CN103657648A - Preparation method of fuel-cell catalyst Pt/WO3/C - Google Patents

Preparation method of fuel-cell catalyst Pt/WO3/C Download PDF

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CN103657648A
CN103657648A CN201210336543.1A CN201210336543A CN103657648A CN 103657648 A CN103657648 A CN 103657648A CN 201210336543 A CN201210336543 A CN 201210336543A CN 103657648 A CN103657648 A CN 103657648A
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catalyst
solution
preparation
metal oxide
ethylene glycol
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侯明
窦美玲
梁栋
邵志刚
衣宝廉
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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    • 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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    • 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 preparation method of a fuel-cell catalyst Pt/WO3/C. According to the catalyst, XC-72 is used as an active component carrier, Pt nano particles are used as a main active component, mesoporous WO3 is used as an assistant, the quality percent of Pt in the catalyst is 10-30 percent, and the mol ratio of Pt to W is 1:0.1-1:1. The preparation method comprises the steps of pouring reduced Pt/ethylene glycol slurry to a carbon carrier added with the mesoporous metal oxide WO3 to obtain a Pt/WO3/C electrocatalyst; preparing the mesoporous WO3 by adopting a molecular sieve template method. The prepared Pt/WO3/C can be used as cathode and anode catalysts of a proton exchange membrane fuel cell.

Description

A kind of fuel-cell catalyst Pt/WO 3the preparation method of/C
Technical field
The present invention relates to a kind of fuel-cell catalyst Pt/WO 3the preparation method of/C, specifically usings XC-72 as active component carrier, take Pt nano particle as main active component, with mesoporous WO 3for auxiliary agent, its preparation method is that as-reduced Pt/ ethylene glycol slurry is cast in and has added mesopore metal oxide WO 3carbon support material on, obtain Pt/WO 3/ C eelctro-catalyst, mesoporous WO 3adopt Molecular Sieves as Template legal system standby.Catalyst proton exchange film fuel cell negative electrode of the present invention and anode catalyst, can be widely used in fuel cell field.
Background technology
Proton Exchange Membrane Fuel Cells (PEMFC) is as a kind of novel energy conversion device, has that operating temperature is low, pollution-free, specific power large, respond the advantages such as rapid, become the hot spot technology that competitively research and develop countries in the world.Pt metal, with its high electro catalytic activity and chemical stability, is widely used in the active component of fuel-cell catalyst.But due to Pt metal resource scarcity, expensive, cause low-temperature fuel cell manufacturing cost high; Meanwhile, Pt catalyst selectivity is poor, and the CO that is subject to trace in anode fuel poisons, and reduces output performance, has limited its extensive use.Therefore, preparation have high catalytic activity simultaneously the poisoning fuel-cell catalyst of anti-CO there is very important practical significance.In traditional noble metal catalyst, add or containing transition metal oxide, can improve the anti-CO poisoning performance of catalyst, improve electrocatalysis characteristic.Some metal oxides are made co-catalyst and in fuel-cell catalyst, have been obtained research, for example TiO widely in recent years 2, SnO 2, CeO 2, WO 3deng.
