CN112397732A - ORR catalyst material and preparation method and application thereof - Google Patents

ORR catalyst material and preparation method and application thereof Download PDF

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Publication number
CN112397732A
CN112397732A CN202011268676.0A CN202011268676A CN112397732A CN 112397732 A CN112397732 A CN 112397732A CN 202011268676 A CN202011268676 A CN 202011268676A CN 112397732 A CN112397732 A CN 112397732A
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catalyst
ceo
solution
orr
catalyst material
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类延华
谭宁
张玉良
常雪婷
范润华
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Shanghai Maritime University
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Shanghai Maritime University
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Priority to CN202310252115.9A priority patent/CN116111120A/en
Priority to PCT/CN2020/131613 priority patent/WO2022099793A1/en
Publication of CN112397732A publication Critical patent/CN112397732A/en
Priority to ZA2023/08558A priority patent/ZA202308558B/en
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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
    • H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
    • H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • 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
    • H01M4/921—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
    • 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
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/22—Fuel cells in which the fuel is based on materials comprising carbon or oxygen or hydrogen and other elements; Fuel cells in which the fuel is based on materials comprising only elements other than carbon, oxygen or hydrogen
    • 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

Abstract

The invention relates to an ORR catalyst material, a preparation method of the ORR catalyst material, application of the ORR catalyst material as a cathode material of a hydrogen-oxygen fuel cell or a metal-air battery, and the hydrogen-oxygen fuel cell or the metal-air battery. An ORR catalyst material characterized by conforming to the general formula: mx/N‑C(1‑x‑y)/(CeO2)y(I) Wherein, the noble metal M is one or more than two of Pt, Pd and Au, x and y are mass percent, the range of x is 5 to 6 percent, and the range of y is 4 to 12 percent. The preparation method of the ORR catalyst material is characterized in that the catalyst precursor material is a conductive polymer composite material doped with noble metal acid radicals. The invention mainly solves the problems of uneven dispersion of noble metals and catalytic performance of ORR catalyst materials in the prior artThe preparation method of the catalyst material is complex, not environment-friendly and high in cost.

Description

ORR catalyst material and preparation method and application thereof
Technical Field
The present invention relates in a first aspect to a catalyst material, in particular to an ORR catalyst material; the second aspect of the present invention also relates to a method for preparing the ORR catalyst material; a third aspect of the invention relates to the use of the ORR catalyst material as a cathode material for a hydrogen-oxygen fuel cell or a metal-air cell, and to a hydrogen-oxygen fuel cell or a metal-air cell.
Background
With the rapid development of global economy, environmental pollution and energy shortage are becoming more serious, and how to produce and utilize renewable energy more effectively and stably becomes a problem to be solved urgently by human beings at present. Although wind, solar, hydroelectric and tidal energy have become alternatives to fossil fuels as green clean energy sources, there are intermittent and fluctuating problems with these energy sources relying heavily on the natural environment. With the continued search, metal air batteries, fuel cells and electrochemical supercapacitors have been developed as very effective and practical electrochemical energy conversion storage technologies and are in wide use in many fields. Among them, fuel cells have attracted much attention because of their high power density and low pollution. The Oxygen Reduction Reaction (ORR), the most important cathode reaction in a fuel cell, has slow reaction kinetics that severely limit the energy output of the fuel cell.
In order to realize the large-scale application of the fuel cell, one of the problems to be solved at present is to improve the activity of the catalyst in the electrode, and reduce the consumption of the noble metal platinum (Pt) so as to reduce the cost. The current commercialized catalyst mainly uses carbon-supported Pt nanoparticles, however, during the operation of the fuel cell, the Pt particles are liable to migrate, agglomerate, and the like, resulting in a decrease in activity. In order to reduce the Pt consumption and improve the activity of the catalyst, transition metal and heteroatom are introduced, so that the catalytic activity is improved, and the Pt is prevented from agglomerating, thereby improving the stability of the catalyst.
The Chinese patent application with the application publication number of CN 108384046A and the application publication date of 2018.08.10 discloses Pt-CeO2Preparation of porous polyaniline electrode material. In this patent application, isPt deposited on CeO by electrodeposition2On polous PANI. The preparation method firstly synthesizes CeO2Then synthesizing and preparing CeO2the/Pani composite, after which Pt was deposited electrochemically. The preparation method has complex process and not uniform distribution of Pt.
Chinese patent application with application publication number CN 107394222A and application publication date 2017.11.24 discloses a cerium oxide/precious metal/graphene ternary composite material and a preparation method and application thereof. In the patent application, the preparation method of the cerium oxide/precious metal/graphene ternary composite material is that trivalent Ce salt is dissolved in a reducing organic solvent, then graphene oxide is added, the mixture is reacted for 12 to 48 hours at the temperature of between 180 and 200 ℃, and then the mixture is washed and dried to obtain the composite material of cerium oxide and graphene; the composite material of cerium oxide and graphene is dispersed in a reductive organic solvent, a compound containing noble metal is added, and after reaction at the temperature of 100-160 ℃ for 1-6 hours, the product is obtained by washing and drying. The patent application takes graphene as a raw material, so that the cost is high; and a plurality of organic solvents are used in the preparation process, so that the preparation method is not convenient for industrial production and is not environment-friendly. The use of reducing organic solvents also introduces impurity ions that affect performance.
The Chinese patent application with the application publication number of CN 104716347A and the application publication date of 2015.06.17 discloses a CeO-containing material2And a method of preparing the same. In the patent application, the preparation method of the catalyst comprises the steps of uniformly mixing chloroplatinic acid solution and cerium nitrate, adding ethylene glycol and carbon black, ultrasonically mixing uniformly, dropwise adding NaOH, and carrying out oil bath heating reflux. And after the reaction solution is cooled to room temperature, washing and drying to obtain a product. The carbon black used in this patent application is not very good in catalytic performance and more Pt needs to be used to make up for the lack of catalytic performance of the carbon black. And in this patent application Pt is mainly distributed on the surface of carbon black. The preparation method of the patent application is mainly used in laboratories, and the industrial application relates to oil bath heating reflux, so that the production is inconvenient.
