CN114497585B - Preparation method of platinum-based synergistic catalyst with structure coupling effect - Google Patents

Preparation method of platinum-based synergistic catalyst with structure coupling effect Download PDF

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CN114497585B
CN114497585B CN202210100451.7A CN202210100451A CN114497585B CN 114497585 B CN114497585 B CN 114497585B CN 202210100451 A CN202210100451 A CN 202210100451A CN 114497585 B CN114497585 B CN 114497585B
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platinum
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salt
transition metal
mesoporous
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CN114497585A (en
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王西龙
梁汉璞
杨晨
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Qingdao Institute of Bioenergy and Bioprocess Technology of CAS
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
    • H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8803—Supports for the deposition of the catalytic active composition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition

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Abstract

The invention belongs to the technical field of electrocatalysis, and particularly relates to a preparation method of a platinum-based synergistic catalyst with a structural coupling effect. Forming a transition metal monoatomic catalyst carrier (M-H-C) with mesoporous distribution in the carbonization pyrolysis process by utilizing the coordination complexing action of transition metal salt and heteroatom-rich carbon precursor; then through mesoporous confinement effect and M-H x site adsorption anchoring effect, nano particle load of platinum simple substance or platinum-based alloy is realized, and finally, structure and component coupling of mesoporous/single atom/platinum is realized, and efficient and stable catalysis of oxygen reduction reaction in oxyhydrogen fuel cells and alcohol fuel cells is realized. The preparation process has low requirements on equipment, short preparation flow, simple operation, outstanding catalyst activity and stability, is environment-friendly, is very beneficial to large-scale production, and has wide industrial application prospect.

Description

Preparation method of platinum-based synergistic catalyst with structure coupling effect
Technical Field
The invention belongs to the technical field of electrocatalysis, and particularly relates to a preparation method of a platinum-based synergistic catalyst with a structural coupling effect.
Background
To achieve the carbon neutralization and carbon peaking goals, more renewable energy sources need to be developed. The hydrogen has the remarkable advantages of diversified sources, high driving efficiency, no pollution to the environment due to the fact that the discharged matter is basically water in the reaction operation process, and the like, and is a key object for research and development (Angew.chem.int.ed., 2021,60,4747-4755). The proton exchange membrane fuel cell, a novel energy conversion and storage electrochemical series facility which can be widely applied to traffic, construction, industry and more efficient energy storage fields, is a device for generating electric energy by chemical reaction of hydrogen and oxygen, and the commercialization completion degree is important for pushing industries such as automobiles to achieve the aim of carbon peak and carbon neutralization (adv. Mater.,2021,33,1908232).
However, the slow dynamic oxygen reduction reaction occurring at the cathode of the fuel cell greatly hinders the popularization and application of proton exchange membrane fuel cell technology, and a catalyst material capable of exhibiting excellent activity and stability in a high-potential acidic electrolyte is required to promote and promote the cathode oxygen reduction reaction. At present, carbon-supported platinum nanoparticle catalysts have electrochemical properties and relatively good stability superior to other catalysts, and commercial applications of the catalysts have been successfully achieved (angelw.chem.int.ed., 2021,60,2-9). However, since most of the commercial carbons used at this stage are Vulcan XC-72R with less surface voids, their specific surface area is low, and the migration, aggregation and shedding of platinum under the conditions of high potential and strong acid environment application are not limited enough, so that stability is always the object of important improvement and improvement of workers (acc. Chem. Res.2021,54,2,311-322). The patent CN112820888A is prepared by adding platinum salt and second transition metal salt in the process of coating a layer of nitrogen-containing organic molecules on commercial carbon, and obtaining the catalyst with a composite structure and good activity and stability through sintering, acid washing and drying. The patent CN110665496B prepares ordered mesoporous carbon by adopting a self-made hard template to combine with a surfactant and a structure directing agent, and takes the ordered mesoporous carbon as a substrate to load platinum-based nano particles, and the synthesized catalyst shows better oxygen reduction catalytic activity and stability. The prior literature report and patent technology prove that the pore canal structure and transition metal element have the regulation function on the limiting area and the anchoring of the platinum nano-particles and the center of the D band, thereby improving the catalytic activity and the stability of the platinum-based nano-catalyst. However, the preparation method adopted at the present stage has obvious defects that a large number of soft and hard templates are needed for preparing mesopores, so that the whole preparation process is complex and the cost is high; secondly, even single-atom doping is difficult to realize on the aspect of transition metal introduction, and meanwhile, post-treatment modes such as acid washing become common means for purifying the catalyst, so that the environment friendliness is not ideal. The current-stage products also face significant challenges in terms of large-scale commercialization.
