ion exchange membrane and the like to synthesize the bimetal material. The bimetallic catalyst material may comprise the materials listed above, including combinations of any two of tin Sn, gallium Ga, germanium Ge, indium In, bismuth Bi, antimony Sb, lead Pb, zinc Zn, cadmium Cd.
As an improvement and demonstration of the technical scheme, the prepared material is BiSn (the molar content of Bi is 0.1-99.9%, and the molar content of Sn is 0.1% -99.9%) alloy material or Bi-doped Sn (the molar content of Bi is 0-0.1%) or Sn-doped Bi (the molar content of Sn is 0-0.1%) solid film or nano structure, and the prepared material is used for a metal electrocatalyst or an electrode material.
As an improvement of the above technical solution, the preparation method includes, but is not limited to, a thermal evaporation coating method, in which metal Bi and metal Sn are respectively loaded in an evaporation boat (molybdenum boat), and placed under a conductive substrate or a gas diffusion electrode or an ion exchange membrane substrate, and the metal Bi and the metal Sn are gasified by heating and deposited on the conductive substrate or the gas diffusion electrode or the ion exchange membrane substrate to form a solid film or a micro-nano structure, so as to obtain a BiSn (Bi molar content 0.1-99.9%, Sn molar content 0.1-99.9%) alloy material or a Bi-doped Sn (Bi molar content 0-0.1%) or a Sn-doped Bi (Sn molar content 0-0.1%) electrocatalyst material.
As an improvement of the technical scheme, the heating evaporation conditions of the metal Bi are as follows: at a certain vacuum degree, the deposition rate
The heating evaporation conditions of the metal Sn are as follows: at a certain vacuum degree, the deposition rate
As an improvement of the technical scheme, the thickness of the catalyst layer is monitored by using a crystal oscillator plate in the deposition process, and after the preparation is finished, the thickness of the catalyst layer is measured by using a thickness measuring instrument (comprising a film thickness instrument and an ellipsometer).
As an improvement of the technical scheme, the deposition rate of metal Bi and metal Sn determines the proportion of bismuth and tin in the BiSn bimetal material, and the component proportion of the BiSn bimetal can be regulated and controlled by regulating and controlling the deposition rate.
As an improvement of the technical scheme, the application of the bimetallic material catalyst is that the prepared metal Sn and another auxiliary metal Ga, Ge, In, Bi, Sb, Pb, Zn, Cd and the like are used for electrocatalysis, and the bimetallic material is deposited on a conductive substrate or a gas diffusion electrode or a substrate such as an ion exchange membrane and the like.
As an improvement of the technical scheme, the application of the bimetallic material catalyst is that the prepared BiSn (with the molar content of Bi being 0.1-99.9 percent and the molar content of Sn being 0.1-99.9 percent) alloy material or Bi-doped Sn (with the molar content of Bi being 0-0.1 percent) or Sn-doped Bi (with the molar content of Sn being 0-0.1 percent) solid film or micro-nano structure material is used for electrocatalysis.
As an improvement of the technical scheme, the application of the bimetallic material catalyst is characterized in that the prepared BiSn bimetallic material is used for preparing at least one single-carbon product by electrocatalytic reduction of carbon dioxide; the electrocatalytic process can be carried out in an alkaline electrolyte.
Compared with the prior art, the invention has the following implementation effects:
1. the metal material selected by the invention has rich reserves, and is green and nontoxic.
2. The method adopted by the invention is prepared in one step, has good repeatability and can be used for large-scale preparation.
3. The prepared material is used for preparing formic acid by electrocatalytic reduction of carbon dioxide, and can be in a range of 100-500 mA cm-2Under the high current density, the Faraday efficiency of the formic acid reaches 95 to 99.9 percent; at 100mAcm-2Under the current density, the energy conversion efficiency of formic acid reaches 70-85%; and the method can be stable for a long time, and has good practical value and application prospect.
Drawings
FIG. 1 shows Bi prepared according to the present invention0.1Scanning electron microscope images of the Sn bimetallic material;
FIG. 2 shows Bi prepared by the present invention0.1A transmission electron microscope image of the Sn bimetallic material;
FIG. 3 shows Bi prepared by the present invention0.1X-ray energy spectrum analysis of the Sn bimetallic material;
FIG. 4 shows Bi prepared by the present invention0.1An X-ray diffraction pattern diagram of the Sn bimetallic material;
FIG. 5 shows Bi prepared by the present invention0.1An X-ray photoelectron energy spectrum of the Sn bimetallic material;
FIG. 6 shows Bi prepared by the present invention0.1LSV curve diagram of Sn bimetallic material, single metal Sn and single metal Bi in 1M KOH electrolyte;
FIG. 7 shows Bi prepared by the present invention0.1A Faraday efficiency and energy conversion efficiency diagram of formic acid produced by the Sn bimetallic material, the single metal Sn and the single metal Bi under different current densities;
FIG. 8 shows Bi prepared by the present invention0.1Impedance spectra of the Sn bimetallic material, the single metal Sn and the single metal Bi;
FIG. 9 shows Bi prepared by the present invention0.1Sn double goldThe material is 100mA cm-2Electrocatalytic reduction of CO at current density2Long term stability test results of;
FIG. 10 shows Bi prepared by the present invention0.1LSV profile of Sn bimetallic material in electrolytes of different pH.
