CN100531914C - solid phase reduction preparation method for platinum, carbon catalyst of fuel cell - Google Patents

solid phase reduction preparation method for platinum, carbon catalyst of fuel cell Download PDF

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CN100531914C
CN100531914C CNB2006100369810A CN200610036981A CN100531914C CN 100531914 C CN100531914 C CN 100531914C CN B2006100369810 A CNB2006100369810 A CN B2006100369810A CN 200610036981 A CN200610036981 A CN 200610036981A CN 100531914 C CN100531914 C CN 100531914C
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catalyst
solid phase
fuel cell
phase reduction
reduction preparation
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CN1915521A (en
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廖世军
叶立炎
刘军民
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South China University of Technology SCUT
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    • 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
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    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

A solid-phase reduction method for preparing the Pt/C catalyst used for fuel battery includes such steps as adding metallic salt and complexing agent to solvent, ultrasonic dissolving, adding alkaline substance to regulate pH=8-11, adding C carrier, ultrasonic mixing, vacuum drying, grinding, immersing in the aqueous solution of reducer, vacuum drying, grinding, reducing reaction in N2, cooling in N2, water washing, and vacuum drying. Said catalyst may be Pt/C, Pt-Ru/C, Pt-Mo-Si/C, Pt-Ru-Mo-Si/C, Pt/CNT, Pt-Ru/CNT, Pt-Mo-Si/CNT, or Pt-Ru-Mo-Si/CNT.

Description

The solid phase reduction preparation method who is used for the Pt/C catalyst of fuel cell
Technical field
The invention belongs to Proton Exchange Membrane Fuel Cells (PEMFC) and direct alcohol fuel battery (DAFC) catalyst preparation technology, particularly a kind of solid phase reduction preparation method who is used for the Pt/C catalyst of this two types of fuel cells.
Background technology
Fuel cell is a kind of device that can directly the chemical energy of fuel efficiently and cleanly be transformed into electric energy.Wherein, low-temperature fuel cell such as Proton Exchange Membrane Fuel Cells (PEMFC), direct alcohol fuel battery (DAFC), it is low to have operating temperature, start fast, characteristics such as energy conversion efficiency height, being the desirable substitute electric power of following electric automobile, open-air power station, compact power, is one of fuel cell type of first developing.Catalyst material, especially anode catalyst are the critical materials of this types of fuel cells.Yet at present the performance of the catalyst that uses is not high enough, causes excessive and too high having become of cost of noble metal dosage to influence PEMFC and the business-like significant obstacle of DAFC fuel cell.Therefore, improving the pt utilization in the catalyst, strengthen the stability and the anti-poisoning capability of catalyst, is to reduce the platinum carrying capacity, reduces one of fuel cell cost fundamental way.From research in the past, metallic particle diameter in the catalyst, degree of crystallinity, component ratio, multiple factor such as alloying level all can produce bigger influence to catalyst performance, adopt different preparation methods, the catalyst that obtains is because the difference of structural factor, and the electrocatalysis characteristic of methanol oxidation is also had very big difference.
In recent years, the researcher has attempted preparing in many ways fuel cell noble metal catalysts, as liquid phase chemical reduction, gas phase reduction process, and B.nnemann method, sol method, high-temperature alloy method, solid reaction process etc.
United States Patent (USP) 20,030,017,378A1 disclose a kind of method for preparing catalyst such as precious metals pt/C and Pt-Ru/C by liquid-phase reduction.Specific practice is: the carbon black suspended dispersed in secondary water, is at room temperature stirred 30min, drip H then 2PtCl 6And RuCl 3Solution, continue to stir, and suspension be warming up to boiling, regulate PH up to 7, make the slaine uniform deposition at carbon surface,, make the slaine reduction, again washing afterwards again toward wherein adding tartaric acid and hydrazine reducing agent, filter, obtain the Pt-Ru/C catalyst after the drying, average grain diameter is 5～6nm.The catalyst bad dispersibility that obtains of this method but, the average grain diameter of metallic is bigger.To multi-component composite catalyst, problem pockety takes place in each component regular meeting.
