CN114843531B - Low-temperature heat treatment preparation method of nano step-shaped metal catalyst - Google Patents

Low-temperature heat treatment preparation method of nano step-shaped metal catalyst Download PDF

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CN114843531B
CN114843531B CN202210387422.3A CN202210387422A CN114843531B CN 114843531 B CN114843531 B CN 114843531B CN 202210387422 A CN202210387422 A CN 202210387422A CN 114843531 B CN114843531 B CN 114843531B
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based catalyst
catalyst
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shaped metal
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CN114843531A (en
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赵红
张勇
武梓云
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Dalian Jiaotong University
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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
    • H01M4/88—Processes of manufacture
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9041—Metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/921—Alloys or mixtures with metallic elements
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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Abstract

The invention relates to a preparation method of a nano step-shaped metal catalyst, and belongs to the technical field of nano catalysts. The preparation method of the nano step-shaped metal catalyst is characterized in that the nano step-shaped metal catalyst is synthesized by taking a metal-based catalyst as a raw material and adopting a low-temperature heat treatment process; the metal-based catalyst is one of an iron-based catalyst, a nickel-based catalyst, a cobalt-based catalyst, a copper-based catalyst, a platinum-based catalyst and a palladium-based catalyst. The nano step-shaped metal catalyst can obviously improve the catalytic performance of a low-temperature fuel cell.

Description

Low-temperature heat treatment preparation method of nano step-shaped metal catalyst
Technical Field
The invention belongs to the technical field of nano catalysts, and relates to a preparation method of a nano step-shaped metal catalyst.
Background
The fuel cell is an electrochemical device that combines hydrogen and oxygen into water using a catalyst to generate direct current, and has advantages of high energy conversion efficiency, environmental friendliness, and the like, and is considered as a new energy technology for solving energy crisis and carbon emission. With the search of footsteps by human beings to deep sea, polar region and other extremely cold regions, how to improve the low-temperature conversion efficiency of fuel cells is becoming a major problem facing the current situation. Increasing the number of the catalytic active centers and improving the catalytic activity of the active centers is a main idea of the design of the novel low-temperature catalyst at present. The research result shows that the high-index crystal face represented by the nano steps is the catalytic activity center of the catalyst. By utilizing the low-temperature reaction environment, a large number of nano metal catalysts with surface step structures can be controllably synthesized, the advantages of the surface effect and quantum size effect of the nano structures can be fully exerted, and the low-temperature conversion efficiency of the fuel cell can be remarkably improved.
Disclosure of Invention
Therefore, the invention provides a preparation method for controllably synthesizing an integrated nano step-shaped metal catalyst by utilizing a low-temperature heat treatment process, which can obviously improve the low-temperature catalytic performance of a fuel cell. In order to achieve the above purpose, the present invention adopts the following technical scheme:
a preparation method of nano step-shaped metal catalyst, which takes metal-based catalyst as raw material and synthesizes nano step-shaped metal catalyst by adopting low temperature heat treatment process; the metal-based catalyst is one of an iron-based catalyst, a nickel-based catalyst, a cobalt-based catalyst, a copper-based catalyst, a platinum-based catalyst and a palladium-based catalyst.
The preparation method of the nano step-shaped metal catalyst specifically comprises the following steps:
1) Grinding and polishing the metal-based catalyst, then placing the metal-based catalyst into a tubular furnace protected by inert gas, and heating and preserving heat;
2) The metal-based catalyst obtained in the step 1) is placed in a coolant for cooling, and a low-temperature heat treatment process is adopted to synthesize the nano step-shaped metal catalyst
Further, the temperature of the low-temperature heat treatment process is-200 ℃ to 0 ℃.
Further, the heating temperature in the step 1) is 700-900 ℃, the heat preservation time is 20-60 minutes, and the inert gas is one of argon and nitrogen.
Further, the coolant in the step 2) is one of liquid nitrogen, an ice-water mixture and ethanol.
Further, the cooling time is 3 to 5 minutes.
The invention provides the nano step-shaped metal catalyst prepared by the method.
Heating at 400-900 deg.c, and cooling in 0-5 deg.c ice-water mixture to prepare nanometer stepped iron-base catalyst;
heating at 400-900 deg.c, and cooling in ice-water mixture at 0-5 deg.c to prepare stepped nanometer copper-base catalyst;
heating at 400-900 deg.c, and cooling in ice-water mixture at 0-5 deg.c to prepare nanometer stepped platinum-base catalyst;
compared with the prior art, the invention has the following technical advantages:
1) The nano step catalysis synthesized at low temperature shows higher catalytic activity, and the highest specific activity is 0.30mA/cm 2 ；
2) The integrated nano metal catalyst prepared by combining the nano step active center and the bulk metal has better catalytic stability.
Drawings
FIG. 1 is a photograph of a microstructure of a nano-stepped iron-based catalyst by scanning electron microscopy
FIG. 2 is a photograph of a microstructure of a nano-step copper-based catalyst observed by a scanning electron microscope
FIG. 3 is a photograph of a microstructure of a nano-step platinum-based catalyst by scanning electron microscopy
FIG. 4 is a graph showing the specific activity test of a nano-stepped iron-based catalyst
FIG. 5 is a graph showing the specific activity test of a nano-step copper-based catalyst
FIG. 6 is a graph showing the specific activity test of a nano-step platinum-based catalyst
FIG. 7 is a graph of current versus time for a nano-stepped iron-based catalyst
FIG. 8 is a graph of current versus time test for a nano-stepped copper-based catalyst
FIG. 9 is a graph of current versus time test for a nano-stepped platinum-based catalyst
Detailed Description
The treatment process according to the invention is further described below with reference to specific examples.
Example 1
(1) Smelting iron-nickel alloy (80% Fe-20% Ni) at 1580 ℃ by adopting an electric arc furnace, performing wire cutting to obtain iron-based bulk catalyst with the size of 20 multiplied by 30mm < 3 >, polishing the bulk iron-based catalyst by using 600-800 # abrasive paper, and polishing on a polishing machine until no scratch exists;
(2) Putting the massive iron-based catalyst into a tubular furnace protected by argon, heating to 700-900 ℃, and preserving heat for 40-60 minutes;
(3) Rapidly placing the blocky iron-based catalyst in an ice-water mixture and cooling for 3-5 minutes to obtain a nano step-shaped iron-based catalyst;
(4) Electrochemical performance of the nano stepped iron-based catalyst was tested using an electrochemical workstation.
Fig. 1 is a photograph of a scanning electron microscope microstructure of the nano stepped iron-based catalyst prepared in this example. As shown in FIG. 4, the specific activity of the 273K low-temperature synthesized nano stepped iron-based catalyst is 0.21mA/cm < 2 >, which is obviously higher than that of the 343K high-temperature synthesized iron-based catalyst by 0.15mA/cm < 2 >; as shown in the current-time curve of fig. 7, the current density of the 273K low-temperature synthesized nano stepped iron-based catalyst is 9.1mA/cm2, which is higher than that of the 343K high-temperature synthesized iron-based catalyst by 8.2mA/cm2, so that the catalytic stability of the low-temperature synthesized catalyst is also higher than that of the 343K high-temperature synthesized iron-based catalyst.
Example 2
(1) Smelting copper-zinc alloy (95% Cu-5% Zn) at 980 ℃ by adopting an electric arc furnace, performing wire cutting to obtain a copper-based block catalyst with the thickness of 20 multiplied by 30mm < 3 >, polishing the block copper-based catalyst by using 600-800 # abrasive paper, and polishing on a polishing machine until no scratch exists;
(2) Putting the massive copper-based catalyst into a tubular furnace protected by argon, heating to 400-600 ℃, and preserving heat for 20-30 minutes;
(3) Rapidly placing the blocky copper-based catalyst in an ice-water mixture and cooling for 3-5 minutes to obtain a nano step-shaped copper-based catalyst;
(4) Electrochemical performance of the nano stepped copper-based catalyst was tested using an electrochemical workstation.
Fig. 2 is a photograph of a scanning electron microscope microstructure of the nano step copper-based catalyst prepared in this example. As shown in FIG. 5, the specific activity of the 273K low-temperature synthesized nano step-shaped copper-based catalyst is 0.30mA/cm < 2 >, which is obviously higher than that of the 343K high-temperature synthesized copper-based catalyst by 0.17mA/cm < 2 >; as shown in the current-time curve of fig. 8, the current density of the 273K low-temperature synthesized nano stepped copper-based catalyst is 8.6mA/cm2, which is higher than that of the 343K high-temperature synthesized copper-based catalyst by 6.5mA/cm2, so that the catalytic stability of the low-temperature synthesized catalyst is also higher than that of the 343K high-temperature synthesized copper-based catalyst.
Example 3
(1) Smelting platinum-iron-nickel alloy (50% Pt-30% Fe-20% Ni) at 1960 ℃ by adopting an electric arc furnace, performing wire cutting to obtain a platinum-based block catalyst with the diameter of 20 multiplied by 30mm < 3 >, polishing the block platinum-based catalyst by using 600-800 # abrasive paper, and polishing on a polishing machine until no scratch exists;
(2) Putting the massive iron-based catalyst into a tubular furnace protected by argon, heating to 700-900 ℃, and preserving heat for 40-60 minutes;
(3) Rapidly placing the blocky iron-based catalyst in an ice-water mixture and cooling for 3-5 minutes to obtain a nano step-shaped platinum-based catalyst;
(4) Electrochemical performance of the nano stepped platinum based catalyst was tested using an electrochemical workstation.
Fig. 3 is a photograph of a scanning electron microscope microstructure of the nano step-shaped platinum-based catalyst prepared in this example. As shown in FIG. 6, the specific activity of the 273K low-temperature synthesized nano-step platinum-based catalyst was 0.25mA/cm 2 0.18mA/cm significantly higher than that of the 343K high-temperature synthesized platinum-based catalyst 2 The method comprises the steps of carrying out a first treatment on the surface of the As shown in FIG. 9, the current density of the 273K low-temperature synthesized nano-step platinum-based catalyst was 8.1mA/cm 2 7.1mA/cm higher than 343K high-temperature synthetic platinum-based catalyst 2 Therefore, the catalytic stability of the catalyst synthesized at low temperature is higher than that of a platinum-based catalyst synthesized at 343K high temperature.
Many possible variations and modifications of the disclosed technology can be made by anyone skilled in the art without departing from the scope of the technology, or the technology can be modified to be equivalent. Therefore, any simple modification, equivalent variation and modification of the above embodiments according to the technical substance of the present invention shall still fall within the scope of the technical solution of the present invention.

Claims (2)

1. The preparation method of the nano step-shaped metal catalyst is characterized by taking a metal-based catalyst as a raw material, wherein the metal-based catalyst is one of an iron-based catalyst, a nickel-based catalyst, a cobalt-based catalyst, a copper-based catalyst, a platinum-based catalyst and a palladium-based catalyst;
the preparation method specifically comprises the following steps:
1) Grinding and polishing the metal-based catalyst, then placing the catalyst into a tube furnace protected by inert atmosphere, and heating and preserving heat;
2) Cooling the metal-based catalyst obtained in the step 1) in a coolant to obtain a nano step-shaped metal catalyst;
the heating temperature in the step 1) is 700-900 ℃, the heat preservation time is 20-60 minutes, and the inert atmosphere is one of argon and nitrogen;
and 2) the coolant is an ice-water mixture, and the cooling time is 3-5 minutes.
2. The nano-step metal catalyst obtained by the preparation method of claim 1.
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Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4320030A (en) * 1980-03-21 1982-03-16 Gas Research Institute Process for making high activity transition metal catalysts
JPS5822364A (en) * 1981-07-29 1983-02-09 Hitachi Ltd Preparation of zirconium base alloy
CN101633975A (en) * 2009-05-21 2010-01-27 瑞科稀土冶金及功能材料国家工程研究中心有限公司 Heat treatment method of RE-Fe-B part hydrogen storage alloy
DE102013221935A1 (en) * 2013-04-11 2014-10-16 Hyundai Motor Company Titanium suboxide carrier materials for a catalyst electrode of a fuel cell and synthesis of the titanium suboxide at low temperatures
CN106086574A (en) * 2016-07-29 2016-11-09 柳州豪祥特科技有限公司 A kind of method preparing Hardmetal materials
CN109590478A (en) * 2018-12-07 2019-04-09 天津大学 The method of iridium nano particle of the ps pulsed laser and ns pulsed laser ablation synthesis rich in atomic steps is utilized in liquid phase
CN112672974A (en) * 2018-07-31 2021-04-16 西北大学 Tetragon nanoparticles
CN113881887A (en) * 2021-10-27 2022-01-04 昆明理工大学 Preparation method of low-melting-point alloy phase change material
CN113937310A (en) * 2021-09-08 2022-01-14 佛山仙湖实验室 Platinum-based catalyst and preparation method and application thereof
CN114094130A (en) * 2021-11-30 2022-02-25 郑州大学 Preparation method of fuel cell platinum alloy catalyst
CN114259959A (en) * 2021-12-21 2022-04-01 大连交通大学 Low-temperature deposition preparation method of two-dimensional nano material

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4320030A (en) * 1980-03-21 1982-03-16 Gas Research Institute Process for making high activity transition metal catalysts
JPS5822364A (en) * 1981-07-29 1983-02-09 Hitachi Ltd Preparation of zirconium base alloy
CN101633975A (en) * 2009-05-21 2010-01-27 瑞科稀土冶金及功能材料国家工程研究中心有限公司 Heat treatment method of RE-Fe-B part hydrogen storage alloy
DE102013221935A1 (en) * 2013-04-11 2014-10-16 Hyundai Motor Company Titanium suboxide carrier materials for a catalyst electrode of a fuel cell and synthesis of the titanium suboxide at low temperatures
CN106086574A (en) * 2016-07-29 2016-11-09 柳州豪祥特科技有限公司 A kind of method preparing Hardmetal materials
CN112672974A (en) * 2018-07-31 2021-04-16 西北大学 Tetragon nanoparticles
CN109590478A (en) * 2018-12-07 2019-04-09 天津大学 The method of iridium nano particle of the ps pulsed laser and ns pulsed laser ablation synthesis rich in atomic steps is utilized in liquid phase
CN113937310A (en) * 2021-09-08 2022-01-14 佛山仙湖实验室 Platinum-based catalyst and preparation method and application thereof
CN113881887A (en) * 2021-10-27 2022-01-04 昆明理工大学 Preparation method of low-melting-point alloy phase change material
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CN114259959A (en) * 2021-12-21 2022-04-01 大连交通大学 Low-temperature deposition preparation method of two-dimensional nano material

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