CN113363520B - Platinum-based efficient stable oxygen reduction electrocatalyst and preparation method and application thereof - Google Patents
Platinum-based efficient stable oxygen reduction electrocatalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN113363520B CN113363520B CN202110709645.2A CN202110709645A CN113363520B CN 113363520 B CN113363520 B CN 113363520B CN 202110709645 A CN202110709645 A CN 202110709645A CN 113363520 B CN113363520 B CN 113363520B
- Authority
- CN
- China
- Prior art keywords
- platinum
- polymer
- salt
- solution
- solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
-
- 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
- H01M4/921—Alloys or mixtures with metallic elements
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
-
- 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
- H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
- H01M2004/8689—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the technical field of electrocatalysis, and particularly relates to a platinum-based high-efficiency stable oxygen reduction electrocatalyst, and a preparation method and application thereof. The platinum nano micelle can be formed by complexing platinum salt with a polymer, and is formed with the metal framework polymer at the same time or synthesized in advance and implanted into the metal framework polymer, and the oxygen reduction electrocatalyst material which has the advantages of uniform dispersion of platinum alloy particles, doping of rich hetero atoms on a carbon substrate, and outstanding performance and stability is prepared by drying, carbonization and post-treatment processes.
Description
Technical Field
The invention belongs to the technical field of electrocatalysis, and particularly relates to a platinum-based high-efficiency stable oxygen reduction electrocatalyst, and a preparation method and application thereof.
Background
With the continuous development of industrial technology, the continuous increase of population and the continuous consumption of traditional fossil fuels, the modern society is facing the great challenges of energy shortage and environmental deterioration, and the development of clean renewable energy has become a task and an important development direction which are urgently needed to be solved in the field of environmental protection in the world.
A proton exchange membrane fuel cell is a power generation device which can directly convert chemical energy into electric energy through electrochemical reaction. The energy-saving device has the advantages of high energy density, environmental friendliness, low noise, zero emission, high reliability and the like, so that governments, enterprises and related research institutions all over the world pay high attention to the research and development of the energy-saving device, and the energy-saving device is considered to be one of the most potential energy devices in the future. The slow characteristic of the oxygen reduction kinetic process of the fuel cell cathode greatly hinders the popularization and application of the new energy technology, and a catalyst material which can show excellent activity and stability in an acid electrolyte is needed to promote and promote the cathode oxygen reduction reaction. At this stage, carbon-supported platinum particle catalysts have electrochemical properties superior to those of other catalysts, and have been successfully commercialized. However, global platinum resource reserves are rare and expensive, and the dissolution segregation phenomenon of the individual platinum particles occurs under long-time operation, and the carrier also has serious corrosion to cause the shedding of the active particles, so that the high manufacturing cost and the relatively short service life of the catalyst limit the further commercialization process of the proton exchange membrane fuel cell, and the development of the catalyst with higher platinum utilization rate, excellent catalytic activity and durability is needed to meet the requirement of the cathode.
Disclosure of Invention
The invention aims to solve the problems that the development limit of a proton exchange membrane fuel cell is limited, the cost of a cathode platinum carbon oxygen reduction electrocatalyst is overhigh at the present stage, and the catalytic activity and the durability of the electrocatalyst cannot meet the current situation of large-scale commercial application of the fuel cell, and provides a platinum-based high-efficiency stable oxygen reduction electrocatalyst, a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of a platinum-based high-efficiency stable oxygen reduction electrocatalyst is characterized in that platinum salt and a polymer are complexed to form a platinum nano micelle, the platinum nano micelle is implanted into a metal framework polymer, and the platinum nano micelle is treated to obtain the oxygen reduction electrocatalyst.
Further, platinum salt and polymer are complexed to form platinum nano-micelles, and the obtained platinum nano-micelles are implanted into the metal framework polymer in the synthesis process of the metal framework polymer, or the platinum nano-micelles are added into the synthesis solution of the metal framework polymer to realize the in-situ implantation of the platinum nano-micelles into the metal framework polymer, and then the oxygen reduction electrocatalyst is obtained through drying, carbonization and post-treatment.
Still further say that:
(1) Preparing a platinum micelle precursor by complexing a platinum source and a polymer: dissolving a polymer capable of complexing a platinum source in a solvent to form a solution A, slowly dropwise adding a platinum salt solution completely dissolved in advance into the solution A, and stirring (25-60 ℃) to uniformly mix; wherein, the molar ratio of the platinum salt to the complexable platinum salt polymer is controlled to be 1-20, and the mixture is stirred and mixed evenly at 25-60 ℃ for standby;
(2) Assembling and coating the metal frame polymer: dissolving zinc salt in a solvent to completely dissolve the zinc salt; then dissolving the transition metal salt and the organic precursor for assembly in a solvent together to fully dissolve the transition metal salt and the organic precursor for assembly; mixing the two solutions to form a solution B, adding the platinum micelle precursor solution obtained in the step (1) into the solution B in a dropwise manner, and stirring (25-60 ℃) to uniformly mix so as to uniformly disperse the platinum salt complex into the metal organic framework polymer; wherein, the mass ratio of the zinc salt to the solvent is 5-40, the mass ratio of the organic precursor for assembly to the solvent is 5-50, and the mass ratio of the zinc salt to the transition metal and the organic precursor is 1.01-0.5.
