CN116666671A - Core-shell structured platinum-based catalyst and preparation method and application thereof - Google Patents

Core-shell structured platinum-based catalyst and preparation method and application thereof Download PDF

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CN116666671A
CN116666671A CN202310590329.7A CN202310590329A CN116666671A CN 116666671 A CN116666671 A CN 116666671A CN 202310590329 A CN202310590329 A CN 202310590329A CN 116666671 A CN116666671 A CN 116666671A
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platinum
core
noble metal
based catalyst
alloy
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唐柳
于力娜
王晶晶
朱雅男
刘江唯
张中天
刘晓雪
高梦阳
赵拓
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FAW Jiefang Automotive Co Ltd
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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
    • H01M4/921—Alloys or mixtures with metallic elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • H01M4/9041—Metals or alloys
    • 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
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • H01M4/9083—Catalytic material 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
    • H01M4/90—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
    • 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

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Abstract

The application relates to a core-shell structured platinum-based catalyst, and a preparation method and application thereof. The preparation method comprises the following steps: s1, mixing a platinum precursor, a non-noble metal precursor, a carrier and a solvent to obtain a mixed solution. S2, adding a reducing agent into the mixed solution, introducing a mixed gas of hydrogen and inert gas, heating for reaction, then performing solid-liquid separation to obtain a solid, and performing first calcination treatment on the solid to obtain a first intermediate; the reducing agent includes at least one of formic acid, ascorbic acid and oleylamine. S3, etching the surface layer of the alloy layer of the first intermediate to remove non-noble metal atoms in the surface layer, so as to obtain a second intermediate; the second intermediate comprises a carrier and a metal layer loaded on the carrier, wherein the metal layer comprises an alloy core of platinum atoms and non-noble metal atoms and a platinum shell coated on the surface of the alloy core. S4, performing secondary calcination treatment on the second intermediate to obtain the core-shell structure platinum-based catalyst.

Description

Core-shell structured platinum-based catalyst and preparation method and application thereof
Technical Field
The application relates to the technical field of fuel cells, in particular to a platinum-based catalyst with a core-shell structure, and a preparation method and application thereof.
Background
The proton exchange membrane fuel cell is a novel energy technology, has the advantages of low working temperature, high power density, quick starting capability and the like, and is considered as an automobile power source with a good application prospect in a double-carbon background. But the commercial development of proton exchange membrane fuel cells is restricted by short service life and high cost. Platinum catalyst degradation is one of the main reasons for reducing fuel cell life, and the amount of platinum in the platinum catalyst directly affects the cost of the fuel cell.
In recent years, researchers have combined platinum with other metals to make platinum alloy catalysts to reduce the amount of platinum used in the catalyst and thus reduce the raw material cost of fuel cells. However, most fuel cells are used under acidic conditions, which makes other metal atoms in the platinum alloy catalyst susceptible to corrosion, resulting in reduced catalyst stability and reduced fuel cell life. In order to solve the problems, researchers found that preparing a pure platinum coated shell on the surface of a platinum alloy can improve the acid resistance of the catalyst. However, in the conventional platinum-based catalyst with a core-shell structure, the coating shell is generally thinner and more loose, so that the coating shell is easy to be corroded by acid, and the inner platinum alloy core is difficult to effectively protect. In the catalyst, the metal bond between the platinum atom and other atoms is weaker, the size of the core-shell structure alloy nano particle is larger, and the binding force between the core-shell structure alloy nano particle and a carbon carrier is weaker, so that the stability of the catalyst is further reduced, and the traditional core-shell structure platinum-based catalyst still cannot meet the requirements of practical application. In addition, the conventional technology mostly adopts methods such as under-potential deposition or chemical vapor deposition to prepare the platinum shell, and the preparation conditions of the methods are complex and harsh, so that mass production is difficult to realize.
Therefore, how to prepare a platinum-based catalyst with a core-shell structure and high stability becomes a technical problem to be solved.
Disclosure of Invention
Based on the above, it is necessary to provide a platinum-based catalyst with a core-shell structure and high stability, and a preparation method and application thereof. In addition, the application also provides a fuel cell comprising the core-shell structure platinum-based catalyst.
In a first aspect, a method for preparing a core-shell platinum-based catalyst is provided, comprising the steps of:
s1, mixing a platinum precursor, a non-noble metal precursor, a carrier and a solvent to obtain a mixed solution;
s2, adding a reducing agent into the mixed solution, introducing a mixed gas of hydrogen and inert gas, heating for reaction, then performing solid-liquid separation to obtain a solid, and performing first calcination treatment on the solid to obtain a first intermediate; the first intermediate comprises a carrier and an alloy layer supported on the carrier, the alloy layer comprises an alloy of platinum atoms and non-noble metal atoms, and the reducing agent comprises at least one of formic acid, ascorbic acid and oleylamine;
s3, etching the surface layer of the alloy layer of the first intermediate to remove non-noble metal atoms in the surface layer, so as to obtain a second intermediate; the second intermediate comprises a carrier and a metal layer loaded on the carrier, wherein the metal layer comprises an alloy core of platinum atoms and non-noble metal atoms and a platinum shell coated on the surface of the alloy core;
s4, performing secondary calcination treatment on the second intermediate to obtain the core-shell structure platinum-based catalyst.
