CN116145175B - Electrocatalyst, preparation method and application thereof - Google Patents

Electrocatalyst, preparation method and application thereof Download PDF

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CN116145175B
CN116145175B CN202310155314.8A CN202310155314A CN116145175B CN 116145175 B CN116145175 B CN 116145175B CN 202310155314 A CN202310155314 A CN 202310155314A CN 116145175 B CN116145175 B CN 116145175B
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cobalt
substrate
electrocatalyst
electrode
carbon cloth
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CN116145175A (en
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殷杰
李庆宇
席聘贤
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Lanzhou University
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Lanzhou University
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/23—Carbon monoxide or syngas
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/042—Electrodes formed of a single material
    • C25B11/043—Carbon, e.g. diamond or graphene
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/01—Products
    • C25B3/07—Oxygen containing compounds
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/25—Reduction
    • C25B3/26—Reduction of carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/54—Electroplating of non-metallic surfaces

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Inorganic Chemistry (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Catalysts (AREA)

Abstract

The invention provides an electrocatalyst, which comprises a substrate and a metallic cobalt simple substance supported on the substrate. The invention also provides a preparation method of the electrocatalyst and application of the electrocatalyst in carbon dioxide reduction. The unique nanostructure of the electrocatalyst of the invention gives it rich geometric edge active sites, better product selectivity and better faraday efficiency.

Description

Electrocatalyst, preparation method and application thereof
Technical Field
The invention belongs to the field of electrochemical catalysis, and particularly relates to an electrocatalyst, a preparation method thereof and application thereof in electrocatalytic carbon dioxide reduction.
Background
Electrocatalytic carbon dioxide reduction (CO) 2 RR) as a clean, efficient use of CO 2 Means (1) for reducing CO 2 CO is discharged at the same time 2 The product is converted into a high added value product, and has important significance for environmental improvement. The main factor limiting its development and application is the synthesis of highly efficient and stable electrocatalysts.
CO 2 Active group in RR CO 2 The manner of adsorption on the catalyst surface has a decisive effect on the structure of the end product. When the O atoms preferentially adsorb to the catalyst surface, the end product is mostly formic acid or formate. When the C atoms are preferentially adsorbed on the surface of the catalyst, the C atoms are deoxidized to form a CO active intermediate, and the subsequent coupling reaction is carried out to obtain a multi-carbon product. At present, the metal such as Ni, fe, bi, sn, au, pd is used as a catalyst, and electrocatalytic CO such as carbon monoxide (CO) or formic acid (HCOO-) can be obtained 2 And (5) reducing the product. With metallic copper as a catalyst, a multi-carbon product can be obtained. Since carbon-carbon coupling (C-C) involves multi-step proton-electron transfer, synthesis of the multi-carbon product places higher demands on the surface structure of the catalyst. The design of the surface structure of the catalyst which is easier to adsorb C atoms is important to obtain a multi-carbon product. Although the copper-based catalyst is to obtain C 2+ General selection of products, poor selectivity andstability limits its large-scale application. Thus, in CO 2 How to obtain higher quality carbon-carbon coupled products (C2) in RR is a difficult problem.
Disclosure of Invention
In order to solve one of the technical problems in the prior art, the invention provides a cobalt-based carbon dioxide electrocatalytic material and a preparation method thereof, thereby solving the problems of complex synthesis method and lower product selectivity of the existing electrocatalytic material.
In a first aspect, the invention provides an electrocatalyst comprising a substrate and elemental metallic cobalt supported on the substrate.
In some embodiments, the elemental metallic cobalt material has a dendrite structure. In some embodiments, the surface of the elemental metallic cobalt material is loaded with carboxylate ions, preferably acetate ions. The metallic cobalt material of the present application has a unique structure with a dendrite structure and a carboxylate modification on the surface, and this independent structure gives it a rich geometrical edge active site, good product selectivity and excellent faraday efficiency.
In some embodiments, the loading of cobalt element on the substrate in the catalyst is 0.1-10mg/cm 2 For example 0.1mg/cm 2 、0.5mg/cm 2 、1mg/cm 2 、2mg/cm 2 、4mg/cm 2 、5mg/cm 2 、10mg/cm 2 Or any value therebetween, preferably 0.2-8mg/cm 2 More preferably 0.4-6mg/cm 2 。
In some embodiments, the substrate is selected from carbon fiber substrates, preferably from one or more of carbon cloth and carbon paper.