(3) Cleaning and freeze-drying treatment of the polymer: centrifugally cleaning the metal frame polymer dispersed with the platinum salt complex obtained in the step (2) for 2-5 times by adopting a solution, and freeze-drying the cleaned metal frame polymer for later use;
(4) Carbonization treatment of the dried polymer: crushing the dried polymer obtained in the step (3), carbonizing at 700-1100 ℃ for 0.5-4 hours after crushing, and then cooling to room temperature to obtain a compound with sufficient carbon matrix graphitization and ordered alloying of platinum and transition metal;
(5) And (3) post-treatment of the catalyst: and (4) crushing the compound obtained in the step (4) into nano powder again, and carrying out hydrophilic treatment on the powder in an acid solution to obtain the platinum-based composite catalyst with good hydrophilicity.
Or, (1) the in-situ implantation strategy is to dissolve the zinc salt and the platinum salt in the solvent to make the zinc salt and the platinum salt completely dissolved; then dissolving the transition metal salt, the complexable platinum salt polymer and the organic precursor for assembly in a solvent together to make the transition metal salt, the complexable platinum salt polymer and the organic precursor for assembly fully dissolved; then mixing the two formed solutions to form a solution C, and uniformly mixing the solution C with stirring (25-60 ℃) to uniformly disperse the platinum salt complex into the metal organic framework polymer; wherein, the mass ratio of the zinc salt to the solvent is 5-40, the mass ratio of the organic precursor for assembly to the solvent is 5-50, and the mass ratio of the zinc salt to the transition metal to the organic precursor is 1.01-0.5.
(2) Cleaning and freeze-drying treatment of the polymer: carrying out centrifugal cleaning on the metal frame polymer dispersed with the platinum salt complex obtained in the step (1) by adopting a solution for 2-5 times, and freeze-drying after cleaning for later use;
(3) Carbonization treatment of the dried polymer: crushing the dried polymer obtained in the step (2), carbonizing at 700-1100 ℃ for 0.5-4 hours after crushing, and then cooling to room temperature to obtain a compound with sufficient carbon substrate graphitization and ordered alloying of platinum and transition metal;
(4) And (3) post-treatment of the catalyst: and (4) crushing the compound obtained in the step (3) into nano powder again, and carrying out hydrophilic treatment on the powder in an acid solution to obtain the platinum-based composite catalyst with good hydrophilicity.
Further, the method comprises the following steps:
(1) Initial complexation of platinum salts with specific polymers in solution: the method comprises the steps of dissolving a polymer capable of complexing platinum ions in a specific solvent, performing ultrasonic treatment for 30-60 minutes at room temperature, and then performing magnetic stirring at a constant speed for 12-24 hours to realize complete dissolution of the polymer in the solvent. Slowly dripping the platinum salt water solution dissolved completely in advance into the polymer water solution, quickly stirring for 1-10 minutes, and then switching to low-speed stirring for 12-24 hours.
(2) Assembling and coating the metal frame polymer: dissolving zinc salt in a specific solvent, and stirring for 10-60 minutes to form a solution A; dissolving transition metal salt and an organic precursor capable of being assembled with zinc salt to form a metal framework polymer into a solvent together, and stirring for 10-60 minutes to form a solution B; and (2) rapidly mixing the solution A and the solution B under rapid stirring to form a solution C, rapidly pouring the solution prepared in the step (1) into the solution C to form a solution D, and uniformly stirring the solution D for 2-24 hours at a temperature ranging from room temperature to 80 ℃ to realize the synthesis and preparation of the metal organic framework polymer with the platinum salt complex uniformly dispersed.
(3) In-situ assembly and cladding of metal frame polymers with platinum salt complexes: dissolving zinc salt and platinum salt in a specific solvent, and stirring for 10-60 minutes to form a solution A; dissolving transition metal salt, complexable platinum salt polymer and an organic precursor capable of being assembled with zinc salt to form a metal frame polymer in a solvent together, and stirring for 10-60 minutes to form a solution B; and rapidly mixing the solution A and the solution B under rapid stirring to form a solution C, and uniformly stirring the solution D for 2-24 hours at the temperature of between room temperature and 80 ℃ to realize the synthesis and preparation of the metal organic framework polymer with the platinum salt complex uniformly dispersed.
(4) Cleaning and freeze-drying treatment of the polymer: and (3) centrifugally cleaning the metal framework polymer obtained in the step (2) or (3) for 2-5 times by adopting an organic reagent such as methanol, wherein the centrifugal rate is selected to be 5000-9000 r/min. And (3) freeze-drying the washed powder at-10 to-50 ℃ for 5 to 24 hours.
(5) Carbonization treatment of the dried polymer: the freeze-dried polymer is crushed into loose and agglomeration-free powder by a grinding bowl and sieved by a 200-mesh sieve. And (2) placing the sieved powder into a corundum crucible, performing final carbonization treatment by using a tubular furnace, wherein the carbonization temperature is 700-1100 ℃, the carbonization atmosphere is inert gas, the carbonization time is 0.5-4 hours, and after the carbonization is finished, performing air cooling along with the furnace to room temperature and taking out to obtain the compound with sufficient carbon matrix graphitization and ordered platinum and transition metal alloying.
(6) And (3) post-treatment of the catalyst: and (3) grinding and crushing the compound obtained in the step (5) into nano powder again, carrying out hydrophilic treatment in a specific acidic solution, removing useless and easily-soluble unstable substances in the subsequent electrochemical catalytic reaction process, namely boiling for 12-24 hours at 60-100 ℃, then carrying out suction filtration and washing by using deionized water until the pH value is 7, and carrying out vacuum drying for 10-48 hours at 60-80 ℃ to obtain the platinum-based composite catalyst with good hydrophilicity.