Chinese patent with application publication No. CN 103078123A and application publication No. 2013.05.01 discloses a fuel cell catalystAnd a method for preparing the same. In this patent application, the catalyst is prepared by dispersing graphite oxide and cerium nitrate in water, adjusting the pH with ammonia water, and reacting to obtain CeO2GN; the obtained CeO2Performing ultrasonic dispersion on/GN in an ethylene glycol solution, adding a chloroplatinic acid solution, adjusting the pH value, and reacting to obtain Pt-CeO2a/GN catalyst. The patent application uses graphite oxide, and the finally obtained catalyst has low porosity and small specific surface area.
The Chinese patent application with the application publication number of CN 101733094A and the application publication date of 2010.06.16 discloses Pt-CeO2A graphene electrocatalyst and a preparation method thereof are provided, wherein the preparation method of the catalyst comprises the steps of ultrasonically dispersing graphite oxide nanosheets in ethylene glycol, then adding a chloroplatinic acid solution, a ceric ammonium nitrate aqueous solution and a sodium acetate aqueous solution, fully mixing, transferring the mixture to a microwave hydrothermal reaction kettle, carrying out microwave heating reaction, filtering, washing and drying to obtain Pt-CeO2A graphene electrocatalyst. The patent application takes graphene as a raw material, so that the cost is high; the preparation method of the patent application relates to microwave hydrothermal reaction and has a complex process.
Disclosure of Invention
The invention aims to provide an ORR catalyst material, which has the advantages of simple preparation method, environmental protection and low cost, and solves the technical problems of uneven dispersion of noble metals, large noble metal consumption, low porosity, small specific surface area, poor stability, poor catalytic performance, complex preparation method, no environmental protection and high cost of the ORR catalyst material in the prior art.
The invention solves the technical problems through the following technical scheme, and achieves the purpose of the invention.
An ORR catalyst is prepared from micro-nano CeO2Noble metal M and nitrogen-doped carbon material, wherein the doping amount of nitrogen in the carbon is 0.05-0.1: 1, CeO in the ORR catalyst material2And a noble metal M uniformly distributed in the nitrogen-doped carbon material, the ORR catalyst material conforming to the general formula:
Mx/N-C(1-x-y)/(CeO2)y (I)
wherein, the noble metal M is one or more than two of Pt, Pd and Au, x and y are mass percent, the range of x is 5 to 6 percent, preferably 5.5 to 5.7 percent, and the range of y is 4 to 12 percent, preferably 4 to 5 percent; more preferably, the noble metal M is Pt, and the particle size of the noble metal Pt particles is 3-8 nm;
preferably, the ORR catalyst material is a porous material with a specific surface area of 40m2/g-800m2G, more preferably 600m2/g-800m2/g。
The second aspect of the invention aims to provide a preparation method of the ORR catalyst material, which is simple, environment-friendly and low in cost.
The method coats cerium oxide in situ by a conductive polymer, and in the preparation process of the conductive polymer, noble metal acid radicals are added, through doping of noble metal acid radicals in the conductive polymer, a catalyst precursor with uniformly dispersed noble metals is obtained, then carbonizing the mixture under the protection of nitrogen or argon atmosphere to obtain the cerium oxide-noble metal-nitrogen doped carbon three-way hybrid catalyst, wherein the prepared ORR catalyst material has the advantages of uniform noble metal dispersion, small noble metal consumption, high porosity, large specific surface area, good stability and good catalytic performance, the technical problems that in the prior art, the ORR catalyst material has uneven dispersion of noble metals, large using amount of the noble metals, low porosity, small specific surface area, poor stability and poor catalytic performance, and the preparation method of the catalyst material is complex, not environment-friendly and high in cost are solved.
The invention solves the technical problems through the following technical scheme, and achieves the purpose of the invention.
A method of preparing an ORR catalyst material, comprising the steps of:
1) obtaining CeO2；
2) Using the CeO2Preparing a catalyst precursor material, wherein the catalyst precursor material is a conductive polymer composite material doped with noble metal acid radicals, and the chemical formula of the catalyst precursor material is CeO2/CP-MXn-(the chemical formula only shows the composition components of the catalyst precursor material and does not represent the proportional relationship among the components), X is an acid radical, and n is 1 or 2;
3) carbonizing the catalyst precursor material at a high temperature to obtain the ORR catalyst material.
Further, the step 2) utilizes the CeO2The preparation of the catalyst precursor material comprises the following steps:
2.1) mixing the CeO2Dispersing in acid or salt solution of noble metal M to obtain solution I;
2.2) adding a conductive high molecular monomer into the solution I to obtain a solution II;
2.3) adding an oxidant or an acid solution of the oxidant into the solution II to carry out in-situ polymerization reaction to prepare the catalyst precursor material.
Still further, in the step 2.1), the CeO2The molar ratio of the acid or salt of the noble metal M to the noble metal M is 8-70: 1; and/or
In the step 2.2), the molar ratio of the conductive polymer monomer to the acid or salt of the noble metal M is 16-128: 1; and/or
In the step 2.3), the molar ratio of the oxidant to the conductive polymer monomer is 2-3: 1; and/or
In the step 2.3), the acid solution of the oxidizing agent is a hydrochloric acid solution of the oxidizing agent, and the molar ratio of the oxidizing agent to HCl in the hydrochloric acid is 1: 3-4.
On the basis of any one of the above technical solutions, preferably, the acid or salt of the noble metal M is H2PdCl4、Pd(NH3)4Cl2、Pd(NH3)2Cl2、Pd(NH3)4SO4、Pd(NH3)4(NO3)2、H2PtCl6、H2PtCl4、K2PtCl6、(NH4)2PtCl6、K2PtCl4、(NH4)2PtCl4、HAuCl4、NaAuCl4、KAuCl4And hydrates thereof.
On the basis of any one of the above technical solutions, preferably, the conductive polymer monomer is one or two of polyaniline and polypyrrole; and/or
The oxidant is APS or FeCl3。
Further, based on the preparation method of the ORR catalyst material, the step 3) of carbonizing the catalyst precursor material at high temperature to prepare the ORR catalyst material includes the following steps: and under the protection of inert gas atmosphere, the temperature of the catalyst precursor material is raised from room temperature to 600-1000 ℃ at the temperature raising rate of 5-20 ℃/min, the reaction is carried out for 2-4 hours, and the ORR catalyst material is obtained after natural cooling.
A third aspect of the invention aims to propose the use of the aforementioned ORR catalyst material. The use of the ORR catalyst material as described hereinbefore is as a cathode electrode for hydrogen-oxygen fuel cells or metal-air cells.
