CN105576263A - High-performance fuel cell catalyst and preparation method thereof - Google Patents

High-performance fuel cell catalyst and preparation method thereof Download PDF

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CN105576263A
CN105576263A CN201510956550.5A CN201510956550A CN105576263A CN 105576263 A CN105576263 A CN 105576263A CN 201510956550 A CN201510956550 A CN 201510956550A CN 105576263 A CN105576263 A CN 105576263A
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ultrasonic
fuel cell
mixing material
60min
metal
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CN105576263B (en
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胡觉
张呈旭
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Institute of Plasma Physics of CAS
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/86Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90Selection of catalytic material
    • H01M4/92Metals of platinum group
    • H01M4/921Alloys or mixtures with metallic elements
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/50Fuel 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, and the metal oxide is positioned at edges and apex corners, having low coordination number, of surfaces of metal nanoparticles. The preparation method of the fuel cell catalyst of a novel structure is simple, convenient to operate and free of environment pollution; the fuel cell catalyst prepared by the method has high oxygen reduction reaction activity and stability and is suitable for fuel cell electrodes and especially suitable for electrolyte membrane fuel cell electrodes.

Description

A kind of high performance fuel cell Catalysts and its preparation method
Technical field
The invention belongs to fuel-cell catalyst field, particularly relate to a kind of high performance fuel cell Catalysts and its preparation method.
Background technology
The development of the energy and social progress, national economy has close ties, and each step that human society advances is all closely bound up with the exploitation of the energy.The mankind along with the progress of science and technology, thus promote the development of productivity to the important breakthrough each time of using energy source.Along with economic growth, technological progress, and the surging of population, the demand of human society to the energy grows with each passing day.Along with the exhaustion increasingly of fossil energy and the day by day serious of problem of environmental pollution, if can not find effective alternative energy source, human society will face comprehensive energy crisis.Fuel cell as a kind of be directly the Blast Furnace Top Gas Recovery Turbine Unit (TRT) of electric energy by chemical energy because its high efficiency, environment friendly, be considered to the clean energy technologies of 21 century first-selection.Dielectric film fuel cell, because of advantages such as it is efficient, clean, low temperature, is considered to fuel cell that is the most promising, the most competitive, that most possibly realize commercial application [R.Borup, etal., Chem.Rev.107 (2007) 3904; R.Dillon, etal., J.PowerSources127 (2004) 112].Electrode is as the critical component of fuel cell, and the quality of its electrocatalysis characteristic directly affects the overall performance of fuel cell.The Cathodic oxygen reduction speed that dielectric film fuel cell is low is the business-like key factor of restriction dielectric film fuel cell [H.A.Gasteiger, etal., Science324 (2009) 48; M.K.Debe, Nature486 (2012) 43; V.R.Stamenkovic, etal., Science315 (2007) 493].Platinum (Pt) is catalyst based due to its high activity and high stability, is current best polymer fuel cell electrodes catalyst, is widely used in yin, yang the two poles of the earth [C.Chen, etal., Science343 (2014) 1339 of fuel cell; L.Zhang, etal., Science349 (2015) 412].But, due to Pt scarcity of resources, expensive, and relative to polymer-membrane fuel battery anode, the oxygen reduction reaction speed of negative electrode is low determines the consumption needing to strengthen Pt at negative electrode, considerably increases the cost of fuel cell.Therefore, development of new high performance fuel cell catalyst becomes one of fuel cell main direction of studying, has important using value and scientific meaning.
The exploitation of new fuel cell catalyst can be started with from two aspects: one is the reactivity and the stability that improve catalyst; Two is keep the reactivity that catalyst is higher reducing Pt consumption while, namely improves the utilization ratio of Pt.The active change with catalyst surface metallic atom and reaction intermediates adsorption strength of the electrocatalytic reaction at fuel cell yin, yang the two poles of the earth and changing, and follow volcano figure Changing Pattern.For oxygen reduction reaction, the increase of the active adsorption strength along with surface metal atoms and oxygen of the oxygen reduction reaction of catalyst and first increase rear reduction [J.Greeley, etal., Nat.Chem.1 (2009) 552].So the reactivity improving catalyst can be realized by the adsorption strength changing catalyst surface metallic atom and reaction intermediates.Density function theory result shows, platinum-oxygen (Pt-O) key bond energy reduces 0.2eV can make oxygen reduction reaction activity reach the highest, and, for Pt nano particle, the Pt-O key bond energy be positioned on smooth crystal face is less than the Pt-O key bond energy [J.Greeley be positioned on drift angle and rib, etal., Nat.Chem.1 (2009) 552].Visible, design a kind of novel fuel-cell catalyst structure, Pt atom is made to be positioned on the smooth crystal face on catalyst nanoparticles surface, obtain lower Pt-O key bond energy, on the rib making metal oxide be positioned at nanocatalyst particles surface and drift angle, oxygen atom in metal oxide and between the oxygen atom being adsorbed on Pt surface, repulsive interaction occurs, can reduce the adsorption strength of Pt Surface Oxygen further, is effective, the feasible method improving catalyst oxygen reduction reactivity.
