CN111715218A - Method for preparing Pt bimetallic catalyst by electrodeposition in organic system - Google Patents

Method for preparing Pt bimetallic catalyst by electrodeposition in organic system Download PDF

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Publication number
CN111715218A
CN111715218A CN202010567280.XA CN202010567280A CN111715218A CN 111715218 A CN111715218 A CN 111715218A CN 202010567280 A CN202010567280 A CN 202010567280A CN 111715218 A CN111715218 A CN 111715218A
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electrodeposition
organic system
preparing
catalyst
bimetallic catalyst
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章俊良
范月恒
沈水云
闫晓晖
吴爱明
罗柳轩
赵路甜
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Shanghai Jiaotong University
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Shanghai Jiaotong University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/42—Platinum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8913—Cobalt and noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/892—Nickel and noble metals
    • B01J35/33—
    • B01J35/393—
    • 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
    • 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 discloses a method for preparing a Pt bimetallic catalyst by electrodeposition in an organic system, which relates to the technical field of nano materials/electrochemical technology and fuel cell catalysts, and the catalyst is prepared by the following steps: the method comprises the following steps: A. adding a Pt source precursor, a second metal source precursor and a supporting electrolyte into an organic solvent to obtain an organic system electrodeposition liquid, and adding a molecular sieve into the organic system electrodeposition liquid; B. under the protection of inert gas, connecting an electrochemical device, performing cyclic voltammetry electrochemical cleaning, and then performing electrochemical deposition on a catalyst conductive carrier under different potentials, wherein the catalyst conductive carrier is a carbon-based carrier. The process has the advantages of simple invention method, higher electrochemical window, and organic complexing adsorption effect which is favorable for controlling the deposition and the appearance of the catalyst, and can obviously improve the performance and the durability of the catalyst.

Description

Method for preparing Pt bimetallic catalyst by electrodeposition in organic system
Technical Field
The invention relates to the technical field of nano materials/electrochemistry technology and fuel cell catalysts, in particular to a method for preparing a Pt bimetallic catalyst by electrodeposition in an organic system.
Background
Proton Exchange Membrane Fuel Cells (PEMFCs) can directly convert chemical energy in hydrogen into electric energy through an electrochemical approach, have the advantages of low working temperature, fast start-up and the like, and are the most ideal choice for electric automobile power devices. Fuel cell technology has been developed into a new energy technology with great potential due to the advantages of high energy conversion efficiency, no environmental pollution, good reliability, etc., but the problem of high cost of the cathode catalyst is the most important challenge.
In view of the present situation, the development of new low platinum high performance catalysts is still the only way to realize the commercialization of Proton Exchange Membrane Fuel Cells (PEMFCs). The main approaches to reduce the Pt dosage of PEMFC cathode electrocatalyst include the development of novel, high activity Pt-M (mainly transition metal) alloy catalysts, Pt core-shell structure catalysts, and non-Pt catalysts.
The electrochemical synthesis method overcomes the defects that the synthesis of the traditional chemical synthesis method is limited by single synthesis means and limited control methods of components and shapes, and has extremely high advantage in controllability. The controllability of electrochemical synthesis can be realized by simply changing the electrode potential (or current density) to regulate the nucleation and growth of particles and induce the growth of high-index crystal faces, thereby controlling the morphology of the nano alloy particles. The organic electrolyte system has a wider electrochemical window, so that the deposition of metals (such as Fe, Co and Ni) with more negative electrode potential can be realized more easily. Therefore, the selection of a proper organic electrolyte system can effectively reduce the difference of different metal electrode potentials, is more favorable for preparing the alloy catalyst in combination with an electrochemical method, can obtain higher controllability in comparison with the traditional chemical synthesis method in the organic system, and is more favorable for synthesizing the Pt alloy catalyst with high ORR activity, uniform size and specific morphology. The method for preparing the Pt bimetallic catalyst by electrodeposition in the organic system has a wider electrochemical window, shows excellent synthesis performance and excellent oxygen reduction electrocatalytic activity and durability, and can be effectively used for accelerating the commercialization of proton exchange membrane fuel cells.