Dissolving a polymer capable of complexing a platinum source in a solvent, performing ultrasonic treatment for 10-100 minutes at room temperature, and then magnetically stirring at a constant speed for 3-30 hours to realize complete dissolution of the polymer in the solvent; slowly dripping the platinum salt solution dissolved completely in advance into the polymer solution, quickly stirring for 1-20 minutes at a stirring speed of 500-1000 revolutions per minute, and then stirring for 5-30 hours at a low speed at a stirring speed of 100-500 revolutions per minute;
the platinum salt is one or a mixture of more of platinum tetrachloride, potassium chloroplatinate, chloroplatinic acid, platinum acetylacetonate and platinum tetrachloride in any proportion;
the polymer complexed with the platinum salt is an anionic polymer and/or a cationic polymer. The anionic polymer is sodium polyacrylate, sodium polystyrene sulfonate, polyacrylamide, polystyrene-polybutadiene-polystyrene triblock copolymer, etc., and the cationic polymer is cetyl trimethyl ammonium bromide, cetyl trimethyl ammonium chloride, dodecyl dimethyl phenyl phosphorus bromide, and octadecyl dimethyl benzyl ammonium chloride.
In the step (2), the platinum micelle precursor in the step (1) is added into the solution B at a dripping speed of 5-20 ml per minute;
the transition metal salt is cobalt salt, iron salt, nickel salt, molybdenum salt, manganese salt and the like which are commercially available;
the organic precursor for assembly is imidazole, amine, pyrrole, pyridine, benzoic acid, etc.
The metal frame polymer dispersed with the platinum salt complex in the step 3) is centrifugally cleaned for 2-5 times by the solution, the centrifugal speed is 5000-9000 r/min, the cleaned powder is at minus 10-50 ℃, and the freeze drying time is 5-24 hours;
the solution is methanol and/or ethanol.
And 4) crushing the dried polymer in the step 4), sieving the crushed polymer with a 200-mesh sieve, and carbonizing the sieved powder by using a tubular furnace, wherein the carbonizing atmosphere is one or more of nitrogen, argon and hydrogen, the heating rate of the carbonizing furnace is 1-20 ℃ per minute, and the gas flow rate is 1-200 ml per minute.
The nanometer powder in the step 5) is subjected to acid cleaning for 12 to 48 hours at a temperature of between 60 and 100 ℃ through an acid solution, and is dried for 10 to 48 hours in vacuum at a temperature of between 60 and 80 ℃ after the acid cleaning; wherein the acid solution is one or more of hydrochloric acid, sulfuric acid, nitric acid and perchloric acid.
The solvents mentioned in the above steps can be the same or different and are selected from one or more of water, deionized water, methanol, isopropanol, acetone and ethanol and mixed in any proportion.
An oxygen reduction electrocatalyst material with uniformly dispersed platinum alloy particles, rich heteroatom doping on a carbon substrate and outstanding performance and stability is prepared by the method.
Use of an oxygen-reducing electrocatalyst for the oxygen-reducing electrocatalysis in a proton exchange membrane fuel cell.
Compared with the existing catalyst preparation method, the invention has the following essential characteristics and creativity:
the method obtains the oxygen reduction electrocatalytic nanomaterial which has the advantages of uniform dispersion of platinum alloy particles, porous carbon skeleton isolation among the particles, carbon layer coating on the surface layer of the particles, rich nitrogen and transition metal monoatomic atoms in the carbon substrate, and gap doping, excellent performance and outstanding stability, has low cost, simple equipment requirement and short preparation flow, and has the advantages of being superior to the preparation of most other noble metal catalysts, and specifically comprises the following steps:
(1) The invention introduces a strategy that platinum is complexed with organic molecules with specific valence and functional groups in advance in the process of preparing the platinum-based catalyst, and platinum-containing nano-micelles uniformly dispersed in the solution are formed in advance. The micelle can be coated in a cavity in the subsequent growth process of the metal framework polymer, and has the advantages obviously different from the traditional synthetic platinum catalyst: can realize the uniform dispersion of the platinum element, and can effectively avoid the agglomeration of the platinum element to form larger platinum particles in the later carbonization process due to the pyrolysis and volatilization of the polymer. The method can well improve the utilization rate of the platinum, reduce the loss of the platinum and the preparation energy consumption of the whole catalyst, and has important significance for reducing the manufacturing cost of the platinum catalyst and improving the catalytic activity and the stability of the platinum catalyst.
(2) The invention combines the structural characteristics of the platinum nano-micelle, introduces the metal framework polymer as a precursor for catalyst synthesis and a supporting body of the platinum nano-micelle, and has obvious structural advantages and creative synthetic strategy. Platinum nano-micelles can better disperse platinum salts, but if the micelles cannot be absorbed, isolated and coated by an effective carrier, high-temperature carbonization still causes severe segregation and agglomeration of platinum. According to the method, the pre-synthesized platinum nano micelle and the transition metal salt are added in the process of assembling the zinc salt and the polymer to generate the metal framework polymer, so that the synthesized metal framework polymer can absorb, disperse and coat the platinum nano micelle, the platinum nano micelle is confined in the pore cavity of the synthesized metal framework polymer, and meanwhile, the in-situ doping of the transition element capable of alloying with platinum is completed, so that the transition element can be well dispersed around the platinum. The precursor synthesized by the method realizes the uniform dispersion of platinum and transition metal, provides structural advantages for avoiding platinum agglomeration in the processes of high-temperature pyrolysis and carbonization at the later stage, and has obvious originality. Meanwhile, the uniform doping of the transition metal and the platinum is realized in the precursor, so that convenience is provided for the reduction of the platinum and the in-situ alloying of the transition metal in the later-stage high-temperature carbonization process, the migration distance of the platinum and the transition metal is greatly reduced, sufficient thermodynamic conditions are provided for ordered crystallization of the alloy, and finally the prepared catalyst has the uniformly dispersed platinum-based alloy distribution with fine particles.