In the preparation method, the catalyst loaded with the core-shell structure platinum-based nano particles is prepared by mixing raw materials, reducing, first calcining treatment, etching treatment and second calcining treatment, so that the activity, acid resistance and stability of the catalyst can be improved while the platinum consumption is reduced. Specifically, at least one of formic acid, ascorbic acid and oleylamine with weaker reducibility is adopted as a reducing agent in the reduction step, and hydrogen with stronger reducibility is matched, so that the rate of reduction reaction can be effectively controlled under the synergistic effect of the two, alloy particles formed by platinum atoms with tiny particles and non-noble metal atoms are obtained, then the arrangement of the platinum atoms and the non-noble metal atoms is more orderly through the first calcination treatment, the metal bond between the platinum atoms and the non-noble metal atoms is reinforced, the anchoring effect between the platinum atoms and the non-noble metal atoms is enhanced, and an alloy layer which is uniformly distributed on a carrier, has smaller particle size and compact structure is obtained; and the reducing agent can be coordinated with platinum atoms and non-noble metal atoms on the surface layer of the alloy layer, so that the problem of agglomeration of alloy particles in the subsequent treatment step is effectively relieved. In the etching treatment process, non-noble metal atoms on the surface layer of the alloy layer are removed, and platinum atoms are reserved, so that the core-shell structure alloy nano particles taking platinum atoms and alloys of the non-noble metal atoms as cores and metal platinum as shells are formed, an alloy layer is formed on the surface of a carrier, and the platinum shell has proper thickness, so that the alloy cores in the interior can be effectively protected. And then, through the second calcination treatment, the compactness of the platinum shell is improved, and the stability of the catalyst is further enhanced. In addition, the preparation method has the advantages of simple steps, less pollution, safe storage and purer prepared platinum-based catalyst with a core-shell structure, so that the preparation method can be used for mass production and has better popularization prospect.
In some of these embodiments, the platinum precursor is H 2 PtCl 6 、K 2 PtCl 6 、Na 2 PtCl 6 、PtCl 2 、H 2 PtCl 4 、K 2 PtCl 4 、Na 2 PtCl 4 And at least one of platinum acetylacetonate.
In some of these embodiments, the non-noble metal precursor is a soluble salt containing a non-noble metal element including at least one of cobalt, nickel, iron, copper, yttrium, cerium, lanthanum, samarium, europium, gadolinium, terbium, dysprosium, and thulium.
In some of these embodiments, the carrier comprises at least one of ketjen black, XC-72 carbon black, carbon nanotubes, mesoporous carbon, and graphene.
In some of these embodiments, the solvent is at least one of water and ethylene glycol.
In some of these embodiments, the inert gas is at least one of nitrogen, argon, and helium.
In some of these embodiments, the molar ratio of platinum in the platinum precursor to the non-noble metal element in the non-noble metal precursor is 1: (0.05-0.3), the mass ratio of the platinum precursor to the carrier is 1: (0.2-4), the concentration of the carrier in the mixed solution is 1 g/L-3 g/L.
In some of these embodiments, in step S1: and mixing the platinum precursor, the non-noble metal precursor, the carrier and the solvent under the mixed gas of hydrogen and inert gas for 30-60 min.
In some of these embodiments, in step S2: the mass ratio of the sum of the mass of the platinum precursor and the mass of the non-noble metal precursor to the mass of the reducing agent is 1: (2-5), the volume ratio of the hydrogen to the inert gas is (0.02-0.1): 1.
in some of these embodiments, in step S2, the heating temperature of the heating reaction is 180 ℃ to 300 ℃ and the reaction time is 1h to 3h.
In some embodiments, the temperature of the first calcination treatment is 750-950 ℃, the time of the first calcination treatment is 4-6 h, and the atmosphere of the first calcination treatment is a mixture of hydrogen and inert gas.
In some of these embodiments, in step S3, the etching treatment is performed with an acidic solution of 0.1mol/L to 1mol/L, the acidic solution including at least one of perchloric acid, sulfuric acid, nitric acid, and hydrochloric acid.
In some embodiments, the etching treatment is performed in a mixture of hydrogen and inert gas at a temperature of 40-90 ℃ for 2-4 hours.
In some embodiments, the temperature of the second calcination treatment is 400-600 ℃, the time of the second calcination treatment is 1-2 h, and the atmosphere of the second calcination treatment is a mixture of hydrogen and inert gas.
In a second aspect, there is provided a core-shell structured platinum-based catalyst prepared by the preparation method of the first aspect.
In a third aspect, there is provided the use of a core-shell structured platinum-based catalyst of the second aspect in the preparation of a fuel cell.
In a fourth aspect, there is provided a fuel cell comprising a catalytic layer, the catalytic layer comprising the core-shell structured platinum-based catalyst of the second aspect.
Drawings
FIG. 1 is a schematic diagram of an alloy nanoparticle with a core-shell structure in which the inner black spheres are non-noble metal atoms, the gray spheres are platinum atoms, and the outer gray shell is a platinum shell, according to an embodiment.
Detailed Description
In order that the application may be readily understood, a more complete description of the application will be rendered by reference to the appended drawings. Preferred embodiments of the present application are shown in the drawings. This application may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein in the description of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
In the description of the present application, the terms "first," "second," and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature. In the description of the present application, the meaning of "plurality" means at least two, for example, two, three, etc., unless specifically defined otherwise.
The weights of the relevant components mentioned in the description of the embodiments of the present application may refer not only to the specific contents of the components, but also to the proportional relationship between the weights of the components, so long as the contents of the relevant components in the description of the embodiments of the present application are scaled up or down within the scope of the disclosure of the embodiments of the present application. Specifically, the weight described in the specification of the embodiment of the present application may be mass units known in the chemical industry field such as μ g, mg, g, kg.