The Chinese patent with the publication number of CN110021758A provides a Pt-M metal alloy catalyst prepared by electrodeposition in an organic system; the catalyst conductive carrier is carbon-based; in an organic solvent, Pt-M metal alloy nano particles prepared by Pt-M metal codeposition are uniformly dispersed on the surface of a carrier in a physical loading mode, wherein the physical loading mode is as follows: firstly synthesizing alloy particles, then adding a carbon carrier into an organic solvent such as ethanol, preparing the alloy particles, and loading the alloy particles on the carbon carrier by ultrasonic. But the structure is not good enough, the appearance is difficult to control, and the binding force and the stability between alloy particles and a carrier are not enough.
Disclosure of Invention
In order to solve the defects in the prior art, the invention aims to provide a method for preparing a Pt bimetallic catalyst by electrodeposition in an organic system and also provides application of the method in a fuel cell. The catalyst has a wider electrochemical window, shows excellent synthesis performance and excellent oxygen reduction electrocatalytic activity and durability, and can be effectively used for accelerating the commercialization of proton exchange membrane fuel cells.
The purpose of the invention is realized by the following technical scheme: a method for preparing Pt and a bimetallic catalyst thereof by electrodeposition in an organic system comprises the following steps:
A. adding a Pt source precursor, a second metal source precursor and a supporting electrolyte into an organic solvent to obtain an organic system electrodeposition liquid, and adding a molecular sieve into the organic system electrodeposition liquid;
B. under the protection of inert gas, connecting an electrochemical device, performing cyclic voltammetry electrochemical cleaning, and then performing electrochemical deposition on a catalyst conductive carrier under different potentials, wherein the catalyst conductive carrier is a carbon-based carrier.
Preferably, the anhydrous operation in step a specifically includes: and ensuring that the Pt source precursor, the second metal source precursor, the supporting electrolyte and the organic solvent are mixed in an anhydrous oxygen-free glove box, wherein the concentrations of the Pt source precursor, the second metal source precursor and the supporting electrolyte are respectively 4mM, 4mM and 0.1M.
Preferably, the second metal of the second metal source precursor in step a is a transition metal based on a 3d, 4d, 5d structure, including one or more of Fe, Co, Ni, Mn, Cu, Ag, Au, Ru, Y, La, Ce, and Gd.
Preferably, the second metal source precursor in step a includes one or more of ferrous phosphate, ferric acetone acetate, cobalt acetone acetate, nickel acetone acetate, manganese acetone acetate, copper acetone acetate, and silver acetone acetate.
Preferably, the supporting electrolyte in step A comprises NaClO4、LiClO4、KOH、KOCH3、NaOCH3、NH4Cl, quaternary ammonium salt (R)4NX)、NaClO4、Mg(ClO4)2、LiCl、NaBF4Tetrafluoroammonium perchlorate (R)4NClO4) Tetrabutylfluoroborate (NBu 4 BF)4)、NaNO3、R4NBF4、NaNO3、KClO4NaOAc, tetrabutylphosphonium chloride (C)16H36ClN) is selected.
Preferably, the method for preparing Pt and the bimetallic catalyst thereof by electrodeposition in an organic system is characterized in that the organic solvent in the step A comprises dimethyl amide (DMF), dimethyl sulfoxide (DMSO) and dimethyl amide
(HOAc), methanol (McOH), benzyl alcohol (BnOH), Tetrahydrofuran (THF), Propylene Carbonate (PC), Nitromethane (NM) and Acetonitrile (AN).
Preferably, the method for preparing Pt and the bimetallic catalyst thereof by electrodeposition in an organic system is characterized in that the inert gas in the step B comprises one or more of nitrogen and argon, and the inert gas protection comprises the following steps: introducing inert gas into the solution by using a conduit for 0.5-3 h to ensure that the inert gas is saturated in the solution so as to ensure that the atmosphere is not removed by removing oxygen.
Preferably, the carbon-based support in step B comprises one or more of carbon black, graphitized carbon, graphite, and activated carbon.
Preferably, the electrochemical cleaning of the electrode in the step B is cyclic voltammetry electrochemical cleaning at 0.3-0.85V; in the electrochemical deposition, the glassy carbon electrode is subjected to different deposition potentials (vs. SCE) from-1.5V to-2.2V; the scanning rate is 1-50 mV/s;
the diameter of the surface of the glassy carbon electrode is 1 mm-20 mm.
The invention provides an application of a Pt bimetallic catalyst prepared by electrodeposition in an organic system in oxidation reduction of a fuel cell.