Summary of the invention
The object of the invention is to propose that a kind of cost is lower, alkali resistance and the better a kind of high performance fuel cell catalyst of acid resistance.
The present invention adopts following technical scheme to achieve these goals:
A kind of high performance fuel cell catalyst, is characterized in that: be made up of metal and metal oxide; Metal forms the metal nanoparticle that surface has crystal face, rib and drift angle; On the rib that metal oxide is positioned at surfaces of metal nanoparticles and drift angle.
Described a kind of high performance fuel cell catalyst, is characterized in that: described metal nanoparticle is monometallic nano particle, or the alloy nano particle of various metals form, or has the metal nanoparticle of nucleocapsid structure; Described metal nanoparticle particle diameter is less than 50nm.
Described a kind of high performance fuel cell catalyst, is characterized in that, described metal oxide is selected from one or more the mixing in titanium oxide, vanadium oxide, tungsten oxide, molybdenum oxide, niobium oxide, chromium oxide.
Described a kind of high performance fuel cell catalyst, is characterized in that, when described metal nanoparticle is monometallic nano particle, monometallic refers to the one in platinum, palladium, gold; When described metal nanoparticle is metal alloy nanoparticles, metal alloy refers to containing two or more in gold, palladium, copper, nickel, cobalt, ruthenium, iron; When described metal nanoparticle is the metallic nanoparticle period of the day from 11 p.m. to 1 a.m with nucleocapsid structure, the core metal in core-shell type metal refers to one or more mixing of gold, palladium or ruthenium.
The preparation method of described high performance fuel cell catalyst, is characterized in that: when described metal nanoparticle is monometallic nano particle, its concrete steps are as follows:
(1) take carbon nano-carrier and be placed in absolute ethyl alcohol, make the mixing material that concentration of carbon is 1-5g/ml, ultrasonic or stirring 10-60min;
(2) in mixing material, add natrium citricum, the quality of the natrium citricum added is 0.5-5 times of carbonaceous amount, ultrasonic or stirring 10-60min;
(3) in mixing material, one or more mixing in the salt of titaniferous, vanadium, tungsten, molybdenum, niobium, chromium element are added, ultrasonic or stirring 10-60min;
(4) add in mixing material and go back original reagent, the amount of substance going back original reagent added be titaniferous, vanadium, tungsten, molybdenum, niobium, chromium element salts substances total amount 1.5-20 doubly, ultrasonic or stir 10-120min;
(5) in mixing material, add the salt of a kind of platiniferous or palladium element, the amount of the salts substances of the platiniferous added, gold or palladium element be titaniferous, vanadium, tungsten, molybdenum, niobium, chromium element salts substances amount summation 0.1-3 doubly, ultrasonic or stir 10-60min;
(6) centrifugal, filter, deionized water washing, dry, the monometallic nano-particle catalyst of obtained modified metal oxide, to obtain final product;
The preparation method of described high performance fuel cell catalyst, is characterized in that: when described metal nanoparticle is metal alloy nanoparticles, its concrete steps are as follows:
(1) take carbon nano-carrier and be placed in absolute ethyl alcohol, make the mixing material that concentration of carbon is 1-5g/ml, ultrasonic or stirring 10-60min;
(2) in mixing material, add natrium citricum, the quality of the natrium citricum added is 0.5-5 times of carbonaceous amount, ultrasonic or stirring 10-60min;
(3) in mixing material, one or more mixing in the salt of titaniferous, vanadium, tungsten, molybdenum, niobium, chromium element are added, ultrasonic or stirring 10-60min;
(4) add in mixing material and go back original reagent, the amount of substance going back original reagent added be titaniferous, vanadium, tungsten, molybdenum, niobium, chromium element salts substances total amount 1.5-20 doubly, ultrasonic or stir 10-120min;
(5) salt adding platiniferous element in mixing material with containing gold, palladium, copper, nickel, cobalt, ruthenium, ferro element salt two or more mix, the amount summation of the salts substances of the platiniferous added, gold, palladium, copper, nickel, cobalt, ruthenium, ferro element be titaniferous, vanadium, tungsten, molybdenum, niobium, chromium element salts substances amount summation 0.1-3 doubly, ultrasonic or stir 10-60min;
