CN114824301A

CN114824301A - Anti-antipole nitrogen-carbon carrier catalyst for proton exchange membrane fuel cell and preparation method thereof

Info

Publication number: CN114824301A
Application number: CN202210450269.4A
Authority: CN
Inventors: 陈立刚; 赵维; 刘敏; 张纪廷; 王晓冉; 柴茂荣
Original assignee: Spic Hydrogen Energy Technology Development Co Ltd
Current assignee: Spic Hydrogen Energy Technology Development Co Ltd
Priority date: 2022-04-26
Filing date: 2022-04-26
Publication date: 2022-07-29

Abstract

The invention discloses a preparation method of a proton exchange membrane fuel cell antipole nitrogen-carbon carrier catalyst, which comprises the following steps: a. dissolving transition metal salt, a nitrogen source and a carbon source in a first dispersing agent to obtain a nitrogen-doped metal organic framework; b. dissolving the nitrogen-doped metal organic framework and the composite pore-forming agent in a second dispersing agent, mixing and stirring, drying, and then placing in a first sintering atmosphere for sintering treatment to obtain a carrier porous metal nitrogen-carbon material; c. and adding the porous metal nitrogen-carbon material and the noble metal precursor into the third dispersing agent for heating treatment, drying, and then placing in a second sintering atmosphere for sintering treatment to obtain the anti-reversal catalyst. The preparation method can effectively inhibit the migration and agglomeration of the iridium-based compound, improves the stability of the catalyst, and enables the catalyst to have excellent performances of high activity and high stability.

Description

Anti-antipole nitrogen-carbon carrier catalyst for proton exchange membrane fuel cell and preparation method thereof

Technical Field

The invention belongs to the technical field of fuel cells, and particularly relates to an anti-reversal nitrogen-carbon carrier catalyst of a proton exchange membrane fuel cell, and more particularly relates to a preparation method of the anti-reversal nitrogen-carbon carrier catalyst of the proton exchange membrane fuel cell.

Background

A pem fuel cell is one that is capable of supplying a fuel (e.g., H) ₂ ) And an oxidizing agent (e.g. O) ₂ ) The energy conversion system is used for directly converting chemical energy into electric energy, and the energy conversion process of the system is not limited by a thermodynamic Carnot cycle. The working principle is fuel (such as H) ₂ ) Oxidation reaction at the anode to produce H ⁺ And e ^- ，H ⁺ Passes through the proton exchange membrane to the cathode, and e-flows to the cathode through an external circuit, thereby enabling the oxidant (such as O) of the cathode ₂ ) And H ⁺ And e ^- Combined to generate H by reduction reaction ₂ And O. Therefore, the proton exchange membrane fuel cell has the advantages of high conversion efficiency, cleanness and no pollution, and in addition, the proton exchange membrane fuel cell also has the advantages of high starting speed, long endurance mileage, short hydrogenation time and the like.

In recent years, proton exchange membrane fuel cells have been applied to buses, trucks, trains, and the like as a power source for vehicles. Among them, the stability and reliability of vehicle operation are one of the important guarantees for large-scale commercialization of proton exchange membrane fuel cells. However, during vehicle start-stop, idling, high-power operation, and frequent load and unload conditions, hydrogen is not supplied to a local area of the anode of the battery, so that the area is not provided with enough hydrogen for oxidation reaction, and thus sufficient current cannot be generated to maintain the power of vehicle operation. In order to maintain the power of the vehicle movement, the potential of the region may rise significantly and even exceed that of the cathode region, so that the oxidation reaction of the carbon carrier occurs to generate sufficient current. This phenomenon in which the anode potential rises and exceeds the cathode potential is called the "reverse pole" phenomenon. Wherein, the oxidation reaction of the carbon carrier is as follows:

C+2H ₂ O→CO ₂ +4H ⁺ +4e ^-

C+H ₂ O→CO+2H ⁺ +2e ^-

thermodynamically, the oxidation reaction of the carbon support occurs at potentials above 0.2V (vs. rhe), however, the reaction proceeds more slowly kinetically, which results in a significant reaction rate only at high potentials (above 0.9V (vs. rhe)). Therefore, only a rapid oxidation reaction of the carbon carrier at a high potential can provide sufficient current to maintain the power for vehicle operation. However, the rapid oxidation of the carbon support can cause the catalyst structure to be seriously damaged and the metal active sites (Pt nanoparticles) to be detached, and meanwhile, the higher potential can cause the metal active sites (Pt nanoparticles) to migrate, agglomerate and grow, thereby causing the performance of the proton exchange membrane fuel cell to be rapidly attenuated and even inactivated. In addition, a large amount of heat is generated at a local region where the "reverse pole" phenomenon occurs, resulting in the formation of pinholes in the proton exchange membrane to reduce the open circuit voltage, thereby abruptly stopping the operation of the fuel cell, and at the same time, the formation of pinholes may cause the anode (H) to be suddenly stopped ₂ ) And cathode (O) ₂ ) The gas is mixed to cause fire.

When the "antipole" phenomenon occurs, it is very important for the stability and reliability of the vehicle operation to adopt an effective strategy to omit the power for maintaining the vehicle operation and evade the oxidation reaction of the carbon carrier. To date, driving the electrolytic water oxidation reaction to proceed when the "antipole" phenomenon occurs has become one of the most effective strategies against "antipole" by providing both sufficient current to maintain vehicle operating power and inhibiting the carbon support oxidation reaction from proceeding. The development of "antipole" catalysts to promote the oxidation reaction of electrolyzed water has become a key issue. However, the conventional "anti-counter-electrode" catalyst undergoes rapid agglomeration of metal active sites during the test process, thereby causing a sharp drop in the activity of the oxidation reaction of the electrolyzed water, which results in that the conventional "anti-counter-electrode" catalyst cannot effectively inhibit the oxidation reaction of the carbon carrier for a long time, resulting in unreliable and unstable vehicle operation. Therefore, the development of a carrier capable of firmly anchoring metal active sites becomes a core technology for improving the stability of the anti-antipole catalyst.

Disclosure of Invention

The present invention is based on the discovery and recognition by the inventors of the following facts and problems: in the related art of the anti-reverse catalyst, chinese patent application No. 202110700833.9 discloses an anti-reverse catalyst for a fuel cell and a preparation method thereof, the patent uses pure carbon powder such as carbon black, acetylene black, activated carbon, carbon nanotubes, graphene or highly graphitized carbon spheres, etc. as a carrier, the pure carbon carrier is difficult to form a strong interaction with a metal active site (iridium oxide), thereby being unfavorable for the stability of the anti-reverse catalyst. Chinese patent application No. 202010447113.1 discloses an anode catalyst, a membrane electrode and a fuel cell, the carrier adopted in the patent is graphitized carbon, and the pure carbon carrier is difficult to form strong interaction with the iridium-ruthenium alloy, so that, in the process of the anti-reversal test, the iridium-ruthenium alloy is easy to migrate, agglomerate and grow up, so that the stability of the anti-reversal is not facilitated, the anti-reversal process is a process of electrolytic water oxidation reaction, in the process of the electrolytic water oxidation reaction, the surface of the iridium-ruthenium alloy prepared by the patent can be oxidized into iridium-ruthenium composite oxide with low crystallinity, the surface lattice oxygen of the iridium ruthenium composite oxide with low crystallinity participates in the electrolytic water oxidation reaction process, resulting in excessive oxidation of iridium and ruthenium atoms of the iridium ruthenium composite oxide to a soluble oxide, resulting in rapid dissolution and sharp decrease in activity of the iridium ruthenium alloy. Chinese patent application No. 202010046117.9 discloses a fuel cell anti-reversal catalyst and a preparation method thereof, the catalyst adopts niobium-doped titanium dioxide as a carrier, the preparation process is complex, a uniformly dispersed catalyst with high loading rate (more than 40 wt%) is difficult to obtain, and the niobium-doped titanium dioxide has low conductivity and is not beneficial to the occurrence of electrochemical reaction.