Detailed Description
The present invention will be described with reference to specific examples.
Example 1
A preparation method of a bismuth-tin (BiSn) bimetallic material comprises the following steps:
s1, loading metal Bi and metal Sn in a thermal evaporation boat (molybdenum boat) respectively, and placing the thermal evaporation boat and the molybdenum boat below the PTFE substrate; and heating metal Bi and metal Sn to gasify the metal Bi and the metal Sn and deposit the metal Bi and the metal Sn on the PTFE substrate to form a solid film to obtain the BiSn bimetal electrocatalyst material.
In step S1, the conditions for heating and evaporating the metal Bi are as follows: under the condition of certain vacuum degree, the current is 6.90A, the voltage is 14V, and the deposition rate is
The heating evaporation conditions of the metal Sn are as follows: under the condition of certain vacuum degree, the current is 120A, the voltage is 1.8V, and the deposition rate is
Further, the thickness of the prepared material is monitored by using a crystal oscillator plate in the deposition process, and the thickness of the prepared material is 500-1500 nm.
Furthermore, the deposition rate of metal Bi and metal Sn determines the proportion of bismuth and tin in the BiSn bimetal material, and the component proportion of the BiSn bimetal can be regulated and controlled by regulating and controlling the deposition rate.
Further, by preference, Bi0.1Sn has optimal electrocatalytic properties towards formic acid products.
FIG. 1 shows Bi obtained in this example0.1SEM image of Sn bimetallic material, Bi can be seen from FIG. 10.1The Sn bimetal material is tightly packed to form a compact film.
FIG. 2 shows Bi obtained in this example0.1TEM image of Sn bimetallic material, Bi can be seen from FIG. 20.1The crystal plane distribution of the Sn bimetal material shows a Bi (003) plane and a Sn (200) plane respectively.
FIG. 3 shows Bi obtained in this example0.1The X-ray energy spectrum analysis chart of the Sn bimetallic material can clearly show that the atomic ratio of Bi to Sn in the obtained material is 1: 10.
FIG. 4 shows Bi obtained in this example0.1The X-ray diffraction pattern of the Sn bimetallic material indicates that the material is a composite of the metals bismuth and tin.
FIG. 5 shows Bi obtained in this example0.1The X-ray photoelectron spectrogram of the Sn bimetallic material respectively shows the valence state distribution of Bi and Sn.
Example 2
Bi is understood by the following experiment0.1The electrocatalytic activity of Sn is different from that of single metals Bi and Sn.
The experiment adopts a flowing electrolytic cell to respectively prepare Bi on a PTFE substrate by a thermal evaporation coating method0.1Sn bimetallic material, single metal material Bi and single metal material Sn (0.5x0.5 cm) are used as working electrodes. The reference electrode is an Ag/AgCl electrode, the counter electrode is foamed nickel (0.5x3 cm), a linear voltammetry scanning method is adopted, the potential window is 0V to-2 Vvs.RHE, and the scanning speed is 50 mV/s.
In the above experimental method, CO2The gas flow rate is 30-100 sccm.
The LSV curve in the 1M KOH electrolyte is shown in FIG. 6 by the above experimental method, which shows that Bi0.1The initial potential and current density of the Sn bimetal composite material have obvious advantages compared with other two materials.
As can be seen from FIG. 7, Bi0.1The current density of the Sn bimetal material is 100-300 mA cm-2Under the condition of (3), the Faraday efficiency of formic acid production reaches more than 95 percent; in addition, the cathodic energy conversion efficiency of formic acid is higher than that of the single metal materials Bi, Sn at each current density. Wherein, at 100mA cm-2At current density, Bi0.1Electroreduction of Sn bimetallic catalystThe cathode energy conversion efficiency of preparing formic acid from carbon oxide reaches 80 percent, which shows that Bi0.1The Sn bimetallic catalyst has good selectivity and catalytic activity to formic acid.
FIG. 8 shows Bi0.1The impedance spectra of the Sn bimetallic material, the single metal material Bi and the single metal material Sn. From the impedance spectrum analysis, Bi0.1The Sn bimetallic material exhibits a smaller semicircle. This indicates that Bi can be improved by the bimetallic synergy of Bi and Sn0.1The Sn bimetal material performs charge transfer, thereby exhibiting smaller charge transfer resistance.
For Bi prepared in example 10.1The Sn bimetallic material was subjected to stability testing.
As can be seen from FIG. 9, in the stability test at 170 hours, at 100mA cm-2Under the current density of (2), the voltage change is not obvious on a voltage-time curve, which shows that the stability of the material is good.
Example 3
In electrolyte solutions of different pH, Bi is used0.1Sn as a catalytic material, the effect of pH on catalytic activity was investigated.
The experiment used a flow-type electrolytic cell. Bi prepared on PTFE substrate by thermal evaporation coating method0.1The Sn bimetal material is used as a working electrode. The reference electrode was an Ag/AgCl electrode and the counter electrode was nickel foam (0.5X3 cm). The electrolyte solution is 1M KHCO3And 10M KOH, the pH of which was controlled to 8, 10, 11, 12, 13 and 14, respectively. Adopting a linear voltammetry scanning method, wherein the potential window is 0V-2V vs. RHE, and the scanning speed is 50 mV/s. As can be seen from fig. 10, the initial potentials and current densities corresponding to the electrolyte solutions with different pH values are different, which indicates that the pH of the electrolyte solution has a certain influence on the catalytic activity.
The foregoing is a detailed description of the invention with reference to specific embodiments, and the practice of the invention is not to be construed as limited thereto. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.
Claims (9)
1. The preparation method of the bimetallic catalyst is characterized by comprising the following steps of:
through physical or chemical methods (including thermal evaporation coating, magnetron sputtering, liquid phase synthesis, electrodeposition and the like), the metal tin Sn and the other auxiliary metal gallium Ga, germanium Ge, indium In, bismuth Bi, antimony Sb, lead Pb, zinc Zn and cadmium Cd are deposited on a conductive substrate or a gas diffusion electrode or an ion exchange membrane and the like to synthesize the bimetal material.
2. The method for preparing a bimetallic catalyst as in claim 1, characterized in that: the prepared material is a BiSn (Bi mol content is 0.1-99.9%, Sn mol content is 0.1% -99.9%) alloy material or a Bi-doped Sn (Bi mol content is 0-0.1%) or Sn-doped Bi (Sn mol content is 0-0.1%) solid film or nano structure, and is used for a metal electrocatalyst or an electrode material.
3. The method for preparing a bimetallic catalyst as in claim 1, characterized in that: the preparation method comprises but is not limited to a thermal evaporation coating method, metal Bi and metal Sn are respectively loaded in an evaporation boat (molybdenum boat), the evaporation boat is placed below a conductive substrate or a gas diffusion electrode or an ion exchange membrane substrate, the metal Bi and the metal Sn are gasified by heating and deposited on the conductive substrate or the gas diffusion electrode or the ion exchange membrane substrate to form a solid film or a micro-nano structure, and a BiSn (Bi mol content is 0.1-99.9%, Sn mol content is 0.1-99.9%) alloy material or a Bi-doped Sn (Bi mol content is 0-0.1%) or a Sn-doped Bi (Sn mol content is 0-0.1%) electrocatalyst material is obtained.
4. The method for preparing a bimetallic catalyst according to claim 3, characterized in that: the heating evaporation conditions of the metal Bi are as follows: at a certain vacuum degree, the deposition rate
Heating of metallic SnThe evaporation conditions were: at a certain vacuum degree, the deposition rate
5. The method for preparing a bimetallic catalyst according to claim 2, characterized in that: the thickness of the catalyst layer is monitored by a crystal oscillator plate during the deposition process, and after the preparation is completed, the thickness of the catalyst layer is measured by a thickness measuring instrument (comprising a film thickness meter and an ellipsometer).
6. The method for preparing a bimetallic catalyst according to claim 3, characterized in that: the deposition rate of metal Bi and metal Sn determines the proportion of Bi and tin in the BiSn bimetal material, and the component proportion of the BiSn bimetal can be regulated and controlled by regulating and controlling the deposition rate.
7. Use of a bimetallic catalyst according to any one of claims 1-6, characterised in that: the prepared bimetal material is a bimetal material which is formed by depositing any two of tin Sn, gallium Ga, germanium Ge, indium In, bismuth Bi, antimony Sb, lead Pb, zinc Zn and cadmium Cd on a conductive substrate or a diffusion gas electrode or an ion exchange membrane and the like for electrocatalysis.
8. Use of a bimetallic catalyst according to claim 7, characterized in that: the prepared BiSn (the molar content of Bi is 0.1-99.9 percent, the molar content of Sn is 0.1-99.9 percent) alloy material or Bi-doped Sn (the molar content of Bi is 0-0.1 percent) or Sn-doped Bi (the molar content of Sn is 0-0.1 percent) solid film or micro-nano structure material is used for electrocatalysis.