Disclosure of Invention
Aiming at the problems that the development limit of the current proton exchange membrane fuel cell and the current stage cost of the cathode platinum carbon oxygen reduction electrocatalyst are too high, and the catalytic activity and durability can not meet the current situation of large-scale commercial application of the fuel cell, the invention provides a preparation method of a platinum-based synergistic catalyst with a structure coupling effect.
In order to achieve the above purpose, the invention adopts the technical scheme that:
A preparation method of a platinum-based synergistic catalyst with a structure coupling effect utilizes transition metal (M) salt and heteroatom-rich carbon precursor (H-C) to form a transition metal monoatomic catalyst carrier (M-H-C) with mesoporous distribution in a carbonization pyrolysis process; then, the nano particles of the platinum simple substance or the platinum-based alloy are loaded on the transition metal monoatomic catalyst carrier through mesoporous confinement effect and M-H x site adsorption anchoring effect, and finally the structure and component coupling platinum-based synergistic catalyst of mesoporous/monoatomic/platinum is realized. Further, in the present description,
1) Dispersing a heteroatom-rich carbon precursor (H-C) into a solvent to form a solution a; wherein the mass ratio of the heteroatom-rich carbon precursor to the solvent is 10-100:1
2) Dispersing a transition metal salt and a pore-forming agent into a solvent to form a solution B; the molar ratio of the pore-forming agent to the carbon-nitrogen precursor is 1:100-100:1; the mol ratio of the transition metal salt to the carbon precursor is 1:100-1:20; the mass ratio of the solvent to the carbon precursor is 100:1-5:1;
3) Rapidly mixing the solution A and the solution B which are dispersed in the step 1) and the step 2) under the stirring condition to form a solution C, and keeping the solution C for 2-48 hours under the stirring speed of 1000-100 r/min;
4) Lyophilizing the solution obtained after the stirring in the step 3), grinding the lyophilized composite powder, carbonizing and pyrolyzing under the protection of inert gas, and mechanically grinding carbonized products to obtain a mesoporous carbon-based single-atom-enriched catalyst carrier with MH x sites;
5) And 4) carrying out platinum or platinum-based alloy nano-particle loading by adopting the single-atom catalyst carrier obtained in the step 4), thus obtaining the platinum-based synergistic catalyst with the structure coupling effect.
The heteroatom (H) in the heteroatom-rich carbon precursor in the step 1) is one or more of oxygen, nitrogen, phosphorus, sulfur and boron; for example, natural biomass such as egg white, pig blood, etc., imidazoles such as 2-methylimidazole, benzimidazole, etc., anilines, dopamine, phenolic resins, urea resins, melamine-formaldehyde resins, etc., and organic matters rich in heteroatoms such as thiophene, pyrrole, pyridine, cysteine, etc., nitrogen, sulfur, boron, phosphorus, etc.;
The transition metal salt in the step 2) is one or more of ferric salt, cobalt salt, nickel salt, molybdenum salt and manganese salt;
The pore-forming agent can be one or more than two of anionic surfactant, cationic surfactant, organic weak acid and organic weak acid salt which are mixed in any proportion. Wherein the anionic surfactant can be sodium polyacrylate, sodium polystyrene sulfonate, polyacrylamide, polystyrene-polybutadiene-polystyrene triblock copolymer, etc., and the cationic surfactant can be cetyltrimethylammonium bromide, cetyltrimethylammonium chloride, dodecyldimethylphenylphosphine bromide, octadecyldimethylbenzyl ammonium chloride, etc. The organic weak acid can be citric acid, ascorbic acid, benzoic acid, acetylsalicylic acid, malic acid, tartaric acid, malic acid, salicylic acid, etc.; the organic weak acid salt is sodium salt, potassium salt, etc. of the organic weak acid.