Platinum alloy catalysts have received great attention because of their ability to reduce the amount of platinum used and to reduce the catalyst cost of fuel cells. And the alloy atoms can also improve the electronic structure of the platinum atoms, and improve the mass specific activity and the specific surface activity of the platinum atoms, so that the catalyst has higher catalytic activity. However, during the use of the fuel cell, the alloy atoms in the platinum alloy catalyst are easily corroded, and the platinum alloy particles are easily cured by Ostwald, so that the catalytic performance is attenuated and the catalyst stability is reduced. Pure platinum coating shells are prepared on the surface of the platinum alloy catalyst, so that the acid resistance of the catalyst can be effectively improved. However, the platinum shell of the conventional core-shell structure platinum-based catalyst is thinner and more loose, and is easily damaged in the use process, so that the alloy nano particles are agglomerated, and the service life of the fuel cell cannot be effectively prolonged by the catalyst. Based on the above, the application provides a novel core-shell structure platinum-based catalyst and a preparation method thereof.
One embodiment of the application provides a preparation method of a core-shell structured platinum-based catalyst, which comprises the following steps S1 to S4.
S1, mixing a platinum precursor, a non-noble metal precursor, a carrier and a solvent to obtain a mixed solution.
In some of these embodiments, the platinum precursor is H 2 PtCl 6 、K 2 PtCl 6 、Na 2 PtCl 6 、PtCl 2 、H 2 PtCl 4 、K 2 PtCl 4 、Na 2 PtCl 4 And at least one of platinum acetylacetonate.
In some of these embodiments, the non-noble metal precursor is a soluble salt containing a non-noble metal element including at least one of cobalt, nickel, iron, copper, yttrium, cerium, lanthanum, samarium, europium, gadolinium, terbium, dysprosium, and thulium. The non-noble metal element has better catalytic activity and lower cost, so that the catalytic activity can be ensured while the cost of the raw material of the catalyst is reduced.
Understandably, to improve Pt 2+ And dispersibility of non-noble metal ions in the mixed solution, the platinum precursor and the non-noble metal precursor can be prepared into solutions respectively, the prepared solutions are mixed with a solvent, and a carrier is added to obtain a mixed solution.
In some of these embodiments, the carrier comprises at least one of ketjen black, XC-72 carbon black, carbon nanotubes, mesoporous carbon, and graphene.
In some of these embodiments, the solvent is at least one of water and ethylene glycol. It is understood that the solvent may be water or ethylene glycol, or a mixed solvent of water and ethylene glycol.
In some of these embodiments, the inert gas is at least one of nitrogen, argon, and helium.
In some of these embodiments, the molar ratio of platinum in the platinum precursor to the non-noble metal element in the non-noble metal precursor is 1: (0.05-0.3). Alternatively, the above molar ratio is 1:0.05, 1:0.1, 1:0.15, 1:0.2, 1:0.25 or 1:0.3. it will be appreciated that the above molar ratio can also be in the range of 1: other choices are made in the range of (0.05 to 0.3).
By regulating the proportion of platinum and non-noble metal elements, the prepared catalyst has proper amounts of platinum atoms and non-noble metal atoms, and has better synergistic catalysis effect between the two atoms, so that the catalytic performance can be ensured while the platinum consumption is reduced.
In some of these embodiments, the mass ratio of platinum precursor to carrier is 1: (0.2-4). Optionally, the mass ratio is 1:0.2, 1:1. 1:1.5, 1:2. 1:2.5, 1:3. 1:3.5 or 1:4. it will be appreciated that the above mass ratio may also be at 1: (0.2 to 4) and other choices are made.
By regulating the mass ratio of the platinum precursor to the carrier, the platinum-based nano particles in the catalyst can be uniformly loaded on the carrier, and the catalytic activity and stability are improved.
In some of these embodiments, the concentration of carrier in the mixed solution is 1g/L to 3g/L. Alternatively, the concentration of the carrier is 1g/L, 1.5g/L, 2g/L, 2.5g/L or 3g/L. It will be appreciated that other choices of the above concentrations can be made in the range 1g/L to 3g/L.
In some of these embodiments, in step S1: and mixing the platinum precursor, the non-noble metal precursor, the carrier and the solvent under the mixed gas of hydrogen and inert gas. Further, the mixing time is 30 min-60 min.
The mixed gas of hydrogen and inert gas is introduced as a shielding gas, so that the oxidation of metal can be reduced. The mixing time is 30-60 min, so that the dispersibility of the raw materials can be improved, and the mixed solution with uniformly dispersed components is obtained.
S2, adding a reducing agent into the mixed solution, introducing a mixed gas of hydrogen and inert gas, heating for reaction, then performing solid-liquid separation to obtain a solid, and performing first calcination treatment on the solid to obtain a first intermediate; the first intermediate includes a support and an alloy layer supported on the support, the alloy layer including an alloy of platinum atoms and non-noble metal atoms, and the reducing agent including at least one of formic acid, ascorbic acid, and oleylamine.
