CN110965071A - A metal catalyst for electrochemical reduction of carbon dioxide and its preparation and application - Google Patents

A metal catalyst for electrochemical reduction of carbon dioxide and its preparation and application Download PDF

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CN110965071A
CN110965071A CN201811145815.3A CN201811145815A CN110965071A CN 110965071 A CN110965071 A CN 110965071A CN 201811145815 A CN201811145815 A CN 201811145815A CN 110965071 A CN110965071 A CN 110965071A
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zinc
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CN110965071B (en
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张华民
张桃桃
邱艳玲
李先锋
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Dalian Institute of Chemical Physics of CAS
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Abstract

本发明涉及一种二氧化碳电化学还原用金属催化剂及其制备和应用，该方法制备的金属催化剂表面为双金属纳米片状或颗粒状多晶结构，为催化剂提供催化性能，其元素组成为Zn、Bi两种元素，纳米片的直径为10～800nm，厚度为3～100nm，纳米颗粒的粒径为5nm～1.5μm；催化剂内部为金属Zn，为催化剂提供强度支撑和导电性。本发明提供了一种简单经济的方法，所制备的金属催化剂成本低，具有表面结构尺寸可调和比表面积高的特点，多晶结构具有更高的催化活性，用于二氧化碳电化学还原，对目标产物具有优良的选择性和催化活性。

Figure 201811145815

The invention relates to a metal catalyst for electrochemical reduction of carbon dioxide and its preparation and application. The surface of the metal catalyst prepared by the method has a bimetallic nano-sheet or granular polycrystalline structure, which provides the catalyst with catalytic performance. Its element composition is Zn, Bi two elements, the diameter of the nanosheets is 10-800nm, the thickness is 3-100nm, and the particle size of the nanoparticles is 5nm-1.5μm; the inside of the catalyst is metal Zn, which provides strength support and conductivity for the catalyst. The invention provides a simple and economical method, the prepared metal catalyst has the characteristics of low cost, adjustable surface structure size and high specific surface area, and the polycrystalline structure has higher catalytic activity, which is used for the electrochemical reduction of carbon dioxide, and has the advantages of low cost to the target. The product has excellent selectivity and catalytic activity.

Figure 201811145815

Description

Metal catalyst for electrochemical reduction of carbon dioxide and preparation and application thereof
Technical Field
The invention relates to the field of electrochemical reduction of carbon dioxide, in particular to a catalyst technology for electrochemical reduction of carbon dioxide.
Background
The gradual exhaustion of fossil energy and global warming are two problems facing human beings and are closely related to the sustainable development of the human beings. Consumption of fossil fuels to make CO in the atmosphere2The content is continuously increased. CO 22As a greenhouse gas, it can cause global warming, causing "greenhouse effect". However, CO2Is also a potential carbon resource, if it can be recovered and converted into useful chemical raw materials, which can reduce CO in the atmosphere2The content of the organic fertilizer is changed into beneficial, the greenhouse effect is slowed down, and the substitute of fossil fuel can be supplemented. In a large number of CO2In the conversion process, electrochemical reduction of CO2Can utilize renewable energy sources to generate electricity and water to convert CO2Conversion into valuable compounds, e.g. formic acid, CO, CH4And C2H2And the like. Electrochemical reduction of CO2Can realize CO at normal temperature and normal pressure2The method has the advantages of high-efficiency conversion, simple equipment, environmental protection, good development prospect and application value, and attracts the high attention of a plurality of researchers at home and abroad.
CO2Is a molecule with very stable chemical structure, and can convert CO into CO2The reduction to an intermediate requires a high overpotential; and CO2The reduction to the product involves multiple step electron transfer, resulting in poor product selectivity. Therefore, the proper catalyst is selected to reduce CO2The overpotential of reduction is important to improve the selectivity of the product. The obtained CO varies according to the type of catalyst2The reduced product is also different. At present, most of catalysts for high-yield formic acid are heavy metals such as Pb, Hg and the like, which pollute the environment and are difficult to meet the requirements of high selectivity and high current density; the catalyst for high yield of CO is mainly noble metal such as Au, Ag and the like, is expensive and is difficult to meet the market application; high yield of CH4And C2H2When the catalyst is mainly metal Cu, the single product has poor selectivity.