The fourth aspect of the invention is to provide a hydrogen-oxygen fuel cell or a metal-air battery, wherein the ORR catalyst material of the hydrogen-oxygen fuel cell or the metal-air battery has the advantages of uniform dispersion of precious metals, less precious metal consumption, high porosity of the catalyst material, large specific surface area, good stability and good catalytic performance, and the preparation method of the ORR catalyst material of the hydrogen-oxygen fuel cell or the metal-air battery is simple, environment-friendly and low in cost, so as to solve the technical problems that the ORR catalyst material of the hydrogen-oxygen fuel cell or the metal-air battery in the prior art has the defects of nonuniform dispersion of the precious metals, large precious metal consumption, low porosity of the catalyst material, small specific surface area, poor stability, poor catalytic performance, complicated preparation method of the catalyst material, environmental pollution and high cost.
The invention solves the technical problems through the following technical scheme, and achieves the purpose of the invention.
A hydrogen-oxygen fuel cell comprising a cathode electrode, the catalyst of the cathode electrode being an ORR catalyst material as hereinbefore described or an ORR catalyst material as prepared according to any of the preceding claims.
A metal-air battery comprising a cathode electrode having a catalyst comprising an ORR catalyst material as hereinbefore described or prepared according to any of the preceding claims.
According to the preparation method of the ORR catalyst material, cerium oxide is coated in situ by a conductive polymer, during the preparation process of the conductive polymer, precious metal acid radicals are added, the precious metal acid radicals are doped in the conductive polymer, a catalyst precursor material with uniformly dispersed precious metals is obtained, and then the catalyst precursor material is carbonized under the protection of nitrogen or argon atmosphere, so that the cerium oxide-precious metal-nitrogen doped carbon ternary hybrid catalyst is obtained. Specifically, cerium oxide is added into a solution synthesized by polyaniline and/or polypyrrole, the polyaniline and/or polypyrrole is chemically polymerized in situ, a precious metal acid radical doped polyaniline and/or polypyrrole-coated cerium oxide composite material is obtained, the catalyst precursor polyaniline and/or polypyrrole-coated cerium oxide is carbonized at high temperature, the polyaniline and/or polypyrrole precursor is gradually converted into an N-doped carbon material in the high-temperature carbonization process, and precious metal acid radicals doped in a polyaniline structure are thermally reduced to generate uniformly dispersed precious metal M nanoparticles. The method can obtain the uniformly dispersed ternary catalytic material of noble metal M nano particles and cerium oxide and N doped carbon in one step. Compared with the prior art, the invention has the following technical effects:
1. the preparation method is simple, convenient, environment-friendly, efficient and low in cost, and the ternary composite system catalyst with high porosity, high specific surface area and high performance is obtained by in-situ polymerization and high-temperature carbonization; the preparation process does not use a reducing agent (the use of the reducing agent in the prior art can introduce unnecessary ions to influence the performance).
2. By taking a conductive polymer as a nitrogen source and a carbon source of a catalyst, adding a noble metal acid radical into a polymerization solution of the conductive polymer, and doping the noble metal acid radical in the conductive polymer in the polymerization process to obtain a catalyst precursor material with uniformly dispersed noble metal; the nano-particles of the noble metal M are obtained in one step by a high-temperature carbonization mode, the particle size is about 5nm, and the nano-particles are uniformly dispersed on the surface of the material.
3. Polyaniline and/or polypyrrole are used as a carbon source and a nitrogen source of the catalyst, nitrogen-doped carbon is obtained through high-temperature carbonization, the defect degree of the catalyst is increased by the doping of nitrogen, a certain aiming effect on the noble metal M is achieved, the particle size and distribution of the generated noble metal are effectively controlled, and the noble metal M is dispersed in a porous carbon material matrix and is loaded on the surface, so that the stability of the catalytic performance of the material is improved, the dispersibility of the particles of the noble metal M and the conductivity of the catalyst are improved, the catalytic activity of the catalyst is further improved, and the using amount of the noble metal M is reduced to a certain extent.
4. Transition metal oxide CeO2The catalytic activity is further improved by the synergistic catalytic action of the nano-particles and the noble metal M. The three-way catalytic system designed by the invention can greatly improve the catalytic performance of the material through the synergistic effect of the three. Oxide CeO of noble metal and transition metal2The heteroatom N is effectively compounded, which is beneficial to the dispersion of noble metal and the transfer of electrons on the surface of the catalyst, thereby having high catalytic activity and stability.
Drawings
FIG. 1 is a flow diagram of a method of preparing an ORR catalyst material in an embodiment.
FIG. 2 shows Pt prepared in example 15.64％/N-C90.14％/(CeO2)4.22％XRD pattern of catalyst.
FIG. 3 shows Pt prepared in example 15.64％/N-C90.14％/(CeO2)4.22％TEM images of the catalyst.
FIG. 4 shows Pt prepared in example 15.64％/N-C90.14％/(CeO2)4.22％STEM picture of the catalyst.
FIG. 5 shows Pt prepared in example 15.64％/N-C90.14％/(CeO2)4.22％Linear Sweep Voltammetry (LSV) versus commercial Pt-carbon 20% (mass fraction, same below) Pt/C catalyst.
FIG. 6 shows Pt prepared in example 15.64％/N-C90.14％/(CeO2)4.22％Stability of the catalyst is compared with that of a commercial Pt-C catalyst with 20% Pt/C.
FIG. 7 shows Pt prepared in example 15.64％/N-C90.14％/(CeO2)4.22％Nitrogen adsorption and desorption isotherm graph of the catalyst (specific surface area value: 636.96 m)2/g)。
FIG. 8 is Pt prepared in example 25.14％/N-C90.44％/(CeO2)4.42％XRD pattern of catalyst.
FIG. 9 is Pt prepared in example 25.14％/N-C90.44％/(CeO2)4.42％TEM images of the catalyst.
FIG. 10 shows Pt prepared in example 25.14％/N-C90.44％/(CeO2)4.42％Linear Sweep Voltammetry (LSV) plots of the catalyst versus a commercial platinum carbon 20% Pt/C catalyst.
FIG. 11 is Pt prepared in example 25.14％/N-C90.44％/(CeO2)4.42％Nitrogen adsorption and desorption isotherm graph of the catalyst (specific surface area value: 603.75 m)2/g)。
FIG. 12 shows Pt prepared in example 36.8％/N-C89.36％/(CeO2)3.84％XRD pattern of catalyst.
