CN105576263B - High-performance fuel cell catalyst and preparation method thereof - Google Patents
High-performance fuel cell catalyst and preparation method thereof Download PDFInfo
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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
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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
Abstract
The invention relates to a high-performance fuel cell catalyst and a preparation method thereof. The high-performance fuel cell catalyst is composed of metal and metal oxide, wherein the metal oxide is positioned on the surface of the metal nanoparticle and has edges and vertex angles with lower coordination numbers. The fuel cell catalyst with the novel structure has the advantages of simple preparation method, convenient operation and no environmental pollution, has high oxygen reduction reaction activity and stability, and is suitable for fuel cell electrodes, in particular electrolyte membrane fuel cell electrodes.
Description
Technical Field
The invention belongs to the field of fuel cell catalysts, and particularly relates to a high-performance fuel cell catalyst and a preparation method thereof.
Background
Energy is closely related to social progress and national economy development, and each step of human society advancement is closely related to development and utilization of energy. Each major breakthrough in human energy utilization is accompanied by technological advances, thereby promoting the development of productivity. With economic growth, technological progress, and a dramatic increase in population, the demand for energy in human society has increased. With the gradual depletion of fossil energy and the increasing severity of environmental pollution, if effective alternative energy cannot be found, the human society faces a comprehensive energy crisis. Fuel cells are a power generation device for directly converting chemical energy into electric energy, and are considered to be the first clean energy technology in the 21 st century because of their high efficiency and environmental friendliness. Electrolyte membrane fuel cells are considered to be the most promising, competitive, and most likely to be industrially applied fuel cells because of their advantages of high efficiency, cleanliness, low temperature, and the like [ r. Borup, et al, chem. rev. 107 (2007) 3904; r. Dillon, et al, J. Power Sources 127 (2004) 112 ]. The electrode is a key component of the fuel cell, and the quality of the electrocatalytic performance of the electrode directly influences the overall performance of the fuel cell. The low cathode oxygen reduction reaction rate of the electrolyte membrane fuel cell is a key factor that limits the commercialization of the electrolyte membrane fuel cell [ h.a. gastiger, et al, Science 324 (2009) 48; m.k. Debe, Nature 486 (2012) 43; v.r. Stamenkovic, et al, Science 315 (2007) 493 ]. Platinum (Pt) -based catalysts, which are currently the best polymer fuel cell electrode catalysts due to their high activity and high stability, are widely used for the cathode and anode electrodes of fuel cells [ c. Chen, et al, Science 343 (2014) 1339; l. Zhang, et al, Science 349 (2015) 412 ]. However, due to the lack of Pt resource, the price is high, and the low oxygen reduction reaction rate of the cathode relative to the anode of the polymer membrane fuel cell determines the need to increase the amount of Pt used at the cathode, which greatly increases the cost of the fuel cell. Therefore, the development of novel high-performance fuel cell catalysts becomes one of the main research directions of fuel cells, and has important application value and scientific significance.
The development of new fuel cell catalysts can be initiated from two aspects: firstly, the reaction activity and stability of the catalyst are improved; and secondly, the use amount of Pt is reduced, and simultaneously, the higher reaction activity of the catalyst is kept, namely, the utilization efficiency of Pt is improved. The electrocatalytic reaction activity of the cathode and the anode of the fuel cell changes along with the change of the adsorption strength of metal atoms on the surface of the catalyst and reaction intermediates, and the change rule of volcano charts is followed. Taking the oxygen reduction reaction as an example, the oxygen reduction reaction activity of the catalyst increases first and then decreases as the adsorption strength of the surface metal atoms with oxygen increases [ j. greenley, et al, nat. chem. 1 (2009) 552 ]. Therefore, the reactivity of the catalyst can be improved by changing the adsorption strength of the metal atoms on the surface of the catalyst and reaction intermediates. The results of density functional theory calculations show that a reduction of the platinum-oxygen (Pt-O) bond energy by 0.2eV maximizes the oxygen reduction reactivity, and that, for Pt nanoparticles, the Pt-O bond energy on flat crystal planes is smaller than the Pt-O bond energy on top and edges [ j. greenley, et al, nat. chem. 1 (2009) 552 ]. Therefore, a novel fuel cell catalyst structure is designed, Pt atoms are located on flat crystal faces on the surfaces of catalyst nano particles, lower Pt-O bond energy is obtained, metal oxides are located on edges and vertex angles on the surfaces of the nano catalyst particles, repulsion action is generated between oxygen atoms in the metal oxides and oxygen atoms adsorbed on the surfaces of the Pt, the adsorption strength of the oxygen on the surfaces of the Pt can be further reduced, and the method is an effective and feasible method for improving the activity of the oxygen reduction reaction of the catalyst.