Formic acidIs an important chemical raw material, can be used for synthesizing other chemical products, can also be used as a metal surface treating agent, a rubber auxiliary agent and an industrial solvent, and is widely used in the industries of pesticides, leather, dyes, medicines, rubber and the like. Therefore, the development of inexpensive and efficient catalysts for the conversion of CO2The electrochemical reduction to formic acid is of great significance.
Zn is a metal which is rich in earth crust, environment-friendly and cheap, and has the potential to convert CO2A catalyst for electrochemical reduction to CO, but with a higher overpotential. Bi is a metal slightly more expensive than Zn, but the price is much cheaper than that of the noble metal, and the metal is safe and nontoxic and can convert CO into CO2Electrochemical reduction to formic acid and CO, but selectivity is to be improved. By changing the composition and microstructure of the material, the catalytic performance can be improved. Therefore, by taking Zn and Bi metals as basic materials, a simple and efficient preparation method is developed to synthesize the ERC catalyst with low cost and high performance, and CO is improved2The selectivity of electrochemical reduction to formic acid is reduced, the overpotential of the formic acid is reduced, and the electrochemical reduction method has important research value and is an important step for converting the ERC into practical application in the future.
Disclosure of Invention
The invention provides a preparation method of a metal catalyst for electrochemical reduction of carbon dioxide, which is simple and efficient, has controllable conditions and is easy to operate. The surface of the catalyst is of a nano-flaky or granular polycrystalline structure, and Zn and Bi provide catalytic performance for the catalyst; the metal Zn is arranged in the catalyst, so that strength support and electrical conductivity are provided for the catalyst. The catalyst is used for electrochemical reduction of carbon dioxide, and has excellent selectivity and catalytic activity on a target product formic acid. The catalyst has low cost and can meet the requirement of large-scale commercial application.
The preparation method of the metal catalyst for electrochemical reduction of carbon dioxide comprises the following 6 steps: 1) using micro-and nano-Al successively2O3Grinding the zinc sheet by using powder, ultrasonically cleaning the zinc sheet by using ultrapure water and ethanol, and drying under the protection of inert gas; 2) putting the washed zinc sheet into a reaction kettle with a polytetrafluoroethylene sleeve inside, andadding Bi (NO) in a concentration of 0.01 to 2mM3)3The volume of the aqueous solution accounts for 20-80% of the volume of the autoclave, and the aqueous solution is kept stand at room temperature for 0.1-5 h; 3) putting the reaction kettle into a temperature-controlled oven, reacting for 2-24 hours at 160-200 ℃, and naturally cooling to room temperature; 4) taking out the zinc sheet, cleaning the zinc sheet with ultrapure water, putting the zinc sheet into a temperature-controlled oven, and drying the zinc sheet for 1-12 hours at the temperature of 60-150 ℃; 5) putting the dried zinc sheet in CO2Or one or more than two saturated salt solutions in inert atmosphere, and reducing for 0.5-4 h under the voltage of-1.2-2V vs SCE; (preferably CO)2In saturated salt solution of atmosphere, CO2Can be reduced on the surface of the catalyst to form bubbles, thereby regulating and controlling the surface appearance of the catalyst and improving the specific surface area of the catalyst); 6) and ultrasonically cleaning the reduced zinc sheet, and drying under the protection of inert gas.
The method comprises the following steps: 1) the thickness of the zinc sheet is 0.01-2 mm, and the optimal thickness is 0.1-0.2 mm;
the method comprises the following steps: 2) the zinc sheet is completely submerged in the solution. During the standing process, Bi (NO)3)3Reacting with Zn to displace part of Zn2+Dissolving in water solution, and forming metal Bi on the surface of the Zn sheet.
The method comprises the following steps: 3) the optimal reaction time is 6-12 hours, and during the optimal reaction time, the oxygen in the reaction kettle oxidizes the Zn metal and the Bi metal on the surface of the Zn sheet.
The method comprises the following steps: 4) in the drying process, Zn on the surface of the Zn sheet exists in the form of ZnO, and Bi finally exists in the form of Bi2O3Or Bi2O2CO3The form exists.
The method comprises the following steps: 5) the salt solution consists of cation Na+Or K+And anion Cl-Or SO4 2-Or CO3 2-Or HCO3 -Or PO4 3-Or NO3 -And (4) forming. In the electroreduction process, ZnO is reduced to metallic Zn, Bi2O3Or Bi2O2CO3Is reduced to metallic Bi, thereby forming a catalyst of ZnBi bimetallic polycrystalline structure.
The inert atmosphere is one or more of nitrogen, argon or helium gas.
The surface of the metal catalyst is of a nano-sheet or granular polycrystalline structure and provides catalytic performance for the catalyst, the metal catalyst comprises Zn and Bi, the diameter of the nano-sheet is 10-800 nm, the thickness of the nano-sheet is 3-100 nm, and the particle size of the nano-particles is 5 nm-1.5 mu m; the oxidation and reduction do not occur in the catalyst, and the catalyst is metallic Zn and provides strength support and conductivity for the catalyst.
The metal catalyst can be used for catalyzing electrochemical reduction reaction of carbon dioxide.
The invention has the following advantages and beneficial effects:
1) the preparation process has low cost, simple operation and high repeatability, and is suitable for large-scale production. The Bi and Zn elements contained in the catalyst are low in price and environment-friendly, and can meet the requirement of large-scale use.
2) The prepared catalyst is an electrode, can be directly used without being supported on other electrodes, and is simple and convenient.
3) The surface of the metal catalyst is of a nano-sheet or granular polycrystalline structure, and the structures have adjustable size and high specific surface area.
4) The high specific surface area increases the electrode and electrolyte and CO2The contact area of the gas effectively increases the reaction active area, thereby improving CO2The conversion efficiency of (a);
5) the polycrystalline structure has more crystal boundaries and can stabilize an intermediate product. Has synergistic effect on CO by bimetallic interface2The electrochemical reduction has higher catalytic activity and excellent selectivity to target products.
6) The existence of a small amount of Bi metal can greatly improve the selectivity of Zn to formic acid, obviously reduce the overpotential of Zn and reduce the cost. The Bi content can be adjusted by changing the preparation conditions, so that the selectivity of the product can be adjusted.
Applications of
The prepared catalyst is used as a catalyst for preparing formic acid by reducing carbon dioxide. Electrochemical testing was performed by a three-electrode system: the working electrode is the prepared catalyst; the counter electrode is a Pt sheet, and the reference electrode isHg/Hg2Cl2Saturated KCl (SCE). Salt bridges are used to reduce the liquid junction potential. Electrolyte is 0.5M NaHCO3Sol, the anolyte and the cathode are separated by a Nafion115 membrane. CO 22The flow is controlled by a flowmeter, and the flow rate is 60 ml/min; .
Drawings
FIG. 1 is an SEM image of an electrode prepared in example 1;
FIG. 2 XRD pattern of the electrode prepared in example 1;
FIG. 3 is an SEM photograph of an electrode prepared in example 2;
FIG. 4 is a graph comparing the selectivity to formic acid for the electrode prepared in example 1 and the electrode prepared in comparative example 1 at different potentials.
Detailed Description
The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.
