A Cu-Ag-Ni multisite electrocatalytic material, its preparation method and application

Abstract

This invention relates to a Cu-Ag-Ni multi-site electrocatalytic material, its preparation method, and its applications, as well as the preparation method and application fields of this material. The method utilizes a sodium borohydride co-reduction method to prepare the Cu-Ag-Ni multi-site electrocatalytic material. The specific steps are as follows: copper salt, silver salt, and nickel salt in a molar ratio of 40:1:1 are dissolved in deionized water to form a homogeneous solution. This solution is then injected into a 1M sodium borohydride solution and stirred in an ice bath for 2 hours. After the reaction, the precipitate is obtained by centrifugation and washed alternately with ethanol and water, then vacuum dried at room temperature for 12 hours to obtain the Cu-Ag-Ni electrocatalytic material. This electrocatalytic material exhibits excellent performance in room temperature electrocatalytic carbon dioxide conversion. Furthermore, the preparation method of the Cu-Ag-Ni multi-site electrocatalytic material of this invention has significant advantages: mild reaction conditions, low energy consumption, simple process flow, and high cost-effectiveness, making it highly suitable for large-scale industrial production and application.

Description

Technical Field

[0001] This invention belongs to the field of catalyst preparation, specifically relating to a Cu-Ag-Ni multisite electrocatalytic material, its preparation method and application, and particularly to a method for preparing a Cu-Ag-Ni multisite electrocatalytic material and its application in the electrocatalytic reduction of carbon dioxide to prepare multi-carbon products. Background Technology

[0002] Carbon dioxide (CO2), as a greenhouse gas, has a profound impact on global climate, but it is also considered an abundant carbon source. Through electrocatalytic reduction technology, CO2 can be converted into high-value chemicals and fuels such as methanol, ethanol, and ethylene, which are widely used in the chemical, energy, and transportation sectors, playing a vital role in sustainable social development. In electrocatalysis, metal catalysts play a central role, with different metals significantly influencing the reduction pathway and product distribution of CO2. For example, copper (Cu) and nickel (Ni) can catalyze the formation of multi-carbon products, while gold, silver (Ag), and lead (Pb) mainly produce single-carbon products such as carbon monoxide (CO) or formic acid (HCOOH). However, this field still faces many challenges, such as the complexity of multi-carbon product formation processes, the need for high energy input and precise control of reaction conditions, and the difficulty for metal catalysts to simultaneously meet the requirements of high activity and high selectivity. Stability and regenerability are also key limiting factors for industrial applications.

[0003] To improve the performance of metal catalysts in the electrocatalytic reduction of CO2 to produce multi-carbon products, researchers have conducted extensive research. By controlling the surface structure and composition of metal catalysts, such as constructing nanostructures, alloying, or surface modification, their adsorption and activation capabilities for CO2 can be optimized, improving catalytic activity and selectivity. Simultaneously, optimizing electrocatalytic reaction conditions, such as electrolyte type, concentration, temperature, and pressure, can further regulate the reaction pathway and product distribution of CO2 reduction. Furthermore, the regenerability and stability of metal catalysts are current research hotspots. Designing rational catalyst structures and preparation processes to improve catalyst resistance to poisoning and durability is key to extending their lifespan and reducing production costs. Developing renewable metal catalysts or utilizing waste metals to prepare catalysts is also an important pathway to achieving sustainable development. In the future, metal catalysts will play an even more important role in promoting sustainable social development, but further in-depth research is still needed in catalyst design, preparation processes, and reaction condition optimization. Summary of the Invention

[0004] The purpose of this invention is to provide a method for preparing Cu-Ag-Ni multi-site electrocatalytic materials. The method is a simple sodium borohydride reduction process and can be used for large-scale preparation of Cu-Ag-Ni multi-site electrocatalytic materials.

[0005] Another objective of this invention is to provide a Cu-Ag-Ni multisite electrocatalytic material product and its application.

[0006] The specific technical solution to achieve the purpose of this invention is as follows: using different metal salts as raw materials, Cu-Ag-Ni multi-site electrocatalytic materials are prepared by sodium borohydride reduction method, including the following steps:

[0007] Step 1: Preparation of copper salt solution:

[0008] Dissolve 3 mM copper salt, 0.75 mM silver salt and 0.75 mM nickel salt in deionized water and stir for 30 min until completely dissolved;

[0009] Step 2: Preparation of Cu-Ag-Ni multi-site electrocatalytic materials:

[0010] The prepared solution was injected into a 1M sodium borohydride solution and stirred in an ice bath for 2 hours. After the reaction was complete, the precipitate was obtained by centrifugation and washed several times alternately with ethanol and water. The precipitate was then dried under vacuum at room temperature for 12 hours to obtain the Cu-Ag-Ni multisite electrocatalytic material.

[0011] Furthermore, in the preparation method of Cu-Ag-Ni multi-site electrocatalytic material, the metal salt solution in step 1 can be any type of metal salt solution among nitrate, acetate, and gluconate.

[0012] Furthermore, in the preparation method of Cu-Ag-Ni multi-site electrocatalytic material, the reducing agent in step 2 can be any one of sodium borohydride, potassium borohydride, lithium borohydride, zinc borohydride, etc., and the amount of reducing agent added is excessive.

[0013] Cu-Ag-Ni multisite electrocatalytic materials were prepared according to the above preparation method.

[0014] This invention also provides the application of Cu-Ag-Ni multisite electrocatalytic materials in the electrocatalytic reduction of carbon dioxide to prepare multicarbon products.

[0015] One of the objectives of this invention is to provide the application of Cu-Ag-Ni multisite electrocatalytic materials prepared according to the method provided by this invention in the electrocatalytic reduction of carbon dioxide, particularly in the electrocatalytic reduction of carbon dioxide to prepare multi-carbon products.

[0016] The advantages of the Cu-Ag-Ni multi-site electrocatalytic material preparation method provided by this invention are as follows:

[0017] This invention proposes a novel method for preparing Cu-Ag-Ni multisite electrocatalytic materials, which uses a mixed solution of widely available and cost-effective copper, silver, and nickel salts as starting materials.

[0018] The sodium borohydride reduction technology makes the entire preparation process not only simple and fast, but also highly scalable, creating favorable conditions for large-scale industrial production.

[0019] The obtained Cu-Ag-Ni multisite electrocatalytic material exhibits excellent electrocatalytic activity and robust structural stability, which gives it significant advantages in electrochemical applications. Attached Figure Description

[0020] Figure 1 The image shows a SEM image of the Cu-Ag-Ni material prepared in Example 1.

[0021] Figure 2 The graph shows the electrocatalytic carbon dioxide reduction performance of the Cu-Ag-Ni material prepared in Example 1.

[0022] Figure 3 This is an electrolytic stability diagram of the Cu-Ag-Ni material prepared in Example 1 for the electrocatalytic reduction of carbon dioxide. Detailed Implementation

[0023] The technical solution of the present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments, but the present invention is not limited to the following embodiments.

[0024] Example 1

[0025] 3 mM copper nitrate, 0.75 mM silver nitrate, and 0.75 mM nickel nitrate were dissolved in 25 mL of deionized water and stirred continuously at room temperature for 30 min to ensure complete dissolution of all metal salts and the formation of a homogeneous solution. The prepared solution was then added to 15 mL of 1 M sodium borohydride solution and stirred in an ice bath for 2 h. After the reaction was complete, the precipitate was obtained by centrifugation and washed several times alternately with ethanol and water. The precipitate was then dried under vacuum at room temperature for 12 h to obtain the Cu-Ag-Ni multisite electrocatalytic material.

[0026] Figure 1 The image shows a SEM image of the Cu-Ag-Ni multisite electrocatalytic material obtained in Example 1. Figure 1 It is known that the Cu-Ag-Ni multisite electrocatalytic material exhibits a network structure composed of interconnected nanoparticles, the size of which is approximately 30–40 nanometers.

[0027] Example 2

[0028] 3 mM copper acetate, 0.75 mM silver acetate, and 0.75 mM nickel acetate were dissolved in 25 mL of deionized water and stirred continuously at room temperature for 30 min to ensure complete dissolution of all metal salts and the formation of a homogeneous solution. The prepared solution was then added to 15 mL of 1 M sodium borohydride solution and stirred in an ice bath for 2 h. After the reaction was complete, the precipitate was obtained by centrifugation and washed several times alternately with ethanol and water. The precipitate was then dried under vacuum at room temperature for 12 h to obtain the Cu-Ag-Ni multisite electrocatalytic material.

[0029] Example 3

[0030] 3 mM copper nitrate, 0.75 mM silver nitrate, and 0.75 mM nickel nitrate were dissolved in 25 mL of deionized water and stirred continuously at room temperature for 30 min to ensure complete dissolution of all metal salts and the formation of a homogeneous solution. The prepared solution was then added to 15 mL of 1 M potassium borohydride solution and stirred in an ice bath for 2 h. After the reaction was complete, the precipitate was obtained by centrifugation and washed several times alternately with ethanol and water. The precipitate was then dried under vacuum at room temperature for 12 h to obtain the Cu-Ag-Ni multisite electrocatalytic material.

[0031] Example 4

[0032] All corresponding electrochemical tests were performed on the Shanghai Chenhua Electrochemical Workstation (CHI 660E). Electrolysis tests were conducted in a flow electrolytic cell using a three-electrode system, including a working electrode (Cu-Ag-Ni multi-site electrocatalytic material), nickel foam as the counter electrode, and Ag / AgCl as the reference electrode. During electrolysis, the cathode and anolyte chambers were separated by anion exchange membranes, and both chambers used 1M KOH electrolyte. Electrolysis was performed at a constant potential for 1 hour at each potential, collecting gaseous and liquid products.

[0033] The components of the gaseous and liquid products were detected and analyzed using a gas chromatograph (Agilent 8890) and a nuclear magnetic resonance spectrometer (¹H NMR, Bruker Ascend 500MHz). For example... Figure 2 As shown, the Cu-Ag-Ni multi-site electrocatalytic material exhibits a Faradaic efficiency of 93.2% and a current density of 818.1 mA cm⁻¹ for multi-carbon products at an electrolysis potential of -1.38 V vs. RHE. -2 .

[0034] We further evaluated the stability of the Cu-Ag-Ni multisite electrocatalytic material at -1.38 V vs. RHE electrolysis potential. Figure 3 As shown, during continuous operation for 9 hours, the system maintained a stable current density, and the Faraday efficiency (FE) of the multi-carbon products remained above 90%.

[0035] The applicant declares that the specific embodiments of the present invention have been described in detail above, but these are merely illustrative examples, and the present invention is not limited to the specific embodiments described above. For those skilled in the art, any equivalent modifications and alternatives to the present invention are within the scope of protection of the present invention. Therefore, all equivalent transformations and adjustments made without departing from the core concept and scope of protection of the present invention are also within the scope of the present invention.

Claims

1. A method for preparing a Cu-Ag-Ni multi-site electrocatalytic material, characterized in that, The specific steps include the following: Step 1: Preparation of metal salt solution: Dissolve 3 mM copper salt, 0.75 mM silver salt and 0.75 mM nickel salt in deionized water and stir for 30 min until completely dissolved; Step 2: Preparation of Cu-Ag-Ni multi-site electrocatalytic materials: The solution prepared in step 1 above was injected into a reducing agent solution with a concentration of 1 M and stirred for 2 hours under ice bath conditions. After the reaction was completed, the precipitate was obtained by centrifugation and washed 6 times alternately with ethanol and water. The precipitate was then dried under vacuum conditions at room temperature for 12 hours to obtain Cu-Ag-Ni multisite electrocatalytic material. The reducing agent in step 2 is any one of sodium borohydride, potassium borohydride, lithium borohydride, and zinc borohydride.

2. The preparation method of the Cu-Ag-Ni multi-site electrocatalytic material according to claim 1, characterized in that, The metal salt solution in step 1 is any one of the metal salt solutions of nitrate or acetate.

3. The Cu-Ag-Ni multisite electrocatalytic material prepared by the preparation method according to any one of claims 1-2.

4. The application of the Cu-Ag-Ni multisite electrocatalytic material according to claim 3 in the electrocatalytic reduction of carbon dioxide to prepare multi-carbon products.

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