In summary, compared with the prior art, the invention has the following beneficial effects:
(1) the invention prepares monodisperse Pt bimetallic catalyst nanoparticles with small particle size by an electrodeposition method; the Pt-M catalyst is synthesized by an organic system, and has excellent performance and structure. The method for synthesizing Pt-M in an organic system has the advantages of being capable of synthesizing an electrochemical catalyst more stably, having a wider electrochemical synthesis window and being more controllable in the synthesis process and the appearance of the catalyst. In addition, in an organic system, the selective adsorption of certain metal ions shortens the reduction potential between metals, and can better realize the codeposition of the bimetal;
(2) the invention loads monodisperse Pt bimetallic catalyst nano-particles on a carbon black carrier by an electrodeposition method, and overcomes the problems of the traditional thermal synthesis method that the reaction conditions are required to high temperature and high pressure, the reaction solvent is difficult to completely remove, and the limitations of the accurate control of particle growth and the exploration of nucleation mechanism.
Detailed Description
The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, which ranges of values are to be considered as specifically disclosed herein, the invention is described in detail below with reference to specific examples:
example 1
The preparation method of the Pt-M metal alloy nanoparticle catalyst with high catalytic performance in the embodiment comprises the following steps:
A. weighing Pt source as chloroplatinic acid hexahydrate and M metal source as cobalt acetylacetonate precursor salt and supporting electrolyte as potassium perchlorate according to a certain mass ratio by using an electronic balance, adding the weighed materials into a certain amount of organic solvent DMF, stirring and mixing to prepare a 4mM chloroplatinic acid hexahydrate +4mM cobalt acetylacetonate +0.1M potassium perchlorate solution system, and fully and uniformly stirring;
B. in an inert atmosphere N2Under protection, removing O2And ultrasonically treating for 5 minutes to disperse uniformly; the electrodes were mechanically polished with 0.5 μm, 0.3 μm, 0.05 μm alumina powder and then sonicated in water and ethanol for 30 seconds in that order prior to use.
Connected with an electrochemical experimental device. All electrodeposition was carried out in a standard three-electrode glass cell, 1cm of which2Platinum foil as counter electrode and saturated calomel electrode as reference electrode, calibrated to 0.312V before use, relative to 0.1MH2ClO4The Reversible Hydrogen Electrode (RHE) in (1).
The electrodes were subjected to different deposition potentials of-1.5V, -1.6V, -1.7V, -1.8V, -1.9V, -2.0V, -2.1V, -2.2V (vs SCE) in the home-made solution, respectively5 minutes, the current densities were normalized to the geometric area of the RDE (0.196 cm)2)。
The synthesized Pt and the bimetallic alloy nano-particle material thereof are used for preparing a working electrode, and an electrochemical test is carried out after subsequent treatment.
Example 2
A method for preparing a Pt bimetallic catalyst by electrodeposition in an organic system, the preparation steps of the Pt-M metal alloy nanoparticle catalyst with high catalytic performance of this example are the same as those of example 1, except that:
A. weighing Pt source of chloroplatinic acid hexahydrate and M metal source of nickel acetylacetonate precursor salt according to a certain mass ratio by adopting an electronic balance, adding a supporting electrolyte of potassium perchlorate into a certain amount of organic solvent, and stirring and mixing DMF to prepare a 4mM chloroplatinic acid hexahydrate +4mM nickel acetylacetonate +0.1M potassium perchlorate solution system, and fully and uniformly stirring;
B. in an inert atmosphere N2Removing O2And ultrasonically treating for 5 minutes to disperse uniformly; the electrodes were mechanically polished with 0.5 μm, 0.3 μm, 0.05 μm alumina powder and then sonicated in water and ethanol for 30 seconds in that order prior to use.
Connected with an electrochemical experimental device. All electrodeposition was carried out in a standard three-electrode glass cell, 1cm of which2Platinum foil as counter electrode and saturated calomel electrode as reference electrode, calibrated to 0.312V before use, relative to 0.1MH2ClO4The Reversible Hydrogen Electrode (RHE) in (1).
The electrodes were subjected to different deposition potentials of-1.5V, -1.6V, -1.7V, -1.8V, -1.9V, -2.0V, -2.1V, -2.2V (vs SCE) for 5 minutes in the home-made solution, with current densities normalized to the geometric area of the RDE (0.196 cm)2)。
The synthesized Pt and the bimetallic alloy nano-particle material thereof are used for preparing a working electrode, and an electrochemical test is carried out after subsequent treatment.