(3) The volatile solvent of the metal organic framework polymer is removed by adopting freeze drying, so that the problem that the precursor is condensed into blocks in a drying mode, oxygen of a carbonized product is incompletely volatilized, a carbon substrate is hard and is difficult to disperse in solvents such as ethanol, active components in the catalyst are embedded, electrolyte is difficult to pass through the catalyst, and finally catalytic activity is insufficient can be effectively avoided. The method aims at the structural characteristics of the framework of the precursor, adopts a freeze drying method, removes the solvent in a sublimation mode, simultaneously completely retains the framework of the catalyst precursor, and provides structural advantages for the later carbonization product with abundant gaps and channels.
(4) The invention solves the defect of poor hydrophilicity of the carbon material through acid washing treatment, can obviously improve the hydrophilicity of the material and remove acidic soluble substances in a carbonized product through acid washing, and lays a component foundation for improving the stability in an acidic electrolyte.
Drawings
FIG. 1 is a scanning electron microscope image of an oxygen reduction catalyst precursor prepared in example 1 of the present invention.
FIG. 2 is an X-ray diffraction spectrum of an oxygen-reducing catalyst prepared in example 1 of the present invention.
FIG. 3 shows the oxygen reduction electrocatalytic performance of the catalyst prepared in example 1 of the present invention.
FIG. 4 is a transmission electron microscope image of the oxygen reduction catalyst prepared in example 2 of the present invention.
FIG. 5 shows the oxygen reduction electrocatalytic performance of the catalyst prepared in example 2 of the present invention.
FIG. 6 is a scanning electron microscope image of the oxygen reduction catalyst precursor prepared in example 3 of the present invention.
FIG. 7 is an X-ray diffraction spectrum of an oxygen-reducing catalyst prepared in example 3 of the present invention.
FIG. 8 shows the electrocatalytic stability of the catalyst prepared in example 3 of the present invention by oxygen reduction.
Detailed Description
The present invention will be further illustrated with reference to the following examples, but the present invention is not limited to the following examples. The method is a conventional method unless otherwise specified. The starting materials are commercially available from the open literature unless otherwise specified.
The preparation method is simple in preparation flow, high in effective product yield, and the prepared platinum-based catalyst material has excellent oxygen reduction electro-catalysis performance and stability. Firstly, respectively dissolving platinum salt and an organic polymer in a solvent, then mixing and stirring the completely dissolved platinum salt solution and the organic polymer solution, and forming a platinum nano micelle in which the polymer is complexed with the platinum salt after a certain time; secondly, respectively dissolving transition metal salt and an organic compound in a solvent, rapidly adding the transition metal salt and the organic compound into a prepared platinum nano micelle while stirring and mixing the two, and assembling and growing the platinum nano micelle for a certain time to form a catalyst precursor; finally, the obtained catalyst precursor is subjected to cleaning, freeze drying, high-temperature carbonization and acid washing treatment to obtain the oxygen reduction electrocatalyst nano material with the advantages of uniform platinum alloy particle dispersion, porous carbon skeleton isolation among particles, carbon layer coating on the particle surface layer, abundant nitrogen and transition metal single atoms in the carbon substrate, excellent performance and outstanding stability.
The method for preparing the platinum-based oxygen reduction catalyst material through in-situ complexing self-assembly has the advantages of simple process steps, short flow, adjustable morphology structure and the like, the prepared catalyst has large carbon substrate specific surface area, catalytic activity and stability which are obviously superior to those of a commercial Pt/C catalyst, and the whole synthesis route has low equipment requirement and good process stability, thereby having important industrial popularization and application values.
Example 1
Dissolving 0.1g of platinum tetrachloride into 100ml of water, performing ultrasonic treatment for 30 minutes at room temperature, and then uniformly stirring for 3 hours at a magneton rotating speed of 300 revolutions per minute to form a platinum salt solution A; dissolving 0.03g of hexadecyl trimethyl ammonium bromide into 100ml of deionized water, performing ultrasonic treatment for 60 minutes at room temperature, and then uniformly stirring for 6 hours at a magneton rotating speed of 350 revolutions per minute to form a solution B; the platinum salt solution A dissolved completely in advance is slowly dripped into the polymer solution B at the dripping rate of 2 milliliters per minute, and the platinum micelle precursor solution C is formed by firstly quickly stirring for 5 minutes at the speed of 800 revolutions per minute and then slowly stirring for 24 hours at the speed of 200 revolutions per minute. Dissolving 5g of zinc salt in 500 ml of deionized water, and uniformly stirring at a magneton rotating speed of 350 revolutions per minute for 60 minutes to form a solution D; dissolving 0.5G of cobalt nitrate and 6G of dimethyl imidazole in 800 ml of deionized water together, stirring at a constant speed for 2 hours at a magneton speed of 320 revolutions per minute to form a solution E, increasing the stirring speed of the solution E to 800 revolutions per minute after stirring is finished, then quickly pouring the solution D into the solution E to form a solution F, quickly stirring for 10 minutes, and then slowly dripping the solution C into the solution F in a dripping manner to form a mixed solution G. And reducing the stirring speed of the G solution to 150 revolutions per minute, setting the temperature to be 30 ℃, and uniformly stirring for 30 hours to realize the synthetic preparation of the metal organic framework polymer precursor with uniformly dispersed platinum (see figure 1). And centrifugally cleaning the obtained precursor for 3 times by adopting ethanol, wherein the centrifugal rate is selected to be 7000 revolutions per minute. And (3) freeze-drying the washed powder at-30 ℃ for 12 hours. And (3) performing carbonization heat treatment after the drying of the precursor, crushing the freeze-dried polymer into loose non-agglomerated powder by using a grinding pot, sieving by using a 200-mesh sieve, placing the sieved powder into a corundum crucible, and performing final carbonization treatment by using a tubular furnace, wherein the carbonization temperature is 800 ℃, the carbonization atmosphere is nitrogen, and the carbonization time is 2 hours. And after carbonization is completed, grinding and crushing the obtained composite into nano powder again, carrying out acid washing treatment in 0.2 mol/L hydrochloric acid solution at the temperature of 60 ℃ for 20 hours, carrying out suction filtration and washing by using deionized water until the pH value is 7, and carrying out vacuum drying at the temperature of 70 ℃ for 20 hours to obtain the final platinum-based composite catalyst (see figure 2).