Centrifuging the solution obtained after the stirring in the step 3), collecting the precipitate, sequentially cleaning the precipitate by a solvent and ethanol, freeze-drying the cleaned precipitate, collecting the freeze-dried composite powder, and then performing the treatment in the step 4);
The solvent for dispersing the heteroatom-rich carbon precursor (H-C) and the solvent for washing the precipitate in step 3) may be the same or different and are selected from one or more of water, methanol, ethanol, N' N-dimethylformamide, oleylamine, trimethylbenzene, oleylamine.
Grinding the freeze-dried composite powder, putting the powder into an alumina crucible and placing the alumina crucible in the middle of a tube furnace, performing carbonization pyrolysis under the protection of gas, and mechanically grinding carbonized products to obtain a mesoporous carbon-based monoatomic catalyst carrier with MH x sites distributed; wherein the pyrolysis temperature is 700-1100 ℃, the heat preservation time is 1-5 hours, the heating rate is 1-10 ℃ per minute, and the airflow rate is 5-100 milliliters per minute; the protective gas is inert gas or mixed gas; the inert gas is one or more of nitrogen, argon and helium, and the mixed gas is the mixture of the inert gas and hydrogen in any proportion.
The platinum-based nanomaterial loading mode in the step 5) is a solvothermal reduction method or an impregnation method.
The platinum or platinum-based alloy nanoparticle load adopts a solvothermal reduction method, and specifically comprises the following steps: dispersing the prepared catalyst carrier in a solvent serving as a reducing agent, adding a platinum precursor and a transition metal salt, and carrying out platinum or platinum-based alloy loading by raising the temperature to 80-200 ℃ in the stirring process; wherein the platinum precursor is one or more of potassium chloroplatinate, chloroplatinic acid, platinum acetylacetonate and platinum chloride; the mass ratio of the carbon carrier to the solvent is 1:100-1:600; the solvent can be one or more of water, ethylene glycol, propylene glycol or glycerol, N-dimethylformamide, oleylamine and oleic acid; the reaction time is 1-60 hours; the mass fraction of platinum on the carrier is controlled to be 5.0wt.% to 80wt.%.
The platinum nano particles or platinum-based alloy nano particles are loaded by adopting an impregnation method, and the method specifically comprises the following steps: when the platinum nano particles are loaded, dissolving platinum salt or a mixture of platinum salt and transition metal salt into a solvent, and adding the catalyst carrier after the platinum salt or the mixture of platinum salt and transition metal salt is fully dissolved; performing ultrasonic treatment, stirring, drying and reducing atmosphere heat treatment to obtain a synergistic catalyst loaded with platinum or platinum-based alloy nano particles; wherein the platinum precursor is one or more of potassium chloroplatinate, chloroplatinic acid, platinum acetylacetonate and platinum chloride; the mole ratio of the platinum salt to the transition metal salt is 5:1-1:5; the solution is one or more of water, ethanol, isopropanol, acetone and methanol; the reducing atmosphere is a mixed gas of hydrogen and inert gas, and the volume ratio of the hydrogen in the reducing atmosphere is 2-20%; the mass ratio of the platinum element to the final catalyst is controlled to be 5.0wt.% to 70wt.%.
The catalyst prepared by the method is a synergistic catalyst of heteroatom-rich carbon-based supported platinum/platinum-based alloy nano particles with mesoporous and transition metal monoatoms distributed simultaneously.
Use of the catalyst in a proton exchange membrane fuel cell.