Example 3
A method for preparing a Pt bimetallic catalyst by electrodeposition in an organic system, the preparation steps of the Pt-M metal alloy nanoparticle catalyst with high catalytic performance of this example are the same as those of example 1, except that:
A. weighing Pt source hexachloroplatinic acid and M metal source nickel acetylacetonate precursor salt according to a certain mass ratio by adopting an electronic balance, adding a supporting electrolyte of tetrabutylammonium chloride into a certain amount of organic solvent, and stirring and mixing DMF to prepare a 4mM hexachloroplatinic acid +4mM nickel acetylacetonate +0.1M tetrabutylammonium chloride solution system, and fully and uniformly stirring;
B. in an inert atmosphere N2Removing O2And ultrasonically treating for 5 minutes to disperse uniformly; the electrodes were mechanically polished with 0.5 μm, 0.3 μm, 0.05 μm alumina powder and then sonicated in water and ethanol for 30 seconds in that order prior to use.
Connected with an electrochemical experimental device. All electrodeposition was carried out in a standard three-electrode glass cell, 1cm of which2Platinum foil as counter electrode and saturated calomel electrode as reference electrode, calibrated to 0.312V before use, relative to 0.1MH2ClO4The Reversible Hydrogen Electrode (RHE) in (1).
The electrodes were subjected to different deposition potentials of-1.5V, -1.6V, -1.7V, -1.8V, -1.9V, -2.0V, -2.1V, -2.2V for 5 minutes in the home-made solution, with current densities normalized to the geometric area of the RDE (0.196 cm)2)。
The synthesized Pt and the bimetallic alloy nano-particle material thereof are used for preparing a working electrode, and an electrochemical test is carried out after subsequent treatment.
Example 4
A method for preparing a Pt bimetallic catalyst by electrodeposition in an organic system comprises the following steps:
A. weighing Pt source as hexachloroplatinic acid hexahydrate and M metal source as cobalt acetylacetonate precursor salt and tetrabutyl ammonium chloride as supporting electrolyte according to a certain mass ratio by adopting an electronic balance, adding the tetrabutyl ammonium chloride and the organic solvent DMF into a certain amount, stirring and mixing to prepare a 4mM hexachloroplatinic acid +4mM cobalt acetylacetonate +0.1M tetrabutyl ammonium chloride solution system, and fully and uniformly stirring;
B. in an inert atmosphere N2Removing O2And ultrasonically treating for 5 minutes to disperse uniformly; 0.5 mu for electrodem, 0.3 μm, 0.05 μm alumina powder was mechanically polished and then sonicated in water and ethanol for 30 seconds in sequence before use.
Connected with an electrochemical experimental device. All electrodeposition was carried out in a standard three-electrode glass cell, 1cm of which2Platinum foil as counter electrode and saturated calomel electrode as reference electrode, calibrated to 0.312V before use, relative to 0.1MH2ClO4The Reversible Hydrogen Electrode (RHE) in (1).
The electrodes were subjected to different deposition potentials of-1.5V, -1.6V, -1.7V, -1.8V, -1.9V, -2.0V, -2.1V, -2.2V (vs SCE) for 5 minutes in the home-made solution, with current densities normalized to the geometric area of the RDE (0.196 cm)2)。
The synthesized Pt and the bimetallic alloy nano-particle material thereof are used for preparing a working electrode, and an electrochemical test is carried out after subsequent treatment.
Example 5
A method for preparing a Pt bimetallic catalyst by electrodeposition in an organic system comprises the following steps:
A. weighing Pt source acetylacetone platinum and M metal source acetylacetone cobalt precursor salt according to a certain mass ratio by using an electronic balance, adding a supporting electrolyte which is potassium perchlorate into a certain amount of organic solvent DMF, stirring and mixing to prepare a 4mM acetylacetone platinum +4mM acetylacetone cobalt +0.1M potassium perchlorate solution system, and fully and uniformly stirring;
B. in an inert atmosphere N2Removing O2And ultrasonically treating for 05 minutes to disperse uniformly; the electrodes were mechanically polished with 0.5 μm, 0.3 μm, 0.05 μm alumina powder and then sonicated in water and ethanol for 30 seconds in that order prior to use.
Connected with an electrochemical experimental device. All electrodeposition was carried out in a standard three-electrode glass cell, 1cm of which2Platinum foil as counter electrode and saturated calomel electrode as reference electrode, calibrated to 0.312V before use, relative to 0.1MH2ClO4The Reversible Hydrogen Electrode (RHE) in (1).
