CN117276566A - Preparation method of Pt-Ce-Zr alloy hydrogen fuel cell catalyst - Google Patents

Preparation method of Pt-Ce-Zr alloy hydrogen fuel cell catalyst Download PDF

Info

Publication number
CN117276566A
CN117276566A CN202311098144.0A CN202311098144A CN117276566A CN 117276566 A CN117276566 A CN 117276566A CN 202311098144 A CN202311098144 A CN 202311098144A CN 117276566 A CN117276566 A CN 117276566A
Authority
CN
China
Prior art keywords
source
deoxidizing
product
platinum
cerium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202311098144.0A
Other languages
Chinese (zh)
Inventor
薛守洪
王焕伟
张若朋
杨耀国
孙启宇
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Inner Mongolia Electric Power Research Institute of Inner Mongolia Power Group Co Ltd
Original Assignee
Inner Mongolia Electric Power Research Institute of Inner Mongolia Power Group Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Inner Mongolia Electric Power Research Institute of Inner Mongolia Power Group Co Ltd filed Critical Inner Mongolia Electric Power Research Institute of Inner Mongolia Power Group Co Ltd
Priority to CN202311098144.0A priority Critical patent/CN117276566A/en
Publication of CN117276566A publication Critical patent/CN117276566A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
    • 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
    • H01M4/88—Processes of manufacture
    • 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 preparation method of a Pt-Ce-Zr alloy hydrogen fuel cell catalyst, and belongs to the technical field of fuel cells. The method comprises the following steps: dissolving a platinum source, a cerium source and a zirconium source in an organic aqueous solution, adding a carrier, uniformly mixing at a low temperature, and deoxidizing and calcining the obtained product at 800-900 ℃; and then water washing and drying are carried out to obtain the product. According to the method, the platinum source, the cerium source and the zirconium source are loaded on the conductive carrier, alloying is carried out, the dosage and proportion of noble metal platinum are effectively reduced, and meanwhile, the obtained catalyst still has good electrochemical performance.