Compared with the existing catalyst preparation method, the invention has the following essential characteristics and creativity:
The catalyst obtained by the method has the advantages that platinum or platinum alloy particles are uniformly dispersed, the particles are in situ limited in inherent mesopores of the carbon substrate, the carbon substrate is rich in hetero atoms anchoring platinum elements, transition metal single atom sites and the like, and is a synergistic oxygen reduction electrocatalytic nano material with excellent electrocatalytic performance and outstanding stability. The synthesis method adopted by the patent has the advantages of low cost, simple equipment requirement, short preparation flow, excellent industrialization prospect, and is specifically as follows:
1. In the process of preparing the carbon-based carrier, besides the surfactant, the organic weak acid or organic weak acid salt also becomes one of raw materials, and can be used as part of carbon sources and nitrogen sources, and can also perform weak interaction with a transition metal single-atom precursor so as to be assembled into the carbon sources, and in-situ forms a mesoporous structure connected with each other in the carbon substrate through pyrolysis in the subsequent carbonization process. The method realizes the preparation of the single-atom, mesoporous and heteroatom co-doped highly graphitized carbon-based material by a one-step method, has the characteristics of simple process and obvious structural advantage characteristics compared with the conventional carbon material in structural morphology and preparation flow, lays a structural foundation for uniform loading of platinum and platinum-based alloy nano particles in the later stage and medium and high stability in a high-potential and strong-corrosion acidic environment, and has very strong innovativeness.
2. The method adopts a solvothermal reduction method and an impregnation method in a targeted manner in the platinum and platinum-based alloy nanoparticle loading process, can realize in-situ reduction and limited-area reduction of platinum salt in mesopores of a carbon substrate, can fully realize uniform dispersion of platinum and platinum-based alloy nanoparticles in a final catalyst, can effectively block migration, ostwald ripening and shedding failure in later electrochemical application, and has important significance for improving the overall performance and stability of the catalyst.
3. In the preparation process of the catalyst, platinum or platinum nano particles are loaded on a transition metal monoatomic carrier with mesoporous distribution, so that double fixation of a MHx site formed by mesoporous and transition metal monoatomic and hetero atoms on the limited domain and anchoring of the platinum or platinum alloy nano particles can be realized, the stability is improved, and simultaneously, the MHx can effectively change the electron cloud distribution of the platinum, and finally, the structural coupling of the mesoporous, the monoatomic site and the platinum is realized. The coupled catalyst has obvious effects of improving stability and improving oxygen reduction catalytic activity compared with a common commercial carbon-supported platinum nanoparticle catalyst. Therefore, the method introduces the concepts of structure coupling effect and synergistic catalysis in the aspect of preparing the platinum-based catalyst, realizes the improvement of the performance and stability of the catalyst by the mutual influence of the structural feature advantages of the finally formed catalyst tissue through the design of the catalyst synthesis strategy, can effectively reduce the adoption of toxic reagents, save the use of surfactants and pore-forming agents, improves the green and environment-friendly properties of the process, and improves the industrial application prospect of the catalyst.
4. The method does not need to adopt strong corrosive liquid and gas such as acid washing and the like in each treatment link of the catalyst, has great significance for improving the overall preparation environmental protection property of the catalyst, and lays a foundation for the industrial application of the catalyst.
Drawings
FIG. 1A scanning electron microscope picture of a catalyst carrier containing Kong Tieshan atoms prepared in example 1 of the present invention.
FIG. 2 is an X-ray diffraction pattern of a catalyst support having Kong Tieshan atoms prepared in example 1 of the present invention.
FIG. 3 shows the oxygen reduction linear sweep voltammogram of a platinum particle catalyst supported on a catalyst carrier of Kong Tieshan atoms prepared in example 1 of the present invention.
FIG. 4 is a transmission electron microscope image of the mesoporous molybdenum single-atom catalyst carrier prepared in example 2 of the present invention.
FIG. 5 is a transmission electron microscope image of a mesoporous molybdenum single-atom carrier-supported platinum-cobalt alloy prepared in example 2 of the invention.
FIG. 6 shows an oxygen reduction linear sweep voltammogram of a mesoporous molybdenum single-atom catalyst carrier supported platinum cobalt particle catalyst prepared in example 2 of the invention.
FIG. 7 shows the evaluation of oxygen reduction stability of a mesoporous molybdenum single-atom catalyst carrier supported platinum cobalt nanoparticle catalyst prepared in the embodiment 2 of the invention.
FIG. 8 is a transmission electron microscope image of a mesoporous nickel-containing monoatomic catalyst carrier prepared in example 3 of the present invention.
FIG. 9 shows an oxygen reduction linear voltammetry scanning curve of a mesoporous nickel-containing single-atom catalyst carrier supported platinum nanoparticle catalyst prepared in example 3 of the invention.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The methods are conventional methods unless otherwise specified. The starting materials are commercially available from the public unless otherwise specified.
The preparation process is simple, the yield of effective products is high, and the prepared platinum-based catalyst material has excellent oxygen reduction electrocatalytic performance and stability. Firstly, mixing the heteroatom-rich carbon precursor, the transition metal salt and the pore-forming agent solution respectively to synthesize a precursor with uniformly dispersed transition metal salt; secondly, cleaning and freeze-drying the synthesized precursor, and placing the precursor in a heat treatment furnace for carbonization and pyrolysis to obtain a monoatomic catalyst carrier with transition metal sites and ordered mesoporous distribution; finally, the obtained single-atom catalyst is used as a carrier to realize the loading of platinum or platinum-based alloy nano particles through a solvothermal reduction or impregnation method, and the oxygen reduction electrocatalyst nano material with excellent performance and outstanding stability, wherein the platinum or platinum-based alloy nano particles are uniformly dispersed, porous carbon frameworks are isolated among the particles, the particles are anchored by transition metal single-atom sites in a substrate, and the electronic structure is optimized.
According to the invention, the transition metal monoatomic catalyst with mesoporous distribution is used as a carbon carrier, the catalytic activity and stability of the platinum-based material are improved by utilizing mesoporous limit and transition monoatomic site adsorption anchoring action, so that the high-efficiency stability of oxygen reduction electrocatalysis realized, and the problems that the cost is too high in the development limit of a proton exchange membrane fuel cell and the current stage of cathode platinum carbon oxygen reduction electrocatalyst, the catalytic activity and durability can not meet the current situation of large-scale commercial application of the fuel cell are solved; the method has the advantages of simple process steps, short flow, adjustable morphology structure and the like, and the prepared catalyst has large specific surface area, remarkably superior catalytic activity and stability to commercial Pt/C catalyst, low equipment requirement of the whole synthesis route, good process stability and important industrial popularization and application values.
Example 1
8 G of dimethylimidazole was dissolved in 0.5 liter of methanol and stirred at 500 rpm for 10 minutes after sonication for 10 minutes to form a uniformly dispersed solution A. After 3.0 g of zinc nitrate, 0.1 g of ferric chloride and 0.5 g of sodium acetate were dissolved in 0.3 liter of methanol and sonicated for 10 minutes, the solution was stirred at 500 rpm for 10 minutes to form a uniformly dispersed solution B. Solutions a and B were mixed and stirred at 500 rpm for 12 hours at room temperature. After the stirring was completed, the synthesized product was collected by centrifugation at 9000 rpm and washed three times with methanol solution at 8000 rpm for 5 minutes. The precipitate obtained finally was put into a freeze-drying apparatus for 12 hours for freeze-drying, whereupon the freeze-dried powder was ground and put into an alumina crucible, finally subjected to carbonization pyrolysis at 900 ℃ for 2 hours under the protection of nitrogen gas, and the carbonized product was subjected to mechanical grinding to obtain a mesoporous carbon-based monoatomic catalyst carrier rich in the distribution of the FeN x sites (see fig. 1 and 2). Finally, 2.0 g of the obtained iron monoatomic catalyst support was dispersed into 1.0 liter of N, N-dimethylformamide, followed by stirring at 500 rpm for 6 hours, and then a solution of potassium chloroplatinate in N, N-dimethylformamide (1.0 mol/L) was added to the above carrier solution and stirring was continued for 6 hours, and heated to 180℃by an oil bath, and heat was preserved for 5 hours. The product was collected by centrifugation and washed with n-hexane, ethanol and lyophilized to obtain the final catalyst and tested for electrochemical properties (see fig. 3). Fig. 1 is a transmission electron microscope image of a metal organic framework polymer precursor derived medium Kong Tieshan atom catalyst, and it can be seen from the image that the iron single atom catalyst carrier prepared in the embodiment has rich mesoporous distribution and pore diameter distribution of 3-5 nanometers. Fig. 2 shows an X-ray diffraction pattern of the iron monoatomic catalyst carrier prepared in this example, and it can be seen from the figure that the X-ray diffraction pattern has only two carbon peaks and no diffraction peak related to iron, which illustrates the monoatomic dispersion state of iron in the carrier. FIG. 3 is a linear sweep voltammogram of the prepared monoatomic carrier loaded with platinum nanoparticles in 0.1mol/L perchloric acid solution, showing that the catalyst synthesized according to the invention, whether it is half-wave potential or current density, is significantly improved and improved over conventional commercial carbon-loaded platinum catalysts.
