Preparation method of copper-manganese loaded biochar composite electrocatalytic material, product and application thereof

Abstract

The present application relates to a kind of copper manganese load biochar composite electrocatalytic material preparation method and its product and application, after screening, washing and drying of coconut shell powder, the coconut shell powder is pyrolyzed carbonization in nitrogen atmosphere at preset temperature, after centrifugal washing and drying treatment, biochar is obtained;The biochar is prepared by equal-volume impregnation method with copper precursor and manganese precursor, and copper manganese load biochar electrode material is obtained.The existence of the synergistic effect of two transition metals can make the material show very excellent electrochemical performance.The preparation method is simple in operation, and the preparation cost is low, suitable for large-scale production.

Description

Technical Field

[0001] This invention relates to the technical field of electrochemical materials, specifically to a method for preparing a copper-manganese supported biochar composite electrocatalytic material, its product, and its application in electrochemical hydrogen production materials. Background Technology

[0002] With the continuous growth of the population and the ever-increasing demand for energy, the two major problems of energy crisis and environmental pollution are escalating daily. Therefore, there is an urgent need to develop green, clean, and sustainable energy sources to address these issues. Hydrogen produced through water electrolysis can effectively solve the problem of renewable energy consumption and represents a promising clean energy technology path. Therefore, improving electrocatalytic efficiency and reducing technological costs are key to breakthroughs in this technological development.

[0003] Biochar is a low-cost carbon material with good porosity and a high specific surface area. Compared to traditional carbon materials, biochar has a wider range of sources, lower production costs, and may contain graphene-like structures. Patent announcement number 202210524170.4 disclosed a ball-milled Fe3O4@biochar cathode material and its preparation method and application, which can obtain supported Fe3O4@biochar cathode material through ball milling. Recent studies have shown that, due to the redox properties of copper and manganese similar to iron, copper-manganese co-modified biochar composites often exhibit superior catalytic performance compared to single-metal modified biochar catalysts, thanks to the potential synergistic effect between the two metals during material preparation and activation. For electrode nanomaterials, existing materials mainly utilize noble metals and transition metal components to form single-metal structures; these methods always suffer from high costs and complex synthesis methods. Developing a low-cost, abundant transition metal electrocatalytic material remains a key issue. Summary of the Invention

[0004] In view of the problems existing in the above materials, and the fact that there are currently no biochar-based electrodes on the market for hydrogen production by water electrolysis, the purpose of this invention is to provide a method for preparing a copper-manganese supported biochar composite electrocatalytic material.

[0005] Another objective of this invention is to provide a copper-manganese supported biochar composite electrocatalytic material product prepared by the above method.

[0006] Another object of the present invention is to provide an application of the above-mentioned product.

[0007] The objective of this invention is achieved through the following scheme: a method for preparing a copper-manganese supported biochar composite electrocatalytic material, comprising the following steps:

[0008] a. Preparation of biochar: Coconut shell powder with a moisture content of less than 1% is placed in a boat-shaped crucible, covered, and pyrolyzed in a tube furnace at a preset temperature of 300~1000℃ under protective gas conditions; after cooling to ambient temperature, the sample is taken out and washed with water, acid washed by water bath heating, and then washed with water to adjust the pH to 6.5 to 7.5 neutral. After drying, coconut shell biochar is obtained.

[0009] b. Preparation of copper-manganese supported biochar composite material: Weigh 10 g of coconut shell biochar obtained in step a and disperse it in an aqueous solution containing copper precursor and manganese precursor in a molar ratio of 1:1 to 3:4; then transfer the obtained solution to a vacuum oven and dry it at 110°C. After the sample is dried, the precursor of the composite material can be obtained; collect the obtained precursor and calcine it in a muffle furnace at 300-600°C for 2 hours to obtain the copper-manganese supported biochar composite material.

[0010] Preferably, the protective gas in step a comprises any one of the following: nitrogen, argon, or helium.

[0011] Preferably, the water bath temperature range in step a is between 50 and 80°C.

