CN111129512A - 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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- CN111129512A CN111129512A CN201911381089.XA CN201911381089A CN111129512A CN 111129512 A CN111129512 A CN 111129512A CN 201911381089 A CN201911381089 A CN 201911381089A CN 111129512 A CN111129512 A CN 111129512A
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- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
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- H—ELECTRICITY
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- H01M4/90—Selection of catalytic material
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M8/10—Fuel cells with solid electrolytes
- H01M2008/1095—Fuel cells with polymeric electrolytes
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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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. Zirconium chloride, benzoic acid, tetracarboxyl porphyrin or porphine in a specific ratio are mixed and reacted with 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, 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: the potential sweep test was carried out at a sweep rate of 10mV/s in 0.1M KOH saturated with oxygen at 25 ℃ and at a voltage of 0-1.2V (vsRhE), with an electrode rotation rate of 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 (7)
1. A preparation method of a nano 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, 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 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 the volume of the N, N-dimethylformamide.
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 according to claim 1, wherein the heat treatment is performed under an argon or nitrogen atmosphere.
4. The method as claimed in claim 1, wherein the heat treatment is carried out at a temperature of 500 ℃ and 900 ℃ for a time of 0.5-10 h.
5. 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.
6. The nano carambola-shaped oxygen reduction catalyst prepared by the preparation method according to any one of claims 1 to 5, 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.
7. The use of the nano carambola-like oxygen reduction catalyst of claim 6 in a polymer membrane fuel cell.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114073922A (en) * | 2020-08-20 | 2022-02-22 | 中国科学院苏州纳米技术与纳米仿生研究所 | Porphyrin-based metal-organic framework nanosphere and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106959279A (en) * | 2017-04-14 | 2017-07-18 | 浙江省农业科学院 | A kind of metal-organic framework materials of PCN 222 and its preparation method and application |
| CN107694605A (en) * | 2017-11-01 | 2018-02-16 | 中国科学院福建物质结构研究所 | Carbon quantum dot@porphyryl metal organic framework catalyst and preparation method and application |
| CN108517038A (en) * | 2018-03-15 | 2018-09-11 | 河南大学 | A kind of size regulation and control method of porphyrin metal organic framework material |
| CN108620136A (en) * | 2018-05-21 | 2018-10-09 | 西北师范大学 | The preparation and application of copper porphyrin functional metal organic frame/composite titania material |
| CN109254066A (en) * | 2018-09-19 | 2019-01-22 | 扬州大学 | The carbon paper electrode and the preparation method and application thereof of PCN-222 (Fe) catalyst modification |
| CN109464986A (en) * | 2018-11-29 | 2019-03-15 | 西北师范大学 | A kind of preparation and application of the nanocomposite based on porphyrin metal organic frame and ternary sulfide |
| CN109647381A (en) * | 2017-10-12 | 2019-04-19 | 中国科学院福建物质结构研究所 | A kind of method of the mesoporous C-base composte material of controllable preparation platinum grain high degree of dispersion as highly effective hydrogen yield elctro-catalyst |
-
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- 2019-12-27 CN CN201911381089.XA patent/CN111129512B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106959279A (en) * | 2017-04-14 | 2017-07-18 | 浙江省农业科学院 | A kind of metal-organic framework materials of PCN 222 and its preparation method and application |
| CN109647381A (en) * | 2017-10-12 | 2019-04-19 | 中国科学院福建物质结构研究所 | A kind of method of the mesoporous C-base composte material of controllable preparation platinum grain high degree of dispersion as highly effective hydrogen yield elctro-catalyst |
| CN107694605A (en) * | 2017-11-01 | 2018-02-16 | 中国科学院福建物质结构研究所 | Carbon quantum dot@porphyryl metal organic framework catalyst and preparation method and application |
| CN108517038A (en) * | 2018-03-15 | 2018-09-11 | 河南大学 | A kind of size regulation and control method of porphyrin metal organic framework material |
| CN108620136A (en) * | 2018-05-21 | 2018-10-09 | 西北师范大学 | The preparation and application of copper porphyrin functional metal organic frame/composite titania material |
| CN109254066A (en) * | 2018-09-19 | 2019-01-22 | 扬州大学 | The carbon paper electrode and the preparation method and application thereof of PCN-222 (Fe) catalyst modification |
| CN109464986A (en) * | 2018-11-29 | 2019-03-15 | 西北师范大学 | A kind of preparation and application of the nanocomposite based on porphyrin metal organic frame and ternary sulfide |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114073922A (en) * | 2020-08-20 | 2022-02-22 | 中国科学院苏州纳米技术与纳米仿生研究所 | Porphyrin-based metal-organic framework nanosphere and preparation method and application thereof |
| CN114073922B (en) * | 2020-08-20 | 2024-02-20 | 中国科学院苏州纳米技术与纳米仿生研究所 | Porphyrin-based metal-organic framework nanosphere and preparation method and application thereof |
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