The electrodes were subjected to different deposition potentials of-1.5V, -1.6V, -1.7V, -1.8V, -1.9V, -2.0V, -2.1V, -2.2V (vs SCE) in the home-made solution, respectively5 minutes, the current densities were normalized to the geometric area of the RDE (0.196 cm)2)。
The synthesized Pt and the bimetallic alloy nano-particle material thereof are used for preparing a working electrode, and an electrochemical test is carried out after subsequent treatment.
Example 6
A method for preparing a Pt bimetallic catalyst by electrodeposition in an organic system comprises the following steps:
A. weighing Pt source acetylacetone platinum and M metal source acetylacetone nickel precursor salt according to a certain mass ratio by using an electronic balance, adding a supporting electrolyte which is potassium perchlorate into a certain amount of organic solvent, stirring and mixing with DMF (dimethyl formamide) to prepare a 4mM acetylacetone platinum +4mM acetylacetone nickel +0.1M potassium perchlorate solution system, and fully and uniformly stirring;
B. in an inert atmosphere N2Removing O2And ultrasonically treating for 5 minutes to disperse uniformly; the electrodes were mechanically polished with 0.5 μm, 0.3 μm, 0.05 μm alumina powder and then sonicated in water and ethanol for 30 seconds in that order prior to use.
Connected with an electrochemical experimental device. All electrodeposition was carried out in a standard three-electrode glass cell, 1cm of which2Platinum foil as counter electrode and saturated calomel electrode as reference electrode, calibrated to 0.312V before use, relative to 0.1MH2ClO4The Reversible Hydrogen Electrode (RHE) in (1).
The electrodes were subjected to different deposition potentials of-1.5V, -1.6V, -1.7V, -1.8V, -1.9V, -2.0V, -2.1V, -2.2V (vs SCE) for 5 minutes in the home-made solution, with current densities normalized to the geometric area of the RDE (0.196 cm)2)。
The synthesized Pt and the bimetallic alloy nano-particle material thereof are used for preparing a working electrode, and an electrochemical test is carried out after subsequent treatment.
Example 7
A method for preparing a Pt bimetallic catalyst by electrodeposition in an organic system comprises the following steps:
A. weighing Pt source of platinum acetylacetonate and supporting electrolyte of potassium perchlorate according to a certain mass ratio by adopting an electronic balance, adding the Pt source of platinum acetylacetonate and the supporting electrolyte of potassium perchlorate into a certain amount of organic solvent, stirring and mixing the mixture, and fully and uniformly stirring the mixture;
B. in an inert atmosphere N2Removing O2And performing ultrasonic treatment for 0.5-5 minutes to disperse uniformly; the electrodes were mechanically polished with 0.5 μm, 0.3 μm, 0.05 μm alumina powder and then sonicated in water and ethanol for 30 seconds in that order prior to use.
Connected with an electrochemical experimental device. All electrodeposition was carried out in a standard three-electrode glass cell, 1cm of which2Platinum foil as counter electrode and saturated calomel electrode as reference electrode, calibrated to 0.312V before use, relative to 0.1MH2ClO4The Reversible Hydrogen Electrode (RHE) in (1).
The electrodes were subjected to different deposition potentials of-1.5V to-2.2V (vs SCE) for 5 minutes in the home-made solution, with current densities normalized to the geometric area of the RDE (0.196 cm)2)。
The synthesized Pt and the bimetallic alloy nano-particle material thereof are used for preparing a working electrode, and an electrochemical test is carried out after subsequent treatment.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes or modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention. The embodiments and features of the embodiments of the present application may be combined with each other arbitrarily without conflict.

Claims (10)

1. A method for preparing a Pt bimetallic catalyst by electrodeposition in an organic system is characterized by comprising the following steps:
A. adding a Pt source precursor, a second metal source precursor and a supporting electrolyte into an organic solvent to obtain an organic system electrodeposition liquid, and adding a molecular sieve into the organic system electrodeposition liquid;
B. under the protection of inert gas, connecting an electrochemical device, performing cyclic voltammetry electrochemical cleaning, and then performing electrochemical deposition on a catalyst conductive carrier under different potentials, wherein the catalyst conductive carrier is a carbon-based carrier.
2. The method for preparing Pt bimetallic catalyst by electrodeposition in organic system according to claim 1, wherein the step A specifically comprises the following steps: and ensuring that the Pt source precursor, the second metal source precursor, the supporting electrolyte and the organic solvent are mixed in an anhydrous oxygen-free glove box, wherein the concentrations of the Pt source precursor, the second metal source precursor and the supporting electrolyte are respectively 4mM, 4mM and 0.1M.
3. The method for preparing Pt bimetallic catalyst by electrodeposition in organic system according to claim 1, wherein the second metal of the second metal source precursor in the step A is a transition metal based on 3d, 4d, 5d structure, and comprises one or more of Fe, Co, Ni, Mn, Cu, Ag, Au, Ru, Y, La, Ce and Gd.
4. The method for preparing the Pt bimetallic catalyst through electrodeposition in an organic system according to claim 1, wherein the second metal source precursor in the step A comprises one or more of ferrous phosphate, ferric acetone acetate, cobalt acetone acetate, nickel acetone acetate, manganese acetone acetate, copper acetone acetate and silver acetone acetate.
5. The method for preparing Pt bimetallic catalyst by electrodeposition in organic system according to claim 1, wherein the supporting electrolyte in step A comprises NaClO4、LiClO4、KOH、KOCH3、NaOCH3、NH4Cl, quaternary ammonium salt, NaClO4、Mg(ClO4)2、LiCl、NaBF4Tetrafluoroammonium perchlorate, tetrabutylfluoroborate, NaNO3、R4NBF4、NaNO3、KClO4One or more of NaOAc, tetrabutylphosphonium chloride.
6. The method for preparing Pt bimetallic catalyst by electrodeposition in an organic system according to claim 1, wherein the organic solvent in the step A comprises one or more of dimethyl amide, dimethyl sulfoxide, dimethyl amide, methanol, benzyl alcohol, tetrahydrofuran, propylene carbonate, nitromethane and acetonitrile.
7. The method for preparing Pt bimetallic catalyst by electrodeposition in organic system according to claim 1, wherein the inert gas in step B comprises one or more of nitrogen and argon, and the inert gas protection comprises the following steps: introducing inert gas into the solution through a conduit for 0.5-3 h to reach gas saturation in the solution.
8. The method for preparing Pt bimetallic catalyst by electrodeposition in organic system according to claim 1, wherein the carbon-based carrier in step B comprises one or more of carbon black, graphitized carbon, graphite and activated carbon.
9. The method for preparing the Pt bimetallic catalyst through electrodeposition in an organic system according to claim 1, wherein the cyclic voltammetry electrochemical cleaning of the electrode in the step B is performed at a voltage of 0.3-0.85V; in the electrochemical deposition, the glassy carbon electrode is subjected to different deposition potentials of-1.5V to-2.2V; the scanning rate is 1-50 mV/s; the diameter of the surface of the glassy carbon electrode is 1 mm-20 mm.
10. Use of the electrodeposited Pt prepared in an organic system according to any one of claims 1 to 9 and its bimetallic catalyst in fuel cell redox.
CN202010567280.XA 2020-06-19 2020-06-19 Method for preparing Pt bimetallic catalyst by electrodeposition in organic system Pending CN111715218A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114784304A (en) * 2022-04-21 2022-07-22 佛山仙湖实验室 Bimetallic atom doped porous carbon material catalyst and preparation method and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1976101A (en) * 2006-12-13 2007-06-06 太原理工大学 Method for producing carbon-carrying platinum-based alloy electrode
CN110021758A (en) * 2019-03-04 2019-07-16 上海交通大学 The Pt-M metal alloy catalyst that in organic system prepared by electro-deposition

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1976101A (en) * 2006-12-13 2007-06-06 太原理工大学 Method for producing carbon-carrying platinum-based alloy electrode
CN110021758A (en) * 2019-03-04 2019-07-16 上海交通大学 The Pt-M metal alloy catalyst that in organic system prepared by electro-deposition

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
李凡: ""高活性Pt基催化剂电化学可控合成及其氧还原性能的研究"", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114784304A (en) * 2022-04-21 2022-07-22 佛山仙湖实验室 Bimetallic atom doped porous carbon material catalyst and preparation method and application thereof
CN114784304B (en) * 2022-04-21 2024-04-02 佛山仙湖实验室 Bimetallic atom doped porous carbon material catalyst and preparation method and application thereof

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Application publication date: 20200929