FIG. 13 shows Pt prepared in example 36.8％/N-C89.36％/(CeO2)3.84％Linear Sweep Voltammetry (LSV) plots of the catalyst versus a commercial platinum carbon 20% Pt/C catalyst.
FIG. 14 is Pt prepared in example 36.8％/N-C89.36％/(CeO2)3.84％Nitrogen adsorption and desorption isotherm graph of the catalyst (specific surface area value: 68.34 m)2/g)。
FIG. 15 shows Pt prepared in example 45.64％/N-C90.14％/(CeO2)4.22％0.1M HClO saturated with commercial Pt-C20% Pt/C catalyst in oxygen4Linear sweep voltammetry measured in solution(LSV) comparison plot.
FIG. 16 shows Pt prepared in example 15.64％/N-C90.14％/(CeO2)4.22％Pt/N-C prepared in comparative example 1 and N-C/CeO prepared in comparative example 22And commercial platinum carbon 20% Pt/C catalyst, in oxygen saturated 0.1M KOH solution in the test of Linear Sweep Voltammetry (LSV) contrast graph.
Detailed Description
In order to make the technical means, the creation characteristics, the achievement purposes and the effects of the invention easy to understand, the following detailed description is combined with the specific embodiments of the invention.
An ORR catalyst material is prepared from micro-or nano-grade CeO2Noble metal M and nitrogen-doped carbon material, wherein the doping amount of nitrogen in the carbon is 0.05-0.1: 1, CeO in the ORR catalyst material2And a noble metal M uniformly distributed in the nitrogen-doped carbon material, the ORR catalyst material conforming to the general formula:
Mx/N-C(1-x-y)/(CeO2)y (I)
wherein, the noble metal M is one or more than two of Pt, Pd and Au, x and y are mass fractions, the range of x is 5-8%, preferably 5.5-5.7%, more preferably 5.6-5.7%, and the range of y is 4-12%, preferably 4-5%, more preferably 4.2-4.3%; preferably, the noble metal M is Pt, and the particle size of the noble metal Pt is 3-8 nm.
Preferably, the ORR catalyst material is a porous material with a specific surface area of 40m2/g-800m2/g。
Referring to fig. 1, a method for preparing the ORR catalyst material includes the following steps:
1) obtaining CeO2；
2) Using the CeO2Preparing a catalyst precursor material, wherein the catalyst precursor material is a conductive polymer composite material doped with noble metal acid radicals, and the chemical formula of the catalyst precursor material is CeO2/CP-MXn-X is an acid radical, n is 1 or 2;
3) carbonizing the catalyst precursor material at a high temperature to obtain the ORR catalyst material.
Step 1) of obtaining Ce02,Commercially available micro-and/or nano-sized Ce0 can be purchased2The preparation method can also comprise the following steps:
1.1) dissolving cerium nitrate and sodium hydroxide in deionized water, adjusting the pH value of the solution, and uniformly stirring to obtain a reaction solution; preferably, in the step 1.1), the molar ratio of the cerium nitrate to the sodium hydroxide is 1:4, the pH value is 12, and the stirring is performed uniformly for 2 hours by magnetic stirring;
1.2) adjusting the environmental temperature of the reaction solution to the reaction temperature for reaction to obtain the CeO-containing2The solution of (1); preferably, the reaction temperature is 60 ℃, and the reaction time is 1 h;
1.3) adding the solution containing CeO2Filtering and washing the solution, drying and annealing to obtain CeO2；Preferably, the drying temperature is 130 ℃ and the annealing time is 4 h.
The step 2) of using the CeO2The preparation of the catalyst precursor material comprises the following steps:
2.1) mixing the CeO2Dispersing in acid or salt solution of noble metal M to obtain solution I;
2.2) adding a conductive high molecular monomer into the solution I to obtain a solution II;
2.3) adding an oxidant or an acid solution of the oxidant (the oxidant can be dissolved in acid because the performance of the polymerized conducting polymer is better because the conducting polymer is polymerized in a protonic acid solution) into the solution II, stirring uniformly during adding, and carrying out in-situ polymerization reaction to prepare the catalyst precursor material.
In the step 2.1), the CeO2The molar ratio of the noble metal M to the acid or salt of the noble metal M is in the range of 8 to 70: 1;
in the step 2.2), the molar ratio of the conductive polymer monomer to the acid or salt of the noble metal M is in a range of 16 to 128: 1;
in the step 2.3), the molar ratio of the oxidant to the conductive polymer monomer is in the range of 2-3: 1; and/or
The acid solution of the oxidizing agent is hydrochloric acid solution of the oxidizing agent, and the molar ratio of the oxidizing agent to HCl in the hydrochloric acid is 1: 3-4.
The acid or salt of the noble metal M is H2PdCl4、Pd(NH3)4Cl2、Pd(NH3)2Cl2、Pd(NH3)4SO4、Pd(NH3)4(NO3)2、H2PtCl6、H2PtCl4、K2PtCl6、(NH4)2PtCl6、K2PtCl4、(NH4)2PtCl4、HAuCl4、NaAuCl4、KAuCl4And hydrates thereof.
The conductive polymer monomer is one or two of polyaniline and polypyrrole; the oxidant is APS or FeCl3。
The step 3) of carbonizing the catalyst precursor material at high temperature to prepare the ORR catalyst material comprises the following steps:
and under the protection of inert gas atmosphere, the temperature of the catalyst precursor material is raised from room temperature to 600-1000 ℃ at the temperature raising rate of 5-20 ℃/min, the reaction is carried out for 2-4 hours, and the ORR catalyst material is obtained after natural cooling.
The use of the ORR catalyst material, as described hereinbefore, can be used as a cathode electrode for hydrogen-oxygen fuel cells or metal-air cells.
A fuel cell comprising a cathode electrode having a catalyst employing an ORR catalyst material as described in this embodiment or employing an ORR catalyst material as prepared in this embodiment.
A metal-air battery comprising a cathode electrode having an ORR catalyst material as described in this embodiment or prepared as described in this embodiment.
The following examples are given by way of illustration and are given in the context of the above-described embodiments and procedures, but the scope of the present invention is not limited to the following examples.
Example 1
Preparing a 0.1M cerium nitrate solution, adjusting the pH value of the solution to 12 by using sodium hydroxide, magnetically stirring for 2 hours, placing the solution in an oven to keep the temperature at 60 ℃ for 1 hour, filtering and washing, placing the yellow solid in the oven to keep the temperature at 130 ℃ for annealing for 4 hours, and cooling for 2 hours to room temperature to obtain cerium oxide.