Description

Preparation method of Pt-Ce-Zr alloy hydrogen fuel cell catalyst
Technical Field
The invention belongs to the technical field of fuel cells, and particularly relates to a preparation method of a Pt-Ce-Zr alloy hydrogen fuel cell catalyst.
Background
The hydrogen has the advantages of high heat value, stable energy output, wide sources, clean and zero pollution of products and the like, and is a stable and clean energy carrier. The fuel cell can directly convert chemical energy into electric energy, and has higher energy conversion efficiency than that of an internal combustion engine, which is up to 60-80%, because the fuel cell is not limited by Carnot cycle. Proton exchange membrane fuel cells (proton exchangemembrane fuel cells, PEMFCs) have the advantages of fast start-up, low operating temperature, etc., and the realization of efficient hydrogen energy utilization through the proton exchange membrane fuel cells is an important part of hydrogen energy economy.
The environmental protection advantage of proton exchange membrane fuel cells is very outstanding, the technical level has reached the application level, but the high cost brought by noble metal platinum used as a catalyst limits the large-scale industrialized application of the technology.
Pt-based catalysts are the most effective catalysts for oxygen reduction reactions, however, pt resources are limited, high Pt loading severely restricts the large-scale application of proton exchange membrane fuel cells, and developing catalysts with low Pt content is an effective way to promote large-scale commercialization of fuel cells.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide a preparation method of a Pt-Ce-Zr alloy hydrogen fuel cell catalyst, which is characterized in that a platinum source, a cerium source and a zirconium source are loaded on a conductive carrier and alloyed, so that the dosage and proportion of noble metal platinum are effectively reduced, and meanwhile, the obtained catalyst still has better electrochemical performance.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of a Pt-Ce-Zr alloy hydrogen fuel cell catalyst, which comprises the following steps:
s1: the platinum source, cerium source and zirconium source are dissolved in an aqueous organic solution.
Preferably, the platinum source comprises chloroplatinic acid; the cerium source comprises cerium nitrate; the zirconium source comprises zirconium nitrate hydrate.
Further, the platinum source, the cerium source and the zirconium source are mixed according to the atomic ratio of Pt to Ce to Zr of (0.4-0.8): (0.08-0.2): (0.08-0.2).
Preferably, the organic matter comprises polyvinyl alcohol and/or polyethylene glycol.
S2: and adding a carrier into the S1 product, and uniformly mixing at a low temperature.
Preferably, the support comprises fullerenes and/or carbon nanotubes.
Further, the low temperature is-20 to-80 ℃.
Preferably, the mixing employs ultrasonic dispersion.
S3: deoxidizing and calcining the product obtained in the step S2 at 800-900 ℃.
Optionally, the deoxidizing calcination is at 10 -3 And the pressure is lower than MPa.
Optionally, the atmosphere of the deoxidizing calcination is an inert atmosphere.
Preferably, after deoxidizing and calcining, the temperature is reduced to 150-200 ℃ for 1-3 hours, and then the temperature is naturally reduced to room temperature.
S4: and S3, washing the obtained product with water and drying to obtain the product.
Compared with the prior art, the invention introduces cerium and zirconium to replace part of platinum on the basis of the existing platinum-based catalyst, thereby greatly reducing the use amount of platinum and lowering the cost; the aerogel is prepared by low-temperature mixing and then deoxidized and calcined for alloying, and the obtained catalyst has controllable particle size and better electrochemical performance.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to specific examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The preparation method of the Pt-Ce-Zr alloy hydrogen fuel cell catalyst provided by the invention comprises the following steps:
s1: the platinum source, cerium source and zirconium source are dissolved in an aqueous organic solution.
In a preferred embodiment, the platinum source may be chloroplatinic acid; the cerium source may be cerium nitrate; the zirconium source may be zirconium nitrate hydrate.
In a preferred embodiment, the platinum source, cerium source, and zirconium source may have a Pt:Ce:Zr atomic ratio of (0.4-0.8): (0.08-0.2): (0.08-0.2).
In a preferred embodiment, the organic substance may be polyvinyl alcohol and/or polyethylene glycol, and the water-soluble organic substance may better mix the metal salt to facilitate subsequent loading.
S2: adding a carrier into the S1 product, and uniformly dispersing and mixing the mixture at the temperature of between minus 20 and minus 80 ℃ by ultrasonic.
In a preferred embodiment, the support comprises fullerenes and/or carbon nanotubes. Other carbon sources, such as those having a relatively high carbon content, may also be used in the present invention.
S3: deoxidizing and calcining the product obtained in the step S2 at 800-900 ℃.
Alternatively, in one embodiment, the deoxidizing calcination is performed at a vacuum level of 10 -3 And the pressure is lower than MPa.
In another alternative embodiment, the deoxidizing calcined atmosphere is an inert atmosphere.
In a more preferred embodiment, after the deoxidizing calcination, the temperature may be reduced to 150-200 ℃ for 1-3 hours, followed by natural cooling to room temperature.
S4: and S3, washing the obtained product with water and drying to obtain the product.
In a preferred embodiment, the water wash is repeated at least 3 times, and the drying is at 80-110 ℃ for 2-5 hours.
And testing the electrochemical stability of the catalyst, and subtracting the half-wave potential after 10000 circles of circulation from the half-wave potential of the first circle to obtain a half-wave potential drop value.
Example 1
(1) 24.54g of H are weighed out 2 PtCl 6 3.28g of Ce (NO) 3 ) 3 And 8.59g of Zr (NO) 3 ) 4 ·5H 2 O is dissolved in an aqueous solution of polyvinyl alcohol.
(2) 15g of fullerene is added into the product of the step (1), and ultrasonic dispersion is carried out at the temperature of minus 60 ℃ until the mixture is uniform.
(3) The product obtained in the step (2) is processed at 850 ℃ and a vacuum degree of 10 -3 Deoxidizing and calcining for 1.5h under MPa, washing with water for three times, and drying at 90 ℃ for 5h to obtain the catalyst, wherein the half-wave potential drop value of the catalyst is 9mV.
Example 2
(1) 16.36g of H are weighed out 2 PtCl 6 3.28g of Ce (NO) 3 ) 3 And 8.59g of Zr (NO) 3 ) 4 ·5H 2 O is dissolved in an aqueous solution of polyvinyl alcohol.
(2) 15g of fullerene is added into the product of the step (1), and ultrasonic dispersion is carried out at the temperature of minus 40 ℃ until the mixture is uniform.
(3) The product obtained in the step (2) is processed at the temperature of 900 ℃ and the vacuum degree of 10 -3 Deoxidizing and calcining for 1.5h under MPa, washing with water for three times, and drying at 90 ℃ for 4h to obtain the catalyst, wherein the half-wave potential drop value of the catalyst is 11mV.
Example 3
(1) 16.36g of H are weighed out 2 PtCl 6 1.31g of Ce (NO) 3 ) 3 And 3.43g of Zr (NO) 3 ) 4 ·5H 2 O is dissolved in an aqueous solution of polyvinyl alcohol.
(2) Adding 12g of fullerene into the product of the step (1), and performing ultrasonic dispersion at the temperature of-80 ℃ until the fullerene is uniformly mixed.
(3) And (3) deoxidizing and calcining the product obtained in the step (2) for 1.5 hours under the protection of argon at the temperature of 800 ℃, washing with water for three times, and drying for 3 hours at the temperature of 110 ℃ to obtain the catalyst, wherein the half-wave potential drop value of the catalyst is 17mV.
Example 4
(1) 24.54g of H are weighed out 2 PtCl 6 3.28g of Ce (NO) 3 ) 3 And 8.59g of Zr (NO) 3 ) 4 ·5H 2 O is dissolved in an aqueous solution of polyvinyl alcohol.
(2) 15g of fullerene is added into the product of the step (1), and ultrasonic dispersion is carried out at the temperature of minus 60 ℃ until the mixture is uniform.
(3) The product obtained in the step (2) is processedThe temperature of the product is 850 ℃ and the vacuum degree is 10 -3 Deoxidizing and calcining for 1.5h under the pressure of MPa, cooling to 180 ℃ and staying for 2h, and naturally cooling to room temperature. And then washed three times with water, and dried at 90 ℃ for 5 hours to obtain the catalyst, wherein the half-wave potential drop value of the catalyst is 6mV.
Example 5
(1) 24.54g of H are weighed out 2 PtCl 6 3.28g of Ce (NO) 3 ) 3 And 8.59g of Zr (NO) 3 ) 4 ·5H 2 O is dissolved in an aqueous solution of polyvinyl alcohol.
(2) 15g of fullerene is added into the product of the step (1), and ultrasonic dispersion is carried out at the temperature of minus 60 ℃ until the mixture is uniform.
(3) The product obtained in the step (2) is processed at 850 ℃ and a vacuum degree of 10 -3 Deoxidizing and calcining for 1.5h under the pressure of MPa, cooling to 150 ℃ and staying for 3h, and naturally cooling to room temperature. Then washed three times with water and dried at 90℃for 5 hours, to give the catalyst whose half-wave potential drop value was 8mV.
Example 6
(1) 24.54g of H are weighed out 2 PtCl 6 3.28g of Ce (NO) 3 ) 3 And 8.59g of Zr (NO) 3 ) 4 ·5H 2 O is dissolved in an aqueous solution of polyvinyl alcohol.
(2) 15g of fullerene is added into the product of the step (1), and ultrasonic dispersion is carried out at the temperature of minus 60 ℃ until the mixture is uniform.
(3) The product obtained in the step (2) is processed at 850 ℃ and a vacuum degree of 10 -3 Deoxidizing and calcining for 1.5h under the pressure of MPa, cooling to 200 ℃ and staying for 1h, and naturally cooling to room temperature. Then washed three times with water and dried at 90℃for 5 hours, to give the catalyst, the half-wave potential drop of which was 9mV.
It can be seen that the catalysts obtained in examples 1-6 have higher electrochemical stability, and in particular, the catalysts obtained in examples 4-6 after the staged heat treatment have better performance. At the same time, the amount of platinum is greatly reduced.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Furthermore, those skilled in the art will appreciate that while some embodiments herein include some features but not others included in other embodiments, combinations of features of different embodiments are meant to be within the scope of the invention and form different embodiments. For example, in the claims below, any of the claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.

Claims (10)

1. The preparation method of the Pt-Ce-Zr alloy hydrogen fuel cell catalyst is characterized by comprising the following steps of:
s1: dissolving a platinum source, a cerium source and a zirconium source in an organic aqueous solution;
s2: adding a carrier into the S1 product, and uniformly mixing at a low temperature;
s3: deoxidizing and calcining the product obtained in the step S2 at 800-900 ℃;
s4: and S3, washing the obtained product with water and drying to obtain the product.
2. The method of claim 1, wherein in step S1, the platinum source comprises chloroplatinic acid; the cerium source comprises cerium nitrate; the zirconium source comprises zirconium nitrate hydrate.
3. The method according to claim 1 or 2, wherein in step S1, the platinum source, the cerium source and the zirconium source are used in such a manner that the atomic ratio of Pt: ce: zr is (0.4-0.8): 0.08-0.2.
4. The method according to claim 1, wherein in step S1, the organic matter comprises polyvinyl alcohol and/or polyethylene glycol.
5. The method according to claim 1, wherein in step S2, the support comprises fullerenes and/or carbon nanotubes.
6. The method according to claim 1, wherein in step S2, the low temperature is-20 to-80 ℃.
7. The method of claim 1, wherein in step S2, the mixing is performed by ultrasonic dispersion.
8. The method according to claim 1, wherein in step S3, the deoxidizing calcination is performed at a temperature of 10 -3 And the pressure is lower than MPa.
9. The method according to claim 1, wherein in step S3, the deoxidizing calcined atmosphere is an inert atmosphere.
10. The method according to claim 1, wherein in step S3, after the deoxidizing and calcining, the temperature is reduced to 150-200 ℃ for 1-3 hours, and then naturally reduced to room temperature.
CN202311098144.0A 2023-08-29 2023-08-29 Preparation method of Pt-Ce-Zr alloy hydrogen fuel cell catalyst Pending CN117276566A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202311098144.0A CN117276566A (en) 2023-08-29 2023-08-29 Preparation method of Pt-Ce-Zr alloy hydrogen fuel cell catalyst

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202311098144.0A CN117276566A (en) 2023-08-29 2023-08-29 Preparation method of Pt-Ce-Zr alloy hydrogen fuel cell catalyst

Publications (1)

Publication Number Publication Date
CN117276566A true CN117276566A (en) 2023-12-22

Family

ID=89213413

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202311098144.0A Pending CN117276566A (en) 2023-08-29 2023-08-29 Preparation method of Pt-Ce-Zr alloy hydrogen fuel cell catalyst

Country Status (1)

Country Link
CN (1) CN117276566A (en)

Similar Documents

Publication Publication Date Title
CN1186838C (en) Preparation method of proton-exchange membrane fuel cell electrode catalyst
CN108134104B (en) Composite catalyst carrier for fuel cell and preparation method and application thereof
CN112652780B (en) Fe/Fe 3 Preparation method of C nano-particle loaded porous nitrogen-doped carbon-based oxygen reduction catalyst
CN103170334A (en) Carbon-supported cobalt oxide catalyst and preparation and application thereof
CN101288849A (en) Carbon nitrogen nano fiber loaded platinum ruthenium nano particle electrode catalyst and preparation method
CN110048134A (en) A kind of universality method preparing porous nitrogen fluorine codope carbon oxygen reduction catalyst
CN113571713A (en) PtZn-loaded nitrogen-doped carbon catalyst, preparation method thereof and hydrogen-oxygen fuel cell
CN114685805B (en) Preparation method for directly synthesizing MOF material for electrocatalytic carbon dioxide reduction at room temperature
CN101596453B (en) Method for preparing Pt catalyst with carbon carrier as carrier
CN109873172B (en) Preparation method of methanol fuel cell catalyst
CN110931815A (en) Preparation method of fuel cell carbon-supported platinum-based catalyst
CN101269327B (en) Process for producing high-stability carbon carried Pt-Au bi-metal nano-electro-catalyst
CN1262030C (en) Electric Pt-C catalyst containing cocatalytic element and its prepn
CN102806106A (en) Preparation method of carbon-supported metal polypyrrole oxygen reduction catalyst
CN108336375A (en) A kind of serrated metal nano wire-carbon-based fuel cell catalyst and preparation method
CN110600752B (en) H2Method for preparing carbon-supported Pt alloy catalyst by gas-phase thermal reduction
CN110931804A (en) CeO carried by Pt-Ni-Cu ternary alloy2Preparation of composite material and research on formic acid catalytic performance of composite material
CN117276566A (en) Preparation method of Pt-Ce-Zr alloy hydrogen fuel cell catalyst
CN115472846A (en) Carbon-supported rhodium-based ordered intermetallic compound, preparation and application as catalyst
CN110224148B (en) Pt or Au modified porous PdFe intermetallic compound and preparation method and application thereof
CN110783580B (en) Preparation method of alkaline system fuel cell anode catalyst
CN113013424B (en) High-efficiency composite catalyst applied to fuel cell and preparation method thereof
CN110048132A (en) A kind of three-dimensional preparation method for propping up forked Pt-Cu-Mn alloy nanoparticle
CN112820888B (en) Preparation method of fuel cell catalyst with monatomic and nanocrystalline composite structure
CN114628693B (en) Preparation method of nitrogen-rich porous carbon material anchored metal ferroelectric catalyst

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication