CN109675586B - Catalyst for preparing formic acid by electro-reduction of carbon dioxide and preparation method thereof - Google Patents

Catalyst for preparing formic acid by electro-reduction of carbon dioxide and preparation method thereof Download PDF

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CN109675586B
CN109675586B CN201811597998.2A CN201811597998A CN109675586B CN 109675586 B CN109675586 B CN 109675586B CN 201811597998 A CN201811597998 A CN 201811597998A CN 109675586 B CN109675586 B CN 109675586B
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formic acid
catalyst
carbon dioxide
carbon
carbon material
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CN109675586A (en
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谢顺吉
马文超
张庆红
王野
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Xiamen University
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/057—Selenium or tellurium; Compounds thereof
    • B01J27/0573—Selenium; Compounds thereof
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/057—Selenium or tellurium; Compounds thereof
    • B01J27/0576—Tellurium; Compounds thereof
    • 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
    • C—CHEMISTRY; METALLURGY
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides

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Abstract

A catalyst for preparing formic acid by electro-reduction of carbon dioxide and a preparation method thereof belong to the field of electro-catalysis, and the catalyst is a metal electro-catalyst doped with a chalcogen element, wherein the chalcogen element comprises at least one of sulfur, selenium and tellurium, and the metal comprises at least one of indium, tin, lead and bismuth; the preparation method comprises the following steps: 1) dissolving a simple substance of the chalcogen or a compound of the chalcogen and metal salt in N, N-dimethylformamide, then putting the carbon material into an autoclave, and transferring the carbon material into the autoclave for solvent heat treatment; 2) and (3) taking out the carbon material after the heat treatment of the solvent is finished, washing the carbon material by using deionized water, drying to obtain a precursor of the chalcogen element doped metal oxide loaded on the carbon material, and then performing electro-reduction to obtain the chalcogen element doped metal electrocatalyst loaded on the carbon material. The catalyst is applied to the reaction of preparing formic acid by electro-reduction of carbon dioxide, has high reaction activity, high selectivity and stable catalytic performance, and maintains high formic acid selectivity in a wide current range.

Description

Catalyst for preparing formic acid by electro-reduction of carbon dioxide and preparation method thereof
Technical Field
The invention belongs to the field of electrocatalysis, and particularly relates to a catalyst for preparing formic acid by electroreduction of carbon dioxide and a preparation method thereof.
Background
The carbon dioxide is catalytically converted into chemicals or fuels with high added values, so that waste materials can be changed into valuable materials, the emission of the carbon dioxide is reduced, renewable energy sources can be converted into fuels with high energy density for storage, and the method has important practical significance. Electrical energy can be generated from renewable energy sources such as solar and wind, and has the advantages of being clean, mild, sustainable, and the like. Therefore, the electrochemical method for converting carbon dioxide into important fuels or chemicals is one of the most attractive ways to realize the resource utilization of carbon dioxide.
Formic acid is the most economically viable product by comparing the energy input costs and market price of the different products of the electro-reduction of carbon dioxide (e.g., carbon monoxide, methane, formic acid, ethane, ethylene, etc.). Furthermore, formic acid is an important industrial raw material, plays an important role in pharmacy, leather and paper making, and can be used as a hydrogen carrier for a direct formic acid fuel cell.
At present, the main challenge of preparing formic acid by electrically reducing carbon dioxide is to develop an electrocatalyst with high activity, high selectivity and high stability. Although some catalysts have been able to achieve higher carbon dioxide reduction selectivity by modulating the catalyst structure, morphology, composition, etc., the high selectivity is very sensitive to applied current and potential. Due to high current density (>60mA cm-2) The hydrogen evolution reaction activity of the competitive reaction is improved, and the Faraday efficiency of the formic acid is obviously reduced, so that the generation rate of the formic acid is difficult to break through 1000 mu mol h-1cm-2。
Therefore, it is very important to develop a catalyst which can significantly improve the activity of preparing formic acid by electro-reduction of carbon dioxide while maintaining high selectivity and stability of formic acid.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a catalyst for preparing formic acid by electrically reducing carbon dioxide and a preparation method thereof, wherein the catalyst has high reaction activity, high selectivity and stable catalytic performance, and maintains high formic acid selectivity in a wide current range.
In order to achieve the purpose, the invention adopts the following technical scheme:
the catalyst for preparing the formic acid by electrically reducing the carbon dioxide is a metal electrocatalyst doped with chalcogen, the chalcogen comprises at least one of sulfur, selenium and tellurium, and the metal comprises at least one of indium, tin, lead and bismuth; the mol percentage of the content of the chalcogen element is 0.01 percent to 25 percent.
The preparation method of the catalyst for preparing the formic acid by electrically reducing the carbon dioxide comprises the following steps:
1) firstly, dissolving a simple substance of a chalcogen element or a compound of the chalcogen element and a metal salt in N, N-dimethylformamide, then putting a carbon material into the N, N-dimethylformamide, and finally transferring the N, N-dimethylformamide into a polytetrafluoroethylene-lined stainless steel autoclave for solvent heat treatment;
2) and after the solvent heat treatment is finished, taking out the carbon material, washing with deionized water, and drying to obtain a precursor of the chalcogen element doped metal oxide loaded on the carbon material, and then performing electro-reduction to obtain the chalcogen element doped metal electrocatalyst loaded on the carbon material.
The carbon material includes at least one of carbon paper, carbon cloth, graphite sheet, carbon foam, and carbon nanotube. More preferably, the carbon material is carbon paper.
The compound of the chalcogen element is selected from at least one of sulfur powder, thiourea, sodium sulfide, thioacetamide, selenium powder, sodium selenite, tellurium powder and tellurite.
The metal salt is selected from at least one of chloride, nitrate and acetylacetonate of indium, tin, lead and bismuth.
The temperature of the solvent heat treatment is 130-200 ℃, the time of the solvent heat treatment is 12-48 h, and the electric reduction treatment potential is-0.98V vs.
The content of the chalcogen element in the chalcogen element doped metal electrocatalyst can be realized by changing the charge ratio of simple substances of the chalcogen element or compounds of the chalcogen element and metal salts.
The catalyst for preparing the formic acid by electrically reducing the carbon dioxide is applied to preparing the formic acid by electrically reducing the carbon dioxide, the reaction is carried out in an H-shaped electrolytic cell, the metal electrocatalyst doped with the chalcogen element is used as a cathode, a Pt sheet or graphite is used as an anode, a saturated calomel electrode is used as a reference electrode, the carbon dioxide is introduced into a cathode electrolyte at a certain flow rate, and a negative potential is applied to carry out electrolysis, so that the formic acid is prepared.
The flow rate of carbon dioxide is 5-100 mL min-1(ii) a The electrolyte comprises NaHCO3、KHCO3、CsHCO3And K2SO4At least one of them, the concentration of the electrolyte is 0.1-2M; the negative potential is-0.33 to-1.23V vs.
The electrochemical reaction in the present invention includes:
cathodic reaction of CO2+H2O+2e-→HCOO-+OH-；
Anodic reaction of 4OH-→O2+2H2O+4e-；
Total reaction 2CO2+2OH-→2HCOO-+O2。
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
the preparation method of the catalyst is simple and easy to implement; compared with the existing system for preparing formic acid by electroreduction, the catalyst of the invention has high reaction activity, high selectivity and stable catalytic performance, and maintains high formic acid selectivity in a wide current range.
In the existing electric reduction carbon dioxide system, the promotion of the activation of water leads to the competition reaction of the reduction reaction of carbon dioxide, and the aggravation of the reduction reaction of hydrogen evolution by water, thereby reducing the selectivity of the reduction of carbon dioxide. The invention realizes the high-efficiency activation of water by doping the chalcogen element, but does not remarkably promote hydrogen production, maintains high carbon dioxide reduction selectivity while promoting the water activation, and remarkably improves the activity of formic acid preparation.
Drawings
FIG. 1 is a scanning electron micrograph of a 4.9% sulfur-doped indium metal electrocatalyst;
FIG. 2 is a nuclear magnetic hydrogen spectrum of a reaction product of preparing formic acid from carbon dioxide;
fig. 3 is a graph of formic acid selectivity for 4.9% sulfur-doped indium metal at different current densities.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects of the present invention clearer and clearer, the present invention is further described in detail below with reference to the accompanying drawings and embodiments.
In the following embodiments, the molar amount of the chalcogen or the chalcogen compound may be 0 to 0.4 mmol; the molar amount of the metal salt is 0.4 to 3mmol, and the volume of DMF is 10 to 100 mL.
Example 1
Mu. mol thioacetamide and 0.4mmol InCl are added3Dissolved in 15mL of DMF, stirred vigorously for 15min and transferred to 25mL of polytetrafluoro-ethyleneThe stainless steel autoclave with the inner lining was placed in a clean 1X 3cm autoclave2Sealing the carbon paper, and heating at 150 ℃ for 12 h; cooling, taking out the carbon paper, washing with deionized water, and drying to obtain S-doped In loaded on the carbon paper2O3A precursor; finally, the temperature is controlled at 0.5M KHCO3Performing electrical reduction In electrolyte at-0.98V vs. RHE for 5min to obtain 4.9 mol% S-doped In metal electrocatalyst (S-In) loaded on carbon paper, wherein the S-doped In metal electrocatalyst is a scanning electron microscope image of 4.9% S-doped In metal electrocatalyst, and the S-doped In metal electrocatalyst has a particle size of about 130nm and is uniformly loaded on carbon fibers of the carbon paper as shown In FIG. 1. The catalyst is used as a cathode, a Pt sheet is used as an anode, a saturated calomel electrode is used as a reference electrode, the reaction is carried out in an H-shaped electrolytic cell, and the cathode chamber and the anode chamber are both 30mL of 0.5MKHCO3An electrolyte; carbon dioxide at a certain rate of 20mL min-1Introducing the mixture into the catholyte at a flow rate, applying a potential of-0.98V to react for 1h, wherein the generation rate of the formic acid is 1002 mu mol h-1cm-2The Faraday efficiency was 93%. FIG. 2 is a nuclear magnetic hydrogen spectrum of a reaction product of preparing formic acid from carbon dioxide, and the formic acid is quantified using dimethyl sulfoxide as an internal standard.
As shown In FIG. 3, the potential applied to the S-In catalyst was changed to-0.83 to-1.23V vs. RHE, and the current density was 25 to 100mAcm-2And the quantitative analysis of nuclear magnetic hydrogen spectrum shows that the Faraday efficiency of formic acid is maintained to be more than 85%.
Example 2
Mu. mol thioacetamide and 0.4mmol InCl are added3Dissolving in 15mL of DMF, and stirring vigorously for 15 min; then transferred to a 25mL Teflon lined stainless steel autoclave and placed in a clean 1X 3cm2Sealing the carbon paper, and heating at 150 ℃ for 12 h; cooling, taking out the carbon paper, washing with deionized water, and drying to obtain S-doped In loaded on the carbon paper2O3A precursor; finally, the temperature is controlled at 0.5M KHCO3And performing electrical reduction on the electrolyte for 5min at-0.98V vs. RHE to obtain the 4.9 mol% S-doped In metal electrocatalyst (S-In) loaded on the carbon paper. The catalyst is used as a cathode, a Pt sheet is used as an anode, and a saturated calomel electrode is used as a reference electrode; the reaction was carried out in an H-type electrolytic cell, with 30mL of 0.5M CsHCO in both the cathode and anode chambers3An electrolyte; carbon dioxide in a certain amount of 20mLmin-1Introducing the mixture into the catholyte at a flow rate, and applying a-0.98V vs. RHE potential for reaction for 1 h; the current density is 84mAcm-2Quantitative nuclear magnetic hydrogen spectrum analysis shows that the Faraday efficiency of the formic acid is 93 percent, and the generation rate is 1449 mu mol h-1cm-2。
Example 3
Mu. mol thioacetamide and 0.4mmol InCl are added3Dissolving in 15mL of DMF, and stirring vigorously for 15 min; then transferred to a 25mL Teflon lined stainless steel autoclave and placed in a clean 1X 3cm2Sealing the carbon cloth, and heating at 150 ℃ for 12 h; cooling, taking out the carbon cloth, washing with deionized water, and drying to obtain S-doped In loaded on the carbon cloth2O3A precursor; finally, the temperature is controlled at 0.5M KHCO3And performing electrical reduction on the electrolyte for 5min at-0.98V vs. RHE to obtain the 4.9 mol% S-doped In metal electrocatalyst (S-In) loaded on the carbon cloth. The catalyst is used as a cathode, a Pt sheet is used as an anode, and a saturated calomel electrode is used as a reference electrode; the reaction was carried out in an H-type electrolytic cell, with 30mL of 0.5M KHCO in both the cathode and anode chambers3An electrolyte; carbon dioxide at a certain rate of 20mL min-1Introducing the mixture into the catholyte at a flow rate, and applying a-0.98V vs. RHE potential for reaction for 1 h; the current density is 35mAcm-2Quantitative nuclear magnetic hydrogen spectrum analysis shows that the Faraday efficiency of the formic acid is 92 percent, and the generation rate is 601 mu mol h-1cm-2。
Example 4
Mu. mol thioacetamide and 0.4mmol InCl are added3Dissolving in 15mL of DMF, and stirring vigorously for 15 min; then transferred to a 25mL Teflon lined stainless steel autoclave and placed in a clean 1X 3cm2Sealing the graphite sheet, and heating at 150 ℃ for 12 h; taking out the graphite flake after cooling, washing with deionized water, and drying to obtain S-doped In loaded by the graphite flake2O3A precursor; finally, the temperature is controlled at 0.5M KHCO3And performing electrical reduction on the electrolyte for 5min at-0.98V vs. RHE to obtain the graphite flake-loaded 4.9 mol% S-doped In metal electrocatalyst (S-In). The catalyst is used as a cathode, a graphite rod is used as an anode, and a saturated calomel electrode is used as a reference electrode; the reaction was carried out in an H-type electrolytic cell, with 30mL of 0.5M KHCO in both the cathode and anode chambers3An electrolyte; dioxygenChanging carbon for a certain period of 20mL min-1Introducing the mixture into the catholyte at a flow rate, and applying a-0.98V vs. RHE potential for reaction for 1 h; the current density is 16mAcm-2Quantitative analysis of nuclear magnetic hydrogen spectrum shows that the Faraday efficiency of formic acid is 88 percent, and the generation rate is 265 mu mol h-1cm-2。
Example 5
Firstly, 16 mu mol of selenium powder and 0.4mmol of InCl3Dissolving in 15mL of DMF, and stirring vigorously for 15 min; then transferred to a 25mL Teflon lined stainless steel autoclave and placed in a clean 1X 3cm2Sealing the carbon paper, and heating at 150 ℃ for 12 h; cooling, taking out the carbon paper, washing with deionized water, and drying to obtain Se-doped In loaded on the carbon paper2O3A precursor; finally, the temperature is controlled at 0.5M KHCO3Performing electrical reduction on the electrolyte for 5min at-0.98V vs. RHE to obtain the Se-doped In metal electrocatalyst (Se-In) loaded on the carbon paper. The catalyst is used as a cathode, a Pt sheet is used as an anode, and a saturated calomel electrode is used as a reference electrode; the reaction was carried out in an H-type electrolytic cell, with 30mL of 0.5M KHCO in both the cathode and anode chambers3An electrolyte; carbon dioxide at a given concentration of 20mLmin-1Introducing the mixture into the catholyte at a flow rate, and applying a-0.98V vs. RHE potential for reaction for 1 h; the current density was 50mA cm-2Quantitative nuclear magnetic hydrogen spectrum analysis shows that the Faraday efficiency of formic acid is 90%, and the generation rate is 841 mu mol h-1cm-2。
Example 6
Firstly 16. mu. mol of H2TeO4And 0.4mmol of InCl3Dissolving in 15mL of DMF, and stirring vigorously for 15 min; then transferred to a 25mL Teflon lined stainless steel autoclave and placed in a clean 1X 3cm2Sealing the carbon paper, and heating at 150 ℃ for 12 h; cooling, taking out the carbon paper, washing with deionized water, and drying to obtain Te doped In loaded on the carbon paper2O3A precursor; finally, the temperature is controlled at 0.5M KHCO3Performing electrical reduction for 5min In the electrolyte at-0.98V vs. RHE to obtain the Te doped In metal electrocatalyst (Te-In) loaded on the carbon paper. The catalyst is used as a cathode, a Pt sheet is used as an anode, and a saturated calomel electrode is used as a reference electrode; the reaction was carried out in an H-type electrolytic cell, with 30mL of 0.5M KHCO in both the cathode and anode chambers3An electrolyte; dioxygenThe carbon is changed by a certain amount of 20mLmin-1Introducing the mixture into the catholyte at a flow rate, and applying a-0.98V vs. RHE potential for reaction for 1 h; the current density was 41mA cm-2Quantitative nuclear magnetic hydrogen spectrum analysis shows that the Faraday efficiency of the formic acid is 89%, and the generation rate is 676 mu mol h-1cm-2。
Example 7
Mu.mol thioacetamide and 20 mu.L SnCl are firstly added4Dissolving in 12mL DMF, and stirring vigorously for 15 min; then transferred to a 15mL Teflon lined stainless steel autoclave and placed in a clean 1X 3cm2Sealing the carbon paper, and heating at 180 ℃ for 24 hours; cooling, taking out the carbon paper, washing with deionized water, and drying to obtain S-doped SnO loaded on the carbon paper2A precursor; finally, the temperature is controlled at 0.5M KHCO3And performing electrical reduction on the electrolyte for 5min at-1.23V vs. RHE to obtain the carbon paper supported S-doped Sn metal electrocatalyst (S-Sn). The catalyst is used as a cathode, a Pt sheet is used as an anode, and a saturated calomel electrode is used as a reference electrode; the reaction was carried out in an H-type electrolytic cell, with 30mL of 0.5M KHCO in both the cathode and anode chambers3An electrolyte; carbon dioxide at a given concentration of 20mLmin-1Introducing the mixture into the catholyte at a flow rate, and applying a-0.98V vs. RHE potential for reaction for 1 h; the current density was 43mA cm-2Quantitative nuclear magnetic hydrogen spectrum analysis shows that the Faraday efficiency of the formic acid is 81 percent, and the generation rate is 640 mu mol h-1cm-2。
Example 8
Mu. mol thioacetamide 6 and BiCl 0.2mmol3Dissolving in 12mL DMF, and stirring vigorously for 15 min; then transferred to a 15mL Teflon lined stainless steel autoclave and placed in a clean 1X 3cm2Sealing the carbon paper, and heating at 180 ℃ for 24 hours; cooling, taking out the carbon paper, washing with deionized water, and drying to obtain S-doped Bi loaded on the carbon paper2O3A precursor; finally, the temperature is controlled at 0.5M KHCO3And performing electrical reduction on the electrolyte for 5min at-0.98V vs. RHE to obtain the carbon paper loaded S-doped Bi metal electrocatalyst (S-Bi). The catalyst is used as a cathode, a Pt sheet is used as an anode, and a saturated calomel electrode is used as a reference electrode; the reaction was carried out in an H-type electrolytic cell, with 30mL of 0.5M KHCO in both the cathode and anode chambers3An electrolyte; carbon dioxide at a certain rate of 20mL min-1Introducing the mixture into the catholyte at a flow rate, and applying a-0.98V vs. RHE potential for reaction for 1 h; the current density was 45mA cm-2Quantitative nuclear magnetic hydrogen spectrum analysis shows that the Faraday efficiency of the formic acid is 92 percent, and the generation rate is 767 mu mol h-1cm-2。
Comparative example 1
Without addition of thioacetamide, 0.4mmol of InCl3Dissolving in 15mL of DMF, and stirring vigorously for 15 min; then transferred to a 25mL Teflon lined stainless steel autoclave and placed in a clean 1X 3cm2Sealing the carbon paper, and heating at 150 ℃ for 12 h; cooling, taking out the carbon paper, washing with deionized water, and drying to obtain the S-free doped In loaded on the carbon paper2O3A precursor; finally, the temperature is controlled at 0.5M KHCO3And performing electrical reduction on the electrolyte for 5min at-0.98V vs. RHE to obtain the carbon paper-loaded In metal electrocatalyst (S0-In) without S doping. The catalyst is used as a cathode, a Pt sheet is used as an anode, and a saturated calomel electrode is used as a reference electrode; the reaction was carried out in an H-type electrolytic cell, with 30mL of 0.5M KHCO in both the cathode and anode chambers3An electrolyte; carbon dioxide at a certain rate of 20mL min-1Introducing into the cathode electrolyte at a flow rate, applying-0.98V potential for reaction for 1h, wherein the generation rate of formic acid is 523 mu mol h-1cm-2The Faraday efficiency was 93%.
Comparative example 2
Commercial indium foil was used as the catalyst. The catalyst is used as a cathode, a Pt sheet is used as an anode, and a saturated calomel electrode is used as a reference electrode; the reaction was carried out in an H-type electrolytic cell, with 30mL of 0.5M KHCO in both the cathode and anode chambers3An electrolyte; carbon dioxide at a certain rate of 20mL min-1Introducing into the cathode electrolyte at a flow rate, applying-0.98V potential for reaction for 1h, wherein the generation rate of formic acid is 60 mu molh-1cm-2The Faraday efficiency was 58%.
Example 1 in comparison with comparative example 1, the formic acid formation rate in example 1 was 1002. mu. mol h-1cm-2Is 2 times of the sulfur-free doped 0mol percent S0-In under the same reaction condition; the faradaic efficiency In example 1 was 93% which was 1.1 times that of the sulfur-free doping 0 mol% S0-In under the same reaction conditions.
Example 1 compared to comparative example 2, the rate of formic acid formation in example 1 was 17 times that of commercial indium foil under the same reaction conditions, and the faradaic efficiency in example 1 was 1.6 times that of commercial indium foil under the same reaction conditions.

Claims (8)

1. The preparation method of the catalyst for preparing the formic acid by electrically reducing the carbon dioxide is characterized in that the catalyst is a metal electrocatalyst doped with a chalcogen element, the chalcogen element comprises at least one of sulfur, selenium and tellurium, the metal comprises at least one of indium, tin, lead and bismuth, and the molar percentage of the chalcogen element is 0.01-25 percent, and the preparation method is characterized in that: the method comprises the following steps:
1) firstly, dissolving a simple substance of a chalcogen element or a compound of the chalcogen element and a metal salt in N, N-dimethylformamide, then putting a carbon material into the N, N-dimethylformamide, and finally transferring the carbon material into a high-pressure kettle to carry out solvent heat treatment;
2) and (3) taking out the carbon material after the heat treatment of the solvent is finished, washing the carbon material by using deionized water, drying to obtain a precursor of the chalcogen element doped metal oxide loaded on the carbon material, and then performing electro-reduction to obtain the chalcogen element doped metal electrocatalyst loaded on the carbon material.
2. The method for preparing a catalyst for producing formic acid by electrically reducing carbon dioxide according to claim 1, which comprises: the carbon material includes at least one of carbon paper, carbon cloth, graphite sheet, carbon foam, and carbon nanotube.
3. The method for preparing a catalyst for producing formic acid by electrically reducing carbon dioxide according to claim 2, which comprises: the carbon material is carbon paper.
4. The method for preparing a catalyst for producing formic acid by electrically reducing carbon dioxide according to claim 1, which comprises: the compound of the chalcogen element is selected from at least one of sulfur powder, thiourea, sodium sulfide, thioacetamide, selenium powder, sodium selenite, tellurium powder and tellurite.
5. The method for preparing a catalyst for producing formic acid by electrically reducing carbon dioxide according to claim 1, which comprises: the metal salt is selected from at least one of chloride, nitrate and acetylacetonate of indium, tin, lead and bismuth.
6. The method for preparing a catalyst for producing formic acid by electrically reducing carbon dioxide according to claim 1, which comprises: the temperature of the solvent heat treatment is 130-200 ℃, the time of the solvent heat treatment is 12-48 h, and the electric reduction treatment potential is-0.98 Vvs.
7. The application of the catalyst for preparing formic acid by electrically reducing carbon dioxide, which is prepared by the preparation method of any one of claims 1 to 6, in preparing formic acid by electrically reducing carbon dioxide is characterized in that: reacting in an H-type electrolytic cell, taking a metal electrocatalyst doped with chalcogen elements as a cathode, taking a Pt sheet or graphite as an anode, taking a saturated calomel electrode as a reference electrode, introducing carbon dioxide into a cathode electrolyte, and applying negative potential for electrolysis to obtain the formic acid.
8. Use according to claim 7, characterized in that: the flow rate of carbon dioxide is 5-100 mL min-1(ii) a The electrolyte comprises NaHCO3、KHCO3、CsHCO3And K2SO4At least one of them, the concentration of the electrolyte is 0.1-2M; the negative potential is-0.33 to-1.23V vs.
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