0.6g (3.5mmol) of cerium oxide, 0.1g (0.2mmol) of potassium chloroplatinate (K)2PtCl6) Adding the solution into 40ml of 1mol/LHCl solution to obtain a solution I, and adding 0.6ml of aniline monomer (6.4mmol) into the solution I after ultrasonic dispersion for 2 hours to obtain a solution II; dissolving 0.6g APS (4mmol) in 10ml 1mol/LHCl solution to obtain solution III, and performing ultrasonic treatment for 2 hours to uniformly disperse the solution III; controlling the dropping speed of the solution III to slowly drop the solution III into the solution II; the reaction was maintained at 5 ℃ for 5 hours. Magnetic stirring is carried out in the reaction process; filtering and washing to obtain the catalyst precursor material.
Catalyst precursor material is added in inert gas Ar2Under the protection of atmosphere, the heating rate is 10 ℃/min, the temperature is increased to 800 ℃ from room temperature, the reaction is carried out for 2 hours, the final product is obtained after natural cooling, and the final product is detected to be Pt5.64％/N-C90.14％/(CeO2)4.22％. The final product obtained above was used as a catalyst for electrochemical testing in 0.1MKOH electrolyte solution using a rotating disk electrode and an electrochemical workstation.
FIG. 2 shows Pt prepared in example 15.64％/N-C90.14％/(CeO2)4.22％Catalyst (abbreviated as Pt in the figure)5.64％/N-C/CeO2Hereinafter, the same) from which it can be known that the final product contains Pt and CeO2. The particle size of the Pt is 3-8nm as determined by the Sherrer equation (Scherrrequation) from the XRD pattern.
FIG. 3 shows Pt prepared in example 15.64％/N-C90.14％/(CeO2)4.22％TEM image of the catalyst, which is accelerated at 200kVFrom this graph obtained at voltage, it can be seen that Pt (black or gray dots in the graph) in the final product is uniformly distributed.
FIG. 4 shows Pt prepared in example 15.64％/N-C90.14％/(CeO2)4.22％STEM diagram of the catalyst, which is obtained at an acceleration voltage of 200kV, from which it can be known that C, O, Pt, N, Ce are uniformly distributed in the final product.
FIG. 5 shows Pt prepared in example 15.64％/N-C90.14％/(CeO2)4.22％Linear Sweep Voltammetry (LSV) versus commercial platinum carbon 20% Pt/C catalyst. 20% Pt/C was purchased from Shanghai Michelin Biochemical technology Ltd (the same applies to the examples below). By comparing the linear scanning graphs of example 1 and commercial platinum carbon 20% Pt/C, it can be seen that the initial potential of example 1 is 0.95V (Vs.RHE), the half-wave potential is 0.88V (Vs.RHE), and the limiting current density is 5.88mA/cm2Initial potential 0.95V (Vs.RHE), half-wave potential 0.87V (Vs.RHE) and limiting current density 4.68mA/cm which are all superior to commercial Pt-C20% Pt/C2。
FIG. 6 shows Pt prepared in example 15.64％/N-C90.14％/(CeO2)4.22％Stability of the catalyst is compared with that of a commercial Pt-C catalyst with 20% Pt/C. Pt prepared by comparative example 15.64％/N-C/CeO2The stability test result of the platinum-carbon 20% Pt/C shows that the half-wave potential of the example 1 is negatively shifted by 30mV, and the limiting current density is increased by 0.39mAcm-2Compared with commercial Pt-C20% Pt/C, the half-wave potential is shifted negatively by 40mV, and the limiting current density is reduced by 0.36mAcm-2It can be seen that the stability of example 1 is better than the commercial platinum carbon 20% Pt/C in 0.1M KOH, an alkaline electrolyte.
FIG. 7 shows Pt prepared in example 15.64％/N-C90.14％/(CeO2)4.22％Nitrogen adsorption and desorption isotherm graph of the catalyst (specific surface area value: 636.96 m)2/g)。
Example 2 (different from example 1 in that potassium chloroplatinate was used in an amount of 0.05g)
Preparing a 0.1M cerium nitrate solution, adjusting the pH value of the solution to 12 by using sodium hydroxide, magnetically stirring for 2 hours, placing the solution in an oven to keep the temperature at 60 ℃ for 1 hour, filtering and washing, placing the yellow solid in the oven to keep the temperature at 130 ℃ for annealing for 4 hours, and cooling for 2 hours to room temperature to obtain cerium oxide.
0.6g (3.5mmol mol) of cerium oxide, 0.05g (0.1mmol) of potassium chloroplatinate (K)2PtCl6) Adding the solution into 40ml of 1mol/LHCl solution to obtain a solution I, and adding 0.6ml (6.4mmol) of aniline monomer into the solution I after ultrasonic dispersion for 2 hours to obtain a solution II; dissolving 0.6g (4mmol) of APS in 10ml of 1mol/LHCl solution to obtain a solution III, and performing ultrasonic treatment for 2 hours to uniformly disperse the solution III; controlling the dropping speed of the solution III to slowly drop the solution III into the solution II; keeping the temperature at 5 ℃ and reacting for 5 hours; magnetic stirring is carried out in the reaction process; filtering and washing to obtain the catalyst precursor material.
Catalyst precursor material is added in inert gas Ar2Under the protection of atmosphere, the heating rate is 10 ℃/min, the temperature is increased to 800 ℃ from room temperature, the reaction is carried out for 2 hours, the final product is obtained after natural cooling, and the final product is detected to be Pt5.14％/N-C90.44％/(CeO2)4.42％. The final product obtained above was made into catalyst slurry and the same electrochemical test as in example 1 was performed in 0.1m koh electrolyte solution using a rotating disk electrode, an electrochemical workstation.
FIG. 8 is Pt prepared in example 25.14％/N-C90.44％/(CeO2)4.42％Catalyst (abbreviated as Pt in the figure)5.14％/N-C/CeO2Hereinafter, the same) from which it can be known that the final product contains Pt and CeO2. The particle size of the Pt is 5-8nm as determined by the Sherrer equation (Scherrrequation) from the XRD pattern.
FIG. 9 is Pt prepared in example 25.14％/N-C90.44％/(CeO2)4.42％TEM image of the catalyst, obtained at an accelerating voltage of 200kV, from which it can be seen that Pt is uniformly distributed in the product.