At present, the failure mechanism of the anti-reversal catalyst is not clear, and the inventor finds out through a large number of experiments that the failure reason of the carbon-supported iridium-based anti-reversal catalyst is related to the weak interaction between the carbon carrier and the iridium-based compound and the agglomeration of iridium-based compound particles. In the prior art, an iridium-based compound is loaded on a pure carbon carrier or a metal oxide carrier to serve as a proton exchange membrane fuel cell anti-reversal catalyst. However, the use of these two vectors has the following problems: (1) the interaction between the pure carbon carrier and the iridium-based compound is weak, and the agglomeration of the iridium-based compound cannot be effectively inhibited in the reaction process, so that the stability of the catalyst is rapidly reduced; (2) iridium-based compounds on a pure carbon carrier and a metal oxide carrier are mainly loaded on the outer surface, and physical obstruction is absent among particles in the reaction process, so that migration and agglomeration are easy to occur, and the stability of the catalyst is rapidly reduced; (3) the high temperature heat treatment can cause the agglomeration of the nitrogen-carbon material, thereby being not beneficial to the uniform loading of the metal active sites; (4) gas molecules generated by high-temperature pyrolysis of the traditional pore-forming agent can damage the structure of the carbon material, so that the structure is easy to collapse, and the pore size is difficult to control; (5) the metal oxide support has poor electrical conductivity, resulting in a low activity of the catalyst.

The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, the embodiment of the invention provides the anti-antipole nitrogen-carbon carrier catalyst for the proton exchange membrane fuel cell and the preparation method thereof, which can effectively inhibit the migration and agglomeration of iridium-based compounds, improve the stability of the catalyst, enable the catalyst to have excellent performances of high activity and high stability, remarkably alleviate the problem of carbon corrosion of an anode of a proton exchange membrane fuel cell automobile under the working conditions of starting and stopping, idling, high-power running, frequent loading and unloading and the like, prolong the service life of the cell and ensure the running reliability of the automobile.

The preparation method of the proton exchange membrane fuel cell anti-antipole nitrogen-carbon carrier catalyst comprises the following steps:

a. dissolving transition metal salt, a nitrogen source and a carbon source in a first dispersing agent to obtain a nitrogen-doped metal organic framework;

b. dissolving the nitrogen-doped metal organic framework and a composite pore-forming agent in a second dispersing agent, mixing and stirring, drying, and then placing in a first sintering atmosphere for sintering treatment to obtain a carrier porous metal nitrogen-carbon material, wherein the composite pore-forming agent comprises a first pore-forming agent and a second pore-forming agent, and the first pore-forming agent comprises at least one of ammonium chloride, ammonium carbonate, ammonium sulfate and ammonium bicarbonate; the second pore-forming agent comprises at least one of sodium chloride, potassium chloride, lithium chloride, rubidium chloride, cesium chloride, sodium sulfate, potassium sulfate, lithium sulfate, rubidium sulfate, cesium sulfate, rubidium nitrate, cesium nitrate, sodium bicarbonate, potassium bicarbonate, rubidium carbonate and cesium carbonate;

c. and adding the porous metal nitrogen-carbon material and the noble metal precursor into the third dispersing agent for heating treatment, drying, and then placing in a second sintering atmosphere for sintering treatment to obtain the anti-reversal catalyst.

The preparation method of the proton exchange membrane fuel cell antipole nitrogen-carbon carrier catalyst provided by the embodiment of the invention brings advantages and technical effects, 1, in the embodiment of the invention, a metal nitrogen-carbon material is adopted as a carrier, the metal nitrogen-carbon material has abundant nitrogen elements, and the doped nitrogen elements can obviously promote the interaction between the carrier and a noble metal active component, so that the migration, agglomeration and growth of a noble metal compound are inhibited, and the stability of the catalyst is obviously promoted; 2. in the embodiment of the invention, the composite pore-forming agent and the nitrogen-doped metal organic framework are introduced to be mixed and sintered at high temperature to prepare the porous metal nitrogen-carbon material, the porous structures can utilize the internal space to load the noble metal compound so as to improve the load, the thickness of a catalyst layer in a membrane electrode can be reduced, the 'limited area' effect of a pore channel can be utilized to effectively inhibit the migration and agglomeration of the noble metal compound, and the stability of the catalyst is obviously improved; 3. in the embodiment of the invention, the introduced composite pore-forming agent is formed by combining a first pore-forming agent and a second pore-forming agent, the first pore-forming agent generates micromolecular gas through calcination to form a certain pore channel structure, so that a channel is provided for the permeation of the second pore-forming agent, the second pore-forming agent becomes molten salt in the calcination process, the catalyst can be wrapped to prevent the catalyst from agglomerating at high temperature and can permeate into the pore channel structure formed by the first pore-forming agent to maintain the stability of the pore channel structure of the catalyst, and the substance adopted by the composite pore-forming agent is water-soluble and is easy to clean; 4. in the embodiment of the invention, the porous metal nitrogen-carbon material obtained by high-temperature sintering has high graphitization property, so that the porous metal nitrogen-carbon material has high conductivity and structural stability, and in addition, the transition metal element doped in the porous metal nitrogen-carbon material can not only adjust the structural property of a nitrogen-carbon carrier, but also effectively adjust the electronic structure of a noble metal compound, thereby being beneficial to the promotion of catalytic activity; 5. the anti-reversal catalyst prepared by the method of the embodiment of the invention has excellent performance, and the anti-reversal time is more than 300 minutes; 6. in the embodiment of the invention, the adopted raw materials have low cost and wide sources, and the synthesis process route is simple and is suitable for industrial production.

In some embodiments, in the step a, the transition metal salt includes at least one of a cobalt salt, a nickel salt, a manganese salt, a copper salt, a zinc salt, and an iron salt; the nitrogen source comprises at least one of 2-methylimidazole, triethylenediamine, chitosan, dicyandiamide, formamide, urea and pyrrole; the carbon source comprises at least one of trimesic acid, terephthalic acid, glucose, thiourea and phytic acid.

In some embodiments, the transition metal salt comprises at least one of cobalt nitrate, cobalt acetylacetonate, cobalt phthalocyanine, cobalt chloride, nickel nitrate, nickel acetylacetonate, nickel phthalocyanine, nickel chloride, manganese nitrate, manganese acetylacetonate, manganese chloride, copper nitrate, copper acetylacetonate, copper chloride, zinc nitrate, zinc chloride, ferric nitrate, ferric acetylacetonate, and iron phthalocyanine;

in some embodiments, in the step b, the mass ratio of the first pore-forming agent to the second pore-forming agent is 1:1 to 1:20, preferably 1:3 to 1: 12; the mass ratio of the nitrogen-doped metal organic framework to the composite pore-forming agent is 1:0.1-1:20, and preferably 1:1-1: 5.

In some embodiments, the first dispersant comprises at least one of methanol, isopropanol, benzyl alcohol, ethanol, N-dimethylformamide, formamide, water; the second dispersing agent comprises at least one of water, isopropanol, methanol, acetone and ethanol; the third dispersant comprises at least one of water, methanol, ethanol, benzyl alcohol, isopropanol and ethylene glycol.

In some embodiments, in step c, the noble metal precursor comprises at least one of an iridium precursor and a ruthenium precursor.

In some embodiments, the noble metal precursor comprises at least one of chloroiridate, iridium chloride, ammonium chloroiridate, iridium acetylacetonate, sodium chloroiridate, ammonium chloroiridate, potassium chloroiridate, ruthenium chloride, ammonium chlororuthenate, ruthenium nitrosyl nitrate, ruthenium acetylacetonate, and potassium chlororuthenate.

In some embodiments, the noble metal precursor has a molar ratio of iridium-containing precursor to ruthenium-containing precursor of from 0.1:4 to 4:0, preferably from 2:2 to 3.5: 0.5.

In some embodiments, in step b, the first sintering atmosphere comprises at least one of nitrogen, argon and hydrogen, the first sintering temperature is 800-; in the step c, the second sintering atmosphere comprises at least one of nitrogen, argon and hydrogen, the second sintering temperature is 150-.

In some embodiments, the step b further comprises an acid washing step and a water washing step after sintering to obtain the porous metal nitrogen-carbon material: washing the porous metal nitrogen-carbon material with ultrapure water, then putting the porous metal nitrogen-carbon material into an acidic water-based solution with the temperature of 30-95 ℃ for dispersing and stirring for 6-48 hours, washing the porous metal nitrogen-carbon material with ultrapure water again until the pH value of filtrate is neutral, and drying the filtrate; wherein the acidic water-based solution comprises at least one of sulfuric acid, nitric acid, formic acid, hydrochloric acid and perchloric acid aqueous solution, and the pH value of the acidic water-based solution is less than or equal to 2; in the step c, after the second sintering atmosphere sintering treatment, a third sintering atmosphere sintering treatment is further included, the sintering temperature is 150-.

In some embodiments, the mixing and stirring temperature in step b is 25-90 ℃; in the step c, the heating temperature is 25-180 ℃, the heating time is 0.5-36 hours, and preferably, when the heating treatment temperature is 25-80 ℃, the heating time is 8-24 hours; when the heating treatment temperature is 80-160 ℃, the heating time is 4-8 hours; when the heating treatment temperature is 160-180 ℃, the heating time is 2-4 hours.

The embodiment of the invention also provides a proton exchange membrane fuel cell antipole nitrogen-carbon carrier catalyst which is prepared by the method of the embodiment of the invention. According to the catalyst provided by the embodiment of the invention, the porous metal nitrogen-carbon material is used as the carrier, the porous metal nitrogen-carbon material has abundant nitrogen elements, can form a strong interaction with a noble metal compound, effectively inhibits the migration and agglomeration of the noble metal compound, and improves the stability of the catalyst. The catalyst provided by the embodiment of the invention has high activity and high stability, the anti-reversal time can be up to more than 300 minutes, and the performance is excellent.

In some embodiments, the support porous metal nitrocarbon material is a cage-like structure.

In some embodiments, the carrier porous metal nitrocarbon material has a pore size of 3 to 8nm, preferably 4 to 8nm, and a pore volume of 0.5 to 2cm ³ /g。

In some embodiments, the nitrogen content of the support is 0.1 to 20 wt%, preferably 8.5 to 13.5 wt%.

In some embodiments, the noble metal compound in the catalyst has a particle size of 1 to 6nm, preferably 2 to 3.5 nm.

In some embodiments, the transition metal content of the support is from 0.1 to 5 wt%, preferably from 1 to 3 wt%.

Drawings

FIG. 1 is a schematic diagram of a preparation method of an anti-antipole nitrogen-carbon carrier catalyst of a proton exchange membrane fuel cell according to an embodiment of the invention;

FIG. 2 is a TEM image of (a) an nitrogen-doped metal-organic framework and (b) a porous metal-nitrocarbon material prepared in example 1, wherein a is the nitrogen-doped metal-organic framework and b is the porous metal-nitrocarbon material;

FIG. 3 is a graph of the electrochemical oxygen evolution reactivity curves for the catalysts, commercial iridium oxides on carbon and commercial iridium oxides prepared in examples 1-5.

Detailed Description

Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.

As shown in fig. 1, the preparation method of the anti-reverse-polarity nitrogen-carbon supported catalyst for the proton exchange membrane fuel cell of the embodiment of the invention comprises the following steps:

According to the preparation method of the proton exchange membrane fuel cell antipole nitrogen-carbon carrier catalyst, the metal nitrogen-carbon material is used as the carrier, the metal nitrogen-carbon material is rich in nitrogen elements, and the doped nitrogen elements can obviously promote the interaction between the carrier and the active components of the noble metal, so that the migration, agglomeration and growth of the noble metal compound are inhibited, and the stability of the catalyst is obviously promoted; in the embodiment of the invention, the composite pore-forming agent and the nitrogen-doped metal organic framework are introduced to be mixed and sintered at high temperature to prepare the porous metal nitrogen-carbon material, the porous structures can utilize the internal space to load the noble metal compound so as to improve the load, the thickness of a catalyst layer in a membrane electrode can be reduced, the 'limited area' effect of a pore channel can be utilized to effectively inhibit the migration and agglomeration of the noble metal compound, and the stability of the catalyst is obviously improved; in the embodiment of the invention, the introduced composite pore-forming agent is formed by combining a first pore-forming agent and a second pore-forming agent, the first pore-forming agent generates micromolecular gas through calcination to form a certain pore channel structure, so that a channel is provided for the permeation of the second pore-forming agent, the second pore-forming agent becomes molten salt in the calcination process, the catalyst can be wrapped to prevent the catalyst from agglomerating at high temperature and can permeate into the pore channel structure formed by the first pore-forming agent to maintain the stability of the pore channel structure of the catalyst, and the substance adopted by the composite pore-forming agent is water-soluble and is easy to clean; in the embodiment of the invention, the porous metal nitrogen-carbon material obtained by high-temperature sintering has high graphitization property, so that the porous metal nitrogen-carbon material has high conductivity and structural stability, and in addition, the transition metal element doped in the porous metal nitrogen-carbon material can not only adjust the structural property of a nitrogen-carbon carrier, but also effectively adjust the electronic structure of a noble metal compound, thereby being beneficial to the promotion of catalytic activity; the anti-reversal catalyst prepared by the method of the embodiment of the invention has excellent performance, and the anti-reversal time is more than 300 minutes; in the embodiment of the invention, the adopted raw materials have low cost and wide sources, and the synthesis process route is simple and is suitable for industrial production.