Disclosure of Invention
The invention aims to provide a high-performance fuel cell catalyst which is lower in cost and better in alkali resistance and acid resistance.
In order to achieve the purpose, the invention adopts the following technical scheme:
a high performance fuel cell catalyst characterized by: is composed of metal and metal oxide; forming metal nano particles with crystal faces, edges and vertex angles on the surface by metal; the metal oxide is positioned on the edges and the top corners of the surfaces of the metal nano particles.
The high-performance fuel cell catalyst is characterized in that: the metal nanoparticles are single metal nanoparticles, or alloy nanoparticles in various metal forms, or metal nanoparticles with a core-shell structure; the particle size of the metal nano particles is less than 50 nm.
The high-performance fuel cell catalyst is characterized in that the metal oxide is one or a mixture of more of titanium oxide, vanadium oxide, tungsten oxide, molybdenum oxide, niobium oxide and chromium oxide.
The high-performance fuel cell catalyst is characterized in that when the metal nanoparticles are single-metal nanoparticles, the single metal refers to one of platinum, palladium and gold; when the metal nanoparticles are metal alloy nanoparticles, the metal alloy refers to two or more of gold, palladium, copper, nickel, cobalt, ruthenium and iron; when the metal nanoparticles are metal nanoparticles having a core-shell structure, the core metal in the core-shell metal refers to one or more of gold, palladium, or ruthenium mixed.
The preparation method of the high-performance fuel cell catalyst is characterized by comprising the following steps: when the metal nanoparticles are single metal nanoparticles, the specific steps are as follows:
(1) weighing carbon nano-carrier, placing in anhydrous ethanol to obtain mixed liquid with carbon concentration of 1-5 g/ml, and performing ultrasonic treatment or stirring for 10-60 min;
(2) adding sodium citrate into the mixed liquid, wherein the mass of the added sodium citrate is 0.5-5 times of the carbonaceous quantity, and performing ultrasonic treatment or stirring for 10-60 min;
(3) adding one or more of salts containing titanium, vanadium, tungsten, molybdenum, niobium and chromium into the mixed liquid, and mixing by ultrasonic treatment or stirring for 10-60 min;
(4) adding a reducing reagent into the mixed liquid, wherein the amount of the added reducing reagent is 1.5-20 times of the total amount of salt substances containing titanium, vanadium, tungsten, molybdenum, niobium and chromium, and performing ultrasonic treatment or stirring for 10-120 min;
(5) adding a salt containing platinum or palladium element into the mixed liquid, wherein the amount of the added salt containing platinum, gold or palladium element is 0.1-3 times of the total amount of the salt substances containing titanium, vanadium, tungsten, molybdenum, niobium and chromium element, and performing ultrasonic treatment or stirring for 10-60 min;
(6) centrifuging, filtering, washing with deionized water, and drying to obtain metal oxide modified single metal nanoparticle catalyst;
the preparation method of the high-performance fuel cell catalyst is characterized by comprising the following steps: when the metal nanoparticles are metal alloy nanoparticles, the specific steps are as follows:
(1) weighing carbon nano-carrier, placing in anhydrous ethanol to obtain mixed liquid with carbon concentration of 1-5 g/ml, and performing ultrasonic treatment or stirring for 10-60 min;
(2) adding sodium citrate into the mixed liquid, wherein the mass of the added sodium citrate is 0.5-5 times of the carbonaceous quantity, and performing ultrasonic treatment or stirring for 10-60 min;
(3) adding one or more of salts containing titanium, vanadium, tungsten, molybdenum, niobium and chromium into the mixed liquid, and mixing by ultrasonic treatment or stirring for 10-60 min;
(4) adding a reducing reagent into the mixed liquid, wherein the amount of the added reducing reagent is 1.5-20 times of the total amount of salt substances containing titanium, vanadium, tungsten, molybdenum, niobium and chromium, and performing ultrasonic treatment or stirring for 10-120 min;
(5) adding two or more of salts containing platinum elements and salts containing gold, palladium, copper, nickel, cobalt, ruthenium and iron elements into the mixed liquid, wherein the total amount of the added salts containing platinum, gold, palladium, copper, nickel, cobalt, ruthenium and iron elements is 0.1-3 times of the total amount of the salts containing titanium, vanadium, tungsten, molybdenum, niobium and chromium elements, and carrying out ultrasonic treatment or stirring for 10-60 min;