(6) centrifugal, filter, deionized water washing, dry, the metal alloy nanoparticles catalyst of obtained modified metal oxide;
The preparation method of described high performance fuel cell catalyst, is characterized in that: when described metal nanoparticle is the metallic nanoparticle period of the day from 11 p.m. to 1 a.m with nucleocapsid structure, its concrete steps are as follows:
(1) take carbon nano-carrier and be placed in absolute ethyl alcohol, make the mixing material that concentration of carbon is 1-5g/ml, ultrasonic or stirring 10-60min;
(2) in mixing material, add natrium citricum, the quality of the natrium citricum added is 0.5-5 times of carbonaceous amount, ultrasonic or stirring 10-60min;
(3) in mixing material, one or more mixing in the salt of titaniferous, vanadium, tungsten, molybdenum, niobium, chromium element are added, ultrasonic or stirring 10-60min;
(4) add in mixing material and go back original reagent, the amount of substance going back original reagent added be titaniferous, vanadium, tungsten, molybdenum, niobium, chromium element salts substances amount 1.5-20 doubly, ultrasonic or stir 10-120min;
(5) in mixing material, add one or more mixing of salt containing gold, palladium or ruthenium element, the amount summation of salts substances containing gold, palladium, ruthenium element added be titaniferous, vanadium, tungsten, molybdenum, niobium, chromium element salts substances amount summation 0.1-3 doubly, ultrasonic or stirring 10-60min;
(6) centrifugal, filter, deionized water washing, dry;
(7) the surfaces of metal nanoparticles deposited monolayers copper of underpotential deposition method obtained by step (6) is adopted, do not deposit at metal oxide surface, be placed on again in the solution containing platinum salt and displacement reaction occurs, copper is made to be formed individual layer platinum by platinum displacement, or repeat step (7) for several times to realize at gold, palladium or ruthenium nano particle surface deposition multilayer platinum, i.e. the core-shell structure metall nano-particle catalyst of obtained modified metal oxide.
The preparation method of described high performance fuel cell catalyst, is characterized in that: described carbon nano-carrier is selected from one or more mixing in carbon black, carbon nano-tube, carbon nano-fiber, Graphene etc.
Beneficial effect of the present invention:
The simple preparation method of the present invention achieves the regulation and control to catalyst surface Elemental composition rank, and the oxygen reduction reaction performance of catalyst is significantly improved.
New structure fuel-cell catalyst preparation method of the present invention is simple, easy to operate, carries out under normal temperature, realize without the need to relying on large-scale, special device and apparatus, easily realize mass production, and do not use poisonous chemical reagent, free from environmental pollution.
The new structure fuel-cell catalyst that the present invention obtains, owing to effectively reducing the oxygen desorption intensity on Pt surface, makes the oxygen reduction reaction activity of catalyst significantly improve.Simultaneously; metal oxide is positioned at the rib and corner position with lower ligancy; inner layer metal atom can be effectively reduced overflow; internal layer atom not only can be protected preferably to reduce it be corroded; but also the obstruction to Pt avtive spot caused because inner layer metal atom overflows can be reduced, thus improve the stability of catalyst.
The new structure fuel-cell catalyst that the present invention obtains, wherein, the core-shell structure metall nano-particle catalyst of modified metal oxide is while effectively improving catalyst activity and stability, also greatly reducing the consumption of Pt, is the fuel-cell catalyst that a kind of performance is very superior, very easily realize Commercialization application.
Accompanying drawing explanation
The core-shell structure metall nano-particle catalyst structural representation of Fig. 1 new structure modified metal oxide.
Fig. 2 titanium dioxide modifies golden nanometer particle scanning transmission microscope-electron energy loss spectroscopy (EELS) element Surface scan figure.
Fig. 3 titanium dioxide modifies the hydrogen reduction Performance comparision schematic diagram of AuPt core-shell structure metall nano-particle catalyst and commercialization Pt catalyst.
Fig. 4 titanium dioxide modifies the stability schematic diagram of AuPt core-shell structure metall nano-particle catalyst.
The hydrogen reduction Performance comparision schematic diagram of AuPt core-shell structure metall nano-particle catalyst and commercialization Pt catalyst modified by Fig. 5 vanadium oxide.
The stability schematic diagram of AuPt core-shell structure metall nano-particle catalyst modified by Fig. 6 vanadium oxide.
Embodiment
Embodiment 1:
Take carbon black 140g and be placed in 50ml absolute ethyl alcohol, after ultrasonic 60min, in mixing material, add natrium citricum 300mg, ultrasonic 30min.Then in mixing material, the titanium isopropoxide of 0.9mmol is added, ultrasonic 30min.Continue the SuperHydride adding 2ml1mol/L in mixing material, add the sodium chloraurate of 0.1mmol after ultrasonic reaction 30min, ultrasonic 60min.Mixing material is centrifugal, filter, deionized water washing to be placed in vacuum drying oven dry.Fig. 1 is scanning transmission microscope-electron energy loss spectroscopy (EELS) (STEM-EELS) the constituent content Surface scan figure that titanium dioxide modifies Au nano particle, the titanium dioxide that this method obtains as can be seen from Figure 1 is modified titanium in golden nanometer particle and is distributed in the surface of golden nanometer particle, and concentrates on rib and the corner position of golden nanometer particle.
Embodiment 2:
Take carbon black 140g and be placed in 50ml absolute ethyl alcohol, after ultrasonic 60min, in mixing material, add natrium citricum 300mg, ultrasonic 30min.Then in mixing material, the titanium isopropoxide of 0.3mmol is added, ultrasonic 30min.Continue the SuperHydride adding 2ml1mol/L in mixing material, add the sodium chloraurate of 0.1mmol after reaction 30min, ultrasonic 60min.Mixing material is centrifugal, filter, deionized water washing to be placed in vacuum drying oven dry.Finally adopt underpotential deposition method at obtained golden nanometer particle surface deposition individual layer copper, do not deposit at titanium dioxide surface, be placed on again in the solution containing platinum salt and displacement reaction occurs, copper is made to be formed individual layer platinum by platinum displacement, repeating this step also can at the double-deck platinum of golden nanometer particle surface deposition, gold (core)-platinum (shell) type catalyst that obtained titanium dioxide is modified.Fig. 2 is the structural representation that titanium dioxide modifies AuPt core-shell structure metall nano-particle catalyst.Fig. 3 is that this method obtains gold (core)-platinum (shell) the type catalyst of titanium dioxide modification and the oxygen reduction reaction Performance comparision of commercialization Pt catalyst (TanakaKikinzokuInternationalInc., 10E50E, 46.6wt%Pt).Oxygen reduction reaction surface area activated of gold (core)-platinum (shell) type catalyst that titanium dioxide is modified as seen in Figure 3 is nearly 5 times of commercialization Pt catalyst, and the mass activity of oxygen reduction reaction is nearly 10 times of commercialization Pt catalyst.Fig. 4 is the stability schematic diagram that this method obtains gold (core)-platinum (shell) type catalyst that titanium dioxide is modified.As seen in Figure 4, through the current potential circulation of 10000 circles, the oxygen reduction reaction performance of gold (core)-platinum (shell) type catalyst that titanium dioxide is modified does not decline completely, illustrates that gold (core)-platinum (shell) type catalyst that titanium dioxide is modified has good stability.
Embodiment 3:
Take carbon black 140g and be placed in 50ml absolute ethyl alcohol, after ultrasonic 60min, in mixing material, add natrium citricum 300mg, ultrasonic 30min.Then in mixing material, the vanadium dichloride of 0.8mmol is added, ultrasonic 30min.Continue the SuperHydride adding 3ml1mol/L in mixing material, add the sodium chloraurate of 0.14mmol after ultrasonic reaction 60min, ultrasonic 60min.Mixing material is centrifugal, filter, deionized water washing to be placed in vacuum drying oven dry.Finally adopt underpotential deposition method at obtained golden nanometer particle surface deposition individual layer copper, do not deposit at vanadium oxide surface, be placed on again in the solution containing platinum salt and displacement reaction occurs, copper is made to be formed individual layer platinum by platinum displacement, repeating this step also can at the double-deck platinum of golden nanometer particle surface deposition, gold (core)-platinum (shell) type catalyst that obtained vanadium oxide is modified.Fig. 5 is that this method obtains gold (core)-platinum (shell) the type catalyst of vanadium oxide modification and the oxygen reduction reaction Performance comparision of commercialization Pt catalyst (TanakaKikinzokuInternationalInc., 10E50E, 46.6wt%Pt).The surface area activated of oxygen reduction reaction of gold (core)-platinum (shell) the type catalyst of vanadium oxide modification is more than 5 times of commercialization Pt catalyst as seen in Figure 5, and the mass activity of oxygen reduction reaction is nearly 8 times of commercialization Pt catalyst.Fig. 6 is the stability schematic diagram that this method obtains gold (core)-platinum (shell) type catalyst that vanadium oxide is modified.As seen in Figure 6, through the current potential circulation of 6000 circles, the oxygen reduction reaction performance of gold (core)-platinum (shell) type catalyst that vanadium oxide is modified does not decline completely, illustrates that gold (core)-platinum (shell) type catalyst that vanadium oxide is modified has good stability.

Claims (8)

1. a high performance fuel cell catalyst, is characterized in that: be made up of metal and metal oxide; Metal forms the metal nanoparticle that surface has crystal face, rib and drift angle; On the rib that metal oxide is positioned at surfaces of metal nanoparticles and drift angle.
2. a kind of high performance fuel cell catalyst according to claim 1, is characterized in that: described metal nanoparticle is monometallic nano particle, or the alloy nano particle of various metals form, or has the metal nanoparticle of nucleocapsid structure; Described metal nanoparticle particle diameter is less than 50nm.
3. a kind of high performance fuel cell catalyst according to claim 1, is characterized in that, described metal oxide is selected from one or more the mixing in titanium oxide, vanadium oxide, tungsten oxide, molybdenum oxide, niobium oxide, chromium oxide.
4. a kind of high performance fuel cell catalyst according to claim 2, is characterized in that, when described metal nanoparticle is monometallic nano particle, monometallic refers to the one in platinum, palladium, gold; When described metal nanoparticle is metal alloy nanoparticles, metal alloy refers to containing two or more in gold, palladium, copper, nickel, cobalt, ruthenium, iron; When described metal nanoparticle is the metallic nanoparticle period of the day from 11 p.m. to 1 a.m with nucleocapsid structure, the core metal in core-shell type metal refers to one or more mixing of gold, palladium or ruthenium.
5. a preparation method for high performance fuel cell catalyst as claimed in claim 1, is characterized in that: when described metal nanoparticle is monometallic nano particle, its concrete steps are as follows:
(1) take carbon nano-carrier and be placed in absolute ethyl alcohol, make the mixing material that concentration of carbon is 1-5g/ml, ultrasonic or stirring 10-60min;
(2) in mixing material, add natrium citricum, the quality of the natrium citricum added is 0.5-5 times of carbonaceous amount, ultrasonic or stirring 10-60min;
(3) in mixing material, one or more mixing in the salt of titaniferous, vanadium, tungsten, molybdenum, niobium, chromium element are added, ultrasonic or stirring 10-60min;
(4) add in mixing material and go back original reagent, the amount of substance going back original reagent added be titaniferous, vanadium, tungsten, molybdenum, niobium, chromium element salts substances total amount 1.5-20 doubly, ultrasonic or stir 10-120min;
(5) in mixing material, add the salt of a kind of platiniferous or palladium element, the amount of the salts substances of the platiniferous added, gold or palladium element be titaniferous, vanadium, tungsten, molybdenum, niobium, chromium element salts substances amount summation 0.1-3 doubly, ultrasonic or stir 10-60min;
(6) centrifugal, filter, deionized water washing, dry, the monometallic nano-particle catalyst of obtained modified metal oxide, to obtain final product.