In a second aspect, the invention provides a method of preparing an electrocatalyst comprising electrochemically depositing a soluble cobalt salt solution on a substrate.
In some embodiments, the soluble cobalt salt is a cobalt carboxylate salt, preferably cobalt acetate. The invention adopts carboxylic acid cobalt salt to carry out electrochemical deposition on a substrate to obtain metallic cobalt simple substance.
In some embodiments, the concentration of cobalt ions in the soluble cobalt salt solution is 10-50mmol/L, such as 10mmol/L, 20mmol/L, 30mmol/L, 40mmol/L, 50mmol/L, or any value therebetween. In some preferred embodiments, the concentration of cobalt ions in the soluble cobalt salt solution is from 15 to 25mmol/L.
In some embodiments, the electrochemical deposition voltage is between-1V and-5V, such as between-1V, -2V, -3V, -4V, -5V, or any value therebetween. In some preferred embodiments, the electrochemical deposition voltage is from-2V to-4V.
In some embodiments, the time of the electrochemical deposition is from 5min to 90min, for example, 5min, 10min, 15min, 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min, 60min, 65min, 70min, 75min, 80min, 90min, or any value therebetween. In some embodiments, the electrochemical deposition time is from 5 minutes to 60 minutes. In some embodiments, the electrochemical deposition time is from 10 minutes to 80 minutes. In some embodiments, the electrochemical deposition time is 20min to 80min. In some embodiments, the electrochemical deposition time is 30min to 70min. In some embodiments, the electrochemical deposition time is 40min to 70min. In some embodiments, the electrochemical deposition time is 50min to 70min.
In some embodiments, the electrochemical deposition employs a three-electrode system; preferably, in the three-electrode system, the working electrode is selected from the substrate, the reference electrode is selected from Ag/AgCl electrode, and the counter electrode is selected from platinum sheet electrode.
In some embodiments, the method further comprises drying the electrochemically deposited substrate.
In some embodiments, the temperature of the drying is from 50 ℃ to 100 ℃, such as 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, or any value therebetween. In some embodiments, the temperature of the drying is from 50 ℃ to 70 ℃.
In some embodiments, the drying time is 1h to 5h, for example 1h, 2h, 3h, 4h, 5h, or any value therebetween. In some embodiments, the drying temperature is 2h to 4h.
In some embodiments, a mixed solution is prepared by mixing a metal acetate with ultrapure water, and the resulting solution has a metal ion concentration of 20 to 30mmol/L. A standard three electrode system was used. The cobalt-based carbon dioxide electrocatalytic material is prepared by immersing three electrodes in the mixed solution and performing electrochemical reduction by taking a platinum sheet as a counter electrode, ag/AgCl as a reference electrode and a platinum electrode clamp with 2cm multiplied by 3cm carbon cloth as a working electrode.
According to the invention, the cobalt simple substance electrocatalyst loaded on the substrate is obtained by a simple one-step electrochemical deposition method, and the nano catalysts with different loadings can be obtained by regulating the deposition duration. The electrocatalyst obtained by the method has better electrocatalytic carbon dioxide reduction selectivity and efficiency, and the electrocatalyst shows better ethanol selectivity under the low-voltage condition.
In a third aspect, the present invention provides the use of an electrocatalyst according to the first aspect or an electrocatalyst prepared by a method according to the second aspect in the reduction of carbon dioxide.
The cobalt-based carbon dioxide electrocatalyst is synthesized in one step by an electrochemical deposition method, and the unique nano structure of the electrocatalyst endows the electrocatalyst with abundant geometric edge active sites, good product selectivity and excellent Faraday efficiency. In addition, the electrochemical reduction method is used for preparing the carbon dioxide reduction electrocatalyst, the synthesis process is simple and easy to amplify, and the method has a higher application prospect.
Drawings
Figure 1 shows the XRD patterns of the target materials obtained according to examples 1-5.
Fig. 2 shows a raman spectrum (a) and a transmission electron microscope image (b) of a target material obtained according to example 1.
Fig. 3 shows the XRD pattern of the target material obtained according to comparative example 1.
Fig. 4 shows the XRD pattern of the target material obtained according to comparative example 2.