As can be seen from figure 1, the prepared precursor has a uniform strip-shaped structure, and the platinum nano-micelle can be successfully coated in the produced metal framework polymer precursor, which lays a precursor foundation for preparing the catalyst with platinum-based alloy particle distribution by later carbonization. It can be seen from FIG. 2 that the catalyst obtained had significant Pt 3 And diffraction peaks of Co alloy particles show that the platinum nano-micelle is reduced and alloyed with transition metal in the carbonization process. For the finally obtained catalyst at 0.1M HClO 4 The oxygen reduction catalytic performance in (1) was evaluated. 2.5 mg of catalyst and 20. Mu.l of adhesive were weighed and dissolved in 980. Mu.l of ethanol, and 5. Mu.l of catalyst solution was weighed and dropped onto a 4 mm diameter disk rotating disk electrode for 2 hours of ultrasound. Linear voltammogram As shown in FIG. 3, a half-wave potential of 0.9V vs. RHE and a near 6mA cm were obtained at a rotation speed of 1600 rpm and a sweep speed of 10 mV/s -2 The current density of (1).
Example 2
Dissolving 0.5 g of chloroplatinic acid into 500 ml of water, performing ultrasonic treatment for 60 minutes at room temperature, and then uniformly stirring for 2 hours at a magneton rotating speed of 300 revolutions per minute to form a platinum salt solution A; dissolving 0.1g of hexadecyl trimethyl ammonium chloride into 500 ml of water, performing ultrasonic treatment for 60 minutes at room temperature, and then uniformly stirring for 10 hours at a magneton rotating speed of 400 revolutions per minute to form a solution B; the platinum salt aqueous solution A dissolved completely in advance is slowly dripped into the polymer solution B at the dripping rate of 5 ml per minute, and the platinum micelle precursor solution C is formed by firstly quickly stirring for 10 minutes at the speed of 600 revolutions per minute and then slowly stirring for 20 hours at the speed of 300 revolutions per minute. Dissolving 30g of zinc salt in 2500 ml of water, and uniformly stirring for 60 minutes at a magneton rotating speed of 300 revolutions per minute to form a solution D; dissolving 5g of cobalt nitrate and 68 g of 1, 2-dimethyl imidazole in 4000 ml of water, and uniformly stirring for 0.5 hour at a magneton rotating speed of 300 revolutions per minute to form a solutionAnd E, after stirring, increasing the stirring speed of the solution E to 800 revolutions per minute, then quickly pouring the solution D into the solution E to form a solution F, and after quickly stirring for 10 minutes, slowly dripping the solution C into the solution F in a dripping mode to form a mixed solution G. And reducing the stirring speed of the solution G to 150 revolutions per minute, setting the temperature to be 30 ℃, and stirring at a constant speed for 30 hours to realize the synthesis and preparation of the metal organic framework polymer precursor with uniformly dispersed platinum. And centrifugally cleaning the obtained precursor for 3 times by adopting methanol, wherein the centrifugal rate is selected to be 8000 revolutions per minute. And (3) freeze-drying the washed powder at the temperature of minus 30 ℃ for 20 hours. And (3) performing carbonization heat treatment after the drying of the precursor, crushing the freeze-dried polymer into loose non-agglomerated powder by using a grinding pot, sieving by using a 200-mesh sieve, placing the sieved powder into a corundum crucible, and performing final carbonization treatment by using a tubular furnace, wherein the carbonization temperature is 900 ℃, the carbonization atmosphere is nitrogen, and the carbonization time is 3 hours. And after carbonization is finished, grinding and crushing the obtained compound into nano powder again, carrying out acid washing treatment in 0.2 mol/L hydrochloric acid solution at the temperature of 60 ℃ for 12 hours, carrying out suction filtration and washing by using deionized water until the pH value is 7, and carrying out vacuum drying at the temperature of 60 ℃ for 24 hours to obtain the final platinum-based composite catalyst. The composite catalyst is analyzed by a transmission electron microscope, and as can be seen from fig. 4, the generated platinum-based alloy particles are about 3-5nm, the platinum alloy particles are uniformly distributed, and the aggregation is less, so that the feasibility of the technical scheme for preparing uniformly dispersed platinum-based alloy nanoparticles is proved. For the finally obtained catalyst at 0.1M HClO 4 The oxygen reduction catalytic performance in (1) was evaluated. 2.5 mg of catalyst and 20. Mu.l of adhesive were weighed and dissolved in 980. Mu.l of ethanol, and 5. Mu.l of catalyst solution was weighed and dropped onto a 4 mm diameter disk rotating disk electrode for 2 hours of ultrasound. As shown in FIG. 5, a half-wave potential of 0.89V s.RHE and a 5mA cm m.H were obtained at a rotation speed of 1600 rpm and a sweeping speed of 10 mV/s -2 The current density of the method shows the universality and stability of the technical scheme.