FIG. 10 shows Pt prepared in example 25.14％/N-C90.44％/(CeO2)4.42％20% Pt/C catalysis with commercial Pt-CDose Linear Sweep Voltammetry (LSV) contrast plot. By comparing the linear scanning curve of example 2 with the 20% Pt/C of commercial Pt-C, the initial potential of example 2 is 0.91V (Vs.RHE), the half-wave potential is 0.83V (Vs.RHE), and the limiting current density is 3.52mA/cm2Inferior to the initial potential of 0.95V (Vs.RHE), half-wave potential of 0.88V (Vs.RHE) and limiting current density of 5.88mA/cm in example 12(ii) a Initial potential 0.95V (Vs.RHE), half-wave potential 0.87V (Vs.RHE), limiting current density 4.68mA/cm, also inferior to commercial 20% Pt/C2。
FIG. 11 is Pt prepared in example 25.14％/N-C90.44％/(CeO2)4.42％Nitrogen adsorption and desorption isotherm graph of the catalyst (specific surface area value: 603.75 m)2/g)。
Example 3 (different from example 1 in that potassium chloroplatinate was used in an amount of 0.2g)
Preparing a 0.1M cerium nitrate solution, adjusting the pH value of the solution to 12 by using sodium hydroxide, magnetically stirring for 2 hours, placing the solution in an oven to keep the temperature at 60 ℃ for 1 hour, filtering and washing, placing the yellow solid in the oven to keep the temperature at 130 ℃ for annealing for 4 hours, and cooling for 2 hours to room temperature to obtain cerium oxide.
0.6g (3.5mmol) of cerium oxide, 0.2g (0.4mmol) of potassium chloroplatinate (K)2PtCl6) Adding the solution into 40ml of 1mol/LHCl solution to obtain a solution I, and adding 0.6ml (6.4mmol) of aniline monomer into the solution I after ultrasonic dispersion for 2 hours to obtain a solution II; dissolving 0.6g of APS (4mmol) in 10ml of 1mol/LHCL solution to obtain a solution III, and performing ultrasonic treatment for 2 hours to uniformly disperse the solution III; controlling the dropping speed of the solution III to slowly drop the solution III into the solution II; keeping the temperature at 5 ℃ and reacting for 5 hours; magnetic stirring is carried out in the reaction process; filtering and washing to obtain the catalyst precursor material.
Catalyst precursor material is added in inert gas Ar2Under the protection of atmosphere, the heating rate is 10 ℃/min, the temperature is increased to 800 ℃ from room temperature, the reaction is carried out for 2 hours, the final product is obtained after natural cooling, and the final product is detected to be Pt6.8％/N-C89.36％/(CeO2)3.84％. Preparing the final product into catalyst slurry, and using a rotating disk electrode and an electrochemical workstation to perform electrolyte treatmentThe same electrochemical test as in example 1 was carried out in 0.1MKOH solution.
FIG. 12 shows Pt prepared in example 36.8％/N-C89.36％/(CeO2)3.84％Catalyst (abbreviated as Pt in the figure)6.8％/N-C/CeO2) From which it can be seen that the final product contains Pt and CeO2。
FIG. 13 shows Pt prepared in example 36.8％/N-C89.36％/(CeO2)3.84％Linear Sweep Voltammetry (LSV) plots of the catalyst versus a commercial platinum carbon 20% Pt/C catalyst. Initial potential 0.89V (Vs.RHE), half-wave potential 0.77V (Vs.RHE), limiting current density 4.24mA/cm for example 32Inferior to the initial potential of 0.95V (Vs.RHE), half-wave potential of 0.88V (Vs.RHE) and limiting current density of 5.88mA/cm in example 12(ii) a Initial potential 0.95V (Vs.RHE), half-wave potential 0.87V (Vs.RHE), limiting current density 4.68mA/cm and also inferior to commercial Pt-C20% Pt/C2。
FIG. 14 is Pt prepared in example 36.8％/N-C89.36％/(CeO2)3.84％Nitrogen adsorption and desorption isotherm plot of the catalyst (specific surface area: 68.34 m)2/g)。
Example 4 (difference from example 1, test in acidic electrolyte)
Dissolving cerium nitrate and sodium hydroxide in a certain amount of deionized water according to a molar ratio of 1:4 to ensure that the pH value of the solution is 12, magnetically stirring for 2 hours, placing the solution in an oven to keep the temperature at 60 ℃ for 1 hour, filtering and washing, placing a yellow solid in the oven to keep the temperature at 130 ℃ and annealing for 4 hours to prepare cerium oxide.
0.6g of cerium oxide, 0.1g of potassium chloroplatinate (K)2PtCl6) Adding the solution into 40ml of 1mol/LHCl solution to obtain a solution I, and adding 0.6ml of aniline monomer into the solution I after ultrasonic dispersion for 2 hours to obtain a solution II. 0.6g of APS was dissolved in 10ml of a 1mol/LHCl solution to give a solution III which was dispersed homogeneously by sonication for 2 hours. And controlling the dropping speed of the solution III to slowly drop the solution III into the solution II. The reaction was maintained at 5 ℃ for 5 hours. Magnetic stirring is accompanied during the reaction. Filtering and washing to obtain the catalyst precursor material。
Catalyst precursor material is added in inert gas Ar2Under the protection of atmosphere, the heating rate is 10 ℃/min, the temperature is increased to 800 ℃ from room temperature, the reaction is carried out for 2 hours, the final product is obtained after natural cooling, and the final product is detected to be Pt5.64％/N-C90.14％/(CeO2)4.22％. Electrochemical testing resulted in a change in the electrolyte solution compared to example 1. Preparing the final product into catalyst slurry, and treating the catalyst slurry with 0.1M HClO in electrolyte solution by using a rotary disk electrode and an electrochemical workstation4The same electrochemical test as in example 1 was performed.
FIG. 15 shows Pt prepared in example 45.64％/N-C90.14％/(CeO2)4.22％(abbreviated as Pt in the drawing)5.64％/N-C/CeO2) 0.1M HClO saturated with commercial Pt-C20% Pt/C catalyst in oxygen4The obtained Linear Sweep Voltammetry (LSV) contrast plot was tested in the solution. Pt prepared by comparative example 45.64％/N-C90.14％/(CeO2)4.22％The linear scanning curve graph of the commercial glassy carbon with 20% Pt/C shows that the initial potential of 0.88V (Vs.RHE) and the half-wave potential of 0.83V (Vs.RHE) of example 4 are superior to the initial potential of 0.87V (Vs.RHE) and the half-wave potential of 0.79V (Vs.RHE) of the commercial platinum carbon with 20% Pt/C.