Example 1
1. Preparation of metal catalyst:
1) taking a block with thickness of 0.1mm and area of 10cm2Zinc sheets with the mass purity of 99.99 percent are sequentially coated with 30 mu m-grade and 30 nm-grade Al2O3Grinding the zinc sheet by using the powder, ultrasonically cleaning the zinc sheet by using ultrapure water and ethanol, and drying under the protection of argon gas;
2) the washed zinc plate was placed in a reaction vessel with a Teflon liner and 60ml of Bi (NO) with a concentration of 0.8mM was added3)3Standing the aqueous solution at room temperature for 3 h;
3) putting the reaction kettle into a temperature-controlled oven, reacting for 12 hours at 180 ℃, and naturally cooling to room temperature;
4) taking out the zinc sheet, cleaning with ultrapure water, placing into a temperature-controlled oven, and drying at 80 ℃ for 4 h;
5) putting the dried zinc sheet in CO2Gas saturated 0.5M NaHCO3Reducing in salt solution for 3h under-1.5V vs SCE voltage;
6) and carrying out ultrasonic cleaning on the reduced zinc sheet, and drying under the protection of argon gas. 2. Metal catalyst pair CO2Performance of electrochemical reduction reactionEvaluation:
in an H-type electrolytic cell, 180ml and 100ml of 0.5M NaHCO are respectively added into a cathode cavity and an anode cavity3Aqueous solution, NF115 from DuPont was used as a diaphragm for the cathode and anode chambers. Wherein the CO of the cathode chamber2Gas enters from the lower end of the electrolytic cell and generates CO on the surface of the working electrode2And after the electrochemical reduction reaction, discharging the reaction product from an outlet at the upper end of the cathode cavity. Before testing, the cathode chamber was first charged with 99.995% pure CO2Gas, CO2The flow rate of (2) was controlled to 20 sccm. After 1h, a metal catalyst is used as a working electrode, a Pt sheet is used as a counter electrode, and a saturated calomel electrode is used as a reference electrode. CO 22And after the electrochemical reduction reaction is carried out for 15min, introducing reaction tail gas into a gas chromatography to carry out quantitative detection on a gas product, and carrying out quantitative analysis on a liquid product by adopting an ion chromatography. Under the potential of-1.47 Vvs SCE, the selectivity of formic acid is the highest and can reach 94%; as can be seen from the SEM image of FIG. 1, the prepared electrode has nanoparticles on the surface, the particle size is 100nm-1.5 μm, and the molar content of Bi element is 20%. XRD showed that the composition of the electrode was metal Bi and metal Zn.
Example 2
1. Preparation of metal catalyst:
1) taking a block with thickness of 0.1mm and area of 8cm2Zinc sheets with purity of 99.99% are prepared by using 100 mu m-grade and 500 nm-grade Al2O3Grinding the zinc sheet by using the powder, ultrasonically cleaning the zinc sheet by using ultrapure water and ethanol, and drying under the protection of argon gas;
2) the washed zinc plate was placed in a reaction vessel with a Teflon liner and 80ml of Bi (NO) with a concentration of 0.1mM was added3)3Standing the aqueous solution at room temperature for 1 h;
3) putting the reaction kettle into a temperature-controlled oven, reacting for 10 hours at 170 ℃, and naturally cooling to room temperature;
4) taking out the zinc sheet, cleaning with ultrapure water, placing into a temperature-controlled oven, and drying at 70 deg.C for 4 h;
5) placing the dried zinc sheet in 0.5M KHCO saturated with nitrogen gas3Reducing in salt solution for 3h under-1.4V vs SCE voltage;
6) and carrying out ultrasonic cleaning on the reduced zinc sheet, and drying under the protection of argon gas. 2. Metal catalyst pair CO2Evaluation of performance of electrochemical reduction reaction:
in an H-type electrolytic cell, 180ml and 100ml of 0.5M NaHCO are respectively added into a cathode cavity and an anode cavity3Aqueous solution, NF115 from DuPont was used as a diaphragm for the cathode and anode chambers. Wherein the gas in the cathode chamber enters from the lower end of the electrolytic cell and generates CO on the surface of the working electrode2And after the electrochemical reduction reaction, discharging the reaction product from an outlet at the upper end of the cathode cavity. Before testing, the cathode chamber was first charged with 99.995% pure CO2Gas, CO2The flow rate of (2) was controlled to 20 sccm. After 1h, a metal catalyst is used as a working electrode, a Pt sheet is used as a counter electrode, and a saturated calomel electrode is used as a reference electrode. CO 22And after the electrochemical reduction reaction is carried out for 15min, introducing reaction tail gas into a gas chromatography to carry out quantitative detection on a gas product, and carrying out quantitative analysis on a liquid product by adopting an ion chromatography. The highest selectivity to formic acid, up to 72%, is achieved at a potential of-1.67V vsSCE. According to an SEM image, the prepared electrode surface is a nano sheet, the diameter of the nano sheet is 30-110 nm, the thickness of the nano sheet is 10-30 nm, and the molar content of Bi element is 3%.
Example 3
1. Preparation of metal catalyst:
1) taking a block with thickness of 0.1mm and area of 5cm2Zinc sheet with purity of 99.99% is prepared by using 50 μm grade and 100nm grade Al2O3Grinding the zinc sheet by using the powder, ultrasonically cleaning the zinc sheet by using ultrapure water and ethanol, and drying under the protection of argon gas;
2) the washed zinc plate is put into a reaction kettle with a polytetrafluoroethylene sleeve, and 70ml of Bi (NO) with the concentration of 0.01mM is added3)3Standing the aqueous solution at room temperature for 5 h;
3) putting the reaction kettle into a temperature-controlled oven, reacting for 15 hours at 180 ℃, and naturally cooling to room temperature;
4) taking out the zinc sheet, cleaning with ultrapure water, placing into a temperature-controlled oven, and drying at 70 deg.C for 5 h;
5) drying the zinc sheetPlacing in 0.2M Na saturated by argon gas2SO4Reducing in salt solution for 3h under-1.5V vs SCE voltage;
6) and carrying out ultrasonic cleaning on the reduced zinc sheet, and drying under the protection of argon gas.
The prepared electrode is provided with nanosheets on the surface, the diameter of each nanosheet is 500-700 nm, the thickness of each nanosheet is 60-80 nm, and the molar content of Bi is 1%.
2. Metal catalyst pair CO2Evaluation of performance of electrochemical reduction reaction:
in an H-type electrolytic cell, 180ml and 100ml of 0.5M NaHCO are respectively added into a cathode cavity and an anode cavity3Aqueous solution, NF115 from DuPont was used as a diaphragm for the cathode and anode chambers. Wherein the gas in the cathode chamber enters from the lower end of the electrolytic cell and generates CO on the surface of the working electrode2And after the electrochemical reduction reaction, discharging the reaction product from an outlet at the upper end of the cathode cavity. Before testing, the cathode chamber was first charged with 99.995% pure CO2Gas, CO2The flow rate of (2) was controlled to 20 sccm. After 1h, a metal catalyst is used as a working electrode, a Pt sheet is used as a counter electrode, and a saturated calomel electrode is used as a reference electrode. CO 22And after the electrochemical reduction reaction is carried out for 15min, introducing reaction tail gas into a gas chromatography to carry out quantitative detection on a gas product, and carrying out quantitative analysis on a liquid product by adopting an ion chromatography. At a potential of-1.77V vsSCE, formic acid selectivity was the highest, reaching 61%.
Example 4
1. Preparation of metal catalyst:
1) taking a block with thickness of 0.2mm and area of 25cm2The zinc sheet with the purity of 99.99 percent is prepared by using 50 mu m-grade and 50 nm-grade Al2O3Grinding the zinc sheet by using the powder, ultrasonically cleaning the zinc sheet by using ultrapure water and ethanol, and drying under the protection of argon gas;
2) the washed zinc plate was placed in a reaction vessel with a Teflon liner and 50ml of 2mM Bi (NO) was added3)3Standing the aqueous solution at room temperature for 2 h;
3) putting the reaction kettle into a temperature-controlled oven, reacting for 10 hours at 190 ℃, and naturally cooling to room temperature;
4) taking out the zinc sheet, cleaning with ultrapure water, placing into a temperature-controlled oven, and drying at 90 ℃ for 4 h;
5) putting the dried zinc sheet into 0.5M KNO saturated by nitrogen gas3Reducing for 2h in a salt solution under the SCE voltage of-1.5V vs;
6) and carrying out ultrasonic cleaning on the reduced zinc sheet, and drying under the protection of argon gas.
The surface of the prepared electrode is provided with nano particles, the particle size of the nano particles is 1-1.4 mu m, and the molar content of Bi element is 8%.
2. Metal catalyst pair CO2Evaluation of performance of electrochemical reduction reaction:
in an H-type electrolytic cell, 180ml and 100ml of 0.5M NaHCO are respectively added into a cathode cavity and an anode cavity3Aqueous solution, NF115 from DuPont was used as a diaphragm for the cathode and anode chambers. Wherein the gas in the cathode chamber enters from the lower end of the electrolytic cell and generates CO on the surface of the working electrode2And after the electrochemical reduction reaction, discharging the reaction product from an outlet at the upper end of the cathode cavity. Before testing, the cathode chamber was first charged with 99.995% pure CO2Gas, CO2The flow rate of (2) was controlled to 20 sccm. After 1h, a metal catalyst is used as a working electrode, a Pt sheet is used as a counter electrode, and a saturated calomel electrode is used as a reference electrode. CO 22And after the electrochemical reduction reaction is carried out for 15min, introducing reaction tail gas into a gas chromatography to carry out quantitative detection on a gas product, and carrying out quantitative analysis on a liquid product by adopting an ion chromatography. The selectivity to formic acid was 69%. At a potential of-1.87V vs SCE, the selectivity to formic acid is highest, reaching 69%.
Comparative example 1
In the same way, but without the addition of Bi (NO)3)3The prepared Zn catalyst is as follows:
1. preparation of metal catalyst:
1) taking a block with thickness of 0.1mm and area of 10cm2Zinc sheets with purity of 99.99% are prepared by using 30 μm-grade and 30 nm-grade Al2O3Grinding the zinc sheet by using the powder, ultrasonically cleaning the zinc sheet by using ultrapure water and ethanol, and drying under the protection of argon gas;
2) placing the washed zinc sheet into a reaction kettle with a polytetrafluoroethylene sleeve inside, adding 60ml of ultrapure water, and standing for 3 hours at room temperature;
3) putting the reaction kettle into a temperature-controlled oven, reacting for 12 hours at 180 ℃, and naturally cooling to room temperature;
4) taking out the zinc sheet, cleaning with ultrapure water, placing into a temperature-controlled oven, and drying at 80 ℃ for 4 h;
5) putting the dried zinc sheet in CO2Gas saturated 0.5M NaHCO3Reducing in salt solution for 3h under-1.5V vs SCE voltage;
6) and carrying out ultrasonic cleaning on the reduced zinc sheet, and drying under the protection of argon gas.
2. Metal catalyst pair CO2Evaluation of performance of electrochemical reduction reaction:
in an H-type electrolytic cell, 180ml and 100ml of 0.5M NaHCO are respectively added into a cathode cavity and an anode cavity3Aqueous solution, NF115 from DuPont was used as a diaphragm for the cathode and anode chambers. Wherein the gas in the cathode chamber enters from the lower end of the electrolytic cell and generates CO on the surface of the working electrode2And after the electrochemical reduction reaction, discharging the reaction product from an outlet at the upper end of the cathode cavity. Before testing, the cathode chamber was first charged with 99.995% pure CO2Gas, CO2The flow rate of (2) was controlled to 20 sccm. After 1h, a metal catalyst is used as a working electrode, a Pt sheet is used as a counter electrode, and a saturated calomel electrode is used as a reference electrode. CO 22And after the electrochemical reduction reaction is carried out for 15min, introducing reaction tail gas into a gas chromatography to carry out quantitative detection on a gas product, and carrying out quantitative analysis on a liquid product by adopting an ion chromatography. The selectivity to formic acid was only 1% at a potential of-1.47V vs SCE and only 5% at a potential of-1.67V vs SCE.
As can be seen, the electrode prepared in the embodiment 1 of the invention has the highest formic acid selectivity (Faraday efficiency) which can reach 94% under the potential of-1.47V vs SCE; whereas the electrode prepared in comparative example 1 had a formic acid selectivity of only 1%.
