CN107910566A - A kind of ternary core-shell structure nano elctro-catalyst and preparation method - Google Patents

A kind of ternary core-shell structure nano elctro-catalyst and preparation method Download PDF

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CN107910566A
CN107910566A CN201711107858.8A CN201711107858A CN107910566A CN 107910566 A CN107910566 A CN 107910566A CN 201711107858 A CN201711107858 A CN 201711107858A CN 107910566 A CN107910566 A CN 107910566A
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shell structure
catalyst
ternary core
preparation
core
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CN107910566B (en
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张丽娟
付予
张伶潇
郭雨萌
梁菊梅
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Beijing University of Technology
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Beijing University of Technology
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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
    • 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
    • H01M4/928—Unsupported catalytic particles; loose particulate catalytic materials, e.g. in fluidised state
    • 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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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Nanotechnology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • General Chemical & Material Sciences (AREA)
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  • Condensed Matter Physics & Semiconductors (AREA)
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Abstract

A kind of ternary core-shell structure nano elctro-catalyst and preparation method, belong to chemical energy source technical field.Process includes：(1) a certain amount of metal precursor is added in deionized water, adds octadecylamine, stirred 12h, obtain uniform mixed liquor；(2) the uniform mixed liquor of gained is put into ptfe autoclave, obtains black mixture solution；(3) by mixture solution centrifuge washing, it is dried at room temperature for obtaining mix powder.It is different using the sequencing being reduced using different metal, the nucleocapsid mechanism nanometer electrical catalyst of inside and outside respectively different metal can be formed.So as to improve the mass activity of ternary core-shell mechanism elctro-catalyst and area activated by non-noble metal dissolution and Kinkendal Effect, its stability and redox property are improved.Because the invention is capable of providing a kind of excellent ternary core-shell structure nano elctro-catalyst of redox property, there is very big industry and commercial value.

Description

A kind of ternary core-shell structure nano elctro-catalyst and preparation method
Technical field
The invention belongs to chemical energy source technical field, more particularly to a kind of ternary core-shell structure nano electrocatalyst materials and Preparation method.
Background technology
In the past few decades, due to platinum scarcity of resources, expensive, catalyst is easily poisoned, and cathodic oxygen reduction moves Mechanics is slow, and Proton Exchange Fuel film battery never obtains extensive commercial applications.At present, researcher generally takes Two methods solve the problems, such as these：1. transition metal is introduced in platinum catalyst to adjust the spacing of pt atom and change platinum week The electronic environment enclosed, so as to produce the geometric effect and electronic effect of uniqueness, improves the catalytic activity of elctro-catalyst.It is 2. platinum is former Son is placed in the surface of catalyst, so as to reduce the usage amount of Pt.In actual life, we can combine two methods Synthesis of ternary nuclear shell structure nano elctro-catalyst together.
Therefore, the present invention proposes one kind under conditions of any surfactant is not added with, and passes through a step coreduction hydro-thermal For method synthesis one kind using Pt as core, the alloy of other metals and Pt are the ternary core-shell structure nano elctro-catalyst of shell.This method is closed It is easy to operate into mild condition, not yet see document report.
The content of the invention
The technical problem to be solved in the present invention is：There is provided that a kind of synthesis condition is gentle, ternary core-shell structure easy to operate Nano electro-catalytic material, the redox active and excellent in stability of the material.
A kind of ternary core-shell structure nano elctro-catalyst preparation method, it is characterised in that comprise the following steps：
(1) sulfate or chloride of the sulfate of Pt or chloride and other metals are dissolved in ethanol or water, Dispersion liquid is ultrasonically formed at room temperature, any two kinds in copper, gold, cobalt or nickel of other metals；
(2) reducing agent is added in dispersion liquid described in step (1), the amount of the material of reducing agent is Pt elements and other gold Belong to 1-3 times of the amount of element total material, stir at room temperature；
(3) mixture in step (2) is put into ptfe autoclave, will be put into the reaction kettle for having mixture The regular hour is reacted under air dry oven high temperature；
(4) black mixture obtained after step (3) is reacted, is centrifuged, is washed, is dry, obtaining ternary core-shell knot Structure nanometer electrical catalyst；
Above-mentioned preparation method is illustrated below：
In step (1) of the present invention, the reduction potential of three kinds of different metals has difference, and the molar ratio of three kinds of different metals is Any ratio.
In step (2) of the present invention, reducing agent is octadecylamine, and it is 12h that the time, which is stirred at room temperature, to ensure that octadecylamine divides completely Solution.
In step (3) of the present invention, reaction temperature is 160~180 DEG C, and the reaction time is 48~78h.
In step (4) of the present invention, when washing, solution used was n-hexane and the mixed liquor of ethanol.
Ternary core-shell structure nano elctro-catalyst is used as fuel cell oxygen reduction catalyst.
A kind of using Pt as core it is an object of the invention to what is obtained, the alloy of other metals and Pt are received for the core shell structure of shell Rice elctro-catalyst, it is an object of the invention to provide a kind of simple, controllable preparation method, is prepared with excellent electrochemical The ternary core-shell structure nano elctro-catalyst of energy.
The present invention has the advantage that compared with prior art：
(1) support type ternary platinum alloy catalysts of the present invention are using coreduction hydro-thermal method, the synthetic method Technique is simple, mild condition, easy to operate, and reaction process is without using any surfactant；And synthesized by this method Material is reproducible.
(2) the of the invention ternary core-shell structure nano catalyst degradation usage amount of platinum, and be circulated throughout in electrochemistry Cheng Zhong, there occurs " changing core " process, improves platinum utilization, so as to be effectively improved the hydrogen reduction performance of catalyst.
Brief description of the drawings
Fig. 1 is the transmission electron microscope photo for the Pt@PtAuCu ternary core-shell structures that embodiment 1 obtains；
Fig. 2 is the Pt@PtAuCu ternary core-shells structures that embodiment 1 obtains and the X-ray diffractogram of comparative example 1PtCu；
The Pt@PtAuCu ternary core-shells structures and business carbon supported platinum catalyst that Fig. 3 is embodiment 1-3, comparative example 1 obtains Hydrogen reduction performance map.
The present invention is further illustrated with reference to specific embodiment and comparative example, but the present invention is not limited to following Embodiment.
Embodiment 1
Weigh 40mgHAuCl4, 50mg H2PtCl4With 17mg CuCl2·2H2O, adds the dissolving of 26ml water.Then add The reducing agent octadecylamine of 0.194g, stirs 12h at room temperature.Gained mixture solution is put into ptfe autoclave, 63h is reacted at 160 DEG C in air dry oven, obtains black mixture solution.By black mixture solution n-hexane and ethanol Mixture centrifuged, wash.Finally it is dried at room temperature for.
Comparative example 1
Weigh 50mg H2PtCl4With 17mg CuCl2·2H2O, adds the dissolving of 26ml water.Then the reduction of 0.194g is added Agent octadecylamine, stirs 12h at room temperature.Gained mixture solution is put into ptfe autoclave, in forced air drying is dry 63h is reacted at 160 DEG C, obtains black mixture solution.Black mixture solution is carried out with the mixture of n-hexane and ethanol Centrifugation, washing.Finally it is dried at room temperature for.
Embodiment 2
Weigh 40mgHAuCl4, 50mg H2PtCl4With 49.7mg CuCl2·2H2O, adds the dissolving of 26ml water.Then add The reducing agent octadecylamine of 0.194g, stirs 12h at room temperature.Gained mixture solution is put into ptfe autoclave, 63h is reacted at 160 DEG C in air dry oven, obtains black mixture solution.By black mixture solution n-hexane and ethanol Mixture centrifuged, wash.Finally it is dried at room temperature for.
Embodiment 3
Weigh 40mgHAuCl4, 50mg H2PtCl4With 98.3mg CuCl2·2H2O, adds the dissolving of 26ml water.Then add The reducing agent octadecylamine of 0.194g, stirs 12h at room temperature.Gained mixture solution is put into ptfe autoclave, 63h is reacted at 160 DEG C in air dry oven, obtains black mixture solution.By black mixture solution n-hexane and ethanol Mixture centrifuged, wash.Finally it is dried at room temperature for.
Fig. 1 is the transmission electron microscope picture of Pt@PtAuCu ternary core-shell structures.As shown in Figure 1, ternary obtained by the present embodiment 1 Nuclear shell structure nano catalyst Monodispersed is uniform.
Fig. 2 is embodiment 1Pt@PtAuCu ternary core-shells structures and the XRD diagram of comparative example 1PtCu.It can be seen from the figure that The PtCu peaks of the catalyst of embodiment 1, significantly as low angle movement, illustrate in PtCu systems relative to the peak of PtCu alloys The larger Au of atomic radius is introduced, Pt-Cu spacings of lattice can be caused to become larger, is conducive to improve the catalytic activity of Pt@PtAuCu..
Fig. 3 is embodiment 1Pt@PtAuCu ternary core-shell structure nanos elctro-catalyst, embodiment 2, embodiment 3 and business carbon The hydrogen reduction performance map of platinum catalyst.It can be found that Pt@PtAuCu ternarys (1 from figure:1:1) core-shell nano elctro-catalyst With most excellent hydrogen reduction performance.

Claims (8)

1. a kind of preparation method of the nano electro-catalytic agent material of ternary core-shell structure, it is characterised in that comprise the following steps：
(1) sulfate or chloride of the sulfate of Pt or chloride and other metals are dissolved in ethanol or water, in room Dispersion liquid is ultrasonically formed under temperature, any two kinds in copper, gold, cobalt or nickel of other metals；
(2) reducing agent is added in dispersion liquid described in step (1), the amount of the material of reducing agent is Pt elements and other metals member 1-3 times of the amount of plain total material, is stirred at room temperature；
(3) mixture in step (2) is put into ptfe autoclave, air blast will be put into the reaction kettle for having mixture The regular hour is reacted under drying box high temperature；
(4) black mixture obtained after step (3) is reacted, is centrifuged, is washed, is dry, obtained ternary core-shell structure and receive Rice elctro-catalyst.
2. a kind of preparation method of the nano electro-catalytic agent material of ternary core-shell structure described in accordance with the claim 1, its feature It is, the reduction potential of three kinds of different metals has difference.
3. a kind of preparation method of the nano electro-catalytic agent material of ternary core-shell structure described in accordance with the claim 1, its feature It is, in (2), reducing agent is octadecylamine, and it is 12h that the time, which is stirred at room temperature, to ensure that octadecylamine decomposes completely.
4. a kind of preparation method of the nano electro-catalytic agent material of ternary core-shell structure described in accordance with the claim 1, its feature It is, in (3), reaction temperature is 160~180 DEG C, and the reaction time is 48~78h.
5. a kind of preparation method of the nano electro-catalytic agent material of ternary core-shell structure described in accordance with the claim 1, its feature It is, when washing, solution used was n-hexane and the mixed liquor of ethanol.
6. the nanometer electrical catalyst material of the ternary core-shell structure obtained according to claim 1-5 any one of them preparation methods Material.
7. the nanometer electrical catalyst material of the ternary core-shell structure obtained according to claim 1-5 any one of them preparation methods Material, it is characterised in that Pt is core, the alloy of other metals and Pt are the nuclear shell structure nano elctro-catalyst of shell.
8. the nano electro-catalytic agent material of the ternary core-shell structure obtained according to claim 1-5 any one of them preparation methods It must apply, it is characterised in that make the application of fuel cell oxygen reduction catalyst.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113206264A (en) * 2021-04-23 2021-08-03 华中科技大学 Platinum-based intermetallic nanocrystalline with ordered structure and medium and low temperature preparation and application thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101359744A (en) * 2008-09-08 2009-02-04 重庆大学 Method for carbon supported ultra-low platinum catalytic electrode preparation by indirect galvanic deposit
CN101379639A (en) * 2005-08-01 2009-03-04 布鲁克哈文科学协会 Electrocatalysts having gold monolayers on platinum nanoparticle cores, and uses thereof
US20150093682A1 (en) * 2012-05-15 2015-04-02 Toyota Jidosha Kabushiki Kaisha Method for producing catalyst for fuel cells, and fuel cell containing catalyst for fuel cells produced by the production method
CN105762378A (en) * 2016-03-14 2016-07-13 北京工业大学 Method for synthesizing supported ternary platinum alloy catalyst
CN105895931A (en) * 2016-06-29 2016-08-24 王尧尧 Pt/PdNi/CNT-MnO2 methanol fuel cell catalyst and application

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101379639A (en) * 2005-08-01 2009-03-04 布鲁克哈文科学协会 Electrocatalysts having gold monolayers on platinum nanoparticle cores, and uses thereof
CN101359744A (en) * 2008-09-08 2009-02-04 重庆大学 Method for carbon supported ultra-low platinum catalytic electrode preparation by indirect galvanic deposit
US20150093682A1 (en) * 2012-05-15 2015-04-02 Toyota Jidosha Kabushiki Kaisha Method for producing catalyst for fuel cells, and fuel cell containing catalyst for fuel cells produced by the production method
CN105762378A (en) * 2016-03-14 2016-07-13 北京工业大学 Method for synthesizing supported ternary platinum alloy catalyst
CN105895931A (en) * 2016-06-29 2016-08-24 王尧尧 Pt/PdNi/CNT-MnO2 methanol fuel cell catalyst and application

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113206264A (en) * 2021-04-23 2021-08-03 华中科技大学 Platinum-based intermetallic nanocrystalline with ordered structure and medium and low temperature preparation and application thereof
CN113206264B (en) * 2021-04-23 2022-04-12 华中科技大学 Platinum-based intermetallic nanocrystalline with ordered structure and medium and low temperature preparation and application thereof

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