Fig. 5 shows XRD patterns of the target materials obtained according to comparative example 3 and comparative example 4.
FIG. 6 shows electrocatalytic CO using the target materials obtained according to examples 1-5 as catalysts 2 Reduced test results.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. The specific embodiments described herein are for purposes of illustration only and are not to be construed as limiting the invention in any way. In addition, in the following description, descriptions of well-known structures and techniques are omitted so as not to unnecessarily obscure the concepts of the present disclosure. Such structures and techniques are also described in a number of publications.
Example 1
Placing the cut carbon cloth (2 cm multiplied by 3 cm) into 50mL of ethanol, ultrasonically cleaning for 15min, taking out, alternately flushing with ultrapure water and ethanol for several times, spreading the flushed carbon cloth on the bottom of a beaker, dripping a little ethanol, and then adding concentrated nitric acid until the carbon cloth is not used. After the reaction is finished, a large amount of ultrapure water is used for flushing for a plurality of times (all the operations are carried out in a fume hood), then ethanol and ultrapure water are respectively used for repeatedly and alternately carrying out ultrasonic treatment for 15min, and finally the treated carbon cloth is stored in the ultrapure water for standby.
50mL of the prepared 20mmol/L cobalt acetate aqueous solution is taken and subjected to electrochemical deposition by adopting a standard three-electrode system. Wherein the platinum sheet is a counter electrode, ag/AgCl is a reference electrode, and the platinum electrode clamp provided with the carbon cloth treated by the method is a working electrode. And (3) reducing for 1h under the voltage of minus 3Vvs. Ag/AgCl to obtain the carbon cloth loaded with the cobalt-based electrocatalyst. Taking out the cobalt-based material from the solution, washing with ultrapure water, placing the solution into a vacuum drying oven, and drying at 60 ℃ for 3 hours to obtain a target material, wherein XRD test shows that the cobalt-based material of the target material is a hexagonal structure metal cobalt simple substance (see figure 1), and ICP test shows that the loading amount of the metal cobalt simple substance is 4.38mg/cm 2 . The raman (fig. 2 a) and transmission electron microscope images (fig. 2 b) of the obtained target material are shown in fig. 2, and the target material is a metal cobalt dendrite structure modified by surface acetate.
Example 2
Placing the cut carbon cloth (2 cm multiplied by 3 cm) into 50mL of ethanol, ultrasonically cleaning for 15min, taking out, alternately flushing with ultrapure water and ethanol for several times, spreading the flushed carbon cloth on the bottom of a beaker, dripping a little ethanol, and then adding concentrated nitric acid until the carbon cloth is not used. After the reaction is finished, a large amount of ultrapure water is used for flushing for a plurality of times (all the operations are carried out in a fume hood), then ethanol and ultrapure water are respectively used for repeatedly and alternately carrying out ultrasonic treatment for 15min, and finally the treated carbon cloth is stored in the ultrapure water for standby.
50mL of the prepared 20mmol/L cobalt acetate aqueous solution is taken and subjected to electrochemical deposition by adopting a standard three-electrode system. Wherein the platinum sheet is a counter electrode, ag/AgCl is a reference electrode, and the platinum electrode clamp provided with the carbon cloth treated by the method is a working electrode. And (3) reducing for 30min under the voltage of minus 3Vvs. Taking out the cobalt-based material from the solution, washing with ultrapure water, placing the solution into a vacuum drying oven, and drying at 60 ℃ for 3 hours to obtain a target material, wherein XRD test shows that the cobalt-based material of the target material is a hexagonal structure metal cobalt simple substance (see figure 1), and ICP test shows that the loading amount of the metal cobalt simple substance is 2.56mg/cm 2 。
Example 3
Placing the cut carbon cloth (2 cm multiplied by 3 cm) into 50mL of ethanol, ultrasonically cleaning for 15min, taking out, alternately flushing with ultrapure water and ethanol for several times, spreading the flushed carbon cloth on the bottom of a beaker, dripping a little ethanol, and then adding concentrated nitric acid until the carbon cloth is not used. After the reaction is finished, a large amount of ultrapure water is used for flushing for a plurality of times (all the operations are carried out in a fume hood), then ethanol and ultrapure water are respectively used for repeatedly and alternately carrying out ultrasonic treatment for 15min, and finally the treated carbon cloth is stored in the ultrapure water for standby.
