CN114843531A - 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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CN114843531A
CN114843531A CN202210387422.3A CN202210387422A CN114843531A CN 114843531 A CN114843531 A CN 114843531A CN 202210387422 A CN202210387422 A CN 202210387422A CN 114843531 A CN114843531 A CN 114843531A
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based catalyst
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catalyst
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metal
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CN114843531B (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
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    • 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, belonging to the technical field of nano catalysts. A preparation method of a nanometer step-shaped metal catalyst is characterized in that a metal-based catalyst is used as a raw material, and a low-temperature heat treatment process is adopted to synthesize the nanometer step-shaped metal catalyst; 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 provided by the invention 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
A fuel cell is an electrochemical device that combines hydrogen and oxygen into water using a catalyst to generate direct current, has the 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 emissions. With the progress of human exploration towards extremely cold regions such as deep sea, polar region and the like, how to improve the low-temperature conversion efficiency of the fuel cell is becoming a major problem facing the present. Increasing the number of catalytic activity centers and improving the catalytic activity of the catalytic activity centers are the main ideas of the design of the current novel low-temperature catalyst. Research results show that the high-index crystal face represented by the nanometer step is the catalytic active center of the catalyst. The nano metal catalyst with a large number of surface step structures can be controllably synthesized by utilizing a low-temperature reaction environment, so that the advantages of the surface effect and the quantum size effect of the nano structure can be fully exerted, and the low-temperature conversion efficiency of the fuel cell can be obviously improved.
Disclosure of Invention
Therefore, the invention provides a preparation method for controllably synthesizing the integrated nano step-shaped metal catalyst by utilizing a low-temperature heat treatment process, which obviously improves the low-temperature catalytic performance of the fuel cell. In order to realize the purpose, the invention adopts the following technical scheme:
a preparation method of a nanometer step-shaped metal catalyst takes a metal-based catalyst as a raw material, and adopts a low-temperature heat treatment process to synthesize the nanometer step-shaped metal catalyst; 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.
A preparation method of a nano step-shaped metal catalyst specifically comprises the following steps:
1) polishing a metal-based catalyst, putting the polished metal-based catalyst into a tubular furnace protected by inert gas, and heating and preserving heat;
2) cooling the metal-based catalyst obtained in the step 1) in a coolant, and synthesizing the nano step-shaped metal catalyst by adopting a low-temperature heat treatment process
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, ice-water mixture and ethanol.
Further, the cooling time is 3-5 minutes.
The invention provides a nano step-shaped metal catalyst prepared by the method.
Heating at a high temperature of 400-900 ℃, and then cooling in an ice-water mixture at a low temperature of 0-5 ℃ to prepare a nano step-shaped iron-based catalyst;
heating at a high temperature of 400-900 ℃, and then cooling in an ice-water mixture at a low temperature of 0-5 ℃ to prepare the nano step-shaped copper-based catalyst;
heating at a high temperature of 400-900 ℃, and then cooling at a low temperature in an ice-water mixture at a temperature of 0-5 ℃ to prepare a nano step-shaped platinum-based 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 shows better catalytic stability.
Drawings
FIG. 1 is a scanning electron microscopic microstructure observation photograph of nano step-shaped iron-based catalyst
FIG. 2 is a scanning electron microscopic microstructure observation picture of the nano-step copper-based catalyst
FIG. 3 is a scanning electron microscopic microstructure observation photograph of nano step-shaped platinum-based catalyst
FIG. 4 is a specific activity test pattern of the nano step-shaped iron-based catalyst
FIG. 5 is a test spectrum of specific activity of nano-step copper-based catalyst
FIG. 6 is a graph showing the specific activity of the nano stepped platinum-based catalyst
FIG. 7 is a current-time test curve of a nano step-shaped iron-based catalyst
FIG. 8 is a current-time test curve of a nano-step copper-based catalyst
FIG. 9 is a current-time test curve of a nano stepped platinum-based catalyst
Detailed Description
The treatment process of the present invention is further illustrated 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, carrying out linear cutting to obtain a 20X 30mm3 iron-based bulk catalyst, grinding the bulk iron-based catalyst by using No. 600-800 abrasive paper, and polishing the bulk iron-based catalyst on a polishing machine until no scratch is formed;
(2) putting the blocky 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 massive iron-based catalyst in an ice water mixture for cooling for 3-5 minutes to obtain a nano step-shaped iron-based catalyst;
(4) and (3) testing the electrochemical performance of the nano step-shaped iron-based catalyst by adopting an electrochemical workstation.
Fig. 1 is a scanning electron microscopic microstructure observation photograph of the nano step-shaped iron-based catalyst prepared in the present example. As shown in FIG. 4, the specific activity of the 273K low-temperature synthesized nano-step-shaped iron-based catalyst is 0.21mA/cm2, which is significantly higher than that of the 343K high-temperature synthesized iron-based catalyst, namely 0.15mA/cm 2; as shown in the current-time curve of FIG. 7, the current density of the 273K low-temperature synthesized nano-step-shaped iron-based catalyst is 9.1mA/cm2, which is higher than 8.2mA/cm2 of the 343K high-temperature synthesized iron-based catalyst, 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 a copper-zinc alloy (95% Cu-5% Zn) at 980 ℃ by adopting an electric arc furnace, carrying out linear cutting to obtain a copper-based bulk catalyst with the thickness of 20 multiplied by 30mm3, grinding the bulk copper-based catalyst by using No. 600-800 abrasive paper, and polishing the bulk copper-based catalyst on a polishing machine until no scratch is formed;
(2) putting the blocky copper-based catalyst into a tubular furnace protected by argon, heating to 400-600 ℃, and preserving heat for 20-30 minutes;
(3) quickly placing the blocky copper-based catalyst in an ice water mixture for cooling for 3-5 minutes to obtain a nano step-shaped copper-based catalyst;
(4) and testing the electrochemical performance of the nano stepped copper-based catalyst by using an electrochemical workstation.
FIG. 2 is a scanning electron microscopic observation photograph of the nano-step-shaped copper-based catalyst prepared in this example. As shown in FIG. 5, the specific activity of the 273K low temperature synthesized nano-step copper-based catalyst is 0.30mA/cm2, which is significantly higher than that of 343K high temperature synthesized copper-based catalyst 0.17mA/cm 2; as shown in the current-time curve of FIG. 8, the current density of the 273K low-temperature synthesized nano-step-shaped copper-based catalyst is 8.6mA/cm2, which is higher than 6.5mA/cm2 of the 343K high-temperature synthesized copper-based catalyst, 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 a platinum-iron-nickel alloy (50% of Pt-30% of Fe-20% of Ni) at 1960 ℃ by adopting an electric arc furnace, carrying out linear cutting to obtain a platinum-based bulk catalyst with the thickness of 20 multiplied by 30mm3, grinding the bulk platinum-based catalyst by using No. 600-800 abrasive paper, and polishing on a polishing machine until no scratch is formed;
(2) putting the blocky iron-based catalyst into a tubular furnace protected by argon, heating to 700-900 ℃, and preserving heat for 40-60 minutes;
(3) quickly placing the massive iron-based catalyst in an ice water mixture for cooling for 3-5 minutes to obtain a nano step-shaped platinum-based catalyst;
(4) and testing the electrochemical performance of the nano stepped platinum-based catalyst by using an electrochemical workstation.
Fig. 3 is a scanning electron microscopic microstructure observation photograph of the nano stepped platinum-based catalyst prepared in this example. As shown in FIG. 6, the specific activity of the 273K low-temperature synthesized nano stepped platinum-based catalyst was 0.25mA/cm 2 Obviously higher than 343K high-temperature synthesized platinum-based catalyst 0.18mA/cm 2 (ii) a As shown in FIG. 9, the current density of 273K low-temperature synthesized nano stepped platinum-based catalyst was 8.1mA/cm 2 7.1mA/cm of high-temperature synthesis platinum-based catalyst higher than 343K 2 Therefore, the catalytic stability of the catalyst synthesized at low temperature is higher than that of the platinum-based catalyst synthesized at high temperature of 343K.
It will be apparent to those skilled in the art that many changes and modifications can be made, or equivalents employed, to the presently disclosed embodiments without departing from the intended scope of the invention. Therefore, any simple modification, equivalent change and modification made to the above embodiments according to the technical essence of the present invention shall still fall within the protection scope of the technical solution of the present invention, unless the contents of the technical solution of the present invention are departed.

Claims (7)

1. A preparation method of a nanometer step-shaped metal catalyst is characterized in that a metal-based catalyst is used as a raw material, and a low-temperature heat treatment process is adopted to synthesize the nanometer step-shaped metal catalyst; 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.
2. The preparation method of the nano stepped metal catalyst according to claim 1, characterized by specifically comprising the steps of:
1) polishing a metal-based catalyst, putting the polished metal-based catalyst into a tubular furnace protected by inert gas, and heating and preserving heat;
2) cooling the metal-based catalyst obtained in the step 1) in a coolant, and synthesizing the nano step-shaped metal catalyst by adopting a low-temperature heat treatment process.
3. The method for preparing a nano stepped metal catalyst according to claim 1, wherein the temperature of the low temperature heat treatment process is-200 ℃ to 0 ℃.
4. The preparation method of the nano stepped metal catalyst according to claim 2, wherein 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.
5. The method for preparing a nano step-shaped metal catalyst according to claim 2, wherein the coolant in the step 2) is one of liquid nitrogen, ice-water mixture and ethanol.
6. The method for preparing the nano stepped metal catalyst according to claim 2, wherein the cooling time is 3-5 minutes.
7. A nano-stepped metal catalyst prepared by the method of any one of claims 1 to 6.
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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
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

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