The prior art mostly adopts strong reducing agents such as sodium borohydride and the like to carry out Pt 2+ The reaction rate of the strong reducing agent is higher, the particle size of the reduced alloy particles is larger, the alloying degree is lower, and the agglomeration is more serious. And the strong reducing agent has larger pollution and higher storage difficulty. In this embodiment, at least one of formic acid, ascorbic acid and oleylamine, which have weak reducibility, is used for the reduction reaction, so as to solve the above-mentioned problems of the conventional strong reducing agent. However, it has been found by experimental investigation that the use of the weakly reducing agent alone does not provide a good reduction effect and makes it difficult to reduce Pt 2+ Fully is provided withReduction results in poor catalytic activity. It is further found that by introducing a proper amount of hydrogen into the system, the reduction capability can be enhanced, the rate of the reduction reaction can be controlled under the synergistic effect of the weak reducing agent and the hydrogen, the agglomeration of the alloy nanoparticles can be effectively relieved, the dispersibility of the alloy nanoparticles can be improved, and the alloy layer comprising the fine alloy nanoparticles can be obtained. In addition, after the reduction reaction is completed, the excessive weak reducing agent can coordinate with platinum atoms and non-noble metal atoms in the alloy nano particles, so that agglomeration of the alloy particles in the subsequent calcination step can be effectively relieved. It should be noted that, in this embodiment, the mixed gas of hydrogen and inert gas is used to provide hydrogen, so that the reaction system has appropriate reducibility, and meanwhile, the safety of the reaction is ensured; the alloy layer comprises alloy nano particles which are discontinuously distributed on the carrier, wherein the alloy nano particles are alloy particles formed by platinum atoms and non-noble metal atoms.
Further, the first calcination treatment is equivalent to the ordered treatment of the reduced alloy nano particles, so that platinum atoms and non-noble metal atoms in the alloy nano particles are arranged into a more ordered structure, the electronic state and compressive strain of the material are improved, a better d-band center is obtained, the metal bond between the platinum atoms and the non-noble metal atoms is further reinforced, the mutual anchoring action of the two atoms is enhanced, the dissolution of the non-noble metal atoms can be reduced, and the Ostwald ripening of the metal nano particles can be inhibited. In addition, the first calcination treatment can promote graphitization of the carrier and enhance the corrosion resistance of the material under the high-potential condition. The durability of the material can be improved through the first calcination treatment, so that the catalyst shows better electrochemical stability under the acidic condition. It should be noted that the alloy nanoparticle obtained after the reduction reaction is different from the alloy nanoparticle obtained after the first calcination treatment in that the arrangement of the platinum atoms and the non-noble metal atoms in the former is disordered, and the bonding force between the two atoms is weak; the latter has a more ordered arrangement of platinum atoms and non-noble metal atoms, and the binding force between the two atoms is enhanced.
In some of these embodiments, in step S2, the mass ratio of the sum of the mass of the platinum precursor and the non-noble metal precursor to the mass of the reducing agent is 1: (2-5). Optionally, the mass ratio is 1:2. 1:2.5, 1:3. 1:3.5, 1:4. 1:4.5 or 1:5. it will be appreciated that the above mass ratio may also be at 1: other choices are made within the range of (2-5).
In some of these embodiments, the volume ratio of hydrogen to inert gas is (0.02-0.1): 1. optionally, the volume ratio is 0.02: 1. 0.04: 1. 0.05: 1. 0.06: 1. 0.08:1 or 0.1:1. it is understood that the above volume ratio may also be between (0.02 and 0.1): other choices are made within the scope of 1.
By regulating the mass ratio of the sum of the mass of the platinum precursor and the mass of the non-noble metal precursor to the reducing agent and the volume ratio of the hydrogen to the inert gas, the synergistic reduction effect of the reducing agent and the hydrogen can be fully exerted, so that the reaction system has proper reducibility, alloy nano particles with smaller particle size are reduced, and the activity of the catalyst is further improved.
In some of these embodiments, in step S2, the heating temperature of the heating reaction is 180 ℃ to 300 ℃ and the reaction time is 1h to 3h. The particle size of the alloy nano particles can be further controlled by regulating and controlling the reduction reaction condition of the step S2, so that the alloy nano particles with the particle size of 2.5-5 nm can be obtained, and meanwhile, the agglomeration of the alloy nano particles can be reduced.
In some embodiments, the temperature of the first calcination treatment is 750-950 ℃, the time of the first calcination treatment is 4-6 h, and the atmosphere of the first calcination treatment is a mixture of hydrogen and inert gas. By regulating and controlling the condition of the first calcination treatment, the effect of metal ordering treatment can be improved, the bonding strength between platinum atoms and non-noble metal atoms can be further enhanced, and the durability and stability of the material can be improved.
S3, etching the surface layer of the alloy layer of the first intermediate to remove non-noble metal atoms in the surface layer, so as to obtain a second intermediate; the second intermediate comprises a carrier and a metal layer loaded on the carrier, wherein the metal layer comprises an alloy core of platinum atoms and non-noble metal atoms and a platinum shell coated on the surface of the alloy core.
It is understood that during the etching process, the non-noble metal atoms on the surface layer of the alloy layer are removed and the platinum atoms remain, so that a core-shell structure metal layer with the alloy of the platinum atoms and the non-noble metal atoms as a core and the metal platinum as a shell is formed.
In some of these embodiments, the etching process is performed with an acidic solution of 0.1mol/L to 1mol/L, the acidic solution including at least one of perchloric acid, sulfuric acid, nitric acid, and hydrochloric acid.
In some embodiments, the etching treatment is performed in a mixture of hydrogen and inert gas at a temperature of 40-90 ℃ for 2-4 hours.
The thickness of the shell layer and the core can be controlled by reasonably selecting the concentration and the type of the acid solution and the etching treatment time and temperature, so that a thicker platinum shell is formed, the catalytic active sites are fully exposed, the utilization rate of platinum is improved, and the performance of the catalyst is further improved. By selecting the atmosphere of etching treatment, the oxidation of the alloy nano-particles can be effectively reduced.