In some embodiments, in step a, the transition metal salt includes at least one of cobalt salt, nickel salt, manganese salt, copper salt, zinc salt and iron salt, preferably at least one of cobalt nitrate, cobalt acetylacetonate, cobalt phthalocyanine, cobalt chloride, nickel nitrate, nickel acetylacetonate, nickel cyanine, nickel chloride, manganese nitrate, manganese acetylacetonate, manganese chloride, copper nitrate, copper acetylacetonate, copper chloride, zinc nitrate, zinc chloride, ferric nitrate, ferric acetylacetonate, and iron phthalocyanine; the nitrogen source comprises at least one of 2-methylimidazole, triethylene diamine, chitosan, dicyandiamide, formamide, urea and pyrrole; the carbon source comprises at least one of trimesic acid, terephthalic acid, glucose, thiourea and phytic acid. In the embodiment of the present invention, if the nitrogen source contains carbon, the carbon source may not be introduced or the content of the carbon source may be reduced. In the embodiment of the invention, the carbon source, the nitrogen source and the transition metal salt are prepared from the raw materials which are low in price and easy to obtain, and are easy to apply industrially.

In some embodiments, in the step b, the mass ratio of the first pore-forming agent to the second pore-forming agent is 1:1 to 1:20, preferably 1:3 to 1: 12; the mass ratio of the nitrogen-doped metal organic framework to the composite pore-forming agent is 1:0.1-1:20, and preferably 1:1-1: 5. In the embodiment of the invention, the mass ratio of the first pore-forming agent to the second pore-forming agent is optimized, which is beneficial to maintaining the stability of the catalyst structure by the sufficient second pore-forming agent so as to avoid the agglomeration of the catalyst and the collapse of the structure, and simultaneously, the sufficient first pore-forming agent can form a certain pore channel structure, so that the second pore-forming agent can fully permeate into the pore channel structure of the catalyst so as to form a porous structure with larger and proper size. In the embodiment of the invention, the mass ratio of the nitrogen-doped metal organic framework to the composite pore-forming agent is further optimized, which is beneficial to forming an effective pore channel structure, causes a proper pore diameter and is beneficial to playing a role of 'limited area', and avoids unstable carrier structure and structural collapse during acid washing caused by adopting excessive pore-forming agents.

In some embodiments, the first dispersant comprises at least one of methanol, isopropanol, benzyl alcohol, ethanol, N-dimethylformamide, formamide, water; the second dispersing agent comprises at least one of water, isopropanol, methanol, acetone and ethanol; the third dispersant comprises at least one of water, methanol, ethanol, benzyl alcohol, isopropanol and ethylene glycol. In the embodiment of the present invention, the dispersant used in each step is not particularly limited as long as sufficient dispersion of the material can be achieved.

In some embodiments, in step c, the noble metal precursor comprises at least one of an iridium precursor and a ruthenium precursor; preferably, the noble metal precursor includes at least one of chloroiridate, iridium chloride, ammonium chloroiridate, iridium acetylacetonate, sodium chloroiridate, ammonium chloroiridate, potassium chloroiridate, ruthenium chloride, ammonium chlororuthenate, ruthenium nitrosyl nitrate, ruthenium acetylacetonate, and potassium chlororuthenate. Further preferably, the molar ratio of the iridium-containing precursor to the ruthenium-containing precursor in the noble metal precursor is 0.1:4 to 4:0, preferably 2:2 to 3.5: 0.5. In the embodiment of the invention, as the adopted carrier is a porous metal nitrogen-carbon material, the performance is excellent, the structure is stable, the migration, agglomeration and growth of a loaded noble metal compound can be effectively avoided, the prepared catalyst has excellent performances of high activity and high stability, and simultaneously, the lattice constants of ruthenium and iridium atoms are close to each other, and the iridium-ruthenium composite compound with the stable structure is easily formed, so that a ruthenium-containing precursor with better activity than iridium can be introduced into the noble metal precursor, a certain amount of ruthenium is doped into an iridium-based compound to form the iridium-ruthenium composite compound, the problem of low activity of the iridium compound is solved, and the cost of the catalyst is greatly reduced because the price of iridium is high and is about 5-10 times of that of ruthenium.

In some embodiments, in step b, the first sintering atmosphere comprises at least one of nitrogen, argon and hydrogen, the first sintering temperature is 800-; in the step c, the second sintering atmosphere comprises at least one of nitrogen, argon and hydrogen, the second sintering temperature is 150-. In the embodiment of the invention, the first sintering temperature is favorable for carbonizing the nitrogen-doped metal organic framework and simultaneously graphitizing carbon. In the embodiment of the invention, the second sintering temperature is further optimized, which is not only beneficial to fully reducing the noble metal iridium precursor and the ruthenium precursor so as to realize the controllability of the loading capacity, but also can improve the crystallinity of the noble metal iridium-based compound so as to promote the stability and the acid resistance, and can further enhance the interaction between the porous metal nitrogen-carbon material carrier and the iridium-based compound.

In some embodiments, the step b further comprises an acid washing step and a water washing step after sintering to obtain the porous metal nitrogen-carbon material: washing the porous metal nitrogen-carbon material with ultrapure water, then putting the porous metal nitrogen-carbon material into an acidic water-based solution with the temperature of 30-95 ℃ for dispersing and stirring for 6-48 hours, washing the porous metal nitrogen-carbon material with ultrapure water again until the pH value of filtrate is neutral, and drying the filtrate; wherein the acidic water-based solution comprises at least one of sulfuric acid, nitric acid, formic acid, hydrochloric acid and perchloric acid aqueous solution, and the pH value of the acidic water-based solution is less than or equal to 2. In the embodiment of the invention, acid washing treatment is preferably adopted, and transition metal and Na possibly existing in the porous metal nitrogen-carbon material can be effectively removed in the acid washing process ⁺ 、K ⁺ 、Rb ⁺ 、Cs ⁺ 、SO ₄ ^2- And Cl ^- And the like, thereby reducing the influence of the impurities on the key parts of the membrane electrode.

In some embodiments, in the step c, after the second sintering atmosphere sintering treatment, a third sintering atmosphere sintering treatment is further included, the sintering temperature is 150-. In the embodiment of the invention, the third sintering treatment is preferably further increased, and the sintering temperature is preferably selected, so that the supported noble metal iridium-based compound is converted into the noble metal iridium-based oxide with high crystallinity, the structural stability of the catalyst is improved, and organic matters and amorphous carbon remained on the surface of the catalyst can be removed.

In some embodiments, in step b, the mixing agitation temperature is from 25 to 90 ℃. In the embodiment of the invention, the mixing and dispersing temperature of the nitrogen-doped metal organic framework and the composite pore-forming agent is optimized, which is favorable for promoting the two to be fully mixed and dispersed in the second dispersing agent.

In some embodiments, in the step c, the heating temperature is 25 to 180 ℃ and the heating time is 0.5 to 36 hours, preferably, when the heat treatment temperature is 25 to 80 ℃, the heating time is 8 to 24 hours; when the heating treatment temperature is 80-160 ℃, the heating time is 4-8 hours; when the heat treatment temperature is 160-180 ℃, the heating time is 2-4 hours. In the embodiment of the invention, the heating treatment temperature and time of the porous metal nitrogen-carbon material and the noble metal precursor are optimized, so that the uniform loading of the noble metal on the carrier is facilitated.

The embodiment of the invention also provides a proton exchange membrane fuel cell antipole nitrogen-carbon carrier catalyst which is prepared by the method of the embodiment of the invention. The catalyst provided by the embodiment of the invention adopts the porous metal nitrogen-carbon material as the carrier, has rich nitrogen elements, can form strong interaction with the noble metal compound, effectively inhibits the migration and agglomeration of the noble metal compound, and improves the stability of the catalyst. According to the catalyst disclosed by the embodiment of the invention, the loading capacity of the noble metal compound can reach more than 30%, the catalyst has high activity and high stability, the anti-reversal time can reach more than 300 minutes, and the performance is excellent.

In some embodiments, the support porous metal nitrocarbon material is a cage structure.

In some embodiments, the porous metallic nitrocarbon material of the support has a pore diameter of 3 to 8nm, preferably 4 to 8nm, and a pore volume of 0.5 to 2cm ³ (ii) in terms of/g. In the embodiment of the invention, the pore diameter of the carrier is optimized, the undersized pore diameter is not beneficial to the high-loading load of the noble metal iridium-based compound, and the oversized pore diameter cannot effectively play a role of limiting the range.

In some embodiments, the nitrogen content of the support is 0.1 to 20 wt%, preferably 8.5 to 13.5 wt%. In the embodiment of the invention, the nitrogen content in the carrier is optimized, which is beneficial to forming effective interaction between the carrier and the iridium-based compound and simultaneously ensuring the electrical conductivity of the catalyst.

In some embodiments, the noble metal compound in the catalyst has a particle size of 1 to 6nm, preferably 2 to 3.5 nm. In the embodiment of the invention, the size of the noble metal iridium-based compound in the antipole catalyst is preferably selected, so that the catalyst has excellent activity and excellent stability, if the size is too small, the iridium-based compound particles have larger surface energy, so that agglomeration is more likely to occur, and the stability is reduced, and if the size is too large, the specific surface area of the iridium-based compound is reduced, so that the number of exposed active sites is reduced, and the activity is reduced.

In some embodiments, the transition metal content of the support is from 0.1 to 5 wt%, preferably from 1 to 3 wt%. In the embodiment of the invention, the content of the transition metal in the carrier is preferably selected, so that a metal nitrogen carbon stable structure can be fully formed, the content is too low to be beneficial to playing an effective electronic regulation effect on the iridium-based compound, and the content is too high to be beneficial to completely forming the metal nitrogen carbon structure, so that transition metal clusters and/or particles can be generated, and can be dissolved in an acidic environment, so that impurity ions are formed, and the anti-reversal performance is influenced.

The present invention will be described in detail below with reference to examples and the accompanying drawings.

Example 1

(1) Dissolving zinc nitrate and cobalt nitrate in methanol, adding the mixture into the methanol containing 2-methylimidazole, stirring, mixing, washing and drying to obtain a nitrogen-doped metal organic framework;

(2) dissolving a nitrogen-doped metal organic framework and a composite pore-forming agent consisting of ammonium chloride and sodium chloride in water, wherein the mass ratio of the metal organic framework to the composite pore-forming agent is 1:5, the mass ratio of the ammonium chloride to the sodium chloride is 1:6, fully stirring and mixing at 90 ℃, drying and grinding by rotary evaporation, sintering at 900 ℃ for 3 hours in a nitrogen atmosphere to prepare a carrier porous metal nitrogen-carbon material, wherein the nitrogen content is 12.8%, the zinc content is 0% (Zn atom is evaporated at high temperature), the cobalt content is 2%, washing the porous metal nitrogen-carbon material with ultrapure water, then putting the material into a nitric acid aqueous solution with the temperature of 60 ℃ and the pH value of 2 for dispersing, fully stirring for 24 hours, finally washing with the ultrapure water again until the pH value of the filtrate is neutral, and then drying;

(3) adding chloroiridic acid and ruthenium chloride with a molar ratio of 3:1 and the porous metal nitrogen carbon material into a reactor filled with ethylene glycol, heating to 160 ℃, maintaining for 4 hours, drying, placing in a nitrogen atmosphere, sintering at 300 ℃ for 3 hours, and then placing a sample sintered in a second atmosphere in an air atmosphere, sintering at 300 ℃ for 3 hours to obtain the anti-reversal catalyst, namely the porous metal nitrogen carbon material loaded iridium-based compound, wherein iridium ruthenium accounts for 45.6% of the total mass of the catalyst.

The parameters and properties of the catalyst prepared in the embodiment are shown in table 1, the synthesis schematic diagram of the iridium-based compound supported by the porous metal nitrogen-carbon material is shown in fig. 1, the TEM of the metal organic framework and the porous metal nitrogen-carbon material is shown in fig. 2, and the electrochemical oxygen evolution reaction activity curve is shown in fig. 3.

Example 2

(1) Dissolving ferric chloride and zinc chloride in ethanol, adding into ethanol containing dicyandiamide and trimesic acid (the mass ratio of the dicyandiamide to the trimesic acid is 8:2), stirring and mixing, and performing rotary evaporation and drying to obtain a nitrogen-doped metal organic framework;

(2) dissolving a composite pore-forming agent consisting of a nitrogen-doped metal organic framework, ammonium carbonate and sodium chloride in water, wherein the mass ratio of the metal organic framework to the composite pore-forming agent is 1:3, the mass ratio of the ammonium carbonate to the sodium chloride is 1:3, fully stirring and mixing at 60 ℃, drying and grinding by rotary evaporation, sintering at 1100 ℃ for 2 hours in an argon atmosphere to prepare a carrier porous metal nitrogen-carbon material, wherein the nitrogen content is 11.5%, the iron content is 3% and the zinc content is 0%, washing the porous metal nitrogen-carbon material with ultrapure water, then putting the porous metal nitrogen-carbon material into a sulfuric acid aqueous solution with the temperature of 80 ℃ and the pH value of 1 for dispersion, fully stirring for 12 hours, finally washing with ultrapure water again until the pH value of the filtrate is neutral, and then drying;

(3) adding potassium chloroiridate and potassium chlororuthenate in a molar ratio of 1:1 and a porous metal nitrogen-carbon material into a reactor filled with benzyl alcohol, heating to 140 ℃, maintaining for 6 hours, drying, placing in an argon atmosphere for sintering treatment at 400 ℃ for 2 hours, then placing a sample sintered in a second atmosphere in a mixed atmosphere of oxygen and nitrogen for sintering treatment at 250 ℃ for 4 hours to prepare the anti-reversal catalyst, namely the porous metal nitrogen-carbon material loaded iridium-based compound, wherein iridium ruthenium accounts for 42.9% of the total mass of the catalyst.

The parameters and properties of the catalyst prepared in this example are shown in Table 1, and the electrochemical oxygen evolution reaction activity curve is shown in FIG. 3.

Example 3

(1) Dissolving manganese chloride in ethanol, adding into ethanol containing pyrrole and phytic acid (the mass ratio of the pyrrole to the phytic acid is 4:6), stirring, mixing, and performing rotary evaporation and drying to obtain the nitrogen-doped metal organic framework;

(2) dissolving a composite pore-forming agent consisting of a nitrogen-doped metal organic framework, ammonium bicarbonate and potassium chloride in ethanol, wherein the mass ratio of the metal organic framework to the composite pore-forming agent is 1:3, the mass ratio of the ammonium bicarbonate to the potassium chloride is 1:6, fully stirring and mixing at 25 ℃, drying and grinding by rotary evaporation, sintering at 800 ℃ for 5 hours in a mixed atmosphere of nitrogen and hydrogen to obtain a porous metal nitrogen-carbon material, wherein the nitrogen content is 8.5% and the manganese content is 1%, washing the porous metal nitrogen-carbon material by using ultrapure water, dispersing in a perchloric acid aqueous solution with the pH value of 1 at 50 ℃, fully stirring for 48 hours, washing again by using the ultrapure water until the pH value of the filtrate is neutral, and drying;

(3) adding iridium chloride and ammonium chlororuthenate and a porous metal nitrogen-carbon material into a reactor filled with ethanol at a molar ratio of 2.5:1.5, heating to 25 ℃, maintaining for 24 hours, drying, placing in a mixed gas atmosphere of argon and hydrogen for sintering treatment at 500 ℃ for 5 hours, then placing a sample sintered in a second atmosphere in a mixed gas atmosphere of air and argon for sintering treatment at 350 ℃ for 2 hours to prepare the antipole catalyst, namely the porous metal nitrogen-carbon material supported iridium-based compound, wherein iridium ruthenium accounts for 44.9% of the total mass of the catalyst.

Example 4

(1) Dissolving nickel nitrate and cobalt chloride in water, adding the nickel nitrate and the cobalt chloride into water containing dicyandiamide and glucose (the mass ratio of the dicyandiamide to the glucose is 6:4), stirring and mixing, and carrying out rotary evaporation and drying to obtain a nitrogen-doped metal organic framework;

(2) dissolving a nitrogen-doped metal organic framework and a composite pore-forming agent consisting of ammonium sulfate and potassium chloride in water, wherein the mass ratio of the metal organic framework to the composite pore-forming agent is 1:5, the mass ratio of the ammonium sulfate to the potassium chloride is 1:4, fully stirring and mixing at 50 ℃, drying and grinding by rotary evaporation, sintering at 950 ℃ for 2.5 hours in an argon and hydrogen mixed atmosphere to prepare a porous metal nitrogen-carbon material, wherein the nitrogen content is 10.2%, the nickel content is 1%, and the cobalt content is 3%, washing the porous metal nitrogen-carbon material with ultrapure water, then putting the porous metal nitrogen-carbon material into a sulfuric acid aqueous solution with the temperature of 95 ℃ and the pH value of 0.5 for dispersion, fully stirring for 6 hours, finally washing with the ultrapure water again until the pH value of the filtrate is neutral, and then drying;

(3) adding sodium chloroiridate and ruthenium chloride with a molar ratio of 3.5:0.5 and the porous metal nitrogen-carbon material into a reactor filled with water, heating to 80 ℃, maintaining for 8 hours, drying, placing in a mixed gas atmosphere of nitrogen and hydrogen for sintering treatment at 600 ℃ for 2 hours, then placing a sample sintered in a second atmosphere in a mixed gas atmosphere of air and nitrogen for sintering treatment at 325 ℃ for 3 hours, and obtaining the antipole catalyst, namely the porous metal nitrogen-carbon material supported iridium-based compound, wherein iridium ruthenium accounts for 46.7% of the total mass of the catalyst.

Example 5

(1) Dissolving iron phthalocyanine in water, adding the water containing dicyandiamide and phytic acid (the mass ratio of the dicyandiamide to the phytic acid is 5:5), stirring and mixing, and carrying out rotary steaming and drying to obtain a nitrogen-doped metal organic framework;

(2) dissolving a nitrogen-doped metal organic framework, a composite pore-forming agent consisting of ammonium chloride and cesium carbonate in methanol, wherein the mass ratio of the metal organic framework to the composite pore-forming agent is 1:1, the mass ratio of the ammonium chloride to the sodium carbonate is 1:10, fully stirring and mixing at 30 ℃, drying and grinding by rotary evaporation, sintering at 850 ℃ for 6 hours in an argon atmosphere to prepare a carrier porous metal nitrogen-carbon material, wherein the nitrogen content is 9.7%, the iron content is 2.5%, washing the porous metal nitrogen-carbon material with ultrapure water, then putting the porous metal nitrogen-carbon material into a hydrochloric acid aqueous solution with the temperature of 30 ℃ and the pH value of 1 for dispersion, fully stirring for 48 hours, finally washing with the ultrapure water again until the pH value of filtrate is neutral, and then drying;

(3) adding potassium chloroiridite and ruthenium nitrosyl nitrate in a molar ratio of 2:1 and the porous metal nitrogen-carbon material into a reactor filled with ethylene glycol, heating to 180 ℃, maintaining for 2 hours, drying, placing in a nitrogen atmosphere, sintering at 300 ℃ for 2 hours, then placing a sample sintered in a second atmosphere in a mixed atmosphere of oxygen and argon, sintering at 300 ℃ for 3 hours, and preparing the anti-reversal catalyst, namely the iridium-based compound loaded on the porous metal nitrogen-carbon material, wherein iridium ruthenium accounts for 45.1% of the total mass of the catalyst.

Example 6

The same procedure as in example 1, except that cobalt nitrate was not added.

The iridium and ruthenium content of the catalyst obtained in example 6 was 44.5%, and the catalyst parameters and properties are shown in Table 1.

Example 7

The same procedure as in example 1 was followed, except that zinc nitrate was not added.

The iridium and ruthenium content of the catalyst obtained in example 7 was 44.9%, and the catalyst parameters and properties are shown in Table 1.

Example 8

The same procedure as in example 2 was followed, except that ferric chloride, a transition metal salt, was replaced with ferric acetylacetonate.

The iridium and ruthenium content of the catalyst prepared in example 8 was 44.8%, and the catalyst parameters and properties are shown in Table 1.

Example 9

The same procedure as in example 2, except that the second pore former, sodium chloride, was replaced with sodium sulfate.

The iridium and ruthenium content of the catalyst obtained in example 9 was 42.7%, and the catalyst parameters and properties are shown in Table 1.

Example 10

The same process as in example 2, except that potassium chlororuthenate was not added in step (3) and only potassium chloroiridate was used for the noble metal precursor.

The iridium content of the catalyst obtained in example 10 was 42.5%, and the catalyst parameters and properties are shown in Table 1.

Comparative example 1

The same procedure as in example 1, except that no composite pore-forming agent was added in step (2).

The iridium-ruthenium content of the catalyst prepared in comparative example 1 was 42.3%, and the catalyst parameters and properties thereof are shown in table 1.

Comparative example 2

The method is the same as the method of example 1, except that the mass ratio of the nitrogen-doped metal-organic framework to the composite pore-forming agent in the step (2) is 1: 25.

The iridium-ruthenium content of the catalyst prepared in comparative example 2 was 41.7%, and the catalyst parameters and properties thereof are shown in table 1.

Comparative example 3

The same method as that of example 1, except that the nitrogen-doped metal-organic framework and the composite pore-forming agent are not dispersed in water and are not sintered, but are directly ground and mixed to prepare the carrier in step (2).

The iridium-ruthenium content of the catalyst prepared in comparative example 3 was 41.9%, and the catalyst parameters and properties thereof are shown in table 1.

Comparative example 4

The same method as in example 1, except that sodium chloride was not added to the pore-forming agent, ammonium chloride was used as the pore-forming agent, and the mass ratio of the metal-organic framework to the pore-forming agent was 1: 5.

The catalyst prepared in comparative example 4 had an iridium ruthenium content of 40.7%, and the catalyst parameters and properties are shown in table 1.

Comparative example 5

The same method as in example 1, except that ammonium chloride was not added to the pore-forming agent, sodium chloride was used as the pore-forming agent only, and the mass ratio of the metal-organic framework to the pore-forming agent was 1: 5.

The iridium-ruthenium content of the catalyst prepared in comparative example 5 was 43.7%, and the catalyst parameters and properties thereof are shown in table 1.

Comparative example 6

The same procedure as in example 1, except that 2-methylimidazole was replaced with melamine.

The iridium-ruthenium content of the catalyst prepared in comparative example 6 was 42.7%, and the catalyst parameters and properties thereof are shown in table 1.

Comparative example 7

The same procedure as in example 2, except that dicyandiamide as a nitrogen source was not added in the step (1), and trimesic acid as a carbon source was used alone.

The catalyst obtained in comparative example 7 had an iridium ruthenium content of 38.7% and the catalyst parameters and properties are given in table 1.

Comparative example 8

The same procedure as in example 3, except that the first sintering temperature in step (2) was 400 ℃.

The catalyst prepared in comparative example 8 had an iridium ruthenium content of 42.1%, and the catalyst parameters and properties are shown in table 1.

Comparative example 9

The same procedure as in example 4 was repeated, except that the second sintering temperature of 600 ℃ in step (3) was adjusted to 1000 ℃.

The catalyst prepared in comparative example 9 had an iridium ruthenium content of 41.5%, and the catalyst parameters and properties are shown in table 1.

Comparative example 10

The same procedure as in example 5, except that ferrocyanine was not added in step (1).

The catalyst obtained in comparative example 10 had an iridium ruthenium content of 46.1% and the catalyst parameters and properties are given in table 1.

TABLE 1

Note: 1. commercial iridium oxide on carbon is purchased from foreign manufacturers, and the loading capacity is 20 wt%;

2. commercial iridium oxide was purchased from domestic manufacturers, pure iridium oxide;

3. crystallite diameter refers to the particle diameter of the iridium-based compound;

4. the activity (potential and mass activity) is tested by a three-electrode method, and an oxygen evolution reaction test is carried out in a perchloric acid electrolyte saturated with oxygen, and the loading of noble metal is 20 mu g/cm ² _IrRu (ii) a The activity index is that the current density reaches 10mA/cm ² Potential at time and current density at 1.53V (vs. rhe) potential.

As can be seen from Table 1, compared with commercial iridium oxide or iridium oxide catalysts supported on carbon, the carriers of examples 1-10 have larger pore size and higher nitrogen content, the iridium-based compound has smaller crystallite diameter, and the catalysts prepared in examples 1-10 show lower electrolytic water oxidation reaction potential, higher quality activity and longer anti-reversal time, and the anti-reversal time can reach more than 300 min. In particular, in example 1, compared with example 7, the addition of the Zn salt enables the Zn salt to form ZIF-8 with 2-methylimidazole, which is a very stable metal-organic framework structure and does not easily cause structural collapse during pyrolysis; the addition of Zn atoms can separate the transition metal atoms from each other and keep away from each other, so that the transition metal atoms can exist in the form of single atoms, therefore, after high-temperature pyrolysis, the Zn atoms are evaporated, the transition metal atoms can not agglomerate to form clusters or particles due to the mutual separation, only an M-NC structure can be formed, the metal clusters or particles can be dissolved in an acid medium, and the M-NC structure has good acid resistance, compared with the example 7 without adding Zn salt, the example 1 can form a metal organic framework with a stable structure with 2-methylimidazole, and further improves the anti-antipole performance of the catalyst.

In comparative example 1, no composite pore-forming agent is added into the nitrogen-doped metal organic framework, the prepared metal nitrogen-carbon material cannot effectively form a larger pore channel structure, so that the pore diameter of the carrier is obviously reduced, and the iridium-based compound can only nucleate and grow on the outer surface of the carrier, so that the diameter of iridium microcrystal is increased, the oxidation reaction potential of electrolyzed water is increased, the quality activity is reduced, and the anti-reversal time is reduced.

In a comparative example 2, the mass ratio of the nitrogen-doped metal organic framework to the composite pore-forming agent is controlled to be 1:25, and the excessive introduction of the composite pore-forming agent causes the overlarge pore diameter of the carrier, so that the 'confinement' effect cannot be effectively played, and the oxidation reaction potential of the electrolyzed water is increased, the quality activity is reduced, and the anti-reversal time is reduced.

In the comparative example 3, the nitrogen-doped metal organic framework and the composite pore-forming agent are directly ground and mixed, and the composite pore-forming agent cannot effectively enter the pore channel structure of the metal organic framework, so that the effective pore-forming effect cannot be achieved, and therefore, the diameter of the iridium-containing microcrystal is increased, the oxidation reaction potential of electrolyzed water is increased, the quality activity is reduced, and the anti-reversal time is reduced.

In comparative example 4, the porous metal nitrogen-carbon material is seriously agglomerated and the structure is collapsed due to the absence of the second pore-forming agent without adding the second pore-forming agent sodium chloride, so that the specific surface area is reduced, and further the diameter of the prepared iridium-containing microcrystal loaded by the catalyst is increased, the oxidation reaction potential of electrolyzed water is increased, the quality activity is reduced and the anti-reversal time is reduced.

In comparative example 5, the first pore-forming agent ammonium chloride was not added, and the smaller pore structure of the nitrogen-carbon support itself could not allow the molten second pore-forming agent sodium chloride to effectively penetrate due to the absence of the first pore-forming agent, resulting in a decrease in the pore size of the support, an increase in the diameter of the iridium-containing crystallite, an increase in the oxidation reaction potential of the electrolyzed water, a decrease in the quality activity, and a decrease in the anti-reversal time.

In comparative example 6, 2-methylimidazole is replaced by melamine, and the content of nitrogen in the synthesized porous metal nitrogen-carbon material is too high due to the high content of nitrogen element in the melamine, so that the conductivity of the porous metal nitrogen-carbon material is reduced, and the oxidation reaction potential of electrolyzed water is increased, the quality activity is reduced, and the anti-reversal time is reduced.

In comparative example 7, without adding dicyandiamide as a nitrogen source, the interaction between the iridium-based compound and the pure carbon support was weak, resulting in a decrease in the anti-reversal time.

In comparative example 8, the first sintering temperature in step (2) was controlled to 400 ℃, and at this temperature, the composite pore-forming agent could not be effectively used to create a larger pore structure, and the metal skeleton structure could not be completely carbonized and transformed into a highly graphitized carbon material, so that the diameter of the iridium-containing crystallite was increased, and further the oxidation reaction activity of the electrolyzed water and the anti-reversal time were both severely reduced.

In comparative example 9, the second sintering temperature in step (3) was controlled to 1000 c, at which severe agglomeration of the iridium-based compound occurred, resulting in severe deterioration of the oxidation reaction activity of electrolyzed water and the anti-reversal time.

In comparative example 10, the transition metal salt iron phthalocyanine was not added in step (1), but a nitrogen-carbon structure was formed, and the electronic structures of the carrier and the iridium-based compound were not sufficiently adjusted due to the absence of the metal atom, thereby causing a decrease in the oxidation reaction activity and the anti-depolarization time of the electrolyzed water.

In the present disclosure, the terms "one embodiment," "some embodiments," "example," "specific example," or "some examples" and the like mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present disclosure. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.

Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.

Claims

1. A preparation method of a proton exchange membrane fuel cell anti-antipole nitrogen-carbon carrier catalyst is characterized by comprising the following steps:

a. dissolving a transition metal salt, a nitrogen source and a carbon source in a first dispersing agent to obtain a nitrogen-doped metal organic framework;

2. The method for preparing the proton exchange membrane fuel cell anti-reversal nitrogen-carbon supported catalyst according to claim 1, wherein in the step a, the transition metal salt includes at least one of cobalt salt, nickel salt, manganese salt, copper salt, zinc salt and iron salt; the nitrogen source comprises at least one of 2-methylimidazole, triethylenediamine, chitosan, dicyandiamide, formamide, urea and pyrrole; the carbon source comprises at least one of trimesic acid, terephthalic acid, glucose, thiourea and phytic acid.

3. The method for preparing the proton exchange membrane fuel cell anti-reversal nitrogen-carbon supported catalyst according to claim 2, wherein the transition metal salt comprises at least one of cobalt nitrate, cobalt acetylacetonate, cobalt phthalocyanine, cobalt chloride, nickel nitrate, nickel acetylacetonate, nickel phthalocyanine, nickel chloride, manganese nitrate, manganese acetylacetonate, manganese chloride, copper nitrate, copper acetylacetonate, copper chloride, zinc nitrate, zinc chloride, ferric nitrate, ferric acetylacetonate, and iron phthalocyanine.

4. The preparation method of the proton exchange membrane fuel cell antipodal nitrogen-carbon carrier catalyst as claimed in claim 1, wherein in the step b, the mass ratio of the first pore-forming agent to the second pore-forming agent is 1:1-1: 20; the mass ratio of the nitrogen-doped metal organic framework to the composite pore-forming agent is 1:0.1-1: 20.

5. The preparation method of the proton exchange membrane fuel cell anti-reversal nitrogen-carbon carrier catalyst according to claim 1, wherein the first dispersing agent comprises at least one of methanol, isopropanol, benzyl alcohol, ethanol, N-dimethylformamide, formamide and water; the second dispersing agent comprises at least one of water, isopropanol, methanol, acetone and ethanol; the third dispersant comprises at least one of water, methanol, ethanol, benzyl alcohol, isopropanol and ethylene glycol.

6. The method for preparing the proton exchange membrane fuel cell anti-reversal nitrogen-carbon supported catalyst according to claim 1, wherein in the step c, the noble metal precursor comprises at least one of an iridium precursor and a ruthenium precursor.

7. The preparation method of the proton exchange membrane fuel cell antipodal nitrogen-carbon supported catalyst according to claim 6, wherein the noble metal precursor comprises at least one of chloro iridic acid, iridium chloride, ammonium chloro iridate, iridium acetylacetonate, sodium chloro iridate, ammonium chloro iridite, potassium chloro iridate, ruthenium chloride, ammonium chloro ruthenate, ruthenium nitrosyl nitrate, ruthenium acetylacetonate, and potassium chloro ruthenate.

8. The preparation method of the proton exchange membrane fuel cell anti-antipodal nitrogen-carbon supported catalyst according to claim 6, wherein the molar ratio of the iridium-containing precursor to the ruthenium-containing precursor in the noble metal precursor is 0.1:4-4: 0.

9. The method for preparing the proton exchange membrane fuel cell anti-reverse-polarity nitrogen-carbon supported catalyst as recited in claim 1, wherein in the step b, the first sintering atmosphere comprises at least one of nitrogen, argon and hydrogen, the first sintering temperature is 800-; in the step c, the second sintering atmosphere comprises at least one of nitrogen, argon and hydrogen, the second sintering temperature is 150-.

10. The preparation method of the proton exchange membrane fuel cell anti-reversal nitrogen-carbon supported catalyst according to claim 1 or 9, wherein in the step b, after the porous metal nitrogen-carbon material is obtained by sintering, the method further comprises the steps of acid washing and water washing: washing the porous metal nitrogen-carbon material with ultrapure water, then putting the porous metal nitrogen-carbon material into an acidic water-based solution with the temperature of 30-95 ℃ for dispersing and stirring for 6-48 hours, washing the porous metal nitrogen-carbon material with ultrapure water again until the pH value of filtrate is neutral, and drying the filtrate; wherein the acidic water-based solution comprises at least one of sulfuric acid, nitric acid, formic acid, hydrochloric acid and perchloric acid aqueous solution, and the pH value of the acidic water-based solution is less than or equal to 2; in the step c, after the second sintering atmosphere sintering treatment, a third sintering atmosphere sintering treatment is further included, the sintering temperature is 150-600 ℃, the sintering time is 0.5-6 hours, and the third sintering atmosphere comprises at least one of nitrogen, argon, air, hydrogen and oxygen.

11. The preparation method of the proton exchange membrane fuel cell antipodal nitrogen-carbon supported catalyst according to claim 1, wherein in the step b, the mixing and stirring temperature is 25-90 ℃; in the step c, the heating temperature is 25-180 ℃, the heating time is 0.5-36 hours, and preferably, when the heating treatment temperature is 25-80 ℃, the heating time is 8-24 hours; when the heating treatment temperature is 80-160 ℃, the heating time is 4-8 hours; when the heating treatment temperature is 160-180 ℃, the heating time is 2-4 hours.

12. A proton exchange membrane fuel cell anti-antipodal nitrogen carbon supported catalyst, characterized in that it is prepared by the method according to any one of claims 1-11.

13. The pem fuel cell antipodal nitrogen-carbon supported catalyst of claim 12 wherein said supported porous metallic nitrogen-carbon material is of a cage structure.

14. The proton exchange membrane fuel cell anti-antipodal nitrogen-carbon supported catalyst as claimed in claim 12, wherein the pore diameter of the supported porous metal nitrogen-carbon material is 3-8nm, and the pore volume is 0.5-2cm ³ /g。

15. The pem fuel cell antipodal nitrogen-carbon support catalyst of claim 12 wherein the nitrogen content in the support is 0.1-20 wt%.

16. The pem fuel cell antipodal nitrogen-carbon supported catalyst of claim 12 wherein the noble metal compound in the catalyst has a particle size of 1-6 nm.

17. The pem fuel cell antipodal nitrogen-carbon support catalyst of claim 12 wherein said support has a transition metal content of 0.1-5 wt%.