S.Alerasool etc. (S.Alerasool, J.Catal.124 (1990) 204) have introduced a kind of with Pt compound dipping or be deposited on active carbon or other carriers, obtain the method for catalyst with the hydrogen high temperature reduction, are called gas phase reduction process.Specific practice is: with Pt (NH 3) 4(NO 3) 2And Ru (NH 3) 6Cl 3Load on the silica, with H 2As 400 ℃ of following reduction 4hr of reducing agent, the result obtains the Pt-Ru/SiO that particle diameter is 2.5～3.0nm 2Catalyst, but ought be at first at O 2Heat treatment is after 1 hour in the atmosphere, again H under similarity condition 2Reduction, the metallic size of acquisition is between 1.0～1.5nm.This method equipment is had relatively high expectations, and is unfavorable for preparation in enormous quantities.
H.
Figure C200610036981D0005113758QIETU
Deng (H.
Figure C200610036981D0005113758QIETU
, Angew.Chem.Int.Ed.Engl, 30 (1991) 1312) and United States Patent (USP) 5641723 a kind of method for preparing nano metal colloidal sol is disclosed.This method is with PtCl 2And N (octyl) 4Bet 3The Pt colloidal sol that H prepares in organic media is adsorbed on the active carbon, obtain dispersed better, equal once higher Pt/C catalyst.The preparation process of Pt-Ru/C is as follows: at first by N (Oct 4) Br and K[Bet 3H] synthetic reducing agent N (Oct in oxolane 4) [Bet 3H]; Again to wherein adding an amount of PtCl 2And RuCl 3THF solution, reduction reaction will take place and obtain Pt in this moment 4RuN (Oct 4) Cl 11, add carbon carrier, filter, drying, and roasting 1h removes organic protective agent in the air under 400 ℃, can obtain the Pt-Ru/C catalyst.This method can be used for preparing the alloy eelctro-catalyst that various different chemicals are formed, and metallic is little in the catalyst of preparation, narrow size distribution, however preparation process is very complicated, the condition harshness, and the cost of material height only is only applicable to laboratory research.
European patent 0898318A2 discloses a kind of process for preparing the activated carbon loaded platinum catalyst of small particle diameter: this method is with H 2PtCl 6Be dissolved in NaHSO 3Regulating pH value in the aqueous solution again is 2, dropwise adds H 2O 2Solution, the colloidal sol of formation Pt, the pH value of colloidal sol is adjusted to 7 with NaOH.Toward wherein adding the water that is dispersed with carbon black, both mix, and stir, and use rare H again 2SO 4Regulating PH is 5, and mixed liquor heats 3hr under boiling, so that Pt colloidal sol is all attached on the carbon.With its washing, drying obtains catalyst Pt/C, and the average grain diameter of catalyst is 1～2nm, and good performance is arranged in electro-chemical test.But this method high hydrogen peroxide of price, the preparation cost height, and need regulate the pH value repeatedly, technological process complexity, process are not easy control.
K.L.Ley etc. (K.L.Ley, J.Electrochem.Soc.144 (1997) 1543) have introduced and have a kind ofly made the multi-element metal alloying with high-temperature technology, thereby obtain the method for high performance catalyst.This method utilizes argon arc to melt (Arc-melt) technology, obtains single-phase Pt-Ru-Os ternary alloy three-partalloy, and this alloy helps to reduce the CO coverage rate on Pt surface, demonstrates good electrocatalysis characteristic.(A.Kabbabi such as A.Kabbabi, J.Electroanal.Chem..444 (1998) 41) also introduced and a kind ofly made the multi-element metal alloying with high-temperature technology, thereby obtain the method for high performance catalyst, the coreless induction furnace that this method utilization has a floating device of magnetic has made the Pt-Ru alloy of different proportion.This method great advantage is that the alloying level of the multi-element metal composite catalyst that obtains is very high.Yet the metallic average grain diameter of this method preparation is bigger, and is difficult for the preparation carbon supported catalyst.
Chinese patent 01127116.7 discloses a kind of method for preparing catalyst of fuel batter with proton exchange film by solid phase reduction, this method uses polyformaldehyde, sodium formate etc. as reducing agent, makes slaine and reducing agent generation solid phase reaction with the preparation catalyst by grinding.This method is saved solvent, because the probability of collision is lower mutually between the particle in the solid system, the average grain diameter of the metallic that reaction generates is less, and degree of crystallinity is lower, but this method hand lapping is not suitable for large-scale production, from practical application bigger distance is arranged.
Generally speaking, traditional preparation method exists some factors that are unfavorable for improving catalyst performance, as, exist fierce Brownian movement in the liquid-phase system; Particle aggregation under the hot conditions; Technological process complexity, process are not easy control; Use harmful reducing agent or produce unfriendly problem of environment such as a large amount of waste liquids or the like, therefore, relevant fuel-cell catalyst preparation method reduces cost in the particle diameter controllability, and the simplification process reduces aspect such as environmental pollution and is still waiting to make improvement.
Summary of the invention
In order to solve above-mentioned the deficiencies in the prior art part, the object of the present invention is to provide that a kind of particle diameter is controlled, technology is simple, easy to operate, with low cost, environmental friendliness, be suitable for adding promoter, the solid phase reduction preparation method of the high dispersive that is easy to get and highly active Pt/C catalyst.
Purpose of the present invention is achieved through the following technical solutions: a kind of solid phase reduction preparation method who is used for the Pt/C catalyst of fuel cell comprises following processing step and process conditions:
(1) slaine presoma and complexing agent are joined in the solvent, ultrasonic slaine presoma and the complexing agent of making dissolves fully; The quality volumetric concentration of slaine presoma is 50～150g/L in the described mixed solution; The slaine presoma is 1～2:5～1 with the amount of substance ratio of complexing agent, and described slaine presoma is H 2PtCl 66H 2O perhaps is H 2PtCl 66H 2O and RuCl 3Mixture.
(2) add alkaline matter in step (1) gained solution, regulating the pH value is 8～11, adds carbon carrier, and Pt:C amount of substance ratio is 0.015～0.09:1, ultrasonic 0.5～1h; Vacuum drying then.
(3) with behind the dried improved grinding of step (2), the aqueous solution that joins reducing agent evenly floods, then 90 ℃ of vacuum drying 3～5h; The quality volumetric concentration of the aqueous solution of described reducing agent is 70～200g/L; The slaine presoma is 1:1～10 with the amount of substance ratio of reducing agent.
(4) behind the improved grinding that step (3) is made, put into ceramic boat, 140～160 ℃ of reduction reaction 2～5h under nitrogen protection continue logical nitrogen and are cooled to room temperature.
(5) prepared material in the step (4) being washed to no chlorion detects and (uses AgNO 3Check), vacuum drying then promptly makes the Pt/C catalyst that is used for fuel cell.
In order to realize the present invention better, described slaine presoma is H 2PtCl 66H 2O, or H 2PtCl 66H 2O and RuCl 3Mixture, the Pt:Ru amount of substance is than for 1:1; Described complexing agent comprises natrium citricum, disodium ethylene diamine tetraacetate or sodium tartrate etc.; Described solvent comprises the mixed solution of water or water and acetone or the mixed solution of water and isopropyl alcohol; Described water and acetone volume ratio are 3:1, and water and isopropyl alcohol volume ratio are 3:1.
In the step (1), the slaine presoma and the complexing agent of catalyst joined in the solvent, ultrasonic it is dissolved fully after, also can add other solid-state promoter again, as silicomolybdic acid; Continue ultrasonic 10min; Described slaine presoma is 1～10:1 with the amount of substance ratio of solid-state promoter.
Described reducing agent comprises sodium formate, glucose, sodium sulfite or sodium thiosulfate etc.
Described alkaline matter is that amount of substance is the NaOH aqueous solution of 2mol/L.
Described carbon carrier comprises XC-72R carbon black or CNT etc.
The reduction reaction that step of the present invention (4) is adopted is the solid phase reduction reaction, and reduction process is carried out in solid phase.
The present invention compared with prior art has following advantage and beneficial effect:
(1) the present invention saves solvent, environmental friendliness, and preparation process is simple and convenient, finds by XRD and tem analysis: the average grain diameter of the catalyst metals particle that makes less (4nm is following), degree of crystallinity is lower, and favorable dispersibility is difficult for producing and reunites.
(2) the present invention increases the specific area of catalyst by regulating pH and adding the particle diameter that complexing agent can effectively reduce catalyst, improves the utilization ratio of catalyst, has solved dipping and the uppity problem of colloid method granularity.
(3) the present invention compares with liquid phase reduction, more help the interpolation of solid-state heteropoly acid promoter, interpolation silicomolybdic acid etc. can significantly improve the antitoxin performance of active component decentralization and catalyst as auxiliary agent, thereby electro-chemical activity surface area, catalytic activity and the antitoxin performance of catalyst are significantly improved, and the combination property of Pt-Mo-Si/CNT catalyst will exceed 2.2 times than the high-performance Pt-Ru/C catalyst of Johnson Matthey company.
(4) the present invention has avoided harmful reducing agents such as use formaldehyde, has reduced the generation of waste water the like waste significantly, has eco-friendly key property.
Description of drawings
Fig. 1 is the transmission electron microscope photo of the Pt/CNT catalyst for preparing of the present invention.
Fig. 2 is the transmission electron microscope photo of the Pt-Mo-Si/CNT catalyst for preparing of the present invention.
Fig. 3 is the transmission electron microscope photo of the Pt-Ru/C catalyst for preparing of the present invention.
Fig. 4 is the transmission electron microscope photo of the Pt-Ru-Mo-Si/C catalyst for preparing of the present invention.
Fig. 5 is that the catalyst for preparing of the present invention is at 0.5mol/LH 2SO 4+ 0.5mol/LCH 3Cyclic voltammetric spectrogram in the OH solution.
The specific embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment one
(1) with slaine presoma H 2PtCl 66H 2O and complexing agent natrium citricum are added to the water, and ultrasonic it are dissolved fully; H in the aqueous solution 2PtCl 66H 2O quality volumetric concentration is 50g/L, H 2PtCl 66H 2O is 2:1 with the amount of substance ratio of natrium citricum.
(2) add the NaOH aqueous solution of 2mol/L in the gained solution in step (1), regulating pH value is 8, and adding XC-72R carbon black, amount of substance be than Pt:C=0.015:1, ultrasonic 0.5h; 90 ℃ of vacuum drying.
(3) after the middle gains abrasive lapping of taking-up step (2), join in the aqueous sodium formate solution (the quality volumetric concentration is 70g/L) and evenly flood 90 ℃ of vacuum drying 3h, H 2PtCl 66H 2O is 1:1 with the amount of substance ratio of sodium formate.
(4) after the middle gains abrasive lapping of taking-up step (3), put into ceramic boat, send into electric tube furnace, under nitrogen protection, handle 2h for 140 ℃, continue logical nitrogen and be cooled to room temperature (room temperature is generally 25 ℃).
(5) prepared material in the step (4) is washed to no chlorion through redistilled water and (uses AgNO 3Check), 90 ℃ of vacuum drying obtain being used for the Pt/C catalyst Pt/C of PEMFC and DAFC.
Embodiment two
(1) with slaine presoma H 2PtCl 66H 2O, RuCl 3Add in the mixed solution (volume ratio is 3:1) of entry and acetone with the sodium tartrate complexing agent, ultrasonic it is dissolved fully; H in the mixed solution 2PtCl 66H 2O and RuCl 3The quality volumetric concentration be 150g/L, H 2PtCl 66H 2O, RuCl 3Amount of substance is than being Pt:Ru=1:1; Slaine presoma H 2PtCl 66H 2O, RuCl 3, with the amount of substance of sodium tartrate than being 1:5.
(2) add the NaOH aqueous solution of 2mol/L in the gained mixed solution in step (1), regulating pH value is 11, and adding XC-72R carbon black, amount of substance be than Pt:C=0.075:1, ultrasonic 1h, 90 ℃ of vacuum drying.
(3) after the middle gains abrasive lapping of taking-up step (2), the aqueous solution (the quality volumetric concentration is 200g/L) that joins glucose evenly floods, then at 90 ℃ of vacuum drying 5h; Slaine presoma H 2PtCl 66H 2O, RuCl 3Be 1:10 with the amount of substance ratio of glucose.
(4) after the middle gains abrasive lapping of taking-up step (3), put into ceramic boat, send into electric tube furnace, under nitrogen protection, handle 4h for 160 ℃, continue logical nitrogen and be cooled to room temperature (room temperature is generally 25 ℃).
(5) prepared material in the step (4) is washed to no chlorion through redistilled water and (uses AgNO 3Check), 90 ℃ of vacuum drying obtain being used for the Pt/C catalyst Pt-Ru/C of PEMFC and DAFC.As shown in Figure 3.
Embodiment three
(1) with slaine presoma H 2PtCl 66H 2O and disodium ethylene diamine tetraacetate complexing agent join in water and the isopropanol solvent (volume ratio is 3:1), ultrasonic it are dissolved fully; Then add solid-state promoter silicomolybdic acid, continue ultrasonic 10min; H in the mixed solution 2PtCl 66H 2The quality volumetric concentration of O is 100g/L, H 2PtCl 66H 2The amount of substance of O and disodium ethylene diamine tetraacetate is than being 1:2, with the amount of substance of silicomolybdic acid than being 1:1.
(2) add the NaOH aqueous solution of 2mol/L in the gained mixed solution in step (1), regulating pH value is 10, and adding XC-72R carbon black, amount of substance be than Pt:C=0.025:1, ultrasonic 0.75h; 90 ℃ of vacuum drying.
(3) after the middle gains abrasive lapping of taking-up step (2), the aqueous solution (the quality volumetric concentration is 100g/L) that joins sodium sulfite evenly floods, then at 90 ℃ of vacuum drying 4h; Slaine presoma H 2PtCl 66H 2O is 1:5 with the amount of substance ratio of sodium sulfite.
(4) after the middle gains abrasive lapping of taking-up step (3), put into ceramic boat, send into electric tube furnace, under nitrogen protection, handle 5h for 150 ℃, continue logical nitrogen and be cooled to room temperature (room temperature is generally 25 ℃).
(5) prepared material in the step (4) is washed to no chlorion through redistilled water and (uses AgNO 3Check), 90 ℃ of vacuum drying obtain being used for the Pt/C catalyst Pt-Mo-Si/C of PEMFC and DAFC.
Embodiment four
(1) with slaine presoma H 2PtCl 66H 2O, RuCl 3Be added to the water with the natrium citricum complexing agent, ultrasonic it dissolved fully; Then add solid-state promoter silicomolybdic acid, continue ultrasonic 10min; H in the solution 2PtCl 66H 2O and RuCl 3The quality volumetric concentration be 120g/L, H 2PtCl 66H 2O, RuCl 3Amount of substance is than being Pt:Ru=1:1; Slaine presoma H 2PtCl 66H 2O, RuCl 3Be 1:1 with the amount of substance ratio of natrium citricum, be 8:1 with silicomolybdic acid amount of substance ratio.
(2) add the NaOH aqueous solution of 2mol/L in the gained solution in step (1), regulating pH value is 11, and adding XC-72R carbon black, amount of substance be than Pt:C=0.09:1, ultrasonic 0.5h; 90 ℃ of vacuum drying.
(3) after the middle gains abrasive lapping of taking-up step (2), the sodium thiosulfate solution that joins (the quality volumetric concentration is 180g/L) is dipping evenly, then at 90 ℃ of vacuum drying 5h, H 2PtCl 66H 2O, RuCl 3Be 1:9 with the amount of substance ratio of sodium thiosulfate.
(4) after the middle gains abrasive lapping of taking-up step (3), put into ceramic boat, send into electric tube furnace, under nitrogen protection, handle 3h for 140 ℃, continue logical nitrogen and be cooled to room temperature (room temperature is generally 25 ℃).
(5) prepared material in the step (4) is washed to no chlorion through redistilled water and (uses AgNO 3Check), 90 ℃ of vacuum drying obtain being used for the Pt/C catalyst Pt-Ru-Mo-Si/C of PEMFC and DAFC.As shown in Figure 4.
Embodiment five
Carbon carrier is a CNT, and other are operated with embodiment one, thereby makes the Pt/C catalyst Pt/CNT that is used for PEMFC and DAFC.As shown in Figure 1.
Embodiment six
Carbon carrier is a CNT, and other are operated with embodiment two, thereby makes the Pt/C catalyst Pt-Ru/CNT that is used for PEMFC and DAFC.
Embodiment seven
Carbon carrier is a CNT, H 2PtCl 66H 2O is 10:1 with the amount of substance ratio of silicomolybdic acid, and other are operated with embodiment three, thereby make the Pt-Mo-Si/CNT catalyst that can be used for PEMFC and DAFC.As shown in Figure 2.
Embodiment eight
Carbon carrier is a CNT, slaine presoma H 2PtCl 66H 2O, RuCl 3Be 5:1 with silicomolybdic acid amount of substance ratio, other are operated with embodiment four, thereby make the Pt-Ru-Mo-Si/CNT catalyst that is used for PEMFC and DAFC.
(PEMFC, Pt/C catalyst DAFC) comprise Pt/C, Pt-Ru/C, Pt-Mo-Si/C, Pt-Ru-Mo-Si/C, Pt/CNT, Pt-Ru/CNT, Pt-Mo-Si/CNT, Pt-Ru-Mo-Si/CNT to the fuel cell that is used for of the present invention's preparation.The cyclic voltammetric spectrogram is seen Fig. 5.
Employing XRD broadening method records the particle diameter mean value of active component Pt, and the catalyst performance data that adopts voltammetry to record is as shown in table 1.
Table 1
Catalyst and composition thereof Particle diameter (nm) Surface-active area (m 2/g) Oxidation peak point current (mA/mgPtcm 2)
Pt/C 4.0 100.2 712.3
Pt/CNT 3.8 181.5 1002.4
Pt-Ru/C 3.5 121.0 690.3
Pt-Ru/CNT 3.2 234.5 1683.2
Pt-Mo-Si/C 3.4 133.3 779.8
Pt-Mo-Si/CNT 3.0 316.1 2258.3
Pt-Ru-Mo-Si/C 2.9 200.3 1369.3
Pt-Ru-Mo-Si/CNT 2.6 400.5 2560.3
As mentioned above, can realize the present invention preferably.

Claims (10)

1, a kind of solid phase reduction preparation method who is used for the Pt/C catalyst of fuel cell is characterized in that comprising following processing step and process conditions:
(1) slaine presoma and complexing agent are joined in the solvent, ultrasonic slaine presoma and the complexing agent of making dissolves fully; The quality volumetric concentration of slaine presoma is 50～150g/L in the described mixed solution; The slaine presoma is 1～2:5～1 with the amount of substance ratio of complexing agent; Described slaine presoma is H 2PtCl 66H 2O perhaps is H 2PtCl 66H 2O and RuCl 3Mixture;
(2) add alkaline matter in step (1) gained solution, regulating the pH value is 8～11, adds carbon carrier, and Pt:C amount of substance ratio is 0.015～0.09:1, ultrasonic 0.5～1h; Vacuum drying then;
(3) with behind the dried improved grinding of step (2), the aqueous solution that joins reducing agent evenly floods, then 90 ℃ of vacuum drying 3～5h; The quality volumetric concentration of the aqueous solution of described reducing agent is 70～200g/L; The slaine presoma is 1:1～10 with the amount of substance ratio of reducing agent;
(4) behind the improved grinding that step (3) is made, put into ceramic boat, 140～160 ℃ of reduction reaction 2～5h under nitrogen protection continue logical nitrogen and are cooled to room temperature;
(5) prepared material in the step (4) is washed to no chlorion and detects, vacuum drying then promptly makes the Pt/C catalyst that is used for fuel cell.
2, the solid phase reduction preparation method who is used for the Pt/C catalyst of fuel cell according to claim 1, it is characterized in that: described slaine presoma is H 2PtCl 66H 2O and RuCl 3Mixture, Pt:Ru amount of substance ratio is 1: 1.
3, the solid phase reduction preparation method who is used for fuel-cell catalyst according to claim 1, it is characterized in that: described complexing agent is natrium citricum, disodium ethylene diamine tetraacetate or sodium tartrate.
4, the solid phase reduction preparation method who is used for the Pt/C catalyst of fuel cell according to claim 1, it is characterized in that: described solvent is a water, or the mixed solution of water and acetone, or the mixed solution of water and isopropyl alcohol.
5, the solid phase reduction preparation method who is used for the Pt/C catalyst of fuel cell according to claim 4, it is characterized in that: described water and acetone volume ratio are 3:1, water and isopropyl alcohol volume ratio are 3:1.
6, the solid phase reduction preparation method who is used for the Pt/C catalyst of fuel cell according to claim 1, it is characterized in that: in the step (1), the slaine presoma and the complexing agent of catalyst are joined in the solvent, ultrasonic it is dissolved fully after, add solid-state promoter silicomolybdic acid again; Continue ultrasonic 10min; Described slaine presoma is 1～10:1 with the amount of substance ratio of solid-state promoter.
7, the solid phase reduction preparation method who is used for the Pt/C catalyst of fuel cell according to claim 1, it is characterized in that: described reducing agent is sodium formate, glucose, sodium sulfite or sodium thiosulfate.
8, the solid phase reduction preparation method who is used for the Pt/C catalyst of fuel cell according to claim 1 is characterized in that: described alkaline matter is that molar concentration is the NaOH aqueous solution of 2mol/L.
9, the solid phase reduction preparation method who is used for the Pt/C catalyst of fuel cell according to claim 1, it is characterized in that: described carbon carrier is XC-72R carbon black or CNT.
10, the solid phase reduction preparation method who is used for the Pt/C catalyst of fuel cell according to claim 1 is characterized in that: the reduction reaction that described step (4) is adopted is the solid phase reduction reaction, and reduction process is carried out in solid phase.
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