50mL of the prepared 20mmol/L cobalt acetate aqueous solution is taken and subjected to electrochemical deposition by adopting a standard three-electrode system. Wherein the platinum sheet is a counter electrode, ag/AgCl is a reference electrode, and the platinum electrode clamp provided with the carbon cloth treated by the method is a working electrode. And (3) reducing for 20min under the voltage of minus 3Vvs. Taking out the solution, washing with ultrapure water, drying in vacuum oven at 60deg.C for 3 hr, and collecting the solutionThe target material is obtained, XRD tests show that the cobalt-based material of the target material is hexagonal structure metal cobalt simple substance (see figure 1), and ICP tests show that the loading capacity of the metal cobalt simple substance is 1.81mg/cm 2 。
Example 4
Placing the cut carbon cloth (2 cm multiplied by 3 cm) into 50mL of ethanol, ultrasonically cleaning for 15min, taking out, alternately flushing with ultrapure water and ethanol for several times, spreading the flushed carbon cloth on the bottom of a beaker, dripping a little ethanol, and then adding concentrated nitric acid until the carbon cloth is not used. After the reaction is finished, a large amount of ultrapure water is used for flushing for a plurality of times (all the operations are carried out in a fume hood), then ethanol and ultrapure water are respectively used for repeatedly and alternately carrying out ultrasonic treatment for 15min, and finally the treated carbon cloth is stored in the ultrapure water for standby.
50mL of the prepared 20mmol/L cobalt acetate aqueous solution is taken and subjected to electrochemical deposition by adopting a standard three-electrode system. Wherein the platinum sheet is a counter electrode, ag/AgCl is a reference electrode, and the platinum electrode clamp provided with the carbon cloth treated by the method is a working electrode. And (3) reducing for 10min under the voltage of minus 3Vvs. Taking out the cobalt-based material from the solution, washing with ultrapure water, placing into a vacuum drying oven, and drying at 60 ℃ for 3 hours to obtain a target material, wherein XRD test shows that the cobalt-based material of the target material is hexagonal structure metal cobalt simple substance (see figure 1), and ICP test shows that the loading amount of the metal cobalt simple substance is 0.95mg/cm 2 。
Example 5
Placing the cut carbon cloth (2 cm multiplied by 3 cm) into 50mL of ethanol, ultrasonically cleaning for 15min, taking out, alternately flushing with ultrapure water and ethanol for several times, spreading the flushed carbon cloth on the bottom of a beaker, dripping a little ethanol, and then adding concentrated nitric acid until the carbon cloth is not used. After the reaction is finished, a large amount of ultrapure water is used for flushing for a plurality of times (all the operations are carried out in a fume hood), then ethanol and ultrapure water are respectively used for repeatedly and alternately carrying out ultrasonic treatment for 15min, and finally the treated carbon cloth is stored in the ultrapure water for standby.
50mL of the prepared 20mmol/L cobalt acetate aqueous solution is taken and subjected to electrochemical deposition by adopting a standard three-electrode system. Wherein the platinum sheet is a counter electrode, and Ag/AgCl is a reference electrodeThe electrode, platinum electrode clip with the carbon cloth processed as above is the working electrode. And (3) reducing for 5min under the voltage of minus 3Vvs. Taking out the cobalt-based material from the solution, washing with ultrapure water, placing into a vacuum drying oven, and drying at 60 ℃ for 3 hours to obtain a target material, wherein XRD test shows that the cobalt-based material of the target material is hexagonal structure metal cobalt simple substance (see figure 1), and ICP test shows that the loading amount of the metal cobalt simple substance is 0.49mg/cm 2 。
Comparative example 1
Placing the cut carbon cloth (2 cm multiplied by 3 cm) into 50mL of ethanol, ultrasonically cleaning for 15min, taking out, alternately flushing with ultrapure water and ethanol for several times, spreading the flushed carbon cloth on the bottom of a beaker, dripping a little ethanol, and then adding concentrated nitric acid until the carbon cloth is not used. After the reaction is finished, a large amount of ultrapure water is used for flushing for a plurality of times (all the operations are carried out in a fume hood), then ethanol and ultrapure water are respectively used for repeatedly and alternately carrying out ultrasonic treatment for 15min, and finally the treated carbon cloth is stored in the ultrapure water for standby.
50mL of the prepared 20mmol/L nickel acetate aqueous solution is taken and subjected to electrochemical deposition by adopting a standard three-electrode system. Wherein the platinum sheet is a counter electrode, ag/AgCl is a reference electrode, and the platinum electrode clamp provided with the carbon cloth treated by the method is a working electrode. And (3) reducing for 1h under the voltage of minus 3Vvs. Taking out the material from the solution, flushing the material with ultrapure water, putting the material into a vacuum drying oven, and drying the material at 60 ℃ for 3 hours to obtain a target material, wherein the target material is shown to be a metallic nickel simple substance through XRD test (see figure 3).
Comparative example 2
Placing the cut carbon cloth (2 cm multiplied by 3 cm) into 50mL of ethanol, ultrasonically cleaning for 15min, taking out, alternately flushing with ultrapure water and ethanol for several times, spreading the flushed carbon cloth on the bottom of a beaker, dripping a little ethanol, and then adding concentrated nitric acid until the carbon cloth is not used. After the reaction is finished, a large amount of ultrapure water is used for flushing for a plurality of times (all the operations are carried out in a fume hood), then ethanol and ultrapure water are respectively used for repeatedly and alternately carrying out ultrasonic treatment for 15min, and finally the treated carbon cloth is stored in the ultrapure water for standby.
50mL of the prepared 20mmol/L zinc acetate aqueous solution is taken and subjected to electrochemical deposition by adopting a standard three-electrode system. Wherein the platinum sheet is a counter electrode, ag/AgCl is a reference electrode, and the platinum electrode clamp provided with the carbon cloth treated by the method is a working electrode. And (3) reducing for 1h under the voltage of minus 3Vvs. Taking out the material from the solution, flushing with ultrapure water, putting the material into a vacuum drying oven, and drying at 60 ℃ for 3 hours to obtain a target material, wherein the target material is shown to be a metallic zinc simple substance through XRD test (see figure 4).
Comparative example 3
Placing the cut carbon cloth (2 cm multiplied by 3 cm) into 50mL of ethanol, ultrasonically cleaning for 15min, taking out, alternately flushing with ultrapure water and ethanol for several times, spreading the flushed carbon cloth on the bottom of a beaker, dripping a little ethanol, and then adding concentrated nitric acid until the carbon cloth is not used. After the reaction is finished, a large amount of ultrapure water is used for flushing for a plurality of times (all the operations are carried out in a fume hood), then ethanol and ultrapure water are respectively used for repeatedly and alternately carrying out ultrasonic treatment for 15min, and finally the treated carbon cloth is stored in the ultrapure water for standby.
50mL of the prepared 20mmol/L cobalt nitrate aqueous solution is taken and subjected to electrochemical deposition by adopting a standard three-electrode system. Wherein the platinum sheet is a counter electrode, ag/AgCl is a reference electrode, and the platinum electrode clamp provided with the carbon cloth treated by the method is a working electrode. And (3) reducing for 5min and 30min under the voltage of-3 Vvs. Taking out the material from the solution, flushing the material with ultrapure water, putting the material into a vacuum drying oven, and drying the material at 60 ℃ for 3 hours to obtain a target material, wherein the XRD test shows that the target material is inconsistent with the XRD spectrum of the metallic cobalt simple substance (see figure 5).
Comparative example 4
Placing the cut carbon cloth (2 cm multiplied by 3 cm) into 50mL of ethanol, ultrasonically cleaning for 15min, taking out, alternately flushing with ultrapure water and ethanol for several times, spreading the flushed carbon cloth on the bottom of a beaker, dripping a little ethanol, and then adding concentrated nitric acid until the carbon cloth is not used. After the reaction is finished, a large amount of ultrapure water is used for flushing for a plurality of times (all the operations are carried out in a fume hood), then ethanol and ultrapure water are respectively used for repeatedly and alternately carrying out ultrasonic treatment for 15min, and finally the treated carbon cloth is stored in the ultrapure water for standby.
50mL of the prepared 20mmol/L cobalt sulfate aqueous solution is taken and subjected to electrochemical deposition by adopting a standard three-electrode system. Wherein the platinum sheet is a counter electrode, ag/AgCl is a reference electrode, and the platinum electrode clamp provided with the carbon cloth treated by the method is a working electrode. And (3) reducing for 5min and 30min under the voltage of-3 Vvs. Taking out the material from the solution, flushing the material with ultrapure water, putting the material into a vacuum drying oven, and drying the material at 60 ℃ for 3 hours to obtain a target material, wherein the XRD test shows that the target material is inconsistent with the XRD spectrum of the metallic cobalt simple substance (see figure 5).
Test case
Cutting carbon cloth loaded with target material into size of 2cm×0.5cm, using platinum sheet as counter electrode, ag/AgCl as reference electrode, using platinum electrode clamp containing the carbon cloth as working electrode, and electrocatalytic CO for the catalysts obtained in the above examples and comparative examples 2 And (5) reduction test. As a result of subjecting the obtained liquid product to nuclear magnetic resonance examination, it was found that the reduced product of the cobalt-based electrocatalyst prepared by the present invention had ethanol, whereas the reduced product of the nickel-based catalyst prepared by comparative example 1 and the zinc-based catalyst prepared by comparative example 2 did not contain ethanol. Among them, the test results of the catalysts prepared in examples 1 to 5 are shown in FIG. 6, and it was found that the material obtained in example 1 reached the maximum ethanol Faraday Efficiency (FE) at a voltage of-0.3V. Lateral comparison of different materials it was found that the material obtained in example 1 has a good selectivity for ethanol at low voltages.
It should be noted that the above-described embodiments are only for explaining the present invention and do not limit the present invention in any way. The invention has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined in the appended claims, and the invention may be modified without departing from the scope and spirit of the invention. Although the invention is described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, as the invention extends to all other means and applications which perform the same function.

Claims (20)

1. An electrocatalyst comprises a substrate and a metallic cobalt simple substance material supported on the substrate, wherein the metallic cobalt simple substance material has a dendrite structure, and the surface of the metallic cobalt simple substance material is supported with acetate ions.
2. The electrocatalyst according to claim 1, wherein the elemental metallic cobalt material is 0.1-10mg/cm on the substrate 2 。
3. The electrocatalyst according to claim 2 wherein the elemental metallic cobalt material is 0.2 to 8mg/cm on the substrate 2 。
4. The electrocatalyst according to claim 2, wherein the elemental metallic cobalt material is 0.4-6mg/cm on the substrate 2 。
5. The electrocatalyst according to claim 1 wherein the substrate is selected from carbon fibre substrates.
6. The electrocatalyst according to claim 5 wherein the substrate is selected from one or more of carbon cloth and carbon paper.
7. A method of preparing the electrocatalyst according to any one of claims 1 to 6, comprising electrochemically depositing a cobalt acetate solution on a substrate.
8. The method of claim 7, wherein the concentration of cobalt ions in the cobalt acetate solution is 10-50mmol/L.
9. The method of claim 8, wherein the concentration of cobalt ions in the cobalt acetate solution is 15-25mmol/L.
10. The method according to any one of claims 7-9, wherein the electrochemical deposition voltage is between-1V and-5V.
11. The method of claim 10, wherein the electrochemical deposition voltage is from-2V to-4V.
12. The method according to any one of claims 7-9, wherein the time of electrochemical deposition is 5min-90min, 5min-60min, 30min-70min, 40min-70min or 50min-70min.
13. The method according to any one of claims 7-9, wherein the electrochemical deposition employs a three-electrode system.
14. The method of claim 13, wherein in the three electrode system, the working electrode is selected from the substrate, the reference electrode is selected from Ag/AgCl electrodes, and the counter electrode is selected from platinum sheet electrodes.
15. The method of any one of claims 7-9, further comprising drying the electrochemically deposited substrate.
16. The method of claim 15, wherein the drying temperature is 50 ℃ to 100 ℃.
17. The method of claim 15, wherein the drying temperature is 50 ℃ to 70 ℃.
18. The method of claim 15, wherein the drying time is 1h to 5h.
19. The method of claim 15, wherein the drying time is 2h to 4h.
20. Use of an electrocatalyst according to any one of claims 1 to 6 or prepared according to a method of any one of claims 7 to 19 in the reduction of carbon dioxide.
CN202310155314.8A 2023-02-22 2023-02-22 Electrocatalyst, preparation method and application thereof Active CN116145175B (en)

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