Example 3
Dissolving 1g of potassium chloroplatinate into 500 ml of methanol, performing ultrasonic treatment for 60 minutes at room temperature, and then uniformly stirring for 2 hours at a magneton rotating speed of 300 revolutions per minute to form a platinum salt solution A; dissolving 0.2 g of sodium dodecyl sulfate into 500 ml of methanol, performing ultrasonic treatment for 60 minutes at room temperature, and then stirring at a constant speed of a magneton of 400 revolutions per minute for 10 hours to form a solution B; the platinum salt aqueous solution A dissolved completely in advance is slowly dripped into the polymer solution B at the dripping rate of 5 ml per minute, and the platinum micelle precursor solution C is formed by firstly quickly stirring for 10 minutes at the speed of 600 revolutions per minute and then slowly stirring for 20 hours at the speed of 300 revolutions per minute. Dissolving 30g of zinc salt in 2500 ml of methanol, and uniformly stirring at a magneton rotating speed of 300 revolutions per minute for 60 minutes to form a solution D; dissolving 5G of cobalt nitrate and 68G of 1, 2-dimethylimidazole in 4000 ml of methanol together, stirring at a constant speed of 300 revolutions per minute for 0.5 hour to form a solution E, increasing the stirring speed of the solution E to 900 revolutions per minute after stirring is finished, then quickly pouring the solution D into the solution E to form a solution F, quickly stirring for 10 minutes, and then slowly dropwise adding the solution C into the solution F in a dropwise manner to form a mixed solution G. And reducing the stirring speed of the G solution to 180 revolutions per minute, setting the temperature to be 40 ℃, and uniformly stirring for 30 hours to realize the synthetic preparation of the metal organic framework polymer precursor with uniformly dispersed platinum (see figure 6). And centrifugally cleaning the obtained precursor for 3 times by adopting methanol, wherein the centrifugal rate is selected to be 8000 revolutions per minute. And (3) freeze-drying the washed powder at-30 ℃ for 20 hours. And (3) performing carbonization heat treatment after drying the precursor, firstly crushing the freeze-dried polymer into loose non-agglomerated powder by using a grinding pot, sieving by using a 200-mesh sieve, then placing the sieved powder into a corundum crucible, and performing final carbonization treatment by using a tubular furnace, wherein the carbonization temperature is 1000 ℃, the carbonization atmosphere is nitrogen, and the carbonization time is 3 hours. After carbonization, the obtained compound is ground and crushed into nano powder again, and is subjected to acid cleaning treatment in 0.1 mol/L hydrochloric acid solution at the temperature of 50 ℃ for 20 hours, then is subjected to suction filtration and washing by deionized water until the pH value is 7, and is subjected to vacuum drying at the temperature of 60 ℃ for 24 hours to obtain the final productThe phase composition of the platinum-based composite catalyst is shown in figure 7, and the oxygen reduction stability of the catalyst is shown in figure 8. As can be seen from FIG. 6, the catalyst prepared by using the prepared catalyst methanol as a solvent is in a polyhedral structure, and the platinum nano-micelle is well implanted into the precursor. The final catalyst phase composition is shown in fig. 7 to successfully realize the alloying of platinum and iron, and the diffraction peak intensity is higher, the peak width is wider, which indicates that the alloy particles are smaller and uniform. For the finally obtained catalyst at 0.1M HClO 4 The oxygen reduction catalytic performance in (1) was evaluated. 2.5 mg of catalyst and 20. Mu.l of adhesive were weighed and dissolved in 980. Mu.l of ethanol, and 5. Mu.l of catalyst solution was weighed and dropped onto a 4 mm diameter disk rotating disk electrode for 2 hours of ultrasound. The stability of the catalyst was evaluated in a three-electrode system, and as shown in fig. 8, the catalyst exhibited excellent stability and current density at a constant voltage of 0.67v/s.
Claims (4)
1. A preparation method of a platinum-based efficient stable oxygen reduction electrocatalyst is characterized in that platinum salt and a polymer are complexed to form platinum nano-micelles, and the obtained platinum nano-micelles are implanted into a metal framework polymer in the synthesis process of the metal framework polymer, or the platinum nano-micelles are implanted into the metal framework polymer in situ by adding the synthesis raw materials of the platinum nano-micelles into the synthesis solution of the metal framework polymer, and then the oxygen reduction electrocatalyst is obtained through drying, carbonization and post-treatment;
the method comprises the following specific steps:
(1) Complexing a platinum source and a polymer to prepare a platinum micelle precursor: dissolving a polymer capable of complexing a platinum source in a solvent to form a solution A, slowly dropwise adding a platinum salt solution completely dissolved in advance into the solution A, and uniformly stirring; wherein the molar ratio of the platinum salt to the polymer precursor is controlled to be 1-20, and the mixture is stirred and uniformly mixed at 25-60 ℃ for later use;
(2) Assembling and coating the metal frame polymer: dissolving zinc salt in a solvent to completely dissolve the zinc salt; then dissolving the transition metal salt and the organic precursor for assembly in a solvent together to fully dissolve the transition metal salt and the organic precursor for assembly; mixing the two solutions to form a solution B, adding the platinum micelle precursor solution obtained in the step (1) into the solution B in a dropwise manner, and uniformly stirring to uniformly disperse the platinum salt complex into the metal organic framework polymer; wherein the mass ratio of the zinc salt to the solvent is 5 to 40, the mass ratio of the organic precursor for assembly to the solvent is 5 to 50, and the mass ratio of the zinc salt to the transition metal to the organic precursor is 1;