Example 2
5.0 G of the polyoxyethylene polyoxypropylene block copolymer, 10.0 g of dopamine hydrochloride, 2.0 g of bithiophene and 50.0 mg of ammonium molybdate were dissolved in 2.0 l of a mixed solution of methanol and water (volume ratio 1:1), stirred at 500 rpm for 1 hour, then 50.0 ml of trimethylbenzene was added, and stirring was continued for 1 hour. Finally, 5ml of ammonia water was added thereto and stirred for 12 hours at 500 rpm. After stirring, the synthesized product is collected by centrifugation at 10000 rpm for 10 minutes, and is washed three times by a mixed solution of water and ethanol, the centrifugal speed is 8000 rpm, and the centrifugal time is 10 minutes. The finally obtained precipitate was put into a freeze-drying apparatus for 12 hours to freeze-dry, whereupon the freeze-dried powder was ground and put into an alumina crucible, finally carbonized and pyrolyzed at 900 ℃ for 3 hours under the protection of nitrogen gas, and the carbonized product was mechanically ground to obtain a mesoporous carbon-based monoatomic catalyst carrier rich in Mo-S x-Ny sites distribution (see fig. 4). Finally, 2.0 g of the obtained molybdenum monoatomic catalyst support was dispersed in 100 ml of ultrapure water, stirred for 5 hours, then chloroplatinic acid and an aqueous cobalt sulfate solution in which the platinum concentration was 2.0mol/L and the molar ratio of platinum to cobalt was 3:1 were dropped into the support solution, the solution was volatilized by stirring at 70 degrees centigrade, the remaining product was subjected to a reduction heat treatment in a tube furnace, an atmosphere of 10% hydrogen-argon mixture gas was kept at 500 degrees centigrade for 2 hours, and then the final catalyst was obtained by cooling with the furnace (see 5). As can be seen from FIG. 4, the prepared Mo-S-N single-atom catalyst has obvious mesoporous distribution, and the mesoporous arrangement is compact and ordered. Fig. 5 shows a transmission electron microscope picture of a Mo-S-N carrier loaded with Pt-Co alloy nanoparticles, and it can be seen from the picture that the loaded Pt-Co nanoparticles are uniformly distributed and firmly combined with a substrate, and the particle size of the prepared alloy particles is generally below 5 nm. FIG. 6 is a linear sweep voltammogram of the catalyst synthesized in this example in a 0.1mol/L perchloric acid solution, showing a significant improvement over conventional commercial carbon-supported platinum catalysts, both in half-wave potential and current density. Fig. 7 is an evaluation of catalytic stability of the catalyst synthesized in this example in oxygen saturated 0.1mol/L perchloric acid solution, and it can be seen that the mass activity and stability of the synthesized catalyst are significantly better than those of commercial platinum carbon catalysts.
Example 3
1.5 G of polyethylene glycol p-isooctylphenyl ether and 60 mg of nickel nitrate were dispersed in 1.8 l of aqueous solution and stirred at 500 rpm for 1 hour, then 24 ml of aniline and 15 ml of pyrrole were added and stirring was continued for 1 hour to form solution A. 10g of ammonium persulfate was dissolved in 0.2 liter of water and stirred at 500 rpm for 0.5 hour to form solution B. Solution B was slowly added to solution a and stirred in an ice-water bath at 300 rpm for 12 hours. After the completion, the synthesized product was collected by centrifugation at 8000 rpm for 10 minutes, and washed three times with a mixed solution of water and ethanol (volume ratio 1:1), at 8000 rpm, for 10 minutes. And (3) putting the finally obtained precipitate into a freeze-drying device for 12 hours for freeze-drying, grinding the freeze-dried powder, putting the powder into an alumina crucible, performing carbonization pyrolysis at 800 ℃ for 2 hours under the protection of nitrogen, and mechanically grinding the carbonized product to obtain the mesoporous carbon-based single-atom-enriched catalyst carrier with NiN x sites. Finally, 2.0 g of the obtained nickel monoatomic catalyst carrier was dispersed in 100 ml of absolute ethanol, stirred for 5 hours, and then an appropriate amount of chloroplatinic acid was added to make the platinum concentration in the solution 0.02mol/L. The solution was evaporated by rotary evaporation at 40 degrees celsius, the remaining product was subjected to a reduction heat treatment in a tube furnace, and then cooled with the furnace to obtain the final catalyst (see fig. 8 and 9). As can be seen from the transmission electron microscope pictures of the platinum nano particles loaded on the nickel monoatomic catalyst carrier prepared in the figure 8, the platinum particles are uniformly distributed on the mesoporous carbon substrate rich in monoatomic nickel, the particle size is smaller, the distribution is uniform, and large aggregated particles are not generated. FIG. 9 is a linear sweep voltammogram of the catalyst in a 0.1mol/L perchloric acid solution, from which it can be seen that the oxygen reduction catalytic performance of the prepared catalyst exceeded that of a carbon-supported platinum nanoparticle catalyst without mesoporous distribution.
Simultaneously, according to the preparation method, the heteroatom-rich carbon precursor and the transition metal salt are replaced to obtain different heteroatom-rich carbon substrate supported platinum/platinum-based alloy nano-particles with mesopores and transition metal single atoms distributed simultaneously, the obtained catalyst can be used in proton exchange membrane fuel cells, the problems that the development limit of the proton exchange membrane fuel cells and the cost of the cathode platinum carbon oxygen reduction electrocatalyst is too high at the present stage can be solved, the catalytic activity and the durability can not meet the current situation of large-scale commercial application of the fuel cells, and the high-efficiency stability of oxygen reduction electrocatalyst is realized.

Claims (8)

1. A preparation method of a platinum-based synergistic catalyst with a structural coupling effect is characterized by comprising the following steps: forming a transition metal monoatomic catalyst carrier (M-H-C) with mesoporous distribution in a carbonization pyrolysis process by using transition metal (M) salt and a carbon precursor rich in heteroatoms (H); then loading nano particles of a platinum simple substance or platinum-based alloy on a transition metal monoatomic catalyst carrier through mesoporous confinement effect and M-H x site adsorption anchoring effect, and finally realizing a platinum-based synergistic catalyst with a mesoporous/monoatomic/platinum structure and coupled components;
the preparation method comprises the following steps:
1) Dispersing a heteroatom-rich carbon precursor into a solvent to form a solution A; wherein the mass ratio of the heteroatom-rich carbon precursor to the solvent is 10-100:1
2) Dispersing a transition metal salt and a pore-forming agent into a solvent to form a solution B; the molar ratio of the pore-forming agent to the heteroatom (H) -rich carbon precursor is 1:100-100:1; the molar ratio of the transition metal salt to the heteroatom (H) -rich carbon precursor is 1:100-1:20; the mass ratio of the solvent to the heteroatom (H) -rich carbon precursor is 100:1-5:1;
3) Rapidly mixing the solution A and the solution B which are dispersed in the step 1) and the step 2) under the stirring condition to form a solution C, and keeping the solution C for 2-48 hours under the stirring speed of 1000-100 r/min;
4) Lyophilizing the solution obtained after the stirring in the step 3), grinding the lyophilized composite powder, carbonizing and pyrolyzing under the protection of inert gas, and mechanically grinding carbonized products to obtain a mesoporous carbon-based single-atom-enriched catalyst carrier with MH x sites;
5) Carrying out platinum or platinum-based alloy nano-particle loading by adopting the single-atom catalyst carrier obtained in the step 4), so as to obtain the platinum-based synergistic catalyst with the structure coupling effect;
the platinum-based nanomaterial loading mode in the step 5) is a solvothermal reduction method or an impregnation method;
The pore-forming agent is one or more than two of anionic surfactant, cationic surfactant, organic weak acid and organic weak acid salt which are mixed in any proportion.
