A metal-anchored graphdiyne material, its preparation method, and applications

Abstract

The present invention belongs to the technical field of catalysts, and particularly relates to a metal-anchored graphdiyne material, a preparation method thereof, and an application. The method is realized through the following steps: putting graphdiyne and metal chloride into two porcelain boats respectively and placing them in a tube furnace; evacuating the tube furnace, and then under an ammonia atmosphere, heating for reaction, and cooling after the reaction ends to obtain the metal-anchored graphdiyne material. The present invention utilizes the evaporation adsorption of metal chloride on NH3, and anchors the metal by using the unique sp hybrid carbon of graphdiyne, and a non-precious metal-based carbon nanoelectrocatalytic material with low cost, high activity and high stability is prepared at low temperature. The electrocatalytic oxygen reduction and oxygen evolution reactions are simultaneously realized by using the synergistic effect of metal, nitrogen-carbon active centers, and the catalytic activity and stability are significantly improved, providing theoretical support and technical support for the industrial application of preparing non-precious metal electrocatalysts at low temperature.

Description

Technical Field

[0001] The present invention belongs to the technical field of catalysts, and particularly relates to a metal-anchored graphdiyne material, a preparation method thereof, and an application thereof. Background Art

[0002] With the growth of energy demand and the aggravation of environmental pollution, the development and utilization of clean energy are important ways to achieve green and sustainable development. Electrocatalytic materials play a key role in energy conversion technologies including fuel cells and metal-air batteries. The electrode reactions in fuel cells and metal-air batteries, including oxygen reduction reaction (ORR), oxygen evolution reaction (OER), and hydrogen evolution reaction (HER), have slow kinetics and require the introduction of catalysts to improve the reaction rate. Noble metals such as Pt and Ir show high activity towards various electrocatalytic processes. For example, Ir shows high activity towards the oxygen evolution reaction, and Pt shows high activity towards the oxygen reduction reaction and the hydrogen evolution reaction. Therefore, they are often used as electrocatalysts. Although noble metals show excellent catalytic performance, their high price hinders their widespread application. Selecting suitable catalyst materials is the key to changing the kinetics of the oxygen electrode reaction. At present, the development of highly efficient and low-cost catalysts has become an urgent need for the application of electrocatalytic technologies.

[0003] In the development of non-noble metal electrocatalysts, carbon materials have received extensive attention due to their high cost performance, good conductivity, high specific surface area, and good stability. The performance in electrocatalytic oxygen reduction and oxygen evolution reactions has an important impact on carbon materials. Therefore, developing a highly active and highly stable metal-anchored graphdiyne material that can be simultaneously applied to electrocatalytic oxygen reduction and oxygen evolution reactions and realizing the widespread application of non-noble metal electrocatalysts in commercial fuel cells has broad economic and social benefits. Summary of the Invention

[0004] In order to obtain a highly active and highly stable non-noble metal electrocatalytic material that can be simultaneously applied to electrocatalytic oxygen reduction and oxygen evolution reactions, the present invention provides a metal-anchored graphdiyne material, which is obtained by adsorbing metal chloride on NH3 and using the sp hybrid carbon of graphdiyne to anchor the metal.

[0005] Another object of the present invention is to provide a preparation method of the above metal-anchored graphdiyne material. The preparation method is simple to operate and solves the problems of high cost and low reserves of noble metal catalysts in the prior art.

[0006] Another object of the present invention is to provide the application of the above metal-anchored graphdiyne material in electrocatalytic oxygen reduction and oxygen evolution reactions. This material has excellent electrocatalytic performance.

[0007] To solve the above technical problems, the present invention adopts the following technical solutions:

[0008] The present invention provides a method for preparing a metal-anchored graphdiyne material, comprising the following steps:

[0009] (1) Place graphdiyne and metal chloride into two porcelain boats respectively, and place them in a tube furnace;

[0010] (2) Evacuate the tube furnace, then under an ammonia atmosphere, raise the temperature for reaction, and after the reaction ends, lower the temperature to obtain the metal-anchored graphdiyne material.

[0011] Further, in step (1), in the tube furnace, the porcelain boat containing metal chloride is close to the air inlet end, and the porcelain boat containing graphdiyne is close to the air outlet end.

[0012] Further, in step (1), the metal chloride is cobalt chloride hexahydrate, ferric chloride, manganese chloride or copper chloride; the mass ratio of the metal chloride to graphdiyne is 1:50 - 150.

[0013] Further, in step (2), the inlet rate of ammonia is 140 - 160 mL / min.

[0014] Further, in step (2), the temperature-raising reaction is to raise the temperature to 700 - 900 °C at a temperature-raising rate of 4 - 6 °C / min and hold for 2 - 4 h.

[0015] The present invention also provides a metal-anchored graphdiyne material prepared by using the above preparation method.

[0016] The present invention also provides an application of the metal-anchored graphdiyne material in the field of electrocatalysis.

[0017] The beneficial effects of the present invention are as follows:

[0018] (1) The present invention utilizes the evaporation adsorption of metal chloride on NH3 and utilizes the unique sp hybrid carbon of graphdiyne to anchor the metal, and a non-noble metal-based carbon nano electrocatalytic material with low cost, high activity and high stability is prepared at low temperature. The synergistic effect of metal, nitrogen-carbon active centers is used to simultaneously realize electrocatalytic oxygen reduction and oxygen evolution reaction, and the catalytic activity and stability are significantly improved, providing theoretical support and technical support for the industrial application of low-temperature preparation of non-noble metal electrocatalysts. Description of the Drawings

[0019] Figure 1 Linear sweep polarization curves of ORR (a) and OER (b) for Examples 1 - 3.

[0020] Figure 2 Linear sweep polarization curves of ORR (a) and OER (b) for Example 1 and Comparative Examples 1 - 2.

[0021] Figure 3 Scanning electron microscopy image of the metal-anchored graphdiyne material prepared in Example 1.

[0022] Figure 4 Transmission electron microscopy image of the metal-anchored graphdiyne material prepared in Example 1. Detailed implementation manners

[0023] The exemplary embodiments disclosed by the present invention will be described in more detail below with reference to the accompanying drawings. These embodiments are for a more thorough understanding of the present invention and for fully communicating the scope of the present invention to those skilled in the art. Although the exemplary embodiments of the present invention are shown in the drawings, it should be understood that the present invention should not be limited by the embodiments described herein.

[0024] Example 1

[0025] (1) Take 0.02 g of graphdiyne and 2 g of cobalt chloride hexahydrate and place them in two porcelain boats respectively, and place them in a tube furnace. The porcelain boat containing cobalt chloride hexahydrate is at the upstream end (inlet), and the porcelain boat containing graphdiyne is at the downstream end (outlet);

[0026] (2) Evacuate the tube furnace for 20 min, then introduce ammonia at an inlet rate of 140 mL / min. Under the ammonia atmosphere, heat it at a heating rate of 5 °C / min to 800 °C and hold for 3 h, then cool down to obtain the metal-anchored graphdiyne material.

[0027] Figure 3 、 Figure 4 Are the scanning electron microscopy image and transmission electron microscopy image of the metal-anchored graphdiyne material respectively.

[0028] Example 2

[0029] (1) Take 0.02 g of graphdiyne and 1 g of cobalt chloride hexahydrate and place them in two porcelain boats respectively, and place them in a tube furnace. The porcelain boat containing cobalt chloride hexahydrate is at the upstream end (inlet), and the porcelain boat containing graphdiyne is at the downstream end (outlet);

[0030] (2) Evacuate the tube furnace for 20 min, then introduce ammonia at an inlet rate of 150 mL / min. Under the ammonia atmosphere, heat it at a heating rate of 5 °C / min to 800 °C and hold for 3 h, then cool down to obtain the metal-anchored graphdiyne material.

[0031] Example 3

[0032] (1) Take 0.02 g of graphdiyne and 3 g of cobalt chloride hexahydrate and place them in two porcelain boats respectively, and place them in a tube furnace. The porcelain boat containing cobalt chloride hexahydrate is at the upstream end (inlet), and the porcelain boat containing graphdiyne is at the downstream end (outlet);

[0033] (2) Evacuate the tubular furnace for 20 min, then introduce ammonia gas at an inlet rate of 160 mL / min. Under an ammonia atmosphere, heat it up to 800 °C at a heating rate of 5 °C / min and hold for 3 h, then cool down to obtain the metal-anchored graphdiyne material.

[0034] Comparative Example 1

[0035] (1) Take 0.02 g of graphdiyne and 2 g of cobalt chloride hexahydrate and place them in two porcelain boats respectively, and place them in the tubular furnace. The porcelain boat containing cobalt chloride hexahydrate is at the upstream end (inlet), and the porcelain boat containing graphdiyne is at the downstream end (outlet);

[0036] (2) Evacuate the tubular furnace for 20 min, then introduce ammonia gas at an inlet rate of 150 mL / min. Under an ammonia atmosphere, heat it up to 500 °C at a heating rate of 5 °C / min and hold for 3 h, then cool down to obtain the metal-anchored graphdiyne material.

[0037] Comparative Example 2

[0038] (1) Take 0.02 g of graphdiyne and 3 g of cobalt chloride hexahydrate and place them in two porcelain boats respectively, and place them in the tubular furnace. The porcelain boat containing cobalt chloride hexahydrate is at the upstream end (inlet), and the porcelain boat containing graphdiyne is at the downstream end (outlet);

[0039] (2) Evacuate the tubular furnace for 20 min, then introduce ammonia gas at an inlet rate of 150 mL / min. Under an ammonia atmosphere, heat it up to 800 °C at a heating rate of 5 °C / min and hold for 1 h, then cool down to obtain the metal-anchored graphdiyne material.

[0040] Effect Example

[0041] Using a three-electrode test system, in electrolyte solutions of 0.1 M KOH and 1 M KOH respectively, the ORR and OER electrocatalytic performance tests of Examples 1, 2, 3 and Comparative Examples 1, 2 were carried out by the Chenhua CHI760E electrochemical workstation.

[0042] (I) From the linear sweep polarization curve graphs of ORR ( Figure 1 ) of Examples 1-3, it can be seen that Example 1 all showed relatively high catalytic activity, indicating that the amount of metal chloride has a significant influence on the catalytic performance of the material.

[0043] (II) From the linear sweep polarization curve graphs of ORR ( Figure 2 ) of Example 1 and Comparative Examples 1, 2, it can be seen that Example 1 still showed the best catalytic activity, indicating that the deposition time of metal chloride of 3 h and the pyrolysis temperature of 800 °C have a strong influence on the performance of the material.

Claims

1. A preparation method of a metal-anchored graphdiyne material, characterized in that, It includes the following steps: (1) Put graphdiyne and metal chloride into two porcelain boats respectively and place them in a tube furnace; The metal chloride is cobalt chloride hexahydrate, iron chloride, manganese chloride or copper chloride; the mass ratio of the metal chloride to graphdiyne is 1:50 - 150; (2) Vacuum the tube furnace, then under an ammonia atmosphere, heat up for reaction, and cool down after the reaction ends to obtain a metal-anchored graphdiyne material; The heating-up reaction is to heat up to 700 - 900 °C at a heating rate of 4 - 6 °C / min and hold for 2 - 4 h.

2. The preparation method according to claim 1, wherein In step (1), in the tube furnace, the porcelain boat containing the metal chloride is close to the air inlet end, and the porcelain boat containing graphdiyne is close to the air outlet end.

3. The preparation method according to claim 1 or 2, characterized in that, In step (2), the inlet speed of the ammonia gas is 140 - 160 mL / min.

4. A metal-anchored graphdiyne material prepared by the preparation method according to any one of claims 1 - 3.

5. An application of the metal-anchored graphdiyne material according to claim 4 in the field of electrocatalysis.

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