Comparative example 2
By hydrothermal method with Bi (NO)3)3Bi catalyst prepared by raw materials:
1. preparation of metal catalyst:
1) 60ml of Bi (NO) with a concentration of 0.8mM was added to the hydrothermal reactor3)3An aqueous solution;
3) putting the reaction kettle into a temperature-controlled oven, reacting for 12 hours at 180 ℃, and naturally cooling to room temperature;
4) centrifuging the precipitate and the solution in the reaction kettle, washing the obtained solid with ultrapure water, putting the washed solid into an oven, and drying the solid at the temperature of 80 ℃ for 4 hours;
5) loading the dried solid on a glassy carbon electrode, and placing the glassy carbon electrode on CO2Gas saturated 0.5M NaHCO3Reducing in salt solution for 3h under-1.5V vs SCE voltage;
2. metal catalyst pair CO2Evaluation of performance of electrochemical reduction reaction:
in an H-type electrolytic cell, 180ml and 100ml of 0.5M NaHCO are respectively added into a cathode cavity and an anode cavity3Aqueous solution, NF115 from DuPont was used as a diaphragm for the cathode and anode chambers. Wherein the gas in the cathode chamber enters from the lower end of the electrolytic cell and generates CO on the surface of the working electrode2And after the electrochemical reduction reaction, discharging the reaction product from an outlet at the upper end of the cathode cavity. Before testing, the cathode chamber was first charged with 99.995% pure CO2Gas, CO2The flow rate of (2) was controlled to 20 sccm. After 1h, a metal catalyst is used as a working electrode, a Pt sheet is used as a counter electrode, and a saturated calomel electrode is used as a reference electrode. CO 22And after the electrochemical reduction reaction is carried out for 15min, introducing reaction tail gas into a gas chromatography to carry out quantitative detection on a gas product, and carrying out quantitative analysis on a liquid product by adopting an ion chromatography. The formic acid selectivity is only 17% at a potential of-1.47V vsSCE, and is the highest, up to 34%, at a potential of-1.67 Vvs SCE.
Comparative example 3
Combining the catalysts in comparative example 1 and comparative example 2:
1. preparation of metal catalyst:
1) the solid obtained in the preparation step 4) in the comparative example 2 is loaded on the surface of the zinc sheet obtained in the preparation step 4) in the comparative example 1, and is placed in CO2Gas saturated 0.5M NaHCO3In a salt solutionReducing for 3h under the SCE voltage of-1.5V vs;
2) and carrying out ultrasonic cleaning on the reduced zinc sheet, and drying under the protection of argon gas. 2. Metal catalyst pair CO2Evaluation of performance of electrochemical reduction reaction:
in an H-type electrolytic cell, 180ml and 100ml of 0.5M NaHCO are respectively added into a cathode cavity and an anode cavity3Aqueous solution, NF115 from DuPont was used as a diaphragm for the cathode and anode chambers. Wherein the gas in the cathode chamber enters from the lower end of the electrolytic cell and generates CO on the surface of the working electrode2And after the electrochemical reduction reaction, discharging the reaction product from an outlet at the upper end of the cathode cavity. Before testing, the cathode chamber was first charged with 99.995% pure CO2Gas, CO2The flow rate of (2) was controlled to 20 sccm. After 1h, a metal catalyst is used as a working electrode, a Pt sheet is used as a counter electrode, and a saturated calomel electrode is used as a reference electrode. CO 22And after the electrochemical reduction reaction is carried out for 15min, introducing reaction tail gas into a gas chromatography to carry out quantitative detection on a gas product, and carrying out quantitative analysis on a liquid product by adopting an ion chromatography. The formic acid selectivity was only 8% at a potential of-1.47V vs SCE, and was highest at-1.67V vs SCE, up to 25%.
The performance of the catalyst prepared by the invention is compared with that of the catalyst prepared by the comparative example, so that the selectivity of formic acid in the electrochemical reduction of carbon dioxide is obviously improved.

Claims (8)

1.一种二氧化碳电化学还原用金属催化剂制备方法，包括如下四个步骤：1. a metal catalyst preparation method for electrochemical reduction of carbon dioxide, comprising the following four steps: 1)先后用30-100μm级和30-500nm级Al2O3粉末对锌片进行打磨，再分别用超纯水和乙醇对锌片进行超声清洗，并在惰性气体保护下进行干燥；1) Use 30-100μm grade and 30-500nm grade Al 2 O 3 powder to grind the zinc flakes successively, then ultrasonically clean the zinc flakes with ultrapure water and ethanol respectively, and dry them under the protection of inert gas; 2)将洗好的锌片置于反应釜中，加入浓度为0.01～2mM的Bi(NO3)3水溶液，室温下静置0.1～5h；优选Bi(NO3)3水溶液浓度0.1-0.8mM；2) Place the washed zinc flakes in the reactor, add Bi(NO 3 ) 3 aqueous solution with a concentration of 0.01-2 mM, and let stand for 0.1-5 h at room temperature; preferably the concentration of Bi(NO 3 ) 3 aqueous solution is 0.1-0.8 mM ; 3)在反应釜中于160～200℃下反应2～24h后自然降温至室温；3) in the reactor at 160～200 ℃, the temperature is naturally cooled to room temperature after 2～24h reaction; 4)将锌片取出，用超纯水清洗后放入烘箱中，在60～150℃下干燥1～12h；4) Take out the zinc flakes, wash them with ultrapure water, put them in an oven, and dry them at 60～150℃ for 1～12h; 5)将干燥后的锌片置于CO2或惰性气氛中一种或二种以上饱和的盐溶液中，在-1.2～-2V vs SCE电压下还原0.5～4h；5) Put the dried zinc flakes in one or more saturated salt solutions in CO 2 or inert atmosphere, and reduce at -1.2～-2V vs SCE voltage for 0.5～4h; 6)将还原后的锌片超声清洗，并在惰性气体保护下进行干燥。6) Ultrasonic cleaning of the reduced zinc flakes, and drying under the protection of inert gas. 2.按照权利要求1所述的制备方法，其特征在于：步骤1)所述的锌片厚度为0.01～2mm，优选0.1～1mm；面积为1～100cm2，优选5～20cm2。2 . The preparation method according to claim 1 , wherein the thickness of the zinc sheet in step 1) is 0.01-2 mm, preferably 0.1-1 mm, and the area is 1-100 cm 2 , preferably 5-20 cm 2 . 3.按照权利要求1所述的制备方法，其特征在于：步骤2)所述锌片完全淹没在溶液中。3. The preparation method according to claim 1, characterized in that: the zinc flakes in step 2) are completely submerged in the solution. 4.按照权利要求1所述的制备方法，其特征在于：步骤5)所述饱和盐溶液中阳离子为Na+或/和K+，阴离子为Cl-、SO4 2-、CO3 2-、HCO3 -、PO4 3-、NO3 -中的一种或二种以上。4. preparation method according to claim 1 is characterized in that: in step 5) described saturated salt solution, cation is Na + or/and K + , and anion is Cl - , SO 4 2- , CO 3 2- , One or more of HCO 3 - , PO 4 3- and NO 3 - . 5.按照权利要求1所述的制备方法，所述的惰性气氛为氮气、氩气、氦气中的一种或二种以上混合。5. The preparation method according to claim 1, wherein the inert atmosphere is a mixture of one or more of nitrogen, argon and helium. 6.一种权利要求1-5任一所述制备方法制备的金属催化剂，其特征在于：生成的催化剂附着于锌片外表面，催化剂为纳米片状或纳米颗粒结构中的一种或二种，其元素组成为Zn、Bi两种元素，催化剂中Bi元素的摩尔含量为0.01％～40％，优选1％～20％。6. a metal catalyst prepared by the arbitrary described preparation method of claim 1-5, it is characterized in that: the catalyst that generates is attached to the outer surface of the zinc sheet, and the catalyst is one or two in nano-sheet or nano-particle structure , its element composition is Zn and Bi, and the molar content of Bi element in the catalyst is 0.01% to 40%, preferably 1% to 20%. 7.按照权利要求6所述的金属催化剂，其特征在于：纳米片的直径为10～800nm，厚度为3～100nm，纳米颗粒的粒径为5nm～1.5μm；催化剂内部未发生氧化还原，为金属Zn。7. The metal catalyst according to claim 6, wherein the diameter of the nano-sheet is 10-800 nm, the thickness is 3-100 nm, and the particle size of the nano-particle is 5 nm-1.5 μm; no redox occurs inside the catalyst, which is Metal Zn. 8.一种权利要求6或7所述金属催化剂用于电催化二氧化碳还原反应。8. A metal catalyst according to claim 6 or 7 is used for electrocatalytic carbon dioxide reduction reaction.
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