(6) centrifuging, filtering, washing with deionized water, and drying to obtain metal oxide modified metal alloy nanoparticle catalyst;
the preparation method of the high-performance fuel cell catalyst is characterized by comprising the following steps: when the metal nanoparticles are metal nanoparticles with a core-shell structure, the specific steps are as follows:
(1) weighing carbon nano-carrier, placing in anhydrous ethanol to obtain mixed liquid with carbon concentration of 1-5 g/ml, and performing ultrasonic treatment or stirring for 10-60 min;
(2) adding sodium citrate into the mixed liquid, wherein the mass of the added sodium citrate is 0.5-5 times of the carbonaceous quantity, and performing ultrasonic treatment or stirring for 10-60 min;
(3) adding one or more of salts containing titanium, vanadium, tungsten, molybdenum, niobium and chromium into the mixed liquid, and mixing by ultrasonic treatment or stirring for 10-60 min;
(4) adding a reducing reagent into the mixed liquid, wherein the amount of the added reducing reagent is 1.5-20 times of that of the salt substance containing titanium, vanadium, tungsten, molybdenum, niobium and chromium, and carrying out ultrasonic treatment or stirring for 10-120 min;
(5) adding one or more of gold, palladium or ruthenium element-containing salts into the mixed liquid, wherein the total amount of the added gold, palladium and ruthenium element-containing salts is 0.1-3 times of the total amount of titanium, vanadium, tungsten, molybdenum, niobium and chromium element-containing salts, and performing ultrasonic treatment or stirring for 10-60 min;
(6) centrifuging, filtering, washing with deionized water, and drying;
(7) and (3) depositing a single layer of copper on the surface of the metal nano particle prepared in the step (6) by adopting an underpotential deposition method, not depositing on the surface of the metal oxide, then placing the metal oxide in a solution containing platinum salt for a displacement reaction to ensure that the copper is displaced by the platinum to form a single layer of platinum, or repeating the step (7) for a plurality of times to deposit a plurality of layers of platinum on the surface of the gold, palladium or ruthenium nano particle, thus preparing the metal oxide modified core-shell structure metal nano particle catalyst.
The preparation method of the high-performance fuel cell catalyst is characterized by comprising the following steps: the carbon nano-carrier is selected from one or more of carbon black, carbon nano-tube, carbon nano-fiber, graphene and the like.
The invention has the beneficial effects that:
the invention realizes the regulation and control of the surface structure atomic level of the catalyst by using a simple preparation method, and greatly improves the oxygen reduction reaction performance of the catalyst.
The preparation method of the fuel cell catalyst with the novel structure is simple, convenient to operate, can be carried out at normal temperature without depending on large-scale and special devices and instruments, is easy to realize batch production, does not use toxic chemical reagents, and does not pollute the environment.
The novel-structure fuel cell catalyst prepared by the invention effectively reduces the oxygen adsorption strength on the Pt surface, so that the oxygen reduction reaction activity of the catalyst is greatly improved. Meanwhile, the metal oxide is positioned at the edge and vertex angle positions with lower coordination number, so that the overflow of inner layer metal atoms can be effectively reduced, the inner layer atoms can be well protected to reduce corrosion, the blockage of Pt active sites caused by the overflow of the inner layer metal atoms can be reduced, and the stability of the catalyst is improved.
According to the fuel cell catalyst with the novel structure, the core-shell structure metal nanoparticle catalyst modified by the metal oxide effectively improves the activity and stability of the catalyst, and greatly reduces the consumption of Pt, so that the fuel cell catalyst is very superior in performance and extremely easy to realize commercial application.
Drawings
FIG. 1 is a schematic structural diagram of a novel structural metal oxide modified core-shell structure metal nanoparticle catalyst.
FIG. 2 is a scanning transmission microscope-electron energy loss spectrum element surface scanning diagram of titanium dioxide modified gold nanoparticles.
FIG. 3 is a schematic diagram comparing the oxygen reduction performance of a titanium dioxide modified Au @ Pt core-shell structure metal nanoparticle catalyst and a commercial Pt catalyst.
FIG. 4 is a schematic diagram of the stability of a titanium dioxide modified Au @ Pt core-shell structured metal nanoparticle catalyst.
FIG. 5 is a graphical representation comparing the oxygen reduction performance of vanadium oxide modified Au @ Pt core-shell structured metal nanoparticle catalysts with that of commercial Pt catalysts.
FIG. 6 is a schematic diagram of the stability of a vanadium oxide modified Au @ Pt core-shell structured metal nanoparticle catalyst.
Detailed Description
Example 1:
weighing 140g of carbon black, putting the carbon black into 50ml of absolute ethyl alcohol, carrying out ultrasonic treatment for 60min, adding 300mg of sodium citrate into the mixed liquid, and carrying out ultrasonic treatment for 30 min. Then 0.9mmol of titanium isopropoxide was added to the mixed liquid and sonicated for 30 min. 2ml of lithium triethylborohydride of 1mol/L is added into the mixed liquid, and after 30min of ultrasonic reaction, 0.1mmol of sodium chloroaurate is added for 60min of ultrasonic treatment. And centrifuging the mixed liquid, filtering, washing with deionized water, and drying in a vacuum oven. Fig. 1 is a scanning transmission microscope-electron energy loss spectroscopy (STEM-EELS) element content surface scanning diagram of the titanium dioxide modified Au nanoparticles, and it can be seen from fig. 1 that titanium in the titanium dioxide modified gold nanoparticles prepared by the method is distributed on the surface of the gold nanoparticles and is concentrated at the edge and vertex angles of the gold nanoparticles.
Example 2:
weighing 140g of carbon black, putting the carbon black into 50ml of absolute ethyl alcohol, carrying out ultrasonic treatment for 60min, adding 300mg of sodium citrate into the mixed liquid, and carrying out ultrasonic treatment for 30 min. Then 0.3mmol of titanium isopropoxide was added to the mixed liquid and sonicated for 30 min. 2ml of lithium triethylborohydride of 1mol/L is added into the mixed liquid, after reaction for 30min, 0.1mmol of sodium chloroaurate is added, and ultrasonic treatment is carried out for 60 min. And centrifuging the mixed liquid, filtering, washing with deionized water, and drying in a vacuum oven. Finally, depositing a single layer of copper on the surfaces of the prepared gold nanoparticles by adopting an underpotential deposition method, not depositing on the surfaces of the titanium dioxide, then placing the gold nanoparticles into a solution containing platinum salt for a displacement reaction to ensure that the copper is displaced by the platinum to form a single layer of platinum, and repeating the step to deposit double layers of platinum on the surfaces of the gold nanoparticles to prepare the titanium dioxide modified gold (core) -platinum (shell) type catalyst. FIG. 2 is a schematic structural diagram of a titanium dioxide modified Au @ Pt core-shell structure metal nanoparticle catalyst. FIG. 3 is a comparison of the oxygen reduction reaction performance of the titania-modified gold (core) -platinum (shell) catalyst prepared by the present method with a commercial Pt catalyst (Tanaka Kikinzoku International Inc., 10E50E, 46.6 wt% Pt). It can be seen from fig. 3 that the surface area activity of the oxygen reduction reaction of the titania-modified gold (core) -platinum (shell) type catalyst is nearly 5 times that of the commercial Pt catalyst, and the mass activity of the oxygen reduction reaction is nearly 10 times that of the commercial Pt catalyst. FIG. 4 is a graph showing the stability of the titanium dioxide modified gold (core) -platinum (shell) type catalyst prepared by the present method. As can be seen from fig. 4, after 10000 cycles of potential cycling, the oxygen reduction reaction performance of the titanium dioxide modified gold (core) -platinum (shell) type catalyst is not reduced at all, which indicates that the titanium dioxide modified gold (core) -platinum (shell) type catalyst has good stability.
Example 3:
weighing 140g of carbon black, putting the carbon black into 50ml of absolute ethyl alcohol, carrying out ultrasonic treatment for 60min, adding 300mg of sodium citrate into the mixed liquid, and carrying out ultrasonic treatment for 30 min. Then 0.8mmol of vanadium dichloride is added into the mixed liquid and the ultrasonic treatment is carried out for 30 min. And continuously adding 3ml of 1mol/L lithium triethylborohydride into the mixed liquid, carrying out ultrasonic reaction for 60min, then adding 0.14mmol sodium chloroaurate, and carrying out ultrasonic reaction for 60 min. And centrifuging the mixed liquid, filtering, washing with deionized water, and drying in a vacuum oven. Finally, depositing a single layer of copper on the surfaces of the prepared gold nanoparticles by adopting an underpotential deposition method, wherein the copper is not deposited on the surfaces of the vanadium oxide, then placing the gold nanoparticles into a solution containing platinum salt for a displacement reaction to ensure that the copper is displaced by the platinum to form a single layer of platinum, and repeating the step to deposit double layers of platinum on the surfaces of the gold nanoparticles to prepare the vanadium oxide modified gold (core) -platinum (shell) type catalyst. FIG. 5 is a comparison of oxygen reduction reaction performance of vanadium oxide modified gold (core) -platinum (shell) catalyst prepared by the present method and a commercial Pt catalyst (Tanaka Kikinzoku International Inc., 10E50E, 46.6 wt% Pt). It can be seen from fig. 5 that the surface area activity of the oxygen reduction reaction of the vanadium oxide modified gold (core) -platinum (shell) type catalyst is more than 5 times that of the commercial Pt catalyst, and the mass activity of the oxygen reduction reaction is nearly 8 times that of the commercial Pt catalyst. FIG. 6 is a schematic diagram showing the stability of the vanadium oxide modified gold (core) -platinum (shell) type catalyst prepared by the present method. As can be seen from fig. 6, after 6000 cycles of potential cycling, the oxygen reduction reaction performance of the vanadium oxide modified gold (core) -platinum (shell) catalyst is not reduced at all, which indicates that the vanadium oxide modified gold (core) -platinum (shell) catalyst has good stability.
Claims (3)
1. A high performance fuel cell catalyst characterized by: is composed of metal and metal oxide; forming metal nano particles with crystal faces, edges and vertex angles on the surface by metal; the metal oxide is positioned on the edge and the vertex angle of the surface of the metal nano particle;
the metal nanoparticles are single metal nanoparticles, or alloy nanoparticles in various metal forms, or metal nanoparticles with a core-shell structure; the particle size of the metal nano particles is less than 50 nm;
when the metal nanoparticles are single metal nanoparticles, the specific steps are as follows:
(1) weighing carbon nano-carrier, placing in anhydrous ethanol to obtain mixed liquid with carbon concentration of 1-5 g/ml, and performing ultrasonic treatment or stirring for 10-60 min;
(2) adding sodium citrate into the mixed liquid, wherein the mass of the added sodium citrate is 0.5-5 times of the carbonaceous quantity, and performing ultrasonic treatment or stirring for 10-60 min;
(3) adding one or more of salts containing titanium, vanadium, tungsten, molybdenum, niobium and chromium into the mixed liquid, and mixing by ultrasonic treatment or stirring for 10-60 min;
(4) adding a reducing reagent into the mixed liquid, wherein the amount of the added reducing reagent is 1.5-20 times of the total amount of salt substances containing titanium, vanadium, tungsten, molybdenum, niobium and chromium, and performing ultrasonic treatment or stirring for 10-120 min;
(5) adding a salt containing platinum, gold or palladium element into the mixed liquid, wherein the amount of the added salt containing platinum, gold or palladium element is 0.1-3 times of the total amount of the salt substances containing titanium, vanadium, tungsten, molybdenum, niobium and chromium element, and carrying out ultrasonic treatment or stirring for 10-60 min;
(6) centrifuging, filtering, washing with deionized water, and drying to obtain metal oxide modified single metal nanoparticle catalyst;
when the metal nanoparticles are metal alloy nanoparticles, the specific steps are as follows:
(1) weighing carbon nano-carrier, placing in anhydrous ethanol to obtain mixed liquid with carbon concentration of 1-5 g/ml, and performing ultrasonic treatment or stirring for 10-60 min;
(2) adding sodium citrate into the mixed liquid, wherein the mass of the added sodium citrate is 0.5-5 times of the carbonaceous quantity, and performing ultrasonic treatment or stirring for 10-60 min;
(3) adding one or more of salts containing titanium, vanadium, tungsten, molybdenum, niobium and chromium into the mixed liquid, and mixing by ultrasonic treatment or stirring for 10-60 min;
(4) adding a reducing reagent into the mixed liquid, wherein the amount of the added reducing reagent is 1.5-20 times of the total amount of salt substances containing titanium, vanadium, tungsten, molybdenum, niobium and chromium, and performing ultrasonic treatment or stirring for 10-120 min;
(5) adding two or more of salts containing platinum elements and salts containing gold, palladium, copper, nickel, cobalt, ruthenium and iron elements into the mixed liquid, wherein the total amount of the added salts containing platinum, gold, palladium, copper, nickel, cobalt, ruthenium and iron elements is 0.1-3 times of the total amount of the salts containing titanium, vanadium, tungsten, molybdenum, niobium and chromium elements, and carrying out ultrasonic treatment or stirring for 10-60 min;
(6) centrifuging, filtering, washing with deionized water, and drying to obtain metal oxide modified metal alloy nanoparticle catalyst;
when the metal nanoparticles are metal nanoparticles with a core-shell structure, the specific steps are as follows:
(1) weighing carbon nano-carrier, placing in anhydrous ethanol to obtain mixed liquid with carbon concentration of 1-5 g/ml, and performing ultrasonic treatment or stirring for 10-60 min;
(2) adding sodium citrate into the mixed liquid, wherein the mass of the added sodium citrate is 0.5-5 times of the carbonaceous quantity, and performing ultrasonic treatment or stirring for 10-60 min;
(3) adding one or more of salts containing titanium, vanadium, tungsten, molybdenum, niobium and chromium into the mixed liquid, and mixing by ultrasonic treatment or stirring for 10-60 min;
(4) adding a reducing reagent into the mixed liquid, wherein the amount of the added reducing reagent is 1.5-20 times of that of the salt substance containing titanium, vanadium, tungsten, molybdenum, niobium and chromium, and carrying out ultrasonic treatment or stirring for 10-120 min;
(5) adding one or more of gold, palladium or ruthenium element-containing salts into the mixed liquid, wherein the total amount of the added gold, palladium and ruthenium element-containing salts is 0.1-3 times of the total amount of titanium, vanadium, tungsten, molybdenum, niobium and chromium element-containing salts, and performing ultrasonic treatment or stirring for 10-60 min;
(6) centrifuging, filtering, washing with deionized water, and drying;
(7) depositing a single layer of copper on the surface of the metal nano particle prepared in the step (6) by adopting an underpotential deposition method, not depositing on the surface of the metal oxide, then placing the metal oxide in a solution containing platinum salt for a displacement reaction to ensure that the copper is displaced by the platinum to form a single layer of platinum, or repeating the step (7) for a plurality of times to realize the deposition of a plurality of layers of platinum on the surface of the gold, palladium or ruthenium nano particle, thus preparing the metal oxide modified core-shell structure metal nano particle catalyst;
the carbon nano-carrier is selected from one or more of carbon black, carbon nano-tube, carbon nano-fiber, graphene and the like.
2. A high performance fuel cell catalyst as claimed in claim 1, wherein the metal oxide is selected from one or more of titanium oxide, vanadium oxide, tungsten oxide, molybdenum oxide, niobium oxide, and chromium oxide.
3. A high performance fuel cell catalyst as claimed in claim 1, wherein when the metal nanoparticles are monometallic nanoparticles, the monometallic means one of platinum, palladium and gold; when the metal nanoparticles are metal alloy nanoparticles, the metal alloy refers to two or more of gold, palladium, copper, nickel, cobalt, ruthenium and iron; when the metal nanoparticles are metal nanoparticles having a core-shell structure, the core metal in the core-shell metal refers to one or more of gold, palladium, or ruthenium mixed.
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| 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 |
| CN101572316A (en) * | 2009-06-06 | 2009-11-04 | 西北师范大学 | Modified catalyst for low-temperature fuel cell and preparation method thereof |
| WO2010065014A1 (en) * | 2008-12-04 | 2010-06-10 | Utc Power Corporation | Method of producing a stabilized platinum catalyst with strong oxide formers |
| CN101909749A (en) * | 2008-01-18 | 2010-12-08 | 昭和电工株式会社 | Catalyst, process for production of the same, and use of the same |
| CN103638925A (en) * | 2013-11-15 | 2014-03-19 | 华南理工大学 | Core-shell structure catalyst for fuel cells and its pulse electrodeposition preparation method |
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| 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 |
| CN101909749A (en) * | 2008-01-18 | 2010-12-08 | 昭和电工株式会社 | Catalyst, process for production of the same, and use of the same |
| WO2010065014A1 (en) * | 2008-12-04 | 2010-06-10 | Utc Power Corporation | Method of producing a stabilized platinum catalyst with strong oxide formers |
| CN101572316A (en) * | 2009-06-06 | 2009-11-04 | 西北师范大学 | Modified catalyst for low-temperature fuel cell and preparation method thereof |
| CN103638925A (en) * | 2013-11-15 | 2014-03-19 | 华南理工大学 | Core-shell structure catalyst for fuel cells and its pulse electrodeposition preparation method |
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