9. Use of a bimetallic catalyst according to claim 7, characterized in that: the prepared BiSn bimetallic material is used for preparing at least one single-carbon product by electrocatalytic reduction of carbon dioxide; the electrocatalytic process can be carried out in an alkaline electrolyte.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112647090A (en) * | 2020-12-17 | 2021-04-13 | 华东理工大学 | Hydrophobic polymer film loaded metal vapor deposition gas diffusion electrode, preparation method and application thereof |
| CN112941560A (en) * | 2021-01-28 | 2021-06-11 | 中南大学 | Bi-In @ Cu foam nano material and preparation method and application thereof |
| CN113638001A (en) * | 2021-08-31 | 2021-11-12 | 南京大学 | Preparation method of metal catalyst for producing formic acid and formate |
| CN114457306A (en) * | 2022-01-18 | 2022-05-10 | 南京大学 | Large-area preparation of single-phase (copper and tin) bimetal alloy by physical (chemical) vapor deposition method and electrochemical application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103252243A (en) * | 2013-06-13 | 2013-08-21 | 南京大学 | Carbon nano tube film load cuprum and palladium bimetallic catalyst, preparation method and application |
| CN104846397A (en) * | 2015-04-21 | 2015-08-19 | 盐城工学院 | Electrode for electrochemical reduction of CO2 and preparation of formic acid and preparation method and application thereof |
| CN107020075A (en) * | 2017-03-30 | 2017-08-08 | 东华大学 | Carbon dioxide electrochemical reduction simple substance bismuth catalyst and its preparation and application |
| CN109092288A (en) * | 2018-09-02 | 2018-12-28 | 河北科技大学 | A kind of preparation and application of Carbon dioxide electrochemical reduction leypewter catalyst |
| CN109518222A (en) * | 2019-01-28 | 2019-03-26 | 苏州大学 | For electro-catalysis CO2It is restored to the bismuth-based catalysts and its preparation method and application of formic acid |
| CN110306199A (en) * | 2019-06-10 | 2019-10-08 | 深圳大学 | A kind of carbon dioxide electro-catalysis reduction film and the preparation method and application thereof |
| CN111074294A (en) * | 2019-12-12 | 2020-04-28 | 中国科学技术大学 | Method for preparing carbon-containing compound by electrocatalysis of carbon dioxide with copper alloy material |
-
2020
- 2020-08-12 CN CN202010808555.4A patent/CN111790371A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103252243A (en) * | 2013-06-13 | 2013-08-21 | 南京大学 | Carbon nano tube film load cuprum and palladium bimetallic catalyst, preparation method and application |
| CN104846397A (en) * | 2015-04-21 | 2015-08-19 | 盐城工学院 | Electrode for electrochemical reduction of CO2 and preparation of formic acid and preparation method and application thereof |
| CN107020075A (en) * | 2017-03-30 | 2017-08-08 | 东华大学 | Carbon dioxide electrochemical reduction simple substance bismuth catalyst and its preparation and application |
| CN109092288A (en) * | 2018-09-02 | 2018-12-28 | 河北科技大学 | A kind of preparation and application of Carbon dioxide electrochemical reduction leypewter catalyst |
| CN109518222A (en) * | 2019-01-28 | 2019-03-26 | 苏州大学 | For electro-catalysis CO2It is restored to the bismuth-based catalysts and its preparation method and application of formic acid |
| CN110306199A (en) * | 2019-06-10 | 2019-10-08 | 深圳大学 | A kind of carbon dioxide electro-catalysis reduction film and the preparation method and application thereof |
| CN111074294A (en) * | 2019-12-12 | 2020-04-28 | 中国科学技术大学 | Method for preparing carbon-containing compound by electrocatalysis of carbon dioxide with copper alloy material |
Non-Patent Citations (2)
| Title |
|---|
| JIANBO TANG，等: "Advantages of eutectic alloys for creating catalysts in the realm of nanotechnology-enabled metallurgy", 《NATURE COMMUNICATIONS》 * |
| WEN, G. ET AL.: "Orbital interactions in Bi-Sn bimetallic electrocatalysts for highly selective electrochemical CO2 reduction toward formate production", 《ADV. ENERGY MATER.》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112647090A (en) * | 2020-12-17 | 2021-04-13 | 华东理工大学 | Hydrophobic polymer film loaded metal vapor deposition gas diffusion electrode, preparation method and application thereof |
| CN112941560A (en) * | 2021-01-28 | 2021-06-11 | 中南大学 | Bi-In @ Cu foam nano material and preparation method and application thereof |
| CN113638001A (en) * | 2021-08-31 | 2021-11-12 | 南京大学 | Preparation method of metal catalyst for producing formic acid and formate |
| CN114457306A (en) * | 2022-01-18 | 2022-05-10 | 南京大学 | Large-area preparation of single-phase (copper and tin) bimetal alloy by physical (chemical) vapor deposition method and electrochemical application thereof |
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