S4, performing secondary calcination treatment on the second intermediate to obtain the core-shell structure platinum-based catalyst.
After etching treatment, the platinum shell of the third intermediate is loose, and the platinum shell is densified through a second calcination treatment to form a platinum shell with the thickness of 0.3-1 nm and an alloy core with the average particle diameter of 2-4 nm, wherein the platinum shell can effectively protect the alloy core inside. In addition, impurities such as oxygen atoms and the like remained in the second intermediate can be removed by the second calcination treatment, so that the impurities are prevented from being covered on the platinum shell, poisoning is generated on the catalyst, and the catalytic activity is influenced.
In some embodiments, the temperature of the second calcination treatment is 400-600 ℃, the time of the second calcination treatment is 1-2 h, and the atmosphere of the second calcination treatment is a mixture of hydrogen and inert gas.
The density of the platinum shell can be further improved by regulating and controlling the conditions of the second calcination treatment, and the stability and activity of the catalyst are improved. By selecting the atmosphere of the second calcination treatment, oxidation of the alloy nanoparticles can be effectively reduced.
In the preparation method, the catalyst loaded with the core-shell structure platinum-based nano particles is prepared by mixing raw materials, reducing, first calcining treatment, etching treatment and second calcining treatment, so that the activity, acid resistance and stability of the catalyst can be improved while the platinum consumption is reduced. Specifically, at least one of formic acid, ascorbic acid and oleylamine with weaker reducibility is adopted as a reducing agent in the reduction step, and hydrogen with stronger reducibility is matched, so that the rate of reduction reaction can be effectively controlled under the synergistic effect of the two, alloy particles formed by platinum atoms with tiny particles and non-noble metal atoms are obtained, then the arrangement of the platinum atoms and the non-noble metal atoms is more orderly through the first calcination treatment, the metal bond between the platinum atoms and the non-noble metal atoms is reinforced, the anchoring effect between the platinum atoms and the non-noble metal atoms is enhanced, and an alloy layer which is uniformly distributed on a carrier, has smaller particle size and compact structure is obtained; and the reducing agent can be coordinated with platinum atoms and non-noble metal atoms on the surface layer of the alloy layer, so that the problem of agglomeration of alloy particles in the subsequent treatment step is effectively relieved. In the etching treatment process, non-noble metal atoms on the surface layer of the alloy layer are removed, and platinum atoms are reserved, so that the core-shell structure alloy nano particles taking platinum atoms and alloys of the non-noble metal atoms as cores and metal platinum as shells are formed, an alloy layer is formed on the surface of a carrier, and the platinum shell has proper thickness, so that the alloy cores in the interior can be effectively protected. And then, through the second calcination treatment, the compactness of the platinum shell is improved, and the stability of the catalyst is further enhanced. In addition, the preparation method has the advantages of simple steps, less pollution, safe storage and purer prepared platinum-based catalyst with a core-shell structure, so that the preparation method can be used for mass production and has better popularization prospect.
Another embodiment of the application provides a core-shell platinum-based catalyst prepared by the preparation method.
In some of these embodiments, the core-shell platinum-based catalyst includes a support, and an alloy layer having a core-shell structure supported on the support. The alloy layer comprises alloy nano particles with the particle size of 2.5 nm-5 nm.
In some of these embodiments, the alloy nanoparticles include platinum atoms and non-noble metal atoms forming an alloy core, and a dense platinum shell coating the surface of the alloy core. Optionally, the particle size of the alloy core is 2 nm-4 nm, and the thickness of the platinum shell is 0.3 nm-1 nm. Referring to fig. 1, the gray coating shell on the surface of the alloy nanoparticle with the core-shell structure is a compact platinum shell; the black spheres in the interior are non-noble metal atoms, the gray spheres are platinum atoms, and the non-noble metal atoms and the platinum atoms in the alloy core are orderly arranged.
In the core-shell structured platinum-based catalyst, the synergistic effect between the platinum atoms and the non-noble metal atoms can improve the ORR activity of the catalyst. The compact platinum shell coated on the surface can fully expose active sites, protect alloy cores in the fuel cell, improve the utilization rate of platinum, reduce the dosage of platinum, and ensure the catalytic performance while reducing the cost of the fuel cell. In addition, the alloy layer with the core-shell structure can be uniformly and firmly loaded on the carrier, and the alloy layer hardly falls off and agglomerates in the use process of the fuel cell, so that the stability and the durability of the catalyst can be improved.
Furthermore, the application also provides application of the core-shell structure platinum-based catalyst in preparation of fuel cells.
Further, the application provides a fuel cell, which comprises a catalytic layer, wherein the raw material of the catalytic layer comprises the platinum-based catalyst with the core-shell structure. The fuel cell has better electrochemical activity, longer service life and lower cost. Can be used in the fields of, but not limited to, automobiles, portable equipment, fixed power supplies and the like.
In some of these embodiments, the fuel cell is a proton exchange membrane fuel cell. The proton exchange membrane fuel cell comprises a proton exchange membrane, a catalyst layer, a diffusion layer and a bipolar plate.
The following are specific examples.
Example 1
(1) The mole ratio of platinum to cobalt is 1:0.1, weighing chloroplatinic acid and cobalt chloride, and weighing graphene with the mass equal to that of the chloroplatinic acid. Mixing weighed chloroplatinic acid, cobalt chloride and graphene with water, and introducing the mixture into a reactor with a volume ratio of 0.05:1 and helium gas, and stirring for 40min to obtain a mixed solution, wherein the concentration of graphene in the mixed solution is 2g/L.
