CN110474059B - Method for solid-phase macro synthesis of non-noble metal oxygen reduction catalyst, catalyst and application thereof - Google Patents
Method for solid-phase macro synthesis of non-noble metal oxygen reduction catalyst, catalyst and application thereof Download PDFInfo
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Abstract
The invention discloses a method for solid-phase macro synthesis of a non-noble metal oxygen reduction catalyst, a catalyst and application thereof. The preparation method comprises the following steps: (1) uniformly mixing a chelating agent and an inorganic metal salt, and carrying out solid-phase grinding to obtain a precursor; (2) and (2) carrying out heat treatment on the precursor obtained in the step (1) in an inert atmosphere, washing, separating and drying the product to obtain the non-noble metal oxygen reduction catalyst. The solid-phase macro-synthesis method disclosed by the invention is simple in process and suitable for large-scale industrial production, and the obtained non-noble metal oxygen reduction catalyst is excellent in performance and has the potential to be used as a substitute of a fuel cell or a metal-air cell oxygen reduction noble metal catalyst.
Description
Technical Field
The invention belongs to the field of catalysts, and relates to a method for solid-phase macro synthesis of a non-noble metal oxygen reduction catalyst, a catalyst and application thereof.
Background art:
at present, the energy crisis and the environmental pollution problem are more and more emphasized by all countries in the world, and the development of new energy which is safe, clean, efficient and can be continuously developed is the best way for solving the energy problem and the environmental crisis. A fuel cell is a device that directly converts chemical energy into electrical energy. The energy conversion device has the outstanding characteristics of high energy conversion efficiency, environmental friendliness, low operation temperature, high specific power and specific energy and the like, and is considered to be the most promising chemical power source for electric automobiles and other civil occasions in the future. Meanwhile, the metal-air battery has good research potential and commercial foundation due to the unique advantages of high energy, low cost, good safety performance, environmental protection and the like, and plays an indispensable role in the field of energy application in the future. The kinetics of oxygen reduction reaction in the key cathode processes of the two batteries are slow, and rare noble metal is required to be used as a catalyst, so that the large-scale application of the fuel battery and the metal-air battery is seriously hindered. Therefore, there is an urgent need to develop non-noble metal oxygen reduction catalysts.
In recent years, a great deal of research is carried out on the preparation of non-noble metal oxygen reduction catalysts at home and abroad, and the non-noble metal oxygen reduction catalysts can be mainly divided into the following categories: carbon materials modified based on iron/cobalt and nitrogen elements, carbon materials doped with heteroatoms, oxides or sulfides or nitrides or oxynitrides based on transition metals, and the like. Among them, carbon materials based on iron/cobalt and nitrogen element modification are considered to have the most potential to replace the current commercial platinum carbon catalyst. However, most of carbon materials modified based on iron/cobalt and nitrogen elements have complex preparation methods, the preparation process conditions are not easy to control, only a small amount of catalyst can be obtained in a single preparation, and the method is extremely not beneficial to large-scale industrial production of the catalyst. As is well known, solid phase synthesis has many advantages in synthesis, such as convenient operation, simple synthesis process, low cost, controllable particle size, safety, environmental protection, and the like, and can avoid or reduce the phenomenon of hard agglomeration easily occurring in liquid phase. The solid phase macro synthesis can greatly simplify the production process and reduce the production cost, thereby industrially synthesizing the catalyst on a large scale. Based on the method, the high-activity non-noble metal oxygen reduction catalyst synthesized in a solid phase in a large scale is developed, and the method has great significance for large-scale industrial economic and efficient acquisition of the non-noble metal oxygen reduction catalyst and industrialization of fuel cells and metal-air cells.
Disclosure of Invention
The invention aims to provide a method for synthesizing a non-noble metal oxygen reduction catalyst by solid phase macro, a catalyst and application thereof, the non-noble metal catalyst synthesized by the solid phase macro can be used as a cathode oxygen reduction catalyst of a fuel cell and a metal-air cell, has excellent catalytic performance, has extremely high oxygen reduction activity compared with other existing non-noble metal materials, and is a potential substitute of a noble metal oxygen reduction catalyst; the invention adopts solid phase macro synthesis without complex chemical synthesis steps. Compared with other preparation methods such as wet chemical synthesis and the like, the preparation method has the advantages of simple process, low cost, convenient operation and easy large-scale industrial production.
The method for solid-phase macro synthesis of the non-noble metal oxygen reduction catalyst provided by the invention comprises the following steps:
(1) uniformly mixing a chelating agent and an inorganic metal salt, and then fully carrying out solid-phase grinding to obtain a precursor;
(2) and carrying out heat treatment on the precursor in an inert atmosphere, washing, separating and drying to obtain the non-noble metal oxygen reduction catalyst.
In the step (1) of the above method, the chelating agent is a compound having an alkylcarboxyl group bonded to a nitrogen atom. Preferably, the chelating agent has three alkylcarboxy groups attached to the nitrogen atom, and most preferably nitrilotriacetic acid (cas: 139-13-9). The chelating agent may be at least one selected from ethylenediaminetetraacetic acid (cas: 60-00-4), cyclohexanediaminetetraacetic acid (cas: 25637-70-1), hydroxyethylethylenediaminetriacetic acid (cas: 150-39-0), diethylenetriaminepentaacetic acid (cas: 67-43-6), and ethyleneglycoldiethylenediaminetetraacetic acid (cas: 67-42-5).
In the step (1) of the above method, the inorganic metal salt may be one or more of inorganic metal salts of iron, cobalt and nickel, and preferably one or more of inorganic metal salts of cobalt.
In the step (1) of the method, the charging molar ratio of the chelating agent to the inorganic metal salt is 1:0.1-10, preferably 1: 1.5-2.5.
In the step (2) of the above method, the heat treatment temperature may be 500 ℃ to 1000 ℃, preferably 800 ℃ to 1000 ℃; the calcination time may be from 0.5 hours to 10 hours, preferably from 2 hours to 3 hours; the heating rate is 3-15 deg.C/min.
The non-noble metal oxygen reduction catalyst preferably has a micropore and mesopore double-distribution structure, and the pore diameter range of the pores is 0nm-100 nm; preferably, the mesopores are 2-50nm, and the micropores are 0.1-2 nm; further preferably, the mesopores are 35 to 45nm and the micropores are 0.5 to 2 nm.
The non-noble metal oxygen reduction catalyst prepared by the method can be used as a cathode oxygen reduction catalyst of a fuel cell or a metal-air cell.
The method for solid-phase mass synthesis of the non-noble metal oxygen reduction catalyst provided by the invention has the advantages that the specific chelating agent and the inorganic metal salt are selected, the solid-phase mixed coordination is adopted, the complex processes such as solvent coordination and the like are omitted, the cost is low, the method is suitable for large-scale industrial production of the non-noble metal oxygen reduction catalyst for the fuel cell or the metal-air cell, and meanwhile, the catalyst has excellent oxygen reduction catalytic performance and has potential to be used as a substitute for the noble metal catalyst for the fuel cell or the metal-air cell.
The preparation method provided by the invention mainly comprises the steps of uniformly mixing the chelating agent and the inorganic metal salt, fully grinding and further carrying out heat treatment. Because the chelating agent has strong coordination capacity with the selected inorganic metal salt, the chelating agent can be fully contacted with metal ions in the inorganic metal salt in the solid-phase grinding process to generate solid-phase coordination reaction. During the high-temperature heat treatment process, the kinetic process of the solid-phase coordination reaction is further accelerated, and a large amount of organic metal complexes are formed. Meanwhile, under the condition of high temperature, partial metal ions are reduced into metal particles, the graphitization process of the catalyst is further catalyzed, and partial products further form the morphology of the catalyst with the phellopterin-shaped micro-mesoporous distribution. The morphology is beneficial for increasing active sites and is convenient for the transmission of reaction substances. Because the selected chelating agent contains carbon and nitrogen elements, cobalt (or nickel or iron carbide) particles and cobalt (or nickel or iron)/nitrogen/carbon active sites can be formed. Based on the characteristics, the obtained coralliform non-noble metal catalyst shows more excellent oxygen reduction performance.