2. The method for preparing a platinum-based catalyst with a structural coupling effect according to claim 1, wherein: the heteroatom (H) in the heteroatom-rich carbon precursor in the step 1) is one or more of oxygen, nitrogen, phosphorus, sulfur and boron;
the transition metal salt in the step 2) is one or more of ferric salt, cobalt salt, nickel salt, molybdenum salt and manganese salt.
3. The method for preparing a platinum-based catalyst with a structural coupling effect according to claim 1, wherein: centrifuging the solution obtained after the stirring in the step 3), collecting the precipitate, sequentially cleaning the precipitate by a solvent and ethanol, freeze-drying the cleaned precipitate, collecting the freeze-dried composite powder, and then performing the treatment in the step 4);
The solvent for dispersing the heteroatom-rich carbon precursor and the solvent for washing the precipitate in step 3) may be the same or different and are selected from one or more of water, methanol, ethanol, N' N-dimethylformamide, oleylamine, trimethylbenzene, oleylamine.
4. The method for preparing a platinum-based catalyst with a structural coupling effect according to claim 1, wherein: grinding the freeze-dried composite powder, putting the powder into an alumina crucible and placing the alumina crucible in the middle of a tube furnace, performing carbonization pyrolysis under the protection of gas, and mechanically grinding carbonized products to obtain a mesoporous carbon-based monoatomic catalyst carrier with MH x sites distributed; wherein the protective gas is inert gas or mixed gas; the pyrolysis temperature is 700-1100 ℃, the heat preservation time is 1-5 hours, the heating rate is 1-10 ℃ per minute, and the airflow rate is 5-100 milliliters per minute.
5. The method for preparing a platinum-based catalyst with a structural coupling effect according to claim 1, wherein: the platinum or platinum-based alloy nanoparticle load adopts a solvothermal reduction method, and specifically comprises the following steps: dispersing the prepared catalyst carrier in a solvent serving as a reducing agent, adding a platinum precursor and a transition metal salt, and carrying out platinum or platinum-based alloy loading by raising the temperature to 80-200 ℃ in the stirring process; wherein the platinum precursor is one or more of potassium chloroplatinate, chloroplatinic acid, platinum acetylacetonate and platinum chloride; the mass ratio of the carbon carrier to the solvent is 1:100-1:600; the solvent can be one or more of water, ethylene glycol, propylene glycol or glycerol, N-dimethylformamide, oleylamine and oleic acid; the reaction time is 1-60 hours; the mass fraction of the platinum on the carrier is controlled to be 5.0 wt-80 wt%.
6. The method for preparing a platinum-based catalyst with a structural coupling effect according to claim 1, wherein: the platinum nano particles or platinum-based alloy nano particles are loaded by adopting an impregnation method, and the method specifically comprises the following steps: when the platinum nano particles are loaded, dissolving platinum salt or a mixture of platinum salt and transition metal salt into a solvent, and adding the catalyst carrier after the platinum salt or the mixture of platinum salt and transition metal salt is fully dissolved; performing ultrasonic treatment, stirring, drying and reducing atmosphere heat treatment to obtain a synergistic catalyst loaded with platinum or platinum-based alloy nano particles; wherein the platinum precursor is one or more of potassium chloroplatinate, chloroplatinic acid, platinum acetylacetonate and platinum chloride; the molar ratio of the platinum salt to the transition metal salt is 5:1-1:5; the solution is one or more of water, ethanol, isopropanol, acetone and methanol; the reducing atmosphere is a mixed gas of hydrogen and inert gas, and the volume ratio of the hydrogen in the reducing atmosphere is 2% -20%; the mass ratio of the loading of the platinum element in the finally formed catalyst is controlled to be 5.0 wt-70 wt%.
7. A catalyst prepared by the process of claim 1, wherein: a synergistic catalyst of heteroatom-rich carbon-based supported platinum/platinum-based alloy nanoparticles having simultaneous mesoporous and transition metal monoatomic distribution prepared by the method of claim 1.
8. Use of the catalyst of claim 7, wherein: the catalyst is applied to proton exchange membrane fuel cells.
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