or (2) respectively dissolving the zinc salt and the platinum salt in a solvent by an in-situ implantation mode to completely dissolve the zinc salt and the platinum salt; then dissolving the transition metal salt, the polymer capable of complexing platinum salt and the organic precursor for assembly in a solvent together to fully dissolve the transition metal salt, the polymer and the organic precursor; then mixing the two formed solutions to form a solution C, and uniformly stirring to uniformly disperse the platinum salt complex into the metal organic framework polymer; wherein the mass ratio of the zinc salt to the solvent is 5 to 40, the mass ratio of the organic precursor for assembly to the solvent is 5 to 50, and the mass ratio of the zinc salt to the transition metal to the organic precursor is 1 to 0.01 to 0.5;
(3) Cleaning and freeze-drying treatment of the polymer: centrifugally cleaning the metal frame polymer dispersed with the platinum salt complex obtained in the step (2) for 2-5 times by adopting a solution, and freeze-drying the cleaned metal frame polymer for later use;
(4) Carbonization treatment of the dried polymer: crushing the dried polymer obtained in the step (3), carbonizing at 700-1100 ℃ for 0.5-4 hours after crushing, and then cooling to room temperature to obtain a compound with sufficient graphitization of the carbon matrix and ordered alloying of platinum and transition metal;
(5) And (3) post-treatment of the catalyst: crushing the compound obtained in the step (4) into nano powder again, and performing hydrophilic treatment on the powder in an acid solution to obtain a platinum-based composite catalyst with good hydrophilicity;
the polymer in the step (1) is an anionic polymer; the anionic polymer is sodium polyacrylate, sodium polystyrene sulfonate, polyacrylamide or polystyrene-polybutadiene-polystyrene triblock copolymer;
in the step (2), the platinum micelle precursor in the step (1) is added into the solution B at a dripping speed of 5-20 ml per minute;
the transition metal salt is cobalt salt, iron salt, nickel salt, molybdenum salt or manganese salt;
the organic precursor for assembly is imidazole, amine or pyrrole;
the metal frame polymer dispersed with the platinum salt complex in the step (3) is centrifugally cleaned for 2-5 times by the solution, the centrifugal speed is 5000-9000 r/min, the cleaned powder is at minus 10-50 ℃, and the freeze drying time is 5-24 hours;
the solution is methanol and/or ethanol;
crushing the polymer after drying in the step (4), sieving with a 200-mesh sieve, and carbonizing the sieved powder by using a tubular furnace, wherein the carbonization atmosphere is one or more of nitrogen, argon and hydrogen, the heating rate of the carbonization furnace is 1-20 ℃ per minute, and the gas flow rate is 1-200 ml per minute;
pickling the nano powder in the step (5) for 12-48 hours in an acid solution at 60-100 ℃, and vacuum-drying for 10-48 hours at 60-80 ℃ after pickling; wherein the acid solution is one or more of hydrochloric acid, sulfuric acid, nitric acid and perchloric acid.
2. The method for preparing a platinum-based highly efficient stable oxygen reduction electrocatalyst according to claim 1, wherein the step (1) comprises dissolving a polymer capable of complexing a platinum source in a solvent, performing ultrasonic treatment at room temperature for 10-100 minutes, and then magnetically stirring at a constant speed for 3-30 hours to achieve complete dissolution of the polymer in the solvent; slowly dripping the platinum salt solution dissolved completely in advance into the polymer solution, quickly stirring for 1-20 minutes at a stirring speed of 500-1000 revolutions per minute, and then stirring for 5-30 hours at a low speed at a stirring speed of 100-500 revolutions per minute;
the platinum salt is one or a mixture of more of platinum tetrachloride, potassium chloroplatinate, chloroplatinic acid or acetylacetone platinum in any proportion.
3. An oxygen-reducing electrocatalyst prepared according to the method of claim 1, wherein: an oxygen-reducing electrocatalyst material having a uniformly dispersed platinum alloy particles, a carbon substrate doped with a rich impurity atom, and excellent performance and stability, prepared by the process of claim 1.
4. Use of the oxygen-reducing electrocatalyst according to claim 3, characterised in that: the catalyst is applied to oxygen reduction electrocatalysis in a proton exchange membrane fuel cell.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110709645.2A CN113363520B (en) | 2021-06-25 | 2021-06-25 | Platinum-based efficient stable oxygen reduction electrocatalyst and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110709645.2A CN113363520B (en) | 2021-06-25 | 2021-06-25 | Platinum-based efficient stable oxygen reduction electrocatalyst and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113363520A CN113363520A (en) | 2021-09-07 |
| CN113363520B true CN113363520B (en) | 2022-11-15 |
Family
ID=77536465
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110709645.2A Active CN113363520B (en) | 2021-06-25 | 2021-06-25 | Platinum-based efficient stable oxygen reduction electrocatalyst and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113363520B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114188557B (en) * | 2021-10-29 | 2023-03-31 | 陕西师范大学 | Preparation method and application of multi-mesoporous transition metal-nitrogen-carbon catalyst |
| CN114628706B (en) * | 2022-04-11 | 2024-02-13 | 西安凯立新材料股份有限公司 | Catalyst for proton exchange membrane fuel cell and preparation method thereof |
| CN115663210B (en) * | 2022-11-06 | 2023-10-13 | 中国人民解放军国防科技大学 | Preparation method of carbon-coated platinum-oxygen reduction electrocatalyst |
| CN117174949B (en) * | 2023-11-03 | 2024-02-02 | 合肥通用机械研究院有限公司 | Coupling transcritical CO 2 SOFC thermal management system with combined heat and power supply |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009301852A (en) * | 2008-06-12 | 2009-12-24 | Canon Inc | Catalyst metal-containing polymer membrane, membrane-electrode assembly, fuel cell, and method of manufacturing the catalyst metal-containing polymer membrane |
| CN110560082A (en) * | 2019-08-28 | 2019-12-13 | 浙江工业大学 | self-supporting mesoporous gold-palladium alloy film electrochemical synthesis ammonia catalyst and preparation method thereof |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104857983A (en) * | 2015-04-30 | 2015-08-26 | 北京化工大学 | Load type metal mesoporous molecular sieve noble metal catalyst and preparation method thereof |
| US9825308B1 (en) * | 2016-07-06 | 2017-11-21 | Uchicago Argonne, Llc | Low platinum catalyst and method of preparation |
| CN107331877A (en) * | 2017-08-03 | 2017-11-07 | 重庆大学 | A kind of preparation method of three-dimensional carbon skeleton embedding nano platinum base alloy catalyst |
| CN109962246A (en) * | 2017-12-14 | 2019-07-02 | 中国科学院大连化学物理研究所 | The loaded low platinum nucleocapsid catalyst of one kind and its preparation and application |
| CN108539218B (en) * | 2018-01-03 | 2022-02-01 | 南京工业大学 | Electrocatalytic material, preparation method and proton exchange membrane fuel cell |
| CN108428906B (en) * | 2018-04-11 | 2020-10-16 | 武汉理工大学 | Preparation method of low-Pt-loading fuel cell catalyst with MOF as template |
| CN111653792A (en) * | 2020-04-28 | 2020-09-11 | 广西大学 | Method for synchronously preparing hierarchical pore cobalt and nitrogen co-doped nanorod supported platinum-cobalt alloy nano oxygen reduction electrocatalyst |
| CN111686782A (en) * | 2020-07-18 | 2020-09-22 | 浙江工业大学 | Catalyst based on different-size platinum-zinc nanoparticles loaded on zinc-containing monatomic carbon nitrogen carrier and preparation method and application thereof |
| CN111933960B (en) * | 2020-08-18 | 2022-01-18 | 哈尔滨工业大学（深圳） | PtCo @ N-GNS catalyst and preparation method and application thereof |
-
2021
- 2021-06-25 CN CN202110709645.2A patent/CN113363520B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009301852A (en) * | 2008-06-12 | 2009-12-24 | Canon Inc | Catalyst metal-containing polymer membrane, membrane-electrode assembly, fuel cell, and method of manufacturing the catalyst metal-containing polymer membrane |
| CN110560082A (en) * | 2019-08-28 | 2019-12-13 | 浙江工业大学 | self-supporting mesoporous gold-palladium alloy film electrochemical synthesis ammonia catalyst and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113363520A (en) | 2021-09-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113363520B (en) | Platinum-based efficient stable oxygen reduction electrocatalyst and preparation method and application thereof | |
| CN109841854B (en) | Nitrogen-doped carbon-supported monatomic oxygen reduction catalyst and preparation method thereof | |
| Bhattacharyya et al. | MOF derived carbon based nanocomposite materials as efficient electrocatalysts for oxygen reduction and oxygen and hydrogen evolution reactions | |
| CN112823880B (en) | Catalyst with high metal loading capacity and preparation and application thereof | |
| CN114497585B (en) | Preparation method of platinum-based synergistic catalyst with structure coupling effect | |
| CN112186207B (en) | Low platinum/non-platinum composite catalyst and preparation method thereof | |
| CN103495432A (en) | Method for preparing efficient stable fuel cell catalyst | |
| CN112968184B (en) | Electrocatalyst with sandwich structure and preparation method and application thereof | |
| Yan et al. | S, N co-doped rod-like porous carbon derived from S, N organic ligand assembled Ni-MOF as an efficient electrocatalyst for oxygen reduction reaction | |
| CN113013427A (en) | High-performance electrocatalyst carrier derived based on Metal Organic Framework (MOF) material and preparation method thereof | |
| Li et al. | Enhanced oxygen reduction reaction performance of ReOx/NC (Re= La, Ce, Pr, Sm, Eu, Tb, Er, Tm and Yb)-especially Pr6O11/NC via accommodating oxygen vacancies and its application for Zn-air battery | |
| Wang et al. | ZIF derived mesoporous carbon frameworks with numerous edges and heteroatom-doped sites to anchor nano-Pt electrocatalyst | |
| Zhao et al. | Nitrogen-doped 3D porous graphene coupled with densely distributed CoOx nanoparticles for efficient multifunctional electrocatalysis and Zn-Air battery | |
| CN113036160A (en) | Preparation method of nanocellulose-derived carbon-supported cobalt electrocatalyst | |
| CN109546166B (en) | Pt/metallic carbide/carbon nano material catalyst and preparation method thereof | |
| Sun et al. | Eu2O3–Cu/NC nanocomposite catalyst with improved oxygen reduction reaction activity for Zn-air batteries | |
| CN114300693A (en) | Method for improving stability of fuel cell carbon-supported platinum-based catalyst through activation of carbon carrier | |
| CN109809389B (en) | High-specific-surface-area and high-nitrogen-doped carbon nanorod and simple preparation and application thereof | |
| CN113937310B (en) | Platinum-based catalyst and preparation method and application thereof | |
| CN113097509B (en) | Hydrogen fuel cell platinum-carbon catalyst and preparation method thereof | |
| Zhang et al. | Mn3O4 nanosheets coated on carbon nanotubes as efficient electrocatalysts for oxygen reduction reaction | |
| CN114284515A (en) | Ternary heterostructure FePc/Ti3C2/g-C3N4Preparation method and application of composite material | |
| WO2022099793A1 (en) | Orr catalyst material, preparation method therefor, and use thereof | |
| Ye et al. | Nitrogen-doped carbon fibers loaded with Co/Co2Mn3O8 alloy nanoparticles as bifunctional oxygen electrocatalysts for rechargeable zinc-air batteries | |
| US20220416260A1 (en) | Hybrid catalyst suitable for use in proton exchange membrane fuel cell |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |