CN115138855A - Preparation method of bimetallic monatomic material and application of bimetallic monatomic material in new energy - Google Patents

Preparation method of bimetallic monatomic material and application of bimetallic monatomic material in new energy Download PDF

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CN115138855A
CN115138855A CN202210810339.2A CN202210810339A CN115138855A CN 115138855 A CN115138855 A CN 115138855A CN 202210810339 A CN202210810339 A CN 202210810339A CN 115138855 A CN115138855 A CN 115138855A
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bimetallic monatomic
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CN115138855B (en
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邓齐波
安翠华
胡宁
武帅
高玲肖
张静宇
焦朋港
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Hebei University of Technology
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Abstract

The invention discloses a preparation method of a bimetallic monatomic material and application thereof in new energy, wherein potassium chloride is adopted as a template in the preparation method, the calcination temperature is low, and the migration and agglomeration of metal atoms are greatly limited, so that a bimetallic monatomic catalyst with atomically dispersed paired copper and zinc metal atoms loaded on microporous nitrogen-doped carbon is prepared; the preparation method only comprises the operations of ball milling, ultrasonic treatment, calcination, freeze drying and the like, and has simple processAnd the sample does not need to be subjected to acid treatment, so that the method is environment-friendly. The CuZn bimetallic monatomic material prepared by the preparation method has excellent ERC performance and can be used for CO 2 Saturated 1M KHCO 3 In the solution, the Faraday efficiency is as high as 84.7 percent, and the current density is-49.7 mA cm under-1.1V (vs. RHE) ‑2 And has excellent stability. At an over-potential of-1.1V, the reduction product is mainly CH 4 And has high selectivity.

Description

Preparation method of bimetallic monatomic material and application of bimetallic monatomic material in new energy
Technical Field
The invention belongs to the field of carbon dioxide reduction electrocatalysts, and particularly relates to a preparation method of a bimetallic monatomic material and application of the bimetallic monatomic material in new energy.
Technical Field
Introducing CO 2 Conversion to chemicals or fuels is one of the effective ways to achieve energy conversion, chemical energy storage, and "carbon neutralization". Methane (CH) 4 ) Is an important fuel and is also the main component of natural gas. CO 2 2 Conversion to CH 4 Is a very efficient solution and can achieve the purposes of energy conservation and emission reduction. In a plurality of CO 2 In the conversion process, electrochemical reduction of CO 2 The ERC has the advantages of simple operation, easy control of experimental conditions and the like. But due to CO 2 Are very stable and therefore require highly efficient catalysts to facilitate the ERC process.
Because of their high metal atom utilization and excellent performance, transition metal monatomic catalysts have been widely used in ERC. However, the limited single metal loading and insufficient activity results in a limited performance of the monatomic catalyst. The controllable synthesis of the bimetallic monatomic catalyst is difficult to realize, and particularly, the separation of metal atoms is ensured to form a large number of stable monatomic active sites. In addition, in the preparation process, metal atoms are easy to migrate and aggregate to form nanoclusters/particles, and often need to be removed by subsequent acid treatment, which is not environment-friendly. Therefore, the development of the environment-friendly and excellent-performance bimetallic monatomic ERC catalyst has great significance and value for solving the energy crisis and relieving the environmental problem.
Disclosure of Invention
Aiming at the defects in the preparation of the bimetallic monatomic ERC catalyst in the prior art, the invention provides a preparation method of a bimetallic monatomic material and application of the bimetallic monatomic material in new energy. The preparation method is simple in process, and the prepared CuZn bimetallic monatomic catalyst has excellent ERC performance.
The technical scheme for solving the technical problems is as follows: the preparation method of the bimetallic monatomic material is characterized by comprising the following steps of:
step 1: placing 0.1-0.2 mmol of hydrated copper acetate, 0.1-0.2 mmol of hydrated zinc acetate and 0.1-0.3 mmol of o-phenanthroline in a centrifuge tube, adding 1-3 mL of absolute ethyl alcohol, and performing ultrasonic treatment for 20-40 minutes to obtain a mixed solution;
step 2: dropwise adding the mixed solution obtained in the step 1 into 100-300 mmol potassium chloride, then placing the mixed solution into a ball milling tank for ball milling, setting the rotating speed of the ball mill to be 200-400rpm, the time to be 2-8 hours, and the ball-material ratio to be 4, wherein a primary mixture is obtained after the ball milling is finished;
and step 3: pouring 0.01-0.05mmol of leucine and 1-3 mL of absolute ethyl alcohol into a centrifuge tube, and carrying out ultrasonic treatment for 10-40 minutes to obtain a clear solution;
and 4, step 4: dropwise adding the clear solution obtained in the step 3 into the primary mixture obtained in the step 2, continuously performing ball milling, setting the rotating speed of a ball mill to be 200-400rpm, the time to be 1-5 hours, the ball-material ratio to be 4;
and 5: scraping the composite mixture obtained in the step 4 from the wall of the ball milling tank, and grinding the composite mixture into powder by using a mortar;
step 6: calcining the powder obtained in the step 5 in an argon atmosphere for 2-6 hours at 400-600 ℃, and naturally cooling to room temperature after the calcination is finished to obtain a mixed product;
and 7: and (3) washing the mixed product obtained in the step (6) with distilled water, filtering to remove a potassium chloride template, transferring the powder obtained by filtering to 50mL of distilled water, and freeze-drying to obtain black powder, namely the copper-zinc bimetallic monatomic material.
Further, the invention designs an application of the bimetallic monatomic material in new energy, which is characterized in that the bimetallic monatomic material is obtained by the preparation method, and the application process is as follows: firstly, accurately weighing 5.0mg of catalyst, 500 mu L of ethanol and 500 mu L of 0.5wt% Nafion solution, mixing the three, and carrying out ultrasonic treatment for 20min to disperse the three into a mixed solution; finally, 200. Mu.L of the mixed solution was added dropwise to 1X 1cm 2 And air-drying the carbon paper for 5 hours at room temperature to obtain the working electrode of the ERC.
Compared with the prior art, the invention has the beneficial effects that:
(1) The preparation method adopts potassium chloride as a template, has lower calcination temperature, and greatly limits the migration and agglomeration of metal atoms, thereby preparing the double-metal monatomic catalyst with the atomically dispersed paired metal atoms (Cu, zn) loaded on the microporous nitrogen-doped carbon;
(2) The preparation method only comprises the steps of ball milling, ultrasonic treatment, calcination, freeze drying and the like, is simple, does not need to carry out acid treatment on the sample, and is environment-friendly.
(3) The CuZn bimetallic monatomic material prepared by the method has excellent ERC (oxygen tolerance) performance and can be used for CO 2 Saturated 1M KHCO 3 In solution, the Faraday Efficiency (FE) is up to 84.7%, and the current density under-1.1V (vs. RHE) is-49.7 mA cm -2 And has excellent stability. At an over-potential of-1.1V, the reduction product is mainly CH 4 Has high selectivity.
Drawings
FIG. 1 is an electrocatalytic CO of a CuZn-SAs/NC catalyst obtained in example 1, a Cu-SAs/NC catalyst obtained in comparative example 1, and a Zn-SAs/NC catalyst obtained in comparative example 2, which are the methods for preparing a bimetallic monatomic material according to the present invention 2 Reduction (ERC) performance versus plot (i.e., linear sweep voltammogram).
Fig. 2 (a) is a scanning electron microscope image of the CuZn SAs/NC catalyst obtained in example 1 of the method for preparing a bimetallic monatomic material according to the present invention; fig. 2 (b) is an aberration-corrected high-angle annular dark-field image (HAADF-STEM) of the CuZn SAs/NC catalyst obtained in example 1 of the method for preparing a bimetallic monatomic material according to the present invention, wherein bright spots circled in white are atomically dispersed Cu atoms and Zn atoms.
FIG. 3 shows that the CuZn-SAs/NC catalyst obtained in example 1, the Cu-SAs/NC catalyst obtained in comparative example 1 and the Zn-SAs/NC catalyst obtained in comparative example 2 are subjected to ERC to prepare CH under different overpotentials in the preparation method of the bimetallic monatomic material of the invention 4 Faradaic Efficiency (FE).
FIG. 4 shows that CuZn-SAs/NC catalyst obtained in example 1, cu-SAs/NC catalyst obtained in comparative example 1 and Zn-SAs/NC catalyst obtained in comparative example 2 catalyze ERC to prepare CH according to the preparation method of bimetallic monatomic material of the invention 4 Tafel plot of (1).
FIG. 5 is the FE values of all ERC products of CuZn-SAs/NC catalysts obtained in example 1 of a method for preparing a bimetallic monatomic material according to the invention at different overpotentials.
FIG. 6 is a graph showing the stability of the catalytic ERC of the CuZn-SAs/NC catalyst obtained in example 1 of the method for preparing a bimetallic monatomic material according to the present invention at an overpotential of-1.1V (vs. RHE) (after 45 hours, there is almost no change in current density and Faraday efficiency).
Detailed Description
The patent relates to a preparation method of a bimetallic monatomic material and application of the bimetallic monatomic material in new energy. The experimental contents will be fully and clearly described below in conjunction with the summary of the patent and the specific examples so as to enable the researchers in the field to better understand the invention.
The catalysts prepared in the following examples and comparative examples were applied and tested for performance by the following methods: the electrocatalytic carbon dioxide reduction reaction (ERC) was carried out in an H-cell with good gas tightness, the anode and cathode compartments being separated by a Nafion-117 proton exchange membrane. The test used a standard three-electrode system: the catalyst supported on carbon paper was used as a working electrode, and the platinum sheet and the reversible hydrogen electrode were used as a counter electrode and a reference electrode, respectively. All tests were performed at ambient temperature and pressure.
Preparation of a working electrode: firstly, accurately weighing 5.0mg of catalyst, 500 mu L of ethanol and 500 mu L of 0.5wt% Nafion solution, mixing the three, and carrying out ultrasonic treatment for 20min to disperse the three into a mixed solution; finally, 200. Mu.L of the mixed solution was added dropwise to 1X 1cm 2 And air-drying the carbon paper for 5 hours at room temperature to obtain the working electrode of the ERC.
ERC measurement process: measurements were performed using an electrochemical workstation (CHI 760E). Before measurement, high purity CO is added 2 Introducing the electrolyte for 30 minutes at the flow rate of 200sccm to ensure that CO in the electrolyte 2 The concentration reached a saturated state. During testing, the sample was first pre-activated by Cyclic Voltammetry (CV). Subsequently, at 10mV s -1 Linear Sweep Voltammograms (LSVs) were recorded between potentials of-1.2V to 0V (vs. rhe) to obtain key performance indicators of the catalyst, such as faraday efficiency, current density, etc.
The invention provides a preparation method of a bimetallic monatomic material, which comprises the following steps:
step 1: placing 0.1-0.2 mmol of hydrated copper acetate, 0.1-0.2 mmol of hydrated zinc acetate and 0.1-0.3 mmol of o-phenanthroline in a centrifuge tube, adding 1-3 mL of absolute ethyl alcohol, and performing ultrasonic treatment for 20-40 minutes to obtain a mixed solution;
and 2, step: dropwise adding the mixed solution obtained in the step 1 into 100-300 mmol of potassium chloride, then putting the mixed solution into a ball milling tank for ball milling, setting the rotating speed of the ball mill to be 200-400rpm, the time to be 2-8 hours, and the ball-material ratio to be 4, wherein a primary mixture is obtained after the ball milling is finished;
and 3, step 3: pouring 0.01-0.05mmol of leucine and 1-3 mL of absolute ethyl alcohol into a centrifuge tube, and carrying out ultrasonic treatment for 10-40 minutes to obtain a clear solution;
and 4, step 4: dropwise adding the clear solution obtained in the step 3 into the primary mixture obtained in the step 2, continuously performing ball milling, setting the rotating speed of a ball mill to be 200-400rpm, the time to be 1-5 hours, the ball-material ratio to be 4;
and 5: scraping the composite mixture obtained in the step 4 from the wall of a ball milling tank, and grinding the composite mixture into powder by using a mortar (no particles with the diameter larger than 1mm are needed, and no strict requirement is required);
step 6: calcining the powder obtained in the step 5 in an argon atmosphere for 2-6 hours at 400-600 ℃, and naturally cooling to room temperature after the calcination is finished to obtain a mixed product;
and 7: and (3) washing the mixed product obtained in the step (6) with distilled water, filtering to remove a potassium chloride template, transferring the powder obtained by filtering to 50mL of distilled water, and freeze-drying to obtain black powder, namely the copper-zinc bimetallic monatomic material (CuZn SAs/NC catalyst for short, the same below).
Example 1
The embodiment provides a preparation method of a bimetallic monatomic material, which comprises the following steps:
step 1: putting 0.1mmol of hydrated copper acetate, 0.1mmol of hydrated zinc acetate and 0.3mmol of o-phenanthroline into a centrifuge tube, adding 1.5mL of absolute ethyl alcohol, and performing ultrasonic treatment for 30 minutes to obtain a mixed solution;
step 2: dropwise adding the mixed solution obtained in the step 1 into 150mmol potassium chloride, then putting the mixed solution into a ball milling tank for ball milling, setting the rotating speed of a ball mill to be 300rpm, the time to be 5 hours, and the ball-material ratio to be 4, and obtaining a primary mixture after the ball milling is finished;
and step 3: pouring 0.03mmol of leucine and 1.5mL of absolute ethyl alcohol into a centrifuge tube, and carrying out ultrasonic treatment for 30 minutes to obtain a clear solution;
and 4, step 4: dropwise adding the clear solution obtained in the step 3 into the primary mixture obtained in the step 2, continuously performing ball milling, setting the rotation speed of a ball mill to be 200rpm, the time to be 3 hours, and the ball-material ratio to be 4;
and 5: scraping the composite mixture obtained in the step 4 from the wall of a ball milling tank, and grinding the composite mixture into powder by using a mortar (no particles with the diameter larger than 1mm are needed, and no strict requirement is required);
and 6: calcining the powder obtained in the step 5 in an argon atmosphere for 4 hours at the calcining temperature of 500 ℃, and naturally cooling to room temperature after the calcining is finished to obtain a mixed product;
and 7: and (3) washing the mixed product obtained in the step (6) with distilled water, filtering to remove a potassium chloride template, transferring the powder obtained by filtering to 50mL of distilled water, and freeze-drying to obtain black powder, namely the copper-zinc bimetallic monatomic material (CuZn SAs/NC catalyst for short, the same below).
The copper-zinc bimetallic monatomic material obtained in the embodiment is subjected to characterization and electrochemical carbon dioxide reduction (ERC) performance test, so that Zn atoms and Cu atoms are uniformly dispersed on a porous carbon substrate, and no nanocluster or particle is generated. The obtained CuZn bimetallic single-atom catalyst (CuZn SAs/NC) has excellent ERC performance in CO 2 Saturated 1M KHCO 3 In the solution, the Faraday Efficiency (FE) is as high as 84.7%, and the current density is-49.7 mA cm at-1.1V -2 And has excellent stability. At an over-potential of-1.1V, the reduction product is mainly CH 4 Has high selectivity.
Example 2
The embodiment provides a preparation method of a bimetallic monatomic material, which comprises the following steps:
step 1: putting 0.2mmol of hydrated copper acetate, 0.1mmol of hydrated zinc acetate and 0.3mmol of phenanthroline into a centrifuge tube, adding 1.5mL of absolute ethyl alcohol, and carrying out ultrasonic treatment for 30 minutes to obtain a mixed solution;
step 2: dropwise adding the mixed solution obtained in the step 1 into 150mmol potassium chloride, then putting the mixed solution into a ball milling tank for ball milling, setting the rotating speed of a ball mill to be 300rpm, the time to be 5 hours, and the ball-material ratio to be 4, and obtaining a primary mixture after the ball milling is finished;
and step 3: pouring 0.03mmol of leucine and 1.5mL of absolute ethyl alcohol into a centrifuge tube, and carrying out ultrasonic treatment for 30 minutes to obtain a clear solution;
and 4, step 4: dropwise adding the clear solution obtained in the step 3 into the primary mixture obtained in the step 2, continuously performing ball milling, setting the rotation speed of a ball mill to be 200rpm, the time to be 3 hours, and the ball-material ratio to be 4;
and 5: scraping the composite mixture obtained in the step 4 from the wall of the ball milling tank, and grinding the composite mixture into powder by using a mortar (no particles with the diameter larger than 1mm are needed, and no strict requirement is required);
and 6: calcining the powder obtained in the step 5 in an argon atmosphere for 4 hours at the calcining temperature of 500 ℃, and naturally cooling to room temperature after the calcining is finished to obtain a mixed product;
and 7: and (4) washing the mixed product obtained in the step (6) with distilled water, filtering to remove a potassium chloride template, transferring the powder obtained by filtering to 50mL of distilled water, and freeze-drying to obtain black powder, namely the copper-zinc bimetal monatomic material (CuZn SAs/NC catalyst for short, the same is applied below).
The copper-zinc bimetallic monatomic material obtained in the embodiment is subjected to characterization and electrochemical carbon dioxide reduction (ERC) performance test, and the obtained CuZn bimetallic monatomic catalyst has excellent ERC performance and can be used for CO 2 Saturated 1M KHCO 3 In the solution, the Faraday Efficiency (FE) is as high as 80.3%, and the current density is-39.8 mA cm at-1.1V -2 And has excellent stability. At an over-potential of-1.1V, the reduction product is mainly CH 4 And has high selectivity.
Example 3
The embodiment provides a preparation method of a bimetallic monatomic material, which comprises the following steps:
step 1: putting 0.1mmol of hydrated copper acetate, 0.2mmol of hydrated zinc acetate and 0.3mmol of o-phenanthroline into a centrifuge tube, adding 1.5mL of absolute ethyl alcohol, and performing ultrasonic treatment for 30 minutes to obtain a mixed solution;
step 2: dropwise adding the mixed solution obtained in the step 1 into 150mmol potassium chloride, then placing the mixed solution into a ball milling tank for ball milling, setting the rotating speed of a ball mill to be 300rpm, the time to be 5 hours, and the ball-material ratio to be 4, and obtaining a primary mixture after ball milling;
and 3, step 3: pouring 0.03mmol of leucine and 1.5mL of absolute ethyl alcohol into a centrifuge tube, and carrying out ultrasonic treatment for 30 minutes to obtain a clear solution;
and 4, step 4: dropwise adding the clear solution obtained in the step 3 into the primary mixture obtained in the step 2, continuously performing ball milling, setting the rotation speed of a ball mill to be 200rpm, the time to be 3 hours, and the ball-material ratio to be 4;
and 5: scraping the composite mixture obtained in the step 4 from the wall of a ball milling tank, and grinding the composite mixture into powder by using a mortar (no particles with the diameter larger than 1mm are needed, and no strict requirement is required);
and 6: calcining the powder obtained in the step 5 in an argon atmosphere for 4 hours at the calcining temperature of 500 ℃, and naturally cooling to room temperature after the calcining is finished to obtain a mixed product;
and 7: and (3) washing the mixed product obtained in the step (6) with distilled water, filtering to remove a potassium chloride template, transferring the powder obtained by filtering to 50mL of distilled water, and freeze-drying to obtain black powder, namely the copper-zinc bimetallic monatomic material (CuZn SAs/NC catalyst for short, the same below).
The copper-zinc bimetallic monatomic material obtained in the embodiment is subjected to characterization and electrochemical carbon dioxide reduction (ERC) performance test, and the obtained CuZn bimetallic monatomic catalyst (CuZn SAs/NC) has excellent ERC performance and can be used for CO 2 Saturated 1M KHCO 3 In the solution, the Faraday Efficiency (FE) is up to 79.5%, and the current density is-44.3 mA cm at-1.1V -2 And has excellent stability. At an over-potential of-1.1V, the reduction product is mainly CH 4 Has high selectivity.
Example 4
The embodiment provides a preparation method of a bimetallic monatomic material, which comprises the following steps:
step 1: putting 0.1mmol of hydrated copper acetate, 0.1mmol of hydrated zinc acetate and 0.3mmol of o-phenanthroline into a centrifuge tube, adding 1.5mL of absolute ethyl alcohol, and performing ultrasonic treatment for 30 minutes to obtain a mixed solution;
and 2, step: dropwise adding the mixed solution obtained in the step 1 into 150mmol potassium chloride, then putting the mixed solution into a ball milling tank for ball milling, setting the rotating speed of a ball mill to be 300rpm, the time to be 5 hours, and the ball-material ratio to be 4, and obtaining a primary mixture after the ball milling is finished;
and step 3: pouring 0.03mmol of leucine and 1.5mL of absolute ethyl alcohol into a centrifuge tube, and carrying out ultrasonic treatment for 30 minutes to obtain a clear solution;
and 4, step 4: dropwise adding the clear solution obtained in the step 3 into the primary mixture obtained in the step 2, continuously performing ball milling, setting the rotating speed of a ball mill to be 300rpm, the time to be 3 hours, the ball-to-material ratio to be 4;
and 5: scraping the composite mixture obtained in the step 4 from the wall of a ball milling tank, and grinding the composite mixture into powder by using a mortar (no particles with the diameter larger than 1mm are needed, and no strict requirement is required);
step 6: calcining the powder obtained in the step 5 in an argon atmosphere for 4 hours at the calcining temperature of 400 ℃, and naturally cooling to room temperature after the calcining is finished to obtain a mixed product;
and 7: and (4) washing the mixed product obtained in the step (6) with distilled water, filtering to remove a potassium chloride template, transferring the powder obtained by filtering to 50mL of distilled water, and freeze-drying to obtain black powder, namely the copper-zinc bimetal monatomic material (CuZn SAs/NC catalyst for short, the same is applied below).
The copper-zinc bimetallic monatomic material obtained in the embodiment is subjected to characterization and electrochemical carbon dioxide reduction (ERC) performance test, and the obtained CuZn bimetallic monatomic catalyst has excellent ERC performance and can be used for CO 2 Saturated 1M KHCO 3 In the solution, the Faraday Efficiency (FE) is up to 70.4%, and the current density is-35.7 mA cm at-1.1V -2 And has excellent stability. At an over-potential of-1.1V, the reduction product is mainly CH 4 And has high selectivity.
Example 5
The embodiment provides a preparation method of a bimetallic monatomic material, which comprises the following steps:
step 1: putting 0.1mmol of hydrated copper acetate, 0.1mmol of hydrated zinc acetate and 0.3mmol of o-phenanthroline into a centrifuge tube, adding 1.5mL of absolute ethyl alcohol, and performing ultrasonic treatment for 30 minutes to obtain a mixed solution;
and 2, step: dropwise adding the mixed solution obtained in the step 1 into 150mmol potassium chloride, then placing the mixed solution into a ball milling tank for ball milling, setting the rotating speed of a ball mill to be 300rpm, the time to be 5 hours, and the ball-material ratio to be 4, and obtaining a primary mixture after ball milling;
and 3, step 3: pouring 0.03mmol of leucine and 1.5mL of absolute ethyl alcohol into a centrifuge tube, and carrying out ultrasonic treatment for 30 minutes to obtain a clear solution;
and 4, step 4: dropwise adding the clear solution obtained in the step 3 into the primary mixture obtained in the step 2, continuously performing ball milling, setting the rotating speed of a ball mill to be 400rpm, the time to be 3 hours, and the ball-material ratio to be 4;
and 5: scraping the composite mixture obtained in the step 4 from the wall of a ball milling tank, and grinding the composite mixture into powder by using a mortar (no particles with the diameter larger than 1mm are needed, and no strict requirement is required);
and 6: calcining the powder obtained in the step 5 in an argon atmosphere for 4 hours at the calcining temperature of 600 ℃, and naturally cooling to room temperature after the calcining is finished to obtain a mixed product;
and 7: and (3) washing the mixed product obtained in the step (6) with distilled water, filtering to remove a potassium chloride template, transferring the powder obtained by filtering to 50mL of distilled water, and freeze-drying to obtain black powder, namely the copper-zinc bimetallic monatomic material (CuZn SAs/NC catalyst for short, the same below).
The copper-zinc bimetallic monatomic material obtained in the embodiment is subjected to characterization and electrochemical carbon dioxide reduction (ERC) performance test, and the obtained CuZn bimetallic monatomic catalyst has excellent ERC performance and can be used for CO 2 Saturated 1M KHCO 3 In the solution, the Faraday Efficiency (FE) was 75.1%, and the current density at-1.1V was-36.9 mA cm -2 And has excellent stability. At an over-potential of-1.1V, the reduction product is mainly CH 4 And has high selectivity.
Comparative example 1
The present comparative example provides a method for preparing a copper monatomic ERC catalyst, comprising the steps of:
step 1: placing 0.1mmol of hydrated copper acetate and 0.3mmol of o-phenanthroline in a centrifuge tube, adding 1.5mL of absolute ethyl alcohol, and performing ultrasonic treatment for 30 minutes to obtain a mixed solution;
step 2: dropwise adding the mixed solution obtained in the step 1 into 150mmol of potassium chloride, then placing the mixed solution into a ball milling tank for ball milling, setting the rotation speed to be 300rpm, the time to be 5 hours, and the ball-material ratio to be 4;
and step 3: pouring 0.03mmol of leucine and a certain amount of ethanol into a centrifuge tube, and carrying out ultrasonic treatment for 30 minutes to obtain a clear solution;
and 4, step 4: dropwise adding the clear solution in the step 3 into the sample subjected to ball milling in the step 2, continuing ball milling, setting the rotation speed to be 200rpm, the duration to be 3 hours, and the ball-to-material ratio to be 4;
and 5: after the ball milling is finished, scraping the sample from the wall of the ball milling tank, and grinding the sample into powder by using a mortar;
step 6: calcining the powder sample obtained in the step 5 in an argon atmosphere for 4 hours at the calcining temperature of 500 ℃, and naturally cooling the sample to room temperature after the calcining is finished;
and 7: and (3) washing the sample obtained in the step (6) by using distilled water until the potassium chloride template is removed, transferring the obtained powder into 50mL of distilled water, and freeze-drying to obtain black powder, namely the copper metal monoatomic ERC catalyst (Cu-SAs/NC catalyst for short).
The copper metal monatomic ERC catalyst obtained in the comparative example is subjected to characterization and electrochemical carbon dioxide reduction (ERC) performance test, and CO is subjected to 2 Saturated 1M KHCO 3 In solution, the Tafel slope is 265Mv dec -1 And a current density of-13.1 mA cm at-1.1V -2 。
Comparative example 2
The comparative example provides a preparation method of a zinc monatomic ERC catalyst, which comprises the following steps:
step 1: placing 0.1mmol of hydrated zinc acetate and 0.3mmol of phenanthroline in a centrifuge tube, adding 1.5mL of absolute ethyl alcohol, and carrying out ultrasonic treatment for 30 minutes to obtain a mixed solution;
step 2: dropwise adding the mixed solution obtained in the step 1 into 150mmol of potassium chloride, then placing the mixed solution into a ball milling tank for ball milling, setting the rotation speed to be 300rpm, the time to be 5 hours, and the ball-material ratio to be 4;
and step 3: pouring 0.03mmol of leucine and a certain amount of ethanol into a centrifuge tube, and carrying out ultrasonic treatment for 30 minutes to obtain a clear solution;
and 4, step 4: dropwise adding the clear solution in the step 3 into the sample subjected to ball milling in the step 2, continuing ball milling, setting the rotation speed to be 200rpm, the duration to be 3 hours, and the ball-to-material ratio to be 4;
and 5: after the ball milling is finished, scraping the sample from the wall of the ball milling tank, and grinding the sample into powder by using a mortar;
step 6: calcining the sample obtained in the step 5 in an argon atmosphere for 4 hours at the calcining temperature of 500 ℃, and naturally cooling the sample to room temperature after the calcining is finished;
and 7: washing the sample obtained in the step 6 by using distilled water until a potassium chloride template is removed, transferring the obtained powder into 50mL of distilled water, and freeze-drying to obtain black powder, namely the zinc monoatomic ERC catalyst (Zn-SAs/NC catalyst for short);
the zinc metal single atom ERC catalyst obtained in the comparative example is subjected to characterization and electrochemical carbon dioxide reduction (ERC) performance test, and CO is subjected to 2 Saturated 1M KHCO 3 In solution, the Tafel slope is 248Mv dec -1 And a current density of-12.2 mA cm at-1.1V -2 。
According to the test results of examples 1-5 and comparative examples 1-2, it can be seen that the copper-zinc bimetallic monatomic material obtained by the preparation method of the bimetallic monatomic material of the invention has excellent ERC performance in CO 2 Saturated 1M KHCO 3 In the solution, the Faraday Efficiency (FE) is 70.4-84.7%, and the current density under-1.1V (vs. RHE) is-35.7 mA cm -2 ～-49.7mA cm -2 And has excellent stability. At an over-potential of-1.1V, the reduction product is mainly CH 4 And has high selectivity.
Nothing in this specification is said to apply to the prior art.

Claims (10)

1. The preparation method of the bimetallic monatomic material is characterized by comprising the following steps of:
step 1: placing 0.1-0.2 mmol of hydrated copper acetate, 0.1-0.2 mmol of hydrated zinc acetate and 0.1-0.3 mmol of o-phenanthroline in a centrifuge tube, adding 1-3 mL of absolute ethyl alcohol, and performing ultrasonic treatment for 20-40 minutes to obtain a mixed solution;
step 2: dropwise adding the mixed solution obtained in the step 1 into 100-300 mmol potassium chloride, then placing the mixed solution into a ball milling tank for ball milling, setting the rotating speed of the ball mill to be 200-400rpm, the time to be 2-8 hours, and the ball-material ratio to be 4, wherein a primary mixture is obtained after the ball milling is finished;
and step 3: pouring 0.01-0.05mmol of leucine and 1-3 mL of absolute ethyl alcohol into a centrifuge tube, and carrying out ultrasonic treatment for 10-40 minutes to obtain a clear solution;
and 4, step 4: dropwise adding the clear solution obtained in the step 3 into the primary mixture obtained in the step 2, continuously performing ball milling, setting the rotating speed of a ball mill to be 200-400rpm, the time to be 1-5 hours, the ball-material ratio to be 4;
and 5: scraping the composite mixture obtained in the step 4 from the wall of the ball milling tank, and grinding the composite mixture into powder by using a mortar;
step 6: calcining the powder obtained in the step 5 in an argon atmosphere for 2-6 hours at 400-600 ℃, and naturally cooling to room temperature after the calcination is finished to obtain a mixed product;
and 7: and (3) washing the mixed product obtained in the step (6) with distilled water, filtering to remove a potassium chloride template, transferring the powder obtained by filtering to 50mL of distilled water, and freeze-drying to obtain black powder, namely the bimetallic monatomic material.
2. The method for preparing the bimetallic monatomic material according to claim 1, wherein in step 1, 0.1mmol of hydrated copper acetate, 0.1mmol of hydrated zinc acetate, and 0.3mmol of o-phenanthroline are used.
3. The method for preparing a bimetallic monatomic material according to claim 1, wherein in step 1, the amount of absolute ethyl alcohol is 1.5mL.
4. The method for preparing a bimetallic monatomic material as defined in claim 1, wherein in the step 2, the potassium chloride is 150mmol.
5. The method for preparing a bimetallic monatomic material according to claim 1, wherein in the step 2, the ball mill rotation speed is set to 300rpm for 5 hours.
6. The method of claim 1, wherein in step 3, the leucine content is 0.03mmol.
7. The method for preparing a bimetallic monatomic material according to claim 1, wherein in step 3, the absolute ethyl alcohol is 1.5mL, and the sonication time is 30 minutes.
8. The method for preparing a bimetallic monatomic material according to claim 1, wherein in step 4, the ball mill rotation speed is set at 200rpm for 3 hours.
9. The method of claim 1, wherein the calcination time in step 6 is 4 hours, and the calcination temperature is 500 ℃.
10. The application of the bimetallic monatomic material in new energy is characterized in that the bimetallic monatomic material is obtained by the preparation method according to any one of the claims 1 to 9 and the application process is as follows: firstly, accurately weighing 5.0mg of catalyst, 500 mu L of ethanol and 500 mu L of 0.5wt% Nafion solution, mixing the three, and carrying out ultrasonic treatment for 20min to disperse the three into a mixed solution; finally, 200. Mu.L of the mixed solution was added dropwise to 1X 1cm 2 And air-drying the carbon paper for 5 hours at room temperature to obtain the working electrode of the ERC.
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