(2) Adding ascorbic acid into the mixed solution, wherein the mass of the ascorbic acid is 3 times of the sum of the masses of chloroplatinic acid and cobalt chloride, and the charging volume ratio is 0.05:1 and helium gas, and heating to 160 ℃ at a heating rate of 5 ℃/min, and reacting for 2 hours. After the reaction is finished, cooling the reaction liquid to room temperature, filtering, taking filter residues and drying. Placing the dried filter residues into a high-temperature tube furnace, wherein the volume ratio is 0.05:1 under the protection of a mixed gas of hydrogen and helium, and carrying out first calcination treatment at 800 ℃, wherein the calcination treatment time is 5 hours. After cooling, a first intermediate is obtained.
(3) Adding 0.5mol/L sulfuric acid solution into the first intermediate, stirring and mixing uniformly, and introducing the solution into the first intermediate with the volume ratio of 0.05:1, heating to 70 ℃ to carry out etching treatment for 3 hours. And then filtering the etching solution, taking filter residues, washing and drying the filter residues to obtain a second intermediate.
(4) Placing the second intermediate in a high-temperature tube furnace, wherein the volume ratio is 0.05:1 under the protection of a mixed gas of hydrogen and helium, and carrying out a second calcination treatment at 500 ℃, wherein the calcination treatment time is 1.5h. After cooling, a catalyst of carbon-supported core-shell structured platinum-cobalt nano particles is obtained and is named PtCo@Pt/C catalyst.
Example 2
(1) The mole ratio of platinum to nickel is 1:0.1 weighing potassium chloroplatinate and nickel chloride. Weighing XC-72 carbon black, wherein the mass ratio of the XC-72 carbon black to potassium chloroplatinate is 0.2:1. mixing weighed potassium chloroplatinate, nickel chloride and XC-72 carbon black with ethylene glycol, and introducing the mixture into a reactor with the volume ratio of 0.1:1 and stirring for 30min to obtain a mixed solution, wherein the concentration of XC-72 carbon black in the mixed solution is 1g/L.
(2) Adding oleylamine into the mixed solution, wherein the mass of the oleylamine is 2 times of the sum of the mass of potassium chloroplatinate and the mass of nickel chloride, and the volume ratio is 0.1:1, and heating to 300 ℃ at a heating rate of 2 ℃/min, and reacting for 1h. After the reaction is finished, cooling the reaction liquid to room temperature, filtering, taking filter residues and drying. Placing the dried filter residues into a high-temperature tube furnace, wherein the volume ratio is 0.1:1 under the protection of a mixed gas of hydrogen and nitrogen at 750 ℃, and the time of the calcination treatment is 6 hours. After cooling, a first intermediate is obtained.
(3) Adding 0.1mol/L perchloric acid solution into the first intermediate, stirring and mixing uniformly, and introducing the solution into the first intermediate in a volume ratio of 0.1:1, heating to 40 ℃ and carrying out etching treatment for 4 hours. And then filtering the etching solution, taking filter residues, washing and drying the filter residues to obtain a second intermediate.
(4) Placing the second intermediate in a high-temperature tube furnace, wherein the volume ratio is 0.1:1 under the protection of a mixed gas of hydrogen and nitrogen at 400 ℃, and the time of the calcination treatment is 2 hours. After cooling, a catalyst of carbon-supported core-shell structured platinum-nickel nano particles is obtained and is named PtNi@Pt/C catalyst.
Example 3
(1) The mole ratio of platinum to yttrium is 1:0.1 weighing sodium chloroplatinate and yttrium chloride. Mesoporous carbon is weighed, wherein the mass ratio of the mesoporous carbon to the sodium chloroplatinate is 4:1. mixing the weighed sodium chloroplatinate, yttrium chloride and mesoporous carbon with water, and introducing the mixture into a reactor with the volume ratio of 0.02:1 and argon, and stirring for 60min to obtain a mixed solution, wherein the concentration of mesoporous carbon in the mixed solution is 3g/L.
(2) Adding formic acid into the mixed solution, wherein the mass of the formic acid is 5 times of the sum of the mass of sodium chloroplatinate and the mass of yttrium chloride, and the introducing volume ratio is 0.02:1 and argon gas, and heating to 120 ℃ at a heating rate of 8 ℃/min, and reacting for 3 hours. After the reaction is finished, cooling the reaction liquid to room temperature, filtering, taking filter residues and drying. Placing the dried filter residues into a high-temperature tube furnace, wherein the volume ratio is 0.02:1 under the protection of a mixed gas of hydrogen and argon, and at 950 ℃, the time of the calcination treatment is 4 hours. After cooling, a first intermediate is obtained.
(4) Adding 1mol/L nitric acid solution into the first intermediate, stirring and mixing uniformly, and introducing the solution into the first intermediate with the volume ratio of 0.02:1, heating to 90 ℃ to carry out etching treatment for 2h. And then filtering the etching solution, taking filter residues, washing and drying the filter residues to obtain a second intermediate.
(5) Placing the second intermediate in a high-temperature tube furnace, wherein the volume ratio is 0.02:1, and carrying out secondary calcination treatment at 600 ℃ under the protection of a hydrogen gas and argon gas mixed gas, wherein the calcination treatment time is 1h. After cooling, a catalyst of carbon-supported core-shell structured platinum yttrium nano-particles is obtained and is named PtY@Pt/C catalyst.
Example 4
The preparation method of example 4 is substantially the same as that of example 1, except that: in the hydrogen and helium mixed gas in the steps (1) to (4), the volume ratio of the hydrogen to the helium is 0.01:1.
example 5
The preparation method of example 5 is substantially the same as that of example 1, except that: in the step (2), the mass of the ascorbic acid is 1 time of the sum of the masses of chloroplatinic acid and cobalt chloride.
Example 6
The preparation method of example 6 was substantially the same as that of example 1, except that: in step (2), the time of the first calcination treatment was 3 hours.
Example 7
The preparation method of example 7 is substantially the same as that of example 1, except that: in the step (3), an etching treatment is performed by using a sulfuric acid solution of 0.05 mol/L.
Comparative example 1
The preparation method of comparative example 1 was substantially the same as that of example 1, except that: the first calcination treatment of step (2) is omitted.
Comparative example 2
The preparation method of comparative example 2 was substantially the same as that of example 1, except that: in the step (2), ascorbic acid which is 3 times of the sum of the masses of chloroplatinic acid and cobalt chloride is only adopted for reduction, helium is introduced as a shielding gas, and hydrogen is not introduced.
Comparative example 3
The preparation method of comparative example 3 was substantially the same as that of example 1, except that: in the step (2), sodium borohydride is adopted as a reducing agent to replace ascorbic acid, the mass of the sodium borohydride is 3 times of the sum of the masses of chloroplatinic acid and cobalt chloride, helium is introduced as a protective gas, and hydrogen is not introduced.
Comparative example 4
The preparation method of comparative example 4 was substantially the same as that of example 1, except that: the second calcination treatment of step (4) is omitted.
The catalysts prepared in examples 1 to 7 and comparative examples 1 to 4 were subjected to electrochemical performance and stability tests, and the test results are shown in table 1 below. Wherein the test method of the electroactive active area is 0.1mol/L HClO saturated by nitrogen 4 In the process, a cyclic voltammetry curve test is carried out, the scanning speed is 20mV/s, and the potential scanning range is 0.05V-1.2V (reversible hydrogen electrode); the mass activity was measured on 0.l mol/L HClO saturated with oxygen 4 In the process, a linear sweep voltammetric test is carried out, the sweep speed is 20mV/s, the potential sweep range is 0.05V-1.2V (reversible hydrogen electrode), and the rotating speed is 1600r/min; the durability test data is the area of electroactive activity and the mass activity measured according to the above test after 5000 cycles or 30000 cycles, and calculated according to the following formula:
electrochemical active area decay= (initial electrochemical active area-electrochemical active area after 5000 or 30000 cycles of endurance)/initial electrochemical active area;
mass activity decay= (initial mass activity-mass activity after 5000 or 30000 cycles of endurance)/initial mass activity.
TABLE 1
From table 1 above, it is clear that the catalysts of examples 1 to 7 showed no significant decrease in electrochemical activity area and mass activity after 5000 and 30000 cycles of durability, whereas the electrochemical properties of comparative examples 1 to 4 showed significant decrease. Wherein, examples 1-3 respectively prepare PtCo@Pt/C catalyst, ptNi@Pt/C catalyst and PtY@Pt/C catalyst, which show that the preparation method of the application has better universality for different alloy atoms, and all three catalysts have better activity and stability. Compared with example 1, example 4 had less hydrogen gas introduced and example 5 had less ascorbic acid added, and both had relatively poor reduction, so that the initial activity was reduced and the attenuation after cycling was more remarkable; the first calcination treatment of example 6 was shorter in time, the ordering degree of the alloy particles was relatively lower, and the attenuation degree after circulation was greater; in the embodiment 7, sulfuric acid with lower concentration is adopted for etching treatment, the etching degree is lower, the formed platinum shell is thinner, the attenuation is obvious, and the stability of the catalyst is reduced.
As can be seen from comparing the test results of example 1 and comparative example 1, in example 1, the alloy nanoparticles were more ordered by the first calcination treatment, the electronic states and compressive strains of the platinum atoms and cobalt atoms were adjusted, a better d-band center was obtained, the metal bond between the platinum atoms and cobalt atoms was reinforced, the mutual anchoring effect between the two atoms was enhanced, the elution of cobalt atoms was reduced, and Ostwald ripening of the nanoparticles was suppressed, so that the electrochemical stability of example 1 was better under acidic conditions. And the first calcination treatment can also graphitize the carbon carrier, so that the corrosion resistance of the catalyst under the high-potential condition is enhanced, and the durability of the catalyst under the high-potential condition is improved.
Comparing the test results of example 1 and comparative example 2, it is understood that the volume ratio of hydrogen to helium of example 1 is 0.05:1, compared with comparative example 2, in example 1, a proper amount of hydrogen is added into inert gas, and the hydrogen and ascorbic acid serving as a weak reducing agent can generate synergistic reduction, so that not only is the reduction strength enhanced, but also the activity of the catalyst is enhanced, the chemical bonds and binding force between metal atoms are enhanced, the binding force between alloy nano particles and carbon carriers and between the alloy nano particles and metals are enhanced, and the stability of the catalyst is further improved.
As is clear from the test results of comparative example 1 and comparative example 3, the synergistic reduction of hydrogen gas and ascorbic acid, which is a weak reducing agent, of example 1 effectively controls the rate of the reduction reaction, and the overall reaction is more uniform, compared to the strong reducing agent of comparative example 3, so that alloy particles having fine and uniform particles can be reduced. However, the sodium borohydride of comparative example 3 was added to the reaction system, and the reduction rate was too fast to control the uniformity of the reduction reaction, so that the obtained alloy particles had a large and non-uniform size, and the catalytic activity and stability of comparative example 3 were poor.