6. a preparation method for high performance fuel cell catalyst as claimed in claim 1, is characterized in that: when described metal nanoparticle is metal alloy nanoparticles, its concrete steps are as follows:
(1) take carbon nano-carrier and be placed in absolute ethyl alcohol, make the mixing material that concentration of carbon is 1-5g/ml, ultrasonic or stirring 10-60min;
(2) in mixing material, add natrium citricum, the quality of the natrium citricum added is 0.5-5 times of carbonaceous amount, ultrasonic or stirring 10-60min;
(3) in mixing material, one or more mixing in the salt of titaniferous, vanadium, tungsten, molybdenum, niobium, chromium element are added, ultrasonic or stirring 10-60min;
(4) add in mixing material and go back original reagent, the amount of substance going back original reagent added be titaniferous, vanadium, tungsten, molybdenum, niobium, chromium element salts substances total amount 1.5-20 doubly, ultrasonic or stir 10-120min;
(5) salt adding platiniferous element in mixing material with containing gold, palladium, copper, nickel, cobalt, ruthenium, ferro element salt two or more mix, the amount summation of the salts substances of the platiniferous added, gold, palladium, copper, nickel, cobalt, ruthenium, ferro element be titaniferous, vanadium, tungsten, molybdenum, niobium, chromium element salts substances amount summation 0.1-3 doubly, ultrasonic or stir 10-60min;
(6) centrifugal, filter, deionized water washing, dry, the metal alloy nanoparticles catalyst of obtained modified metal oxide.
7. a preparation method for high performance fuel cell catalyst as claimed in claim 1, is characterized in that: when described metal nanoparticle is the metallic nanoparticle period of the day from 11 p.m. to 1 a.m with nucleocapsid structure, its concrete steps are as follows:
(1) take carbon nano-carrier and be placed in absolute ethyl alcohol, make the mixing material that concentration of carbon is 1-5g/ml, ultrasonic or stirring 10-60min;
(2) in mixing material, add natrium citricum, the quality of the natrium citricum added is 0.5-5 times of carbonaceous amount, ultrasonic or stirring 10-60min;
(3) in mixing material, one or more mixing in the salt of titaniferous, vanadium, tungsten, molybdenum, niobium, chromium element are added, ultrasonic or stirring 10-60min;
(4) add in mixing material and go back original reagent, the amount of substance going back original reagent added be titaniferous, vanadium, tungsten, molybdenum, niobium, chromium element salts substances amount 1.5-20 doubly, ultrasonic or stir 10-120min;
(5) in mixing material, add one or more mixing of salt containing gold, palladium or ruthenium element, the amount summation of salts substances containing gold, palladium, ruthenium element added be titaniferous, vanadium, tungsten, molybdenum, niobium, chromium element salts substances amount summation 0.1-3 doubly, ultrasonic or stirring 10-60min;
(6) centrifugal, filter, deionized water washing, dry;
(7) the surfaces of metal nanoparticles deposited monolayers copper of underpotential deposition method obtained by step (6) is adopted, do not deposit at metal oxide surface, be placed on again in the solution containing platinum salt and displacement reaction occurs, copper is made to be formed individual layer platinum by platinum displacement, or repeat step (7) for several times to realize at gold, palladium or ruthenium nano particle surface deposition multilayer platinum, i.e. the core-shell structure metall nano-particle catalyst of obtained modified metal oxide.
8. the preparation method of the high performance fuel cell catalyst according to claim 5 or 6 or 7, is characterized in that: described carbon nano-carrier is selected from one or more mixing in carbon black, carbon nano-tube, carbon nano-fiber, Graphene etc.
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CN107123815A (en) * 2017-05-18 2017-09-01 成都艾欧新能源科技有限公司 Preparation method for fuel-cell catalyst
CN112952121A (en) * 2019-12-10 2021-06-11 中国科学院大连化学物理研究所 Electrode material with fiber structure, preparation and application
CN115050973A (en) * 2022-06-01 2022-09-13 北京化工大学 Preparation method of metal oxide modified electrocatalyst for direct formate fuel cell anode

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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
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CN107123815A (en) * 2017-05-18 2017-09-01 成都艾欧新能源科技有限公司 Preparation method for fuel-cell catalyst
CN112952121A (en) * 2019-12-10 2021-06-11 中国科学院大连化学物理研究所 Electrode material with fiber structure, preparation and application
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CN115050973B (en) * 2022-06-01 2024-03-26 北京化工大学 Preparation method of metal oxide modified electrocatalyst for anode of direct formate fuel cell

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