Comparative example 1 (without cerium oxide)
0.1g of potassium chloroplatinate (K)2PtCl6) Adding the solution into 40ml of 1mol/LHCl solution to obtain a solution I, and adding 0.6ml of aniline monomer into the solution I after ultrasonic dispersion for 2 hours to obtain a solution II. 0.6g of APS was dissolved in 10ml of a 1mol/LHCl solution to give a solution III which was dispersed homogeneously by sonication for 2 hours. And controlling the dropping speed of the solution III to slowly drop the solution III into the solution II. The reaction was maintained at 5 ℃ for 5 hours. Magnetic stirring is accompanied during the reaction. Filtering and washing to obtain the catalyst precursor material. Catalyst precursor material is added in inert gas Ar2Under the protection of atmosphere, the heating rate is 10 ℃/min, the temperature is increased from room temperature to 800 ℃, the reaction is carried out for 2 hours, the final product is obtained after natural cooling, and the final product is detected to be Pt/N-C. In contrast to example 1, no cerium oxide was added to example 2. Mixing the aboveThe final product was used as a catalyst for electrochemical testing in 0.1MKOH electrolyte solution using a rotating disk electrode, an electrochemical workstation.
FIG. 16 shows Pt prepared in example 15.64％/N-C90.14％/(CeO2)4.22％Pt/N-C prepared in comparative example 1 and N-C/CeO prepared in comparative example 22And commercial platinum carbon 20% Pt/C catalyst, in oxygen saturated 0.1M KOH solution in the test of Linear Sweep Voltammetry (LSV) contrast graph. It was found from the linear scanning graph of comparative example 1 that the initial potential of comparative example 1 was 0.94V (Vs.RHE), the half-wave potential was 0.69V (Vs.RHE), and the limiting current density was 4.47mA/cm2All of which were inferior to example 1 in initial potential of 0.95V (Vs.RHE), half-wave potential of 0.88V (Vs.RHE), and limiting current density of 5.88mA/cm2。
COMPARATIVE EXAMPLE 2 (without Pt)
Dissolving cerium nitrate and sodium hydroxide in a certain amount of deionized water according to a molar ratio of 1:4 to ensure that the pH value of the solution is 12, magnetically stirring for 2 hours, placing the solution in an oven to keep the temperature at 60 ℃ for 1 hour, filtering and washing, placing a yellow solid in the oven to keep the temperature at 130 ℃ and annealing for 4 hours to prepare cerium oxide. 0.6g of cerium oxide was added to 40ml of a 1mol/LHCl solution to obtain a solution I, and after 2 hours of ultrasonic dispersion, 0.6ml of an aniline monomer was added to the solution I to obtain a solution II. 0.6g of APS was dissolved in 10ml of a 1mol/LHCl solution to give a solution III which was dispersed homogeneously by sonication for 2 hours. And controlling the dropping speed of the solution III to slowly drop the solution III into the solution II. The reaction was maintained at 5 ℃ for 5 hours. Magnetic stirring is accompanied during the reaction. Filtering and washing to obtain the catalyst precursor material. Catalyst precursor material is added in inert gas Ar2Under the protection of atmosphere, the heating rate is 10 ℃/min, the temperature is increased from room temperature to 800 ℃, the reaction is carried out for 2 hours, the final product is obtained after natural cooling, and the final product is detected to be N-C/CeO2. In contrast to example 1, comparative example 2 did not add potassium chloroplatinate. Taking 2mg of the final product, adding 400 microliters of ethanol and 25 microliters of perfluorosulfonic acid to prepare catalyst slurry, and taking 10 microliters of catalyst slurry to coat on a glassy carbon electrode. Adopts a three-electrode system, a glassy carbon electrode loaded with catalyst slurry as a working electrode and platinumThe wire electrode is a counter electrode, and the silver-silver chloride electrode is a reference electrode to perform electrochemical test in 0.1MKOH electrolyte solution.
Referring to FIG. 16, it was found from the linear scan graph of comparative example 1 that the initial potential of comparative example 2 was 0.88V (Vs.RHE), the half-wave potential was 0.79V (Vs.RHE), and the limiting current density was 3.38mA/cm2All of which were inferior to example 1 in initial potential of 0.95V (Vs.RHE), half-wave potential of 0.88V (Vs.RHE), and limiting current density of 5.88mA/cm2。
The specific methods for the tests mentioned in the examples and comparative examples of the present invention are as follows:
1. electrochemical testing
Preparing electrocatalyst slurry: 2.0mg of electrocatalyst powder is mixed with 400 mul of absolute ethyl alcohol and 25 mul of 5 percent (mass fraction) Nafion solution, and the mixture is evenly dispersed by ultrasonic for 60 min.
Preparation method of commercial Pt-C20% (mass fraction) Pt/C electrocatalyst slurry: 2.0mg of 20 percent (mass fraction) Pt/C electrocatalyst powder is mixed with 400 mu L of absolute ethyl alcohol and 25 mu L of 5 percent (mass fraction) Nafion solution, and the mixture is evenly dispersed by ultrasonic for 60 min.
Rotating Disk Electrode (RDE) test: the ORR performance of the electrocatalyst was evaluated using an electrochemical workstation (model: Interface 1010E, Gamry, USA) and an electrode rotation apparatus (model: AFMSRCE, PINE, USA) under a three-electrode system. Ag/AgCl as reference electrode, platinum wire as counter electrode, and glassy carbon electrode coated with electrocatalyst as working electrode (model: E5GC, glassy carbon disk area of 0.196 cm)2Pin corporation, usa). The working electrode is prepared by dripping 10 μ L of electrocatalyst paste onto the surface of glassy carbon electrode by using a liquid-transfer gun, and oven-drying with infrared lamp to obtain uniformly dispersed electrocatalyst thin layer with loading capacity of 0.24mg cm-2. Test at O2Saturated 0.1 mol. L-1In KOH aqueous solution, at a scanning speed of 10mV s-1The scanning interval is 0.2-1.2V (vs RHE), and the electrode rotation speed is 1600 r.min-1. Stability test in O2Saturated 0.1 mol. L-1In KOH solution, setting the cyclic voltammetry scanning potential interval of the working electrode to be 0.2-1.2V (V)s RHE), the number of scanning turns is 2000 turns, and the scanning speed is 50mV s-1. Recording the cyclic voltammetry curve chart of the working electrode after 2000 circles and the electrode rotating speed of 1600 r.min-1Linear sweep voltammograms.
2. XRD pattern analysis
The phase purity and crystal form of the synthetic samples were characterized using an X-ray diffractometer (XRD) (model: X' Pert PRO manufacturer: PANALYTICAL, the Netherlands) and tested under conditions of a voltage of 40kV, a current of 100mA, a scanning rate of 1 DEG/min and a 2 theta range of 10 DEG to 90 deg.
3. TEM image
The appearance and structure of the catalyst were observed using a Transmission Electron Microscope (TEM) model JEOL JEM2010 with an acceleration voltage of 200 kV. Meanwhile, the internal structure and element distribution of the catalyst are deeply analyzed by using a High Resolution (HR) TEM, a High Angle Annular Dark Field (HAADF) and a Scanning TEM (STEM).
4. STEM picture
The appearance and structure of the catalyst were observed using a Transmission Electron Microscope (TEM) model JEOL JEM2010 with an acceleration voltage of 200 kV. Meanwhile, the internal structure and element distribution of the catalyst are deeply analyzed by using a High Resolution (HR) TEM, a High Angle Annular Dark Field (HAADF) and a Scanning TEM (STEM).
5. Low temperature nitrogen adsorption and desorption test
The specific surface area of the electrocatalyst was calculated using the Brunauer-Emmett-Teller (BET) method using a BELSORP-max type apparatus (MicrotracBEL, Japan) for low temperature nitrogen adsorption/desorption tests.
6. Pt content and CeO2Measurement of content
Pt content and CeO2The content test method comprises the following steps: ICP-OES: the exact content of the metal in the catalyst was determined using inductively coupled plasma emission spectrometer (ICP-OES) (model: Agilent 720ES) to calculate therefromTrue mass activity of the catalyst. Sample preparation: dissolving the catalyst in aqua regia to obtain a solution with a mass concentration of 5-10mg L-1After the solution is completely dissolved, the middle layer of clear liquid is taken out, filtered and tested.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are given by way of illustration of the principles of the present invention, and that various changes and modifications may be made without departing from the spirit and scope of the invention as defined by the appended claims. The scope of the invention is indicated by the appended claims and their equivalents.

Claims (10)

1. An ORR catalyst material is characterized by comprising micro-nano CeO2Noble metal M and nitrogen-doped carbon material, wherein the doping amount of nitrogen in the carbon is 0.05-0.1: 1, CeO in the ORR catalyst material2And a noble metal M uniformly distributed in the nitrogen-doped carbon material, the ORR catalyst material conforming to the general formula:
Mx/N-C(1-x-y)/(CeO2)y (I)
wherein, the noble metal M is one or more than two of Pt, Pd and Au, x and y are mass percent, the range of x is 5 to 6 percent, preferably 5.5 to 5.7 percent, and the range of y is 4 to 12 percent, preferably 4 to 5 percent; more preferably, the noble metal M is Pt, and the particle size of the noble metal Pt particles is 3-8 nm;
preferably, the ORR catalyst material is a porous material with a specific surface area of 40m2/g-800m2/g。
2. A method of preparing the ORR catalyst material of claim 1, comprising the steps of:
1) obtaining CeO2；
2) Using the CeO2Preparing a catalyst precursor material, wherein the catalyst precursor material is a noble metal acid radical doped conductive high-molecular materialThe catalyst precursor material is CeO2/CP-MXn-X is an acid radical, n is 1 or 2;
3) carbonizing the catalyst precursor material at a high temperature to obtain the ORR catalyst material.
3. The method of preparing the ORR catalyst material of claim 2, wherein the step 2) utilizes the CeO2The preparation of the catalyst precursor material comprises the following steps:
2.1) mixing the CeO2Dispersing in acid or salt solution of noble metal M to obtain solution I;
2.2) adding a conductive high molecular monomer into the solution I to obtain a solution II;
2.3) adding an oxidant or an acid solution of the oxidant into the solution II to carry out in-situ polymerization reaction to prepare the catalyst precursor material.
4. The method of preparing the ORR catalyst material of claim 3, wherein in step 2.1), the CeO is used2The molar ratio of the noble metal M to the acid or salt of the noble metal M is in the range of 8 to 70: 1; and/or
In the step 2.2), the molar ratio of the conductive polymer monomer to the acid or salt of the noble metal M is in a range of 16 to 128: 1; and/or
In the step 2.3), the molar ratio of the oxidant to the conductive polymer monomer is in the range of 2-3: 1; and/or
In the step 2.3), the acid solution of the oxidizing agent is a hydrochloric acid solution of the oxidizing agent, and the molar ratio of the oxidizing agent to HCl in the hydrochloric acid is 1: 3-4.
5. The method of preparing an ORR catalyst material of claim 3 or 4, wherein the acid or salt of noble metal M is H2PdCl4、Pd(NH3)4Cl2、Pd(NH3)2Cl2、Pd(NH3)4SO4、Pd(NH3)4(NO3)2、H2PtCl6、H2PtCl4、K2PtCl6、(NH4)2PtCl6、K2PtCl4、(NH4)2PtCl4、HAuCl4、NaAuCl4、KAuCl4And hydrates thereof.
6. The method of preparing an ORR catalyst material of claim 3 or 4, wherein the conductive polymer monomer is one or both of polyaniline and polypyrrole; and/or
The oxidant is APS or FeCl3。
7. The method of preparing an ORR catalyst material of claim 2, wherein the step 2) of high temperature carbonizing the catalyst precursor material to obtain the ORR catalyst material comprises the steps of: and under the protection of inert gas atmosphere, the temperature of the catalyst precursor material is raised from room temperature to 600-1000 ℃ at the temperature raising rate of 5-20 ℃/min, the reaction is carried out for 2-4 hours, and the ORR catalyst material is obtained after natural cooling.
8. Use of the ORR catalyst material of claim 1, as a cathode electrode for a hydrogen-oxygen fuel cell or a metal-air battery.
9. A hydrogen-oxygen fuel cell comprising a cathode electrode, wherein the catalyst of the cathode electrode is the ORR catalyst material of claim 1 or the ORR catalyst material prepared according to any of claims 2-7.
10. A metal-air battery comprising a cathode electrode, wherein the catalyst of the cathode electrode is the ORR catalyst material of claim 1 or the ORR catalyst material prepared according to any of claims 2-7.
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