Compared with other prior art, the invention has the following advantages:
1. the raw materials provided by the invention have low cost and wide sources, can generate solid phase coordination, and have simple process.
2. Compared with other materials, the non-noble metal oxygen reduction catalyst prepared by the preparation method has specific morphological characteristics, higher specific surface area and micropore (0.1-2nm) and mesoporous structure (2-50nm) distribution.
3. Compared with the synthesis and complicated preparation processes of other various raw materials, the preparation method of the invention adopts cheap chelating agents such as nitrilotriacetic acid, ethylene diamine tetraacetic acid, hydroxyethyl ethylenediamine triacetic acid and the like as carbon sources and nitrogen sources, and inorganic metal salts as metal sources, and has the advantages of easy control of the material feeding amount and very simple preparation process if ammonia gas post-treatment is needed and liquid phase, surfactant and the like are involved.
4. The chelating agent provided by the invention can react with inorganic metal salt in a solid phase coordination reaction in a grinding process to form an organic metal complex, so that metal ions can be fully contacted with nitrogen and carbon elements in a ligand, more active sites are easily formed, and the activity of the catalyst is improved. Meanwhile, the specific chelating agents involved in the solid phase coordination process are all specific chelating agents with similar structures, and compared with almost all liquid phase coordination processes for preparing catalysts with similar performances at present, the solid phase coordination process is more convenient and easier to implement, and is more suitable for industrial production.
5. The non-noble metal oxygen reduction catalyst prepared by the method has excellent catalytic performance, and has higher oxygen reduction activity compared with other non-noble metal catalysts reported in documents.
6. The solid-phase macro-synthesis non-noble metal oxygen reduction catalyst adopted in the invention has the advantages of simple preparation process, economy, convenient operation, controllable strength, safety and environmental protection, and can avoid or reduce the hard agglomeration phenomenon and the like easily appearing in the liquid phase, is suitable for large-scale production of fuel cells and metal-air cell non-noble metal oxygen reduction catalysts, has the potential to replace fuel cells and metal-air cell noble metal oxygen reduction catalysts, and has huge potential application value in a plurality of industrial catalysis or other scientific fields.
Drawings
FIG. 1 is an X-ray powder diffraction plot of a non-noble metal oxygen reduction catalyst prepared in example 1 of the present invention.
Fig. 2 is a laser raman spectroscopy analysis curve of the non-noble metal oxygen reduction catalyst prepared in example 1 of the present invention.
FIG. 3 is a scanning electron micrograph of a non-noble metal oxygen reduction catalyst prepared in example 1 of the present invention.
FIG. 4 is a TEM micrograph of a non-noble metal oxygen reduction catalyst prepared in example 1 of the present invention.
FIG. 5 is a plot of the surface area distribution of the elements of the energy dispersive X-ray spectrum of the non-noble metal oxygen reduction catalyst prepared in example 1 of the present invention (FIG. 5(a), FIG. 5(b), FIG. 5(c), FIG. 5 (f)).
Fig. 6 is a nitrogen adsorption-desorption isotherm curve (fig. 6 (a)) and a pore size distribution test curve (fig. 6(b)) of the non-noble metal oxygen reduction catalyst prepared in example 1 of the present invention.
FIG. 7 is a graph of the experimental plot of the oxygen reduction of the non-noble metal oxygen reduction catalyst prepared in example 1 of the present invention and the platinum-carbon catalyst used commercially (FIG. 7(a)) and the number of transferred electrons of the non-noble metal oxygen reduction catalyst from 0.3V to 0.6V (FIG. 7 (b)).
Fig. 8 is a stability test experimental plot of the non-noble metal oxygen reduction catalyst prepared in example 1 of the present invention and a commercially used platinum carbon catalyst.
FIG. 9 is a graph of methanol resistance tests for non-noble metal oxygen reduction catalysts prepared in example 1 of the present invention and for commercially used platinum carbon catalysts.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples, but the present invention is not limited to the following examples. The method is a conventional method unless otherwise specified. The starting materials are commercially available from the open literature unless otherwise specified.
Example 1
Uniformly mixing 0.600g of nitrilotriacetic acid and 0.77g of cobalt chloride (the molar ratio of the nitrilotriacetic acid to the cobalt chloride is 1:2), fully grinding the mixture in a solid phase, placing the mixture in a quartz tube of a tube furnace, removing air by using nitrogen for half an hour, heating the mixture to 800 ℃ at the speed of 3 ℃/min, and carrying out heat treatment for 2 hours under the protection of the nitrogen to obtain a heat-treated product; and collecting the heat-treated product, washing with water, centrifuging and drying in vacuum at 60 ℃ to obtain the non-noble metal oxygen reduction catalyst.
The X-ray powder diffraction curve of the non-noble metal oxygen reduction catalyst prepared in this example is shown in fig. 1, and it can be seen that the catalyst prepared in this example contains metallic cobalt and graphitized carbon.
The laser raman spectrum curve of the non-noble metal oxygen reduction catalyst prepared in the embodiment is shown in fig. 2, and it can be seen from the graph that the ID/IG ratio of the non-noble metal oxygen reduction catalyst prepared in the embodiment is 1.01, which indicates that the catalyst has a higher graphitization degree.
As shown in fig. 3, it can be seen from the scanning electron microscope that the non-noble metal oxygen-reducing catalyst prepared in this example has a coral-like morphology.
As shown in fig. 4, it can be seen that the non-noble metal oxygen reduction catalyst prepared in this example has a three-dimensional coral-like morphology with numerous burrs.
The surface distribution diagrams of the elements of the energy dispersive X-ray spectrum of the non-noble metal oxygen reduction catalyst prepared in this example are shown in fig. 5(a-d), and it can be seen from these diagrams that the cobalt, carbon and nitrogen elements are uniformly distributed in the catalyst.
The nitrogen adsorption-desorption isotherms and pore size distributions of the non-noble metal oxygen reduction catalyst prepared in this example are shown in fig. 6: wherein (a) is a nitrogen adsorption-desorption curve chart, and (b) is a pore size distribution curve chart. As is clear from FIG. (a), the specific surface area of the catalyst prepared in this example was 216.8m 2/g. As can be seen from the graph (b), the non-noble metal oxygen reduction catalyst prepared in this example has a micropore and mesopore structure, wherein the pore diameter of the micropore is about 0.8nm, and the pore diameter of the mesopore is about 39 nm.
The experimental curves for oxygen reduction of the non-noble metal oxygen reduction catalyst prepared in this example and the commercially used platinum carbon catalyst are shown in fig. 7. The specific experimental method comprises the following steps: the oxygen reduction experiment curve was measured with a rotating disk electrode in 0.1 mole per liter of potassium hydroxide solution, the rotating speed of the rotating disk electrode was 1600 rpm, and the curve scan rate was 10 millivolts per second.
The comparative commercially used platinum-carbon catalyst was a commercial platinum-carbon catalyst having a platinum content of 20% by weight purchased from Johnson-Matthey (Shanghai) Limited.
Comparing the two curves, it can be seen that the half-wave potential of the non-noble metal oxygen reduction catalyst prepared in this example in the oxygen reduction experiment is 0.82V (relative to the standard hydrogen electrode), which is only 30 mv lower than the half-wave potential of 0.85V of the commercial platinum-carbon catalyst, and meanwhile, the electron transfer numbers corresponding to 0.3V to 0.6V obtained from the K-L equation are both close to 4, thus showing good oxygen reduction catalytic performance.
The experimental curves for stability testing of the non-noble metal oxygen reduction catalyst prepared in this example and the commercially used platinum carbon catalyst are shown in fig. 8. The specific experimental method comprises the following steps: the chronoamperometric experimental curve was measured with a rotating disk electrode at 1600 rpm in 0.1 mol/l potassium hydroxide solution saturated with oxygen, at a constant potential of 0.765 v (relative to a standard hydrogen electrode) and for 20000 seconds.
Comparing the two curves, it can be seen that the non-noble metal oxygen reduction catalyst prepared in this example and the commercial platinum-carbon catalyst both undergo constant potential aging of 0.765 volt (relative to the standard hydrogen electrode) for 20000 seconds, and the reaction current of the non-noble metal oxygen reduction catalyst prepared in this example is 87.5% of the initial reaction current after 20000 seconds, which is higher than 58.5% of the commercial platinum-carbon catalyst, which indicates that the non-noble metal oxygen reduction catalyst prepared in this example has better stability than the commercial platinum-carbon catalyst.
The experimental curves for methanol resistance tests of the non-noble metal oxygen reduction catalysts prepared in this example and the commercially used platinum carbon catalyst are shown in fig. 9. The specific experimental method comprises the following steps: the test time is 1000 seconds, the rotating disc electrode is added into 0.1 mol/L potassium hydroxide solution saturated by oxygen, the methanol solution is added in the middle of the test to ensure that the concentration of methanol in the electrolyte reaches 0.5 mol/L, the rotating speed of the rotating disc electrode is 1600 rpm, the constant potential is 0.765V (relative to the standard hydrogen electrode).
As can be seen from a comparison of the graphs, the non-noble metal oxygen reduction catalyst prepared in this example has excellent methanol poisoning resistance compared to the commercial platinum-carbon catalyst.
Example 2
The other preparation was carried out in the same manner as in example 1 except that the chelating agent was changed to ethylenediaminetetraacetic acid in an amount of 0.92g (molar ratio of ethylenediaminetetraacetic acid to cobalt chloride: 1: 2).
The obtained non-noble metal oxygen reduction catalyst has a half-wave potential of about 0.80V (relative to a standard hydrogen electrode) obtained by testing an oxygen reduction curve in 0.1 mol/L potassium hydroxide solution, which is only 50 mV lower than the half-wave potential of 0.85V of a commercial platinum-carbon catalyst, and the electron transfer numbers corresponding to 0.3V-0.6V obtained by a K-L equation are all close to 4, so that the non-noble metal oxygen reduction catalyst has good oxygen reduction catalytic performance. The current is reduced to 80% of the original current in a stability test of 20000s, and the methanol resistance is also realized. But did not have a coral-like morphology of the catalyst and had a reduced specific surface area relative to example 1.
Example 3
The other preparation process was the same as that of example 1 except that the chelating agent was replaced with ethylenediamine tetraacetic acid and the amount used was 1.07g (molar ratio of hexamethylenediamine tetraacetic acid to cobalt chloride was 1: 2).
The obtained non-noble metal oxygen reduction catalyst has the half-wave potential of 0.81V (relative to a standard hydrogen electrode) obtained by testing an oxygen reduction curve in 0.1 mol/L potassium hydroxide solution, is only 40 mV lower than the half-wave potential of 0.85V of a commercial platinum-carbon catalyst, and simultaneously has electron transfer numbers corresponding to 0.3V-0.6V obtained by a K-L equation close to 4, so the non-noble metal oxygen reduction catalyst has good oxygen reduction catalytic performance. The current is reduced to 82% in 20000s stability test, and the methanol-resistant performance is also provided. However, the catalyst did not have a coral-like morphology, and the specific surface area was reduced as compared with example 1.
Example 4
The other preparation process was the same as example 1 except that the inorganic metal salt was changed to ferrous chloride in an amount of 0.76g (molar ratio of nitrilotriacetic acid to ferrous chloride: 1: 2).
The obtained non-noble metal oxygen reduction catalyst has the half-wave potential of 0.80V (relative to a standard hydrogen electrode) obtained by testing an oxygen reduction curve in 0.1 mol/L potassium hydroxide solution, is only 50 mV lower than the half-wave potential of 0.85V of a commercial platinum-carbon catalyst, and simultaneously has electron transfer numbers corresponding to 0.3V-0.6V obtained by a K-L equation close to 4, so the non-noble metal oxygen reduction catalyst has good oxygen reduction catalytic performance. The current is reduced to 78% in the stability test of 20000s, and the methanol resistance is also realized, but the coral-shaped catalyst morphology is not realized, and the specific surface area is reduced compared with that of the example 1.
Example 5
The other preparation was carried out in the same manner as in example 1 except that the amount of cobalt chloride was changed to 0.70g (molar ratio of nitrilotriacetic acid to cobalt chloride: 1.8).
The obtained non-noble metal oxygen reduction catalyst has the half-wave potential of 0.80V (relative to a standard hydrogen electrode) obtained by testing an oxygen reduction curve in 0.1 mol/L potassium hydroxide solution, is only 50 mV lower than the half-wave potential of 0.85V of a commercial platinum-carbon catalyst, and the electron transfer numbers corresponding to 0.3V-0.6V obtained by a K-L equation are both close to 4, so that the non-noble metal oxygen reduction catalyst has good oxygen reduction catalytic performance, the current is reduced to 85 percent of the original current in a stability test of 20000s, and the non-noble metal oxygen reduction catalyst also has methanol resistance. The catalyst also exhibited a coral-like morphology.
Example 6
The other preparation was carried out in the same manner as in example 1 except that the amount of cobalt chloride was changed to 0.86 g. (the molar ratio of nitrilotriacetic acid to cobalt chloride was 1: 2.2).
The obtained non-noble metal oxygen reduction catalyst has the half-wave potential of 0.79V (relative to a standard hydrogen electrode) obtained by testing an oxygen reduction curve in 0.1 mol/L potassium hydroxide solution, is only 60 mV lower than the half-wave potential of 0.85V of a commercial platinum-carbon catalyst, and the electron transfer numbers corresponding to 0.3V-0.6V obtained by a K-L equation are both close to 4, so that the non-noble metal oxygen reduction catalyst has good oxygen reduction catalytic performance, the current is reduced to 80 percent of the original current in a stability test of 20000s, and the non-noble metal oxygen reduction catalyst also has methanol resistance. The catalyst also exhibited a coral-like morphology.
Example 7
The other preparation was carried out in the same manner as in example 1 except that the chelating agent was changed to diethylenetriaminepentaacetic acid and hydroxyethylethylenediaminetriacetic acid and the amount used was 0.86g (molar ratio of the sum of diethylenetriaminepentaacetic acid and hydroxyethylethylenediaminetriacetic acid to cobalt chloride: 1: 2).
The obtained non-noble metal oxygen reduction catalyst has the half-wave potential of 0.80V (relative to a standard hydrogen electrode) obtained by testing an oxygen reduction curve in 0.1 mol/L potassium hydroxide solution, is only 50 mV lower than the half-wave potential of 0.85V of a commercial platinum-carbon catalyst, and the electron transfer numbers corresponding to 0.3V-0.6V obtained by a K-L equation are both close to 4, so that the non-noble metal oxygen reduction catalyst has good oxygen reduction catalytic performance, the current is reduced to 81 percent of the original current in a stability test of 20000s, and the non-noble metal oxygen reduction catalyst also has methanol resistance. However, the catalyst did not have a coral-like morphology, and the specific surface area was reduced as compared with example 1.
Example 8
The other preparation was carried out in the same manner as in example 1 except that the chelating agent was changed to dihydroxyethylglycine and nitrilotriacetic acid only, and the amount was 0.65g (molar ratio of the sum of dihydroxyethylglycine and nitrilotriacetic acid to cobalt chloride was 1: 2).
The obtained non-noble metal oxygen reduction catalyst has the half-wave potential of 0.78V (relative to a standard hydrogen electrode) obtained by testing an oxygen reduction curve in 0.1 mol/L potassium hydroxide solution, is only 70 mV lower than the half-wave potential of 0.85V of a commercial platinum-carbon catalyst, and the electron transfer numbers corresponding to 0.3V-0.6V obtained by a K-L equation are both close to 4, so that the non-noble metal oxygen reduction catalyst has good oxygen reduction catalytic performance, the current is reduced to 78% of the original current in a stability test of 20000s, and the non-noble metal oxygen reduction catalyst also has methanol resistance. However, the catalyst did not have a coral-like morphology, and the specific surface area was reduced as compared with example 1.
Comparative example 1
Dissolving 0.6g of nitrilotriacetic acid in hot water at 90 ℃, adding 0.77g of cobalt chloride (the molar ratio of the nitrilotriacetic acid to the cobalt chloride is 1:2), stirring for 8h, further evaporating and grinding the catalyst, placing the obtained powder in a quartz tube of a tube furnace, removing air by using nitrogen for 30 min, heating to 800 ℃ at the speed of 5 ℃/min, and carrying out heat treatment for 2.5 h under the protection of the nitrogen to obtain a heat-treated product; and collecting the heat-treated product, washing with water, centrifuging and drying in vacuum at 50 ℃ to obtain the non-noble metal oxygen reduction catalyst.
The performance of the obtained non-noble metal oxygen reduction catalyst is slightly reduced compared with that of the example 1, the stability of the catalyst is also reduced compared with the example 1, and meanwhile, the coral-shaped appearance of the obtained catalyst is not well maintained, so that the performance of the catalyst obtained in the complicated preparation process is not improved, but is reduced, and manpower and material resources are greatly wasted.
Comparative example 2
Dissolving 0.92g of ethylenediamine tetraacetic acid in hot water of 90 ℃, adding 0.77g of cobalt chloride (the molar ratio of the ethylenediamine tetraacetic acid to the cobalt chloride is 1:2), stirring for 8h, further evaporating and grinding the catalyst, placing the obtained powder in a quartz tube of a tube furnace, removing air by using nitrogen for 30 min, heating to 800 ℃ at the speed of 5 ℃/min, and carrying out heat treatment for 2 hours under the protection of the nitrogen to obtain a heat-treated product; the heat treated product was collected, washed with water, centrifuged and dried under vacuum at 50 ℃ to obtain a non-noble metal oxygen reduction catalyst.
The half-wave potential of the obtained non-noble metal oxygen reduction catalyst obtained by testing an oxygen reduction curve in 0.1 mol/L potassium hydroxide solution is 0.80V (relative to a standard hydrogen electrode), the performance of the catalyst obtained by the complicated steps of liquid phase coordination and evaporation to dryness is reduced by 20mv compared with that of the catalyst obtained in the embodiment 2, the stability of the catalyst is basically the same as that of the catalyst obtained in the embodiment 2, and meanwhile, the coral-shaped appearance of the catalyst is not well maintained, so that the catalyst obtained in the complicated preparation process is not improved, but is reduced, and manpower and material resources are greatly wasted.
Comparative example 3
The other preparation was carried out in the same manner as in example 1 except that the amount of cobalt chloride was changed to 0.05 g.
The obtained non-noble metal oxygen reduction catalyst has the half-wave potential of 0.60V (relative to a standard hydrogen electrode) obtained by testing an oxygen reduction curve in 0.1 mol/L potassium hydroxide solution, which is far lower than the activity of the catalyst obtained in example 1, and meanwhile, the morphology of the catalyst is greatly changed, and the specific surface area of the catalyst is reduced.
Comparative example 4
The other preparation was carried out in the same manner as in example 1 except that the amount of cobalt chloride was changed to 8 g.
The obtained non-noble metal oxygen reduction catalyst has the half-wave potential of 0.70V (relative to a standard hydrogen electrode) obtained by testing an oxygen reduction curve in 0.1 mol/L potassium hydroxide solution, which is far lower than the activity of the catalyst obtained in example 1, and simultaneously the morphology of the catalyst is changed, and the specific surface area of the catalyst is reduced.
Claims (7)
1. A method for solid-phase macro synthesis of a non-noble metal oxygen reduction catalyst comprises the following steps:
(1) uniformly mixing a chelating agent with inorganic metal salt, and then fully carrying out solid-phase grinding to obtain a precursor, wherein the mixed raw material in the step (1) only consists of the chelating agent and the inorganic metal salt; the feeding molar ratio of the chelating agent to the inorganic metal salt is 1: 0.1-10;
(2) carrying out heat treatment on the precursor in an inert atmosphere, washing, separating and drying to obtain the non-noble metal oxygen reduction catalyst;
in the step (1) of the above method, the chelating agent is a compound having an alkylcarboxyl group attached to a nitrogen atom, and the inorganic metal salt is selected from inorganic metal cobalt salts; the chelating agent is nitrilotriacetic acid;
the non-noble metal oxygen reduction catalyst has a micropore and mesopore double-distribution structure.
2. A method according to claim 1, characterized in that: the charging molar ratio of the chelating agent to the inorganic metal salt is 1: 1.5-2.5.
3. A non-noble metal oxygen reduction catalyst prepared according to the process of claim 1.
4. The catalyst according to claim 3, wherein the mesopores are 2 to 50nm and the micropores are 0.1 to 2 nm.
5. The catalyst of claim 4, wherein the mesopores are 35-45nm and the micropores are 0.5-2 nm.
6. Use of the non-noble metal oxygen reduction catalyst of any one of claims 3 to 5 as a fuel cell or metal-air cell cathode oxygen reduction catalyst.
7. A fuel cell or metal-air cell having a cathode oxygen reduction catalyst which is a non-noble metal oxygen reduction catalyst as claimed in any one of claims 3 to 5.
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| CN113937310B (en) * | 2021-09-08 | 2022-09-27 | 佛山仙湖实验室 | Platinum-based catalyst and preparation method and application thereof |
| CN115275227A (en) * | 2022-06-29 | 2022-11-01 | 合肥工业大学智能制造技术研究院 | Method for solid-phase macro synthesis of coral-shaped metal selenide composite nitrogen-doped carbon catalyst and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101083325A (en) * | 2007-07-03 | 2007-12-05 | 中国科学院上海微***与信息技术研究所 | Method for preparing nano-Pd or Pd platinum alloy electrocatalyst for fuel cell |
| CN102104154A (en) * | 2011-01-19 | 2011-06-22 | 清华大学 | Nitrogenous transition metal microbial fuel-cell catalyst and preparation method thereof |
| CN102500365A (en) * | 2011-10-19 | 2012-06-20 | 华南理工大学 | Preparation method of catalyst with core-shell structure for low-temperature fuel cell |
| CN103747872A (en) * | 2011-08-08 | 2014-04-23 | 昭和电工株式会社 | Method for producing redox catalyst and use of redox catalyst |
| CN104923204A (en) * | 2015-05-21 | 2015-09-23 | 大连理工大学 | Preparation method for graphene-coated metal nanometer particle catalyst and application of graphene-coated metal nanometer particle catalyst |
-
2018
- 2018-05-11 CN CN201810451109.5A patent/CN110474059B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101083325A (en) * | 2007-07-03 | 2007-12-05 | 中国科学院上海微***与信息技术研究所 | Method for preparing nano-Pd or Pd platinum alloy electrocatalyst for fuel cell |
| CN102104154A (en) * | 2011-01-19 | 2011-06-22 | 清华大学 | Nitrogenous transition metal microbial fuel-cell catalyst and preparation method thereof |
| CN103747872A (en) * | 2011-08-08 | 2014-04-23 | 昭和电工株式会社 | Method for producing redox catalyst and use of redox catalyst |
| CN102500365A (en) * | 2011-10-19 | 2012-06-20 | 华南理工大学 | Preparation method of catalyst with core-shell structure for low-temperature fuel cell |
| CN104923204A (en) * | 2015-05-21 | 2015-09-23 | 大连理工大学 | Preparation method for graphene-coated metal nanometer particle catalyst and application of graphene-coated metal nanometer particle catalyst |
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