Related documents research report shows WO 3can significantly strengthen electro catalytic activity and the anti-CO poisoning performance of Pt/C catalyst.WO 3there is good electron conduction and ionic conducting property, in acid solution, can form the blue or green ketone of compound tungsten of a kind of non-stoichiometric conduction, can be compared with discharging proton (seeing reaction equation 1 and 2) under electronegative potential; Meanwhile, WO 3quite stable in sour environment, and there is excellent CO resistance performance.Therefore, by WO 3adulterate or add in Pt/C catalyst and be prepared into Pt/WO 3/ C is for anode of proton exchange membrane fuel cell catalyst, WO 3can form certain concerted catalysis effect with Pt, improve its hydroxide catalytic activity, strengthen its CO resistance performance simultaneously.（N.P.Lebedeva,V.Rosca,G.J.M.Janssen，CO?oxidation?and?CO 2?reduction?on?carbon?supported?Pt/WO 3catalyst.Electrochimica?Acta?55(2010)7659-7668.）
WO 3+xH ++xe -＝H xWO 3(0<x<1)
（1）
WO 3+2yH ++2ye -=WO 3-y+yH 2O(0<y<1)
（2）
By Pt/WO 3/ C catalyst is used as fuel battery cathode with proton exchange film, when Pt can not fully contact with Nafion, and WO 3can serve as proton conductor, promote the conduction of proton in hydrogen reduction process, increase three-phase reaction interface, thereby improve cell cathode performance.The people such as Sun have prepared the Pt/WO of high dispersive 3/ C catalyst, and used as fuel battery cathode with proton exchange film, result shows the WO that adulterated 3pt/C composite catalyst in hydrogen reduction performance, be better than unadulterated Pt/C catalyst (Z.Sun, H.C.Chiu, A.C.C.Tseung.Oxygen reduction on teflon bonded Pt/WO 3/ C Electrode in sulfuric acid.Electrochemical and Solid-State Letters 4 (2001) E9-E12).
At present, for Pt/WO 3the preparation method of/C mainly contains two kinds, and a kind of is by WO 3precursor and Pt/C catalyst mix, under acid condition, make Pt-WO 3/ C catalyst.Catalyst prepared by the method, WO 3do not participate in Pt catalyst forming process (Joongpyo Shim, Chang-Rae Lee, Hong-Ki Lee, Ju-Seong Lee, Elton J.Cairns, Electrochemical characteristicsof Pt-WO directly 3/ C and Pt-TiO 2/ C electrocatalysts in a polymer electrolyte fuel cell.J.Power Sources, 102 (2001) 172-177.).Another kind method is by two step synthesis Pt/WO 3/ C catalyst, first synthesizes WO by solid phase method 3/ C composite carrier, and then Pt presoma is loaded on to (Jilei Ye, Jianguo Liu, Zhigang Zou on complex carrier by dipping reduction, sodium borohydride or hydrogen reduction method, Jun Gua, TaoYu.Preparation of Pt supported on WO 3-C with enhanced catalyticactivity by microwave-pyrolysis method.J.Power Sources 195 (2010) 2633-2637).Adopting dipping-reducing process to prepare loaded Pt catalyst need to be at high temperature reduction under alkali condition, due to WO 3dissolve in strong basicity (as the NaOH) solution of dense heat, this method is for preparation Pt/WO 3/ C catalyst is also not exclusively applicable.While adopting sodium borohydride reduction, Pt particle is easily reunited, and is difficult to control the size of Pt particle, therefore when Pt load amount is relatively high, cannot obtain the catalyst that Pt particle homogeneous disperses.And when Pt presoma in hydrogen atmosphere during high temperature reduction (T.Maiyalagan, B.Viswanathan.J.Power Sources.2008,175,789-793), due to WO 3to Pt surface migration, easily cover the active sites on Pt nano particle.
WO 3pattern and size be to improve the effective ways of the dispersed and stability of catalyst.Control pattern except improving dispersiveness and the catalytic activity of catalyst, can also improve oxidation resistance and the antilysis performance of oxide.In existing report, WO 3as auxiliary agent, prepare Pt/WO 3/ C catalyst, exists mainly with nanoparticle form.We take the mesoporous WO that silicon oxide molecular sieve is prepared as hard template 3nano-cluster, as auxiliary agent, adopts a kind of microwave reduction casting to prepare Pt/WO 3/ C catalyst, this catalyst has high hydroxide and hydrogen reduction is active, can be used as anode of proton exchange membrane fuel cell and cathod catalyst.At present, there is not yet this class material both at home and abroad, especially for the report in catalyst of fuel batter with proton exchange film.
Summary of the invention
The object of the present invention is to provide a kind of fuel-cell catalyst Pt/WO 3the preparation method of/C.
In this catalyst, using XC-72 as active component carrier, take Pt nano particle as active component, with mesoporous WO 3for auxiliary agent.Its preparation method is that as-reduced Pt/ ethylene glycol slurry is cast in and has added mesopore metal oxide WO 3carbon support material on, obtain Pt/WO 3/ C eelctro-catalyst, mesoporous WO 3adopt Molecular Sieves as Template legal system standby.Catalyst prepared by the present invention can be used as fuel battery cathode with proton exchange film and anode catalyst.
For achieving the above object, the technical solution used in the present invention is as follows:
(1) take mesoporous silicon oxide molecular sieve as template, add W presoma, in solution, by the method for dipping, prepare mesopore metal oxide WO 3;
(2) by above-mentioned mesopore metal oxide WO 3be dispersed in nonaqueous solvents with carbon carrier, obtain WO 3mixed slurry with carbon carrier;
Described nonaqueous solvents is absolute ethyl alcohol or ethylene glycol;
Carbon carrier is 0.1～0.5M in molar concentration wherein.
(3) chloroplatinic acid is dissolved in ethylene glycol solution, the ethylene glycol solution that drips NaOH is adjusted to 9～13 by pH; Wherein the ethylene glycol solution concentration of NaOH is 1～4M, and Pt concentration in ethylene glycol solution is 0.0005M～0.005M;
(4) adopt microwave heating method by the Pt presoma reduction in above-mentioned solution, cooling and stirring is to room temperature;
Described microwave method comprises continuous microwave and gap microwave method, and 20～50 ml solns adopt microwave power 50～100W;
Wherein the continuous microwave heat time is 0.5～5min;
Gap microwave method is heating 5～20s, and gap stops 5～20s, repeats 3～15 times.
(5) the Pt/ ethylene glycol slurry of above-mentioned reduction is incorporated in to described mesoporous WO 3in the mixed solution of carbon carrier, the mol ratio of Pt and W is 1:0.1 ~ 1:1;
Drip salpeter solution and make system pH=1-3, stir after 24～48h standing 3～6 days;
Salpeter solution concentration is 0.1～2.5M;
(6) by gained suspension after centrifugal, washing, vacuum drying, obtain end product Pt/WO 3/ C
Catalyst.
Described vacuum drying temperature is 40～80 ° of C, and be 5～24h drying time.
The described catalyst promoter WO of above-mentioned steps (1) 3be to take the mesopore metal oxide that silicon oxide molecular sieve prepared as template, in solution, W presoma be impregnated in silica duct, after evaporation, roasting, etching is removed silica template and is prepared from; Mesopore metal oxide WO prepared by described method 3copied the pore passage structure of template mesopore molecular sieve.It is characterized in that:
(1) take mesoporous silicon oxide molecular sieve as hard template, molecular sieve is dispersed in nonaqueous solvents, adds soluble tungsten precursor, stir it is fully dissolved, the metal molar concentration that tungsten presoma salt is dissolved in ethanol is 0.03～1.0M, and the mol ratio of silica and tungsten is controlled at 1～10;
Described molecular sieve is the silicon oxide molecular sieve of various removal surfactants, as SBA-15, KIT-6 or MCM-41;
Described soluble tungsten precursor is silico-tungstic acid;
Described nonaqueous solvents is absolute ethyl alcohol.
(2) above-mentioned solution is stirred to 12～48h under 10～50 ° of C, under 20～80 ° of C, after solvent evaporated, obtain the complex solid powder of tungsten presoma and silica;
(3) under air or oxygen atmosphere, by above-mentioned pressed powder high-temperature roasting, 300～800 ° of C of sintering temperature, 1～5 ° of C min of temperature programming speed -1, roasting time 3～8h, obtains metal oxide WO 3complex with silica;
(4) complex is joined in HF or NaOH solution, take the etching agent that HF or NaOH solution is silica, remove above-mentioned metal oxide WO 3with the silica composition of silicon oxide composite unit, separation, solid product washes with water in the vacuum drying oven that is placed on 40～80 ° of C, obtains end product metal oxide WO 3; The concentration of HF or NaOH solution is 1～40%, and the processing time is 5～48h, and temperature is 10～60 ° of C, and the mol ratio of the silica in metal oxide and silicon oxide composite unit and HF or NaOH is 0.01～1.0.
The good implementation condition of the present invention is:
The mesoporous WO of described auxiliary agent 3be to take silicon oxide molecular sieve as template preparation, there is large specific area (30～100m 2g -1), the pore passage structure of homogeneous and high heat endurance, be conducive to the dispersion of Pt nano particle.
The mesoporous WO of described auxiliary agent 3have good electron conduction and fast ion conduction performance, especially its hydrated compound often has proton conductivity of phosphoric acid, and simultaneously also quite stable under acid condition, is conducive to the raising of catalyst activity.
Described nonaqueous solvents is absolute ethyl alcohol or ethylene glycol, can improve the degree of scatter of carrier material.
Described method of reducing adopts microwave method, can effectively control the reduction of Pt presoma.
In standing process, the Oswald that Pt nano particle occurs is aging, be conducive to evenly supporting of Pt particle.
Advantage of the present invention is mainly reflected in:
The present invention utilizes microwave reduction casting to prepare Pt/WO 3/ C catalyst, relatively has quick, simple, energy-conservation and economic dispatch advantage with existing synthetic method, not only can realize evenly supporting of Pt nano particle, has also avoided the contingent variation under the condition of high temperature of catalyst promoter and carrier material simultaneously.
The Pt/WO that the present invention obtains 3/ C catalyst is with mesopore metal oxide WO 3as auxiliary agent, described mesoporous WO 3oppositely copied the pore passage structure of mesopore silicon oxide, presented nano-cluster shape structure, nano-cluster is comprised of parallel nanometer rods, and nanometer rods diameter is about 8 ~ 9nm.At Pt/WO 3in the building-up process of/C catalyst, the mesoporous WO adding 3nano-cluster, particle diameter (particle diameter reaches 1.5 ~ 2.0nm) that can refinement Pt nano particle, is conducive to its high dispersive on carrier.
The Pt/WO that the present invention obtains 3/ C catalyst is with mesopore metal oxide WO 3as auxiliary agent, described mesoporous WO 3in acid solution, can form a kind of blue or green ketone of compound tungsten of non-stoichiometric, be conducive to the adsorption desorption process of hydrogen, for hydroxide reaction, can with Pt concerted catalysis (see and react 3 and 4), contribute to improve the hydroxide activity of catalyst.
WO 3+xPt-H→H XWO 3+xPt
（3）
H XWO 3→WO 3+xH ++xe -
（4）
The Pt/WO that the present invention obtains 3/ C catalyst is with mesopore metal oxide WO 3as auxiliary agent, described mesoporous WO 3the compound W hydrogen ketone that can form a kind of non-stoichiometric in acid solution, can discharge proton compared with under electronegative potential, when Pt can not fully contact with Nafion, and WO 3can serve as proton conductor, increase three-phase reaction interface, the surface-active site utilization rate of Pt be improved, thereby improve hydroxide and hydrogen reduction catalytic activity, contribute to improve battery performance.
The Pt/WO that the present invention obtains 3/ C catalyst has higher hydroxide and hydrogen reduction catalytic activity than Pt/C catalyst, and better CO resistance performance, can extensive use as the eelctro-catalyst of Proton Exchange Membrane Fuel Cells.
Fuel-cell catalyst Pt/WO prepared by the present invention 3/ C is in fuel battery cathode with proton exchange film and anode-side application.
Accompanying drawing explanation
Fig. 1. mesoporous WO 3xRD collection of illustrative plates.
Fig. 2 .Pt/C and Pt/WO 3the XRD spectra of/C (Pt:W=1:0.21,1:0.42,1:0.84) catalyst.
Fig. 3. (a) WO 3, (b) Pt/C, (c) Pt/WO 3/ C (Pt:W=1:0.21), (d) Pt/WO 3/ C (Pt:W=1:0.42) and (e) Pt/WO 3the TEM figure of/C (Pt:W=1:0.84) catalyst.
Fig. 4 .Pt/WO 3/ C(Pt:W=1:0.21) EDX of catalyst figure.
Fig. 5 .Pt/C and Pt/WO 3the cyclic voltammetry curve of/C catalyst (Pt:W=1:0.21,1:0.42,1:0.84), electrolyte is 0.5M H 2sO 4, sweep limits is 0～1.2V vs.NHE, sweep speed is 50mV s -1.
Fig. 6 .Pt/C and Pt/WO 3the hydrogen reduction curve of/C catalyst (Pt:W=1:0.21,1:0.42,1:0.84), electrolyte is 0.5M H 2sO 4, sweep limits is 0.2～1.0V vs.NHE, sweep speed is 5mV s -1, revolution is 1600rpm min -1.
Fig. 7. the polarization curve of Proton Exchange Membrane Fuel Cells, catalyst is respectively Pt/C and Pt/WO 3/ C (Pt:W=1:0.21,1:0.42,1:0.84) catalyst, anode and cathode Pt loading is all 0.2mgcm -2, electrode area 5cm 2, 60 ° of C of probe temperature, pressure 0.05MPa, anode and cathode is saturated humidification all, and hydrogen flowing quantity is 20ml min -1, oxygen flow is 100ml min -1.
The specific embodiment
Embodiment 1
Adopt continuous microwave legal system for Pt/WO 3/ C catalyst, specific implementation method is:
The SBA-15 of take prepares mesopore metal oxide WO as template 3, specific implementation method is: 2g SBA-15 is well-dispersed in 40mL ethanolic solution, adds 6g metal precursor silicon W acid, solvent evaporated after fully stirring moves into gained dusty material in tube furnace 600 ° of C roasting 4h in air, 2 ° of C min of temperature programming speed -1.After cooling, with mass concentration 15%HF, remove silica template, centrifugation, deionized water washing 4～6 times, 40 ° of C are dried 12h, obtain the mesopore metal oxide WO of nano-cluster shape structure 3, its XRD collection of illustrative plates (as accompanying drawing 1) result shows prepared WO 3the crystallinity with height, TEM morphology characterization can be seen prepared mesopore metal oxide WO 3present nano-cluster shape structure, nano-cluster is comprised of parallel nanometer rods, and nanometer rods diameter is about 8 ~ 9nm(as accompanying drawing 3).
Take the mesoporous WO of 46.8mg XC-72 and 3.2mg 3be well-dispersed in 10mL ethanolic solution, ultrasonic 1h, stirs 2h, obtains mesoporous WO 3mixed solution with carbon carrier.By 3.4ml chloroplatinic acid/ethylene glycol solution (3.7mg ml -1) be uniformly mixed with 30ml ethylene glycol, making Pt and W mol ratio is 1:0.21.Then drip 2M NaOH/ethylene glycol solution to pH=10, placed continuous microwave in micro-wave oven and heat after 1min, be naturally down to room temperature, obtain Pt/ ethylene glycol slurry.The Pt/ ethylene glycol slurry of above-mentioned reduction is dropwise cast in and contains mesoporous WO 3carbon carrier on, add 2M nitric acid to make pH value of solution=2, stir after 36h standing 3 days.Gained suspension, after centrifugal, washing, 60 ° of C vacuum drying 8h, is obtained to end product Pt/WO 3/ C, is designated as Pt/WO 3/ C (Pt:W=1:0.21), Pt load amount is 20%.
As a comparison, in synthetic solvent, do not add mesoporous WO 3nano-cluster, with the synthetic Pt/C catalyst (mass fraction of platinum is 20%) of above-mentioned identical method.
Embodiment 2
By the method identical with embodiment 1, test, but change rate of charge, making Pt and W mol ratio is 1:0.42, synthetic Pt/WO 3/ C catalyst, is designated as Pt/WO 3/ C (Pt:W=1:0.42)
Embodiment 3
By the method identical with embodiment 1, test, but change rate of charge, making Pt and W mol ratio is 1:0.84, synthetic Pt/WO 3/ C catalyst, is designated as Pt/WO 3/ C (Pt:W=1:0.84), the catalyst prepared by embodiment 1,2,3 can detect Pt and WO from XRD collection of illustrative plates 3and the existence of C, as accompanying drawing 2.From TEM figure, also can see WO 3after adding, Pt and WO 3be dispersed in uniformly in carbon support material, Pt particle diameter is about 1.5 ~ 2nm, as accompanying drawing 3.
Embodiment 4
By the method identical with embodiment 1, test, but adopt ethylene glycol to make solvent, disperse mesoporous WO 3and XC-72, synthetic Pt/WO 3/ C catalyst.Exist (as Fig. 4) of Pt and W from EDX figure, can be detected.
Embodiment 5
By the Pt/WO of preparation in embodiment 1,2,3 3/ C catalyst characterizes the chemical property of catalyst under room temperature with cyclic voltammetry (CV) and hydrogen reduction (ORR) test.By 1ml isopropyl alcohol and 50 μ L
Figure BDA00002129270100071
solution (5wt%) joins in 5mg catalyst to be measured, ultrasonic being uniformly dispersed.Then with microsyringe, pipette 10 μ L slurries, minute being applied to area for four times is 0.1256cm 2glass-carbon electrode surface, under infrared lamp, dry.Adopt under three-electrode system normal temperature and test, electrolyte solution is 0.5mol L -1sulfuric acid solution, during the cyclic voltammetric of detecting catalyst, its sweep limits be 0-1.2V with respect to standard hydrogen electrode (vs.NHE), sweep speed is 50mV s -1.During hydrogen reduction test, sweep limits is 0.2-1.0V vs.NHE, and sweep speed is 5mV s -1, rotating speed is 1600rpm min -1.Its CV and ORR curve as shown in Figure 5 and Figure 6, can be seen Pt/WO 3/ C has higher hydroxide with respect to 20%Pt/C catalyst and hydrogen reduction is active.
Embodiment 6
By the Pt/WO of preparation in embodiment 1,2,3 3/ C catalyst is as fuel battery cathode with proton exchange film and anode catalyst, by itself and 5%
Figure BDA00002129270100072
solution, ethanol is ultrasonic mix after, brush in Torry carbon paper surface, 60 ° of C are dried 2h, as negative electrode and the anode of Proton Exchange Membrane Fuel Cells, both sides Pt load amount is 0.2mg cm respectively -2.Negative electrode and anode are placed in
Figure BDA00002129270100073
the both sides of 212 films, at 140 ° of C, under 10atm, are pressed into membrane electrode.
Cell evaluation parameter is as follows: 60 ° of C of operating temperature, and anode and cathode humidification temperature is 65 ° of C, under 0.05M Pa, operates, hydrogen flowing quantity is 20ml min -1, oxygen flow is 100ml min -1, electrode effective area is 5cm 2.
Test result: by Pt/WO 3/ C is as the battery of Proton Exchange Membrane Fuel Cells anode and cathode catalyst assembling, Fig. 7 be its at 60 ° of C, polarization curve during 0.05M Pa operation, relative 20%Pt/C electrode, has obtained high battery performance and power density.
Embodiment 7
Adopt gap microwave method to prepare Pt/WO 3/ C catalyst, specific implementation method is:
Take the mesoporous WO of 46.8mgXC-72 and 3.2mg 3be well-dispersed in 10mL ethanolic solution, ultrasonic 1h, stirs 2h, obtains mesoporous WO 3mixed solution with carbon carrier.By 3.4ml chloroplatinic acid/ethylene glycol solution (3.7mg ml -1) be uniformly mixed with 30ml ethylene glycol, making Pt and W mol ratio is 1:0.21.Then drip 2M NaOH/ethylene glycol solution to pH=10, placed the heating using microwave of micro-wave oven intermediate gap, heat 10s, stop 10s, repeat 6 times, be down to room temperature, obtain Pt/ ethylene glycol slurry.The Pt/ ethylene glycol slurry of above-mentioned reduction is dropwise cast in and contains mesoporous WO 3carbon carrier on, add 2M nitric acid to make pH value of solution=2, stir after 36h standing 3 days.Gained suspension, after centrifugal, washing, 60 ° of C vacuum drying 8h, is obtained to end product Pt/WO 3/ C, is designated as Pt/WO 3/ C (Pt:W=1:0.21), Pt load amount is 20%.
Embodiment 8
By the method identical with embodiment 7, test, but change rate of charge, making Pt and W mol ratio is 1:0.42, synthetic Pt/WO 3/ C catalyst, is designated as Pt/WO 3/ C (Pt:W=1:0.42).
Embodiment 9
By the method identical with embodiment 7, test, but change rate of charge, making Pt and W mol ratio is 1:0.84, synthetic Pt/WO 3/ C catalyst, is designated as Pt/WO 3/ C (Pt:W=1:0.84).
Embodiment 10
As a comparison, immersion reduction method for preparing Pt/WO routinely 3/ C catalyst, concrete steps are: take the mesoporous WO of 46.8mg XC-72 and 3.2mg 3be well-dispersed in 30mL ethylene glycol solution, ultrasonic 1h, stirs 2h, obtains mesoporous WO 3with the mixed solution of carbon carrier, add 3.4ml chloroplatinic acid/ethylene glycol solution (3.7mg ml -1), making Pt and W mol ratio is 1:0.21.Then drip 2M NaOH/ethylene glycol solution to pH=10, above-mentioned mixed solution is placed to continuous microwave in micro-wave oven and heat after 1min, be naturally down to room temperature.Add 2M nitric acid to make pH value of solution=2, stir after 36h standing 3 days.Gained suspension, after centrifugal, washing, 60 ° of C vacuum drying 8h, is obtained to end product Pt/WO 3/ C, is designated as Pt/WO 3/ C (Pt:W=1:0.21), Pt load amount is 20%.Through characterizing, knownly by the prepared catalyst Pt nano particle diameter of conventional immersion reduction method, be about 2 ~ 4nm, by the Pt/WO of preparation 3/ C catalyst is assembled into battery (concrete electrode preparation method and cell evaluation parameter are identical with embodiment 6) as Proton Exchange Membrane Fuel Cells anode and cathode catalyst, and when voltage is 0.6V, current density is 1000mA cm -2, power density reaches 0.6W cm -2.
With respect to conventional method, the Pt/WO that the inventive method is prepared 3/ C catalyst has obtained less particle diameter, is about 1.5 ~ 2.0nm.Using it as the assembled battery of Proton Exchange Membrane Fuel Cells anode and cathode catalyst, obtained higher battery performance and power density, when voltage is 0.6V, current density is 1190mA cm -2, power density is 0.72W cm -2, as shown in Figure 7.

Claims (7)

1. a fuel-cell catalyst Pt/WO 3the preparation method of/C, described catalyst is to using XC-72 as carrier, take Pt nano particle as active component, with WO 3for auxiliary agent, in catalyst, the mass fraction of Pt is that the mol ratio of 10 ~ 30%, Pt and W is 1:0.1 ~ 1:1; It is characterized in that:
(1) take mesoporous silicon oxide molecular sieve as template, add W presoma, in solution, by the method for dipping, prepare mesopore metal oxide WO 3;
(2) by above-mentioned mesopore metal oxide WO 3be dispersed in nonaqueous solvents with carbon carrier, obtain WO 3mixed slurry with carbon carrier;
(3) chloroplatinic acid is dissolved in ethylene glycol solution, the ethylene glycol solution that drips NaOH is adjusted to 9～13 by pH; Wherein the ethylene glycol solution concentration of NaOH is 1～4M, and Pt concentration in ethylene glycol solution is 0.0005M～0.005M;
(4) adopt microwave heating method by the Pt presoma reduction in above-mentioned solution, cooling and stirring is to room temperature;
(5) the Pt/ ethylene glycol slurry of above-mentioned reduction is incorporated in to described mesoporous WO 3in the mixed solution of carbon carrier, the mol ratio of Pt and W is 1:0.1 ~ 1:1;
Drip salpeter solution and make system pH≤3, stir after 24～48h standing 3～6 days;
Salpeter solution concentration is 0.1～2.5M;
(6) by gained suspension after centrifugal, washing, vacuum drying, obtain end product Pt/WO 3/ C catalyst.
2. according to preparation method claimed in claim 1, it is characterized in that: described auxiliary agent WO 3be to take the mesopore metal oxide that silicon oxide molecular sieve prepared as template, in solution, W presoma be impregnated in silica duct, after evaporation, roasting, etching is removed silica template and is prepared from; Mesopore metal oxide WO prepared by described method 3copied the pore passage structure of template mesopore molecular sieve.
3. according to preparation method claimed in claim 2, it is characterized in that:
(1) take mesoporous silicon oxide molecular sieve as hard template, molecular sieve is dispersed in nonaqueous solvents, adds soluble tungsten precursor, stir it is fully dissolved, the metal molar concentration that tungsten presoma salt is dissolved in ethanol is 0.03～1.0M, and the mol ratio of silica and tungsten is controlled at 1～10;
Described molecular sieve is the silicon oxide molecular sieve of various removal surfactants, as SBA-15, KIT-6 or MCM-41; Described soluble tungsten precursor is silico-tungstic acid; Described nonaqueous solvents is absolute ethyl alcohol;
(2) above-mentioned solution is stirred to 12～48h under 10～50 ° of C, under 20～80 ° of C, after solvent evaporated, obtain the complex solid powder of tungsten presoma and silica;
(3) under air or oxygen atmosphere, by above-mentioned pressed powder high-temperature roasting, 300～800 ° of C of sintering temperature, 1～5 ° of C min of temperature programming speed -1, roasting time 3～8h, obtains metal oxide WO 3complex with silica;
(4) complex is joined in HF or NaOH solution, take the etching agent that HF or NaOH solution is silica, remove above-mentioned metal oxide WO 3with the silica composition of silicon oxide composite unit, separation, solid product washes with water in the vacuum drying oven that is placed on 40～80 ° of C, obtains end product metal oxide WO 3; The concentration of HF or NaOH solution is 1～40%, and the processing time is 5～48h, and temperature is 10～60 ° of C, and the mol ratio of the silica in metal oxide and silicon oxide composite unit and HF or NaOH is 0.01～1.0.
4. according to preparation method claimed in claim 1, it is characterized in that: described nonaqueous solvents is absolute ethyl alcohol or ethylene glycol, carbon carrier is 0.1～0.5M in molar concentration wherein.
5. according to preparation method claimed in claim 1, it is characterized in that: described microwave method comprises continuous microwave and gap microwave method, 20～50 ml solns adopt microwave power 50～100W;
Wherein the continuous microwave heat time is 0.5～5min;
Gap microwave method is heating 5～20s, and gap stops 5～20s, repeats 3～15 times.
6. according to preparation method claimed in claim 1, it is characterized in that: described vacuum drying temperature is 40～80 ° of C, and be 5～24h drying time.
7. according to preparation method claimed in claim 1, it is characterized in that: step (5) drips salpeter solution and makes system pH=1-3.
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