[0012] Preferably, the acid solution used in the pickling process in step a includes any one of the following: dilute hydrochloric acid, dilute sulfuric acid, or dilute nitric acid.

[0013] Preferably, the copper precursor in step b includes any one of the following: copper chloride, cuprous chloride, copper nitrate, copper sulfate, copper acetate, copper sulfide, cuprous sulfide, copper carbonate, and copper perchlorate.

[0014] The manganese precursor mentioned in step b includes any one of the following: manganese chloride, manganese chloride, manganese nitrate, manganese sulfate, manganese acetate, manganese sulfide, manganese carbonate, and manganese perchlorate.

[0015] This invention provides a copper-manganese supported biochar composite electrocatalytic material, which is prepared according to any of the methods described above.

[0016] This invention provides an application of a copper-manganese supported biochar composite electrocatalytic material in electrochemical hydrogen production materials.

[0017] Compared with existing technologies, the technical features of this invention are that, according to the embodiments of this disclosure, the copper-manganese / biochar composite material, as an amorphous catalyst, possesses excellent lattice defects and catalytic performance, resulting in copper-manganese / biochar electrodes made from the copper-manganese / biochar composite material exhibiting good conductivity, mass transfer efficiency, and significant electrocatalytic performance. The synthesis method of this composite material is simple, the preparation cost is low, and it has good prospects for practical applications. The synergistic effect of the two transition metals enables the material to exhibit excellent electrochemical performance. The preparation method is simple to operate, low in cost, and suitable for large-scale production. Detailed Implementation

[0018] This embodiment is implemented based on the technical solution of the present invention, and provides detailed implementation methods and specific operation processes. However, the scope of protection of the present invention is not limited to the following embodiment.

[0019] Example 1:

[0020] A copper-manganese supported biochar composite electrocatalytic material is prepared according to the following steps:

[0021] a. Preparation of biochar: 10 g of coconut shell powder with a moisture content of less than 1% was placed in a boat-shaped crucible, covered, and pyrolyzed in a tube furnace at 500℃ under nitrogen protection. After cooling to ambient temperature, the sample was taken out and washed with water, then acid-washed with 0.2 mol / L hydrochloric acid in a 50℃ water bath, then washed with water to adjust the pH to 7, and dried to obtain coconut shell biochar.

[0022] b. Preparation of copper-manganese supported biochar composite material: Weigh 10 g of coconut shell biochar obtained in step a, disperse it in an aqueous solution of copper acetate and manganese acetate mixed in a molar ratio of 1:1, then transfer the obtained solution to a vacuum oven and dry it at 110°C. After the sample is dried, the precursor of the composite material can be obtained. Collect the obtained precursor and calcine it in a muffle furnace at 350°C for 2 hours to obtain the copper-manganese supported biochar composite material.

[0023] The electrode material obtained in Example 1 was subjected to electrocatalytic testing. The electrolyte was 1M H2SO4, the silver / silver chloride electrode was used as the reference electrode, and the platinum sheet electrode was used as the counter electrode. It could achieve 10 mA / cm² with only 100 mV overpotential. 2 The current density is high, and the material can remain stable for less than 4 hours. In contrast, commercially available Pt / C (20%) requires 50 mV. This demonstrates the superior performance of this electrode.

[0024] Example 2:

[0025] A copper-manganese supported biochar composite electrocatalytic material was prepared using steps similar to those in Example 1, as follows:

[0026] a. Preparation of biochar: 12 g of coconut shell powder with a moisture content of less than 1% was placed in a boat-shaped crucible, covered, and pyrolyzed in a tube furnace at 600℃ under helium protection. After cooling to ambient temperature, the sample was removed, washed with water, heated in a 55℃ water bath with 0.5 mol / L nitric acid, washed again with water to adjust the pH to 6.8 to 7.2, and dried to obtain coconut shell biochar.

[0027] b. Preparation of copper-manganese supported biochar composite material: Weigh 10 g of coconut shell biochar obtained in step a, disperse it in an aqueous solution of copper nitrate and manganese acetate mixed in a molar ratio of 1:2, then transfer the resulting solution to a vacuum oven and dry it at 110°C. After the sample is dried, the precursor of the composite material can be obtained. Collect the obtained precursor and calcine it in a muffle furnace at 450°C for 2 hours to obtain the copper-manganese supported biochar composite material.

[0028] The electrode material obtained in Example 2 was subjected to electrocatalytic testing. The electrolyte was 1M H2SO4, the silver / silver chloride electrode was used as the reference electrode, and the platinum sheet electrode was used as the counter electrode. It could reach 10 mA / cm² with an overpotential of only 110 mV. 2 The current density is stable, and the material can maintain this stability for up to 5 hours. This demonstrates that the electrode exhibits excellent performance and stability.

[0029] Example 3:

[0030] A method for preparing a copper-manganese supported biochar composite electrocatalytic material includes the following steps:

[0031] a. Preparation of biochar: 8 g of coconut shell powder with a moisture content of less than 1% was placed in a boat-shaped crucible, covered, and pyrolyzed in a tube furnace at 700℃ under helium protection. After cooling to ambient temperature, the sample was taken out and washed with water, then acid-washed with 0.5 mol / L sulfuric acid in a 60℃ water bath, then washed with water to adjust the pH to 7, and dried to obtain coconut shell biochar.

[0032] b. Preparation of copper-manganese supported biochar composite material: Weigh 10 g of coconut shell biochar obtained in step a, disperse it in an aqueous solution of copper acetate and manganese acetate mixed in a molar ratio of 2:3, then transfer the obtained solution to a vacuum oven and dry it at 110°C. After the sample is dried, the precursor of the composite material can be obtained. Collect the obtained precursor and calcine it in a muffle furnace at 400°C for 2 hours to obtain the copper-manganese supported biochar composite material.

[0033] The electrode material obtained in Example 3 was subjected to electrocatalytic testing. The electrolyte was 1M H2SO4, the silver / silver chloride electrode was used as the reference electrode, and the platinum sheet electrode was used as the counter electrode. It could reach 10 mA / cm with an overpotential of only 115 mV. 2 The current density is stable, and the material can maintain this stability for up to 4.5 hours. This demonstrates that the electrode exhibits good performance and stability.

[0034] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. The application of a copper-manganese supported biochar composite electrocatalytic material in electrochemical hydrogen production materials, characterized in that, The copper-manganese supported biochar composite electrocatalytic material was prepared using the following steps: a. Preparation of biochar: Place coconut shell powder with a moisture content of less than 1% in a boat-shaped crucible, cover it, and pyrolyze it in a tube furnace at a preset temperature of 300~1000℃ under protective gas conditions. After cooling to ambient temperature, the sample is removed and washed with water, then acid-washed by water bath heating, then washed with water again to adjust the pH to 6.5 to 7.5 neutral, and dried to obtain coconut shell biochar. b. Preparation of copper-manganese supported biochar composite material: Weigh 10 g of coconut shell biochar obtained in step a and disperse it in an aqueous solution containing copper precursor and manganese precursor in a molar ratio of 1:1 to 3:4; then transfer the obtained solution to a vacuum oven and dry it at 110°C. After the sample is dried, the precursor of the composite material can be obtained; collect the obtained precursor and calcine it in a muffle furnace at 300-600°C for 2 hours to obtain the copper-manganese supported biochar composite material.

2. The application of the copper-manganese supported biochar composite electrocatalytic material according to claim 1 in electrochemical hydrogen production materials, characterized in that, The protective gas mentioned in step a includes any one of the following: nitrogen, argon, and helium.

3. The application of the copper-manganese supported biochar composite electrocatalytic material according to claim 1 in electrochemical hydrogen production materials, characterized in that, The water bath temperature range mentioned in step a refers to 50~80℃.

4. The application of the copper-manganese supported biochar composite electrocatalytic material according to claim 1 in electrochemical hydrogen production materials, characterized in that, The acid solution used in the pickling process described in step a includes any one of the following: dilute hydrochloric acid, dilute sulfuric acid, or dilute nitric acid.

5. The application of the copper-manganese supported biochar composite electrocatalytic material according to claim 1 in electrochemical hydrogen production materials, characterized in that, The copper precursor mentioned in step b includes any one of the following: copper chloride, cuprous chloride, copper nitrate, copper sulfate, copper acetate, copper sulfide, cuprous sulfide, copper carbonate, and copper perchlorate; The manganese precursor mentioned in step b includes any one of manganese chloride, manganese chloride, manganese nitrate, manganese sulfate, manganese acetate, manganese sulfide, manganese carbonate, and manganese perchlorate.

6. The application of the copper-manganese supported biochar composite electrocatalytic material according to any one of claims 1 to 5 in electrochemical hydrogen production materials, characterized in that, Prepare according to the following steps: a. Preparation of biochar: 10 g of coconut shell powder with a moisture content of less than 1% was placed in a boat-shaped crucible, covered, and pyrolyzed in a tube furnace at 500℃ under nitrogen protection. After cooling to ambient temperature, the sample was taken out and washed with water, then acid-washed with 0.2 mol / L hydrochloric acid in a 50℃ water bath, then washed with water to adjust the pH to 7, and dried to obtain coconut shell biochar. b. Preparation of copper-manganese supported biochar composite material: Weigh 10 g of coconut shell biochar obtained in step a, disperse it in an aqueous solution of copper acetate and manganese acetate mixed in a molar ratio of 1:1, then transfer the obtained solution to a vacuum oven and dry it at 110°C. After the sample is dried, the precursor of the composite material can be obtained. Collect the obtained precursor and calcine it in a muffle furnace at 350°C for 2 hours to obtain the copper-manganese supported biochar composite material.

7. The application of the copper-manganese supported biochar composite electrocatalytic material according to any one of claims 1 to 5 in electrochemical hydrogen production materials, characterized in that, Prepare according to the following steps: a. Preparation of biochar: 12 g of coconut shell powder with a moisture content of less than 1% was placed in a boat-shaped crucible, covered, and pyrolyzed in a tube furnace at 600℃ under helium protection. After cooling to ambient temperature, the sample was removed, washed with water, heated in a 55℃ water bath with 0.5 mol / L nitric acid, washed again with water to adjust the pH to 6.8 to 7.2, and dried to obtain coconut shell biochar. b. Preparation of copper-manganese supported biochar composite material: Weigh 10 g of coconut shell biochar obtained in step a, disperse it in an aqueous solution of copper nitrate and manganese acetate mixed in a molar ratio of 1:2, then transfer the resulting solution to a vacuum oven and dry it at 110°C. After the sample is dried, the precursor of the composite material can be obtained. Collect the obtained precursor and calcine it in a muffle furnace at 450°C for 2 hours to obtain the copper-manganese supported biochar composite material.

8. The application of the copper-manganese supported biochar composite electrocatalytic material according to any one of claims 1 to 5 in electrochemical hydrogen production materials, characterized in that, Prepare according to the following steps: a. Preparation of biochar: Place 8 g of coconut shell powder with a moisture content of less than 1% in a boat-shaped crucible, cover it, and pyrolyze it in a tube furnace at 700℃ under the protection of helium. After cooling to ambient temperature, the sample was removed and washed with water, then heated in a 60°C water bath with 0.5 mol / L sulfuric acid, then washed again with water to adjust the pH to 7, and dried to obtain coconut shell biochar. b. Preparation of copper-manganese supported biochar composite material: Weigh 10 g of coconut shell biochar obtained in step a, disperse it in an aqueous solution of copper acetate and manganese acetate mixed in a molar ratio of 2:3, then transfer the obtained solution to a vacuum oven and dry it at 110°C. After the sample is dried, the precursor of the composite material can be obtained. Collect the obtained precursor and calcine it in a muffle furnace at 400°C for 2 hours to obtain the copper-manganese supported biochar composite material.