As is apparent from the test results of comparative example 1 and comparative example 4, the secondary calcination treatment in example 1 can sufficiently remove impurities remaining in the second intermediate, reduce poisoning effects of the impurities on the catalyst, increase the density of the platinum shell, and further enhance the stability of the catalyst, as compared with the case where only one calcination treatment is used in comparative example 4.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the application, which are described in detail and are not to be construed as limiting the scope of the application. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the application, which are all within the scope of the application. Accordingly, the scope of protection of the present application is to be determined by the appended claims.

Claims (10)

1. The preparation method of the core-shell structured platinum-based catalyst is characterized by comprising the following steps:
s1, mixing a platinum precursor, a non-noble metal precursor, a carrier and a solvent to obtain a mixed solution;
s2, adding a reducing agent into the mixed solution, introducing a mixed gas of hydrogen and inert gas, heating for reaction, then carrying out solid-liquid separation to obtain a solid, and carrying out first calcination treatment on the solid to obtain a first intermediate; the first intermediate comprises a carrier and an alloy layer supported on the carrier, the alloy layer comprises an alloy of platinum atoms and non-noble metal atoms, and the reducing agent comprises at least one of formic acid, ascorbic acid and oleylamine;
s3, carrying out etching treatment on the surface layer of the alloy layer of the first intermediate to remove the non-noble metal atoms in the surface layer, so as to obtain a second intermediate; the second intermediate comprises a carrier and a metal layer loaded on the carrier, wherein the metal layer comprises an alloy core of the platinum atoms and the non-noble metal atoms and a platinum shell coated on the surface of the alloy core;
s4, performing second calcination treatment on the second intermediate to obtain the core-shell structure platinum-based catalyst.
2. The method for preparing a core-shell structured platinum-based catalyst according to claim 1, wherein the platinum precursor is H 2 PtCl 6 、K 2 PtCl 6 、Na 2 PtCl 6 、PtCl 2 、H 2 PtCl 4 、K 2 PtCl 4 、Na 2 PtCl 4 And at least one of platinum acetylacetonate;
and/or the non-noble metal precursor is a soluble salt containing a non-noble metal element, wherein the non-noble metal element comprises at least one of cobalt, nickel, iron, copper, yttrium, cerium, lanthanum, samarium, europium, gadolinium, terbium, dysprosium and thulium;
and/or the carrier comprises at least one of ketjen black, XC-72 carbon black, carbon nanotubes, mesoporous carbon and graphene;
and/or the solvent is at least one of water and ethylene glycol;
and/or the inert gas is at least one of nitrogen, argon and helium.
3. The method for preparing a core-shell structured platinum-based catalyst according to claim 2, wherein the molar ratio of platinum in the platinum precursor to the non-noble metal element in the non-noble metal precursor is 1: (0.05-0.3), the mass ratio of the platinum precursor to the carrier is 1: (0.2-4), wherein the concentration of the carrier in the mixed solution is 1 g/L-3 g/L.
4. A method for preparing a core-shell structured platinum-based catalyst according to any one of claims 1 to 3, wherein in step S1: mixing the platinum precursor, the non-noble metal precursor, the carrier and the solvent under the mixed gas of the hydrogen and the inert gas, wherein the mixing time is 30-60 min;
and/or, in step S2: the mass ratio of the sum of the mass of the platinum precursor and the mass of the non-noble metal precursor to the mass of the reducing agent is 1: (2-5), the volume ratio of the hydrogen gas to the inert gas is (0.02-0.1): 1.
5. the method for preparing a core-shell structured platinum-based catalyst according to any one of claims 1 to 3, wherein in step S2, the heating temperature of the heating reaction is 180 ℃ to 300 ℃ and the reaction time is 1h to 3h;
and/or the temperature of the first calcination treatment is 750-950 ℃, the time of the first calcination treatment is 4-6 h, and the atmosphere of the first calcination treatment is the mixed gas of the hydrogen and the inert gas.
6. The method for preparing a core-shell structured platinum-based catalyst according to any one of claims 1 to 3, wherein in step S3, the etching treatment is performed with an acidic solution of 0.1mol/L to 1mol/L, the acidic solution including at least one of perchloric acid, sulfuric acid, nitric acid and hydrochloric acid;
and/or the temperature of the etching treatment is 40-90 ℃, the time of the etching treatment is 2-4 hours, and the etching treatment is performed in the mixed gas of the hydrogen and the inert gas.
7. The method for preparing a core-shell structured platinum-based catalyst according to any one of claims 1 to 3, wherein the temperature of the second calcination treatment is 400 ℃ to 600 ℃, the time of the second calcination treatment is 1h to 2h, and the atmosphere of the second calcination treatment is a mixture of the hydrogen and an inert gas.
8. A core-shell structured platinum-based catalyst, characterized by being prepared by the method for preparing a core-shell structured platinum-based catalyst as claimed in any one of claims 1 to 7.
9. Use of the core-shell structured platinum-based catalyst according to claim 8 for the preparation of fuel cells.
10. A fuel cell comprising a catalytic layer, wherein the catalytic layer comprises the core-shell platinum-based catalyst of claim 8.
CN202310590329.7A 2023-05-24 2023-05-24 Core-shell structured platinum-based catalyst and preparation method and application thereof Pending CN116666671A (en)

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