CN111129512B - Nano carambola-shaped oxygen reduction electrocatalyst and preparation method and application thereof - Google Patents
Nano carambola-shaped oxygen reduction electrocatalyst and preparation method and application thereof Download PDFInfo
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- CN111129512B CN111129512B CN201911381089.XA CN201911381089A CN111129512B CN 111129512 B CN111129512 B CN 111129512B CN 201911381089 A CN201911381089 A CN 201911381089A CN 111129512 B CN111129512 B CN 111129512B
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- H01M4/90—Selection of catalytic material
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- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
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- H01M8/10—Fuel cells with solid electrolytes
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Abstract
The invention discloses a nano carambola-shaped oxygen reduction electrocatalyst, a preparation method and application thereof, and belongs to the field of polymer membrane fuel cell catalysts. Zirconium chloride, benzoic acid, tetracarboxyl porphyrin or porphin in a specific ratio are mixed and reacted in an N, N dimethylformamide solution, and the obtained product is pyrolyzed at high temperature under inert gas to obtain the nanometer carambola-shaped oxygen reduction electrocatalyst. The method is simple to operate and easy to control, and the prepared nano carambola-shaped electrocatalyst has uniform and attractive micro-morphology and good oxygen reduction activity, and can be used for polymer membrane fuel cells.
Description
Technical Field
The invention belongs to the field of polymer membrane fuel cell electrocatalysts, and relates to a nanometer carambola-shaped oxygen reduction electrocatalyst, and a preparation method and application thereof.
Background
Polymer membrane fuel cells have received much attention due to their advantages of high power density, environmental friendliness, and the like. Platinum-based electrocatalysts are one of the core materials of polymer membrane fuel cells, but platinum is expensive, which limits the wide application of polymer membrane fuel cells. One of the solutions is to develop a non-noble metal electrocatalyst with low cost, high efficiency and high stability to replace the platinum-based electrocatalyst in order to promote the commercialization process of the polymer membrane fuel cell.
Since Jasinski discovered from 1964 that cobalt phthalocyanine has oxygen reduction activity in a basic system (Nature,1964,201,1212-1213), many oxygen reduction electrocatalysts of macrocyclic compounds such as metallophthalocyanines and metalloporphyrins have been studied extensively. However, the non-noble metal electrocatalysts prepared by simply using macrocyclic compounds such as metal phthalocyanine or metalloporphyrin and the like as precursors have irregular microscopic appearance, small specific surface area and poor performance.
Disclosure of Invention
The invention aims to provide a preparation method and application of a nano carambola-shaped oxygen reduction electrocatalyst. The porphyrin material after pyrolysis has better performance as a catalyst in the current research. The invention mixes zirconium chloride, benzoic acid, tetracarboxyl porphyrin or porphine with a specific ratio in N, N dimethylformamide solution for reaction,and pyrolyzing the obtained product at high temperature under inert gas to obtain the nano carambola-shaped oxygen reduction electrocatalyst. The method is simple to operate, the prepared catalyst has good consistency and beautiful appearance in microscopic morphology, and the specific surface area reaches 594m2Has excellent oxygen reduction activity and can be used for polymer membrane fuel cells. The electrocatalyst shows better oxygen reduction activity and stability.
The method is simple to operate and easy to control. The nano carambola-shaped oxygen reduction electrocatalyst has high specific surface area and high conductivity, porphyrin or porphin with oxygen reduction catalytic capability is coordinated with metal zirconium, and then the obtained reaction product is subjected to high-temperature heat treatment in inert gas, so that the finally prepared nano carambola-shaped electrocatalyst has good oxygen reduction comprehensive performance and can be used for the oxygen reduction side of a polymer membrane fuel cell.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a preparation method of a nano carambola-shaped oxygen reduction electrocatalyst comprises the following steps:
uniformly dispersing zirconium chloride, benzoic acid, tetracarboxylporphyrin or tetracarboxylporphyrin and water in N, N Dimethylformamide (DMF), carrying out hydrothermal reaction, carrying out centrifugal separation on the obtained mixed solution, washing the obtained solid product with ethanol until the washed filtrate is colorless, drying, and carrying out heat treatment on the dried product to obtain the nanometer carambola-shaped oxygen reduction catalyst.
Wherein the concentration of the benzoic acid in the DMF is 45-150mg/ml, the concentration of the zirconium chloride in the DMF is 3-10mg/ml, and the concentration of the tetracarboxylporphyrin or the tetracarboxylporphyrin in the N, N-dimethylformamide is 3-10 mg/ml. The mass ratio of the benzoic acid to the tetracarboxyl porphyrin or the tetracarboxyl porphine to the zirconium chloride is 8-30: 0.8-1.2: 1, the volume of the water is 5-20% of the volume of the DMF.
Further, the hydrothermal reaction condition is that the reaction is carried out for 4 to 48 hours at a temperature of between 80 and 150 ℃.
Further, the heat treatment is performed under an argon or nitrogen atmosphere.
Further, the temperature of the heat treatment is 500-900 ℃, and the time is 0.5-10 h.
All of the above reaction conditions need to be satisfied simultaneously.
Further, the tetracarboxylporphyrin or tetracarboxylporphyrin comprises: one, two or more of 5,10,15, 20-tetra (4-carboxyphenyl) porphin, 5,10,15, 20-tetra (4-carboxyphenyl) ferriporphyrin, 5,10,15, 20-tetra (4-carboxyphenyl) cobalt porphyrin, 5,10,15, 20-tetra (4-carboxyphenyl) manganese porphyrin and 5,10,15, 20-tetra (4-carboxyphenyl) copper porphyrin.
The invention also provides the nano carambola-shaped oxygen reduction catalyst prepared by the preparation method, wherein the cross section of the nano carambola-shaped oxygen reduction catalyst is hexagonal, and the micro appearance of the nano carambola-shaped oxygen reduction catalyst is similar to that of a carambola (five corners). The transverse section diameter is 50nm-3 μm, and the longitudinal diameter is 100nm-10 μm.
The invention also provides the application of the nano carambola-shaped oxygen reduction catalyst electrocatalyst in a polymer membrane fuel cell. Particularly for use on the oxygen reduction side of a polymer membrane fuel cell.
Compared with the existing reports, the beneficial effects of the invention are as follows: the catalyst has large specific surface area, special and regular microstructure, good appearance, good consistency and excellent performance.
Drawings
FIG. 1 is a comparison of the microscopic morphology (SEM) of the nano carambola-like catalyst obtained in example 1 of the present invention with a fruit carambola photograph;
FIG. 2 is a graph showing the oxygen reduction polarization curve of the product obtained in example 1 of the present invention compared with the oxygen reduction curve of a currently commercially available 20% Pt/C catalyst;
FIG. 3 is a nitrogen adsorption and desorption curve of the specific surface area of the nano carambola catalyst.
Detailed Description
The invention is further described in the following with reference to the drawings and examples, which are provided only for the purpose of illustrating the invention more clearly, but the scope of the invention as claimed is not limited to the scope of the embodiments presented below.
Example 1
75mg of benzoic acid, 8.5mg of 5,10,15, 20-tetra (4-carboxyphenyl) cobalt porphyrin, 8.5mg of zirconium chloride and 0.15mL of water are dispersed in 1.5mL of DMF solution, the mixture is subjected to oil bath reaction at 120 ℃ for 4 hours, a product is centrifuged, the lower layer is left and washed by ethanol, the filtrate is washed to be colorless, the filtrate is dried at 65 ℃ to finally obtain solid powder, and the powder is subjected to heat treatment at 600 ℃ for 8 hours under the argon condition to obtain the final nanometer carambola-shaped oxygen reduction catalyst.
As shown in fig. 1, the scanning electron microscope image of the final nano carambola-shaped oxygen reduction catalyst is compared with the photo of the fruit carambola.
Fig. 2 shows the oxygen reduction polarization curve of the prepared nano carambola-shaped oxygen reduction catalyst.
And (3) testing conditions are as follows: potential sweep tests were performed at a sweep rate of 10mV/s in 0.1M KOH saturated with oxygen at 25 ℃ and at a voltage of 0-1.2V (vs RHE), with electrode rotation at 1600 r/min. The polarization curve shows that the non-noble metal electrocatalyst obtained in example 1 has better oxygen reduction catalytic activity.
Example 2
105mg of benzoic acid, 10mg of 5,10,15, 20-tetra (4-carboxyphenyl) ferriporphyrin, 12mg of zirconium chloride and 0.18mL of water are dispersed in 2mL of DMF solution, hydrothermal reaction is carried out in a reaction kettle at 120 ℃ for 48h, a product is centrifuged, a lower layer is left and washed by ethanol, the filtrate is washed to be colorless, drying is carried out at 65 ℃ to finally obtain solid powder, and the powder is subjected to heat treatment for 1h under the condition of 800 ℃ nitrogen to obtain the final nanometer carambola-shaped oxygen reduction catalyst.
Example 3
2000mg of benzoic acid, 120mg of 5,10,15, 20-tetra (4-carboxyphenyl) copper porphyrin, 100mg of zirconium chloride and 5mL of water are dispersed in 30mL of DMF solution, the mixture is subjected to oil bath reaction at 110 ℃ for 20 hours, a product is centrifuged, a lower layer is left and washed by ethanol, the filtrate is washed to be colorless, the filtrate is dried at 65 ℃ to obtain solid powder finally, and the powder is subjected to heat treatment at 800 ℃ for 5 hours under the condition of nitrogen, so that the final nanometer carambola-shaped oxygen reduction catalyst is obtained.
Example 4
Dispersing 500mg of benzoic acid, 15mg of 5,10,15, 20-tetra (4-carboxyphenyl) porphin, 20mg of 5,10,15, 20-tetra (4-carboxyphenyl) ferriporphyrin, 30mg of zirconium chloride and 0.4mL of water in 5mL of DMF solution, reacting in a hydrothermal reaction kettle at 130 ℃ for 10h, centrifuging a product, taking a lower layer, washing the lower layer with ethanol, washing the filtrate until the filtrate is colorless, drying at 65 ℃ to finally obtain solid powder, and performing heat treatment on the powder for 4h at 900 ℃ under the condition of argon gas to obtain the final nanometer carambola-shaped oxygen reduction catalyst.
Example 5
5800mg of benzoic acid, 200mg of 5,10,15, 20-tetra (4-carboxyphenyl) manganese porphyrin, 300mg of 5,10,15, 20-tetra (4-carboxyphenyl) cobalt porphyrin, 550mg of zirconium chloride and 7mL of water are dispersed in 50mL of DMF solution, oil bath reaction is carried out at 90 ℃ for 48h, the product is centrifuged, the lower layer is left and washed by ethanol, the filtrate is washed to be colorless and dried at 65 ℃ to finally obtain solid powder, and the powder is thermally treated for 3h under the condition of argon gas at 500 ℃ to obtain the final nanometer carambola-shaped oxygen reduction catalyst.
Claims (5)
1. A preparation method of a nanometer carambola-shaped oxygen reduction catalyst is characterized by comprising the following steps:
dispersing zirconium chloride, benzoic acid, tetracarboxylporphyrin or tetracarboxylporphyrin and water in N, N dimethylformamide, carrying out hydrothermal reaction, centrifugally separating the obtained mixed solution, washing the obtained solid product with ethanol until the washed filtrate is colorless, drying, and carrying out heat treatment on the dried product in argon or nitrogen atmosphere at the temperature of 500-900 ℃ for 0.5-10h to obtain the nano carambola-shaped oxygen reduction catalyst;
wherein, the concentration of the benzoic acid in the N, N-dimethylformamide is 45-150mg/mL, the concentration of the zirconium chloride in the N, N-dimethylformamide is 3-10mg/mL, and the concentration of the tetracarboxylporphyrin or the tetracarboxylporphyrin in the N, N-dimethylformamide is 3-10 mg/mL; the mass ratio of the benzoic acid to the tetracarboxyl porphyrin or the tetracarboxyl porphine to the zirconium chloride is 8-30: 0.8-1.2: 1; the volume of the water is 5-20% of that of the N, N-dimethylformamide;
the cross section of the nanometer carambola-shaped oxygen reduction catalyst is hexagonal, the microscopic appearance of the nanometer carambola-shaped oxygen reduction catalyst is similar to carambola, the diameter of the transverse cross section is 50nm-3 mu m, and the diameter of the longitudinal cross section is 100nm-10 mu m; the nano carambola-shaped oxygen reduction catalyst is applied to the oxygen reduction side of a polymer membrane fuel cell.
2. The preparation method according to claim 1, wherein the hydrothermal reaction is carried out at 80-150 ℃ for 4-48 h.
3. The method of claim 1, wherein the tetracarboxylporphyrin or tetracarboxylporphyrin comprises: one, two or more of 5,10,15, 20-tetra (4-carboxyphenyl) porphin, 5,10,15, 20-tetra (4-carboxyphenyl) ferriporphyrin, 5,10,15, 20-tetra (4-carboxyphenyl) cobalt porphyrin, 5,10,15, 20-tetra (4-carboxyphenyl) manganese porphyrin and 5,10,15, 20-tetra (4-carboxyphenyl) copper porphyrin.
4. The nano carambola-shaped oxygen reduction catalyst prepared by the preparation method of any one of claims 1 to 3, wherein the cross section of the nano carambola-shaped oxygen reduction catalyst is hexagonal, the transverse section diameter is 50nm to 3 μm, and the longitudinal diameter is 100nm to 10 μm.
5. Use of the nano carambola-like oxygen reduction catalyst of claim 4 in a polymer membrane fuel cell.
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