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CN100531914C - Preparation method of solid-phase reduction of platinum-carbon catalysts for fuel cells - Google Patents

Preparation method of solid-phase reduction of platinum-carbon catalysts for fuel cells 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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platinum
fuel cells
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phase reduction
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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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Abstract

本发明提供了一种用于燃料电池的铂碳类催化剂的固相还原制备方法,步骤是将金属盐前驱体与络合剂加入到溶剂中,超声使其完全溶解;加入碱性物质,调节pH值为8~11;加入碳载体,超声0.5~1h,真空干燥;取出物料研磨后,加入到还原剂的水溶液中均匀浸渍,然后在90℃真空干燥3~5h;干燥后的物料经过研磨后,在氮气保护下140~160℃还原反应2~5h,继续通氮气冷却至室温;水洗至无氯离子,真空干燥,得到用于燃料电池的铂碳类催化剂,包括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。本发明方法简单,操作方便,成本低廉,环境友好,有利于添加促进剂,可用于制备高分散、高活性、强抗毒性的燃料电池铂碳类催化剂。

Figure 200610036981

The invention provides a solid-phase reduction preparation method of a platinum-carbon catalyst used in a fuel cell. The steps are: adding a metal salt precursor and a complexing agent to a solvent, and ultrasonically dissolving it completely; adding an alkaline substance, adjusting The pH value is 8-11; add carbon carrier, ultrasonic 0.5-1h, and vacuum-dry; take out the material and grind it, add it into the aqueous solution of reducing agent and soak it evenly, and then vacuum-dry it at 90°C for 3-5h; the dried material is ground Afterwards, under the protection of nitrogen, the reduction reaction was performed at 140-160°C for 2-5 hours, and continued to cool to room temperature with nitrogen; washed with water until there was no chloride ion, and dried in vacuum to obtain platinum-carbon catalysts for fuel cells, including 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. The method of the invention is simple, convenient to operate, low in cost, friendly to the environment, beneficial for adding accelerators, and can be used to prepare platinum-carbon catalysts for fuel cells with high dispersion, high activity and strong toxicity resistance.

Figure 200610036981

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、一种用于燃料电池的铂碳类催化剂的固相还原制备方法,其特征在于包括如下工艺步骤和工艺条件:1. A solid-phase reduction preparation method for platinum-carbon catalysts for fuel cells, characterized in that it comprises the following process steps and process conditions: (1)将金属盐前驱体与络合剂加入到溶剂中,超声使金属盐前驱体和络合剂完全溶解;所述混合溶液中金属盐前驱体的质量体积浓度为50~150g/L;金属盐前驱体与络合剂的物质的量比为1~2:5~1;所述金属盐前驱体为H2PtCl6·6H2O,或者为H2PtCl6·6H2O和RuCl3的混合物;(1) adding the metal salt precursor and the complexing agent to the solvent, and ultrasonically dissolving the metal salt precursor and the complexing agent completely; the mass volume concentration of the metal salt precursor in the mixed solution is 50-150 g/L; The molar ratio of the metal salt precursor to the complexing agent is 1-2:5-1; the metal salt precursor is H 2 PtCl 6 ·6H 2 O, or H 2 PtCl 6 ·6H 2 O and RuCl a mixture of 3 ; (2)向步骤(1)所得溶液中加入碱性物质,调节pH值为8~11,加入碳载体,Pt:C物质的量比为0.015~0.09:1,超声0.5~1h;然后真空干燥;(2) Add alkaline substances to the solution obtained in step (1), adjust the pH value to 8-11, add carbon carrier, the ratio of Pt:C substance is 0.015-0.09:1, ultrasonic 0.5-1h; then vacuum dry ; (3)将步骤(2)干燥后的物料研磨后,加入到还原剂的水溶液均匀浸渍,然后90℃真空干燥3~5h;所述还原剂的水溶液的质量体积浓度为70~200g/L;金属盐前驱体与还原剂的物质的量比为1:1~10;(3) Grinding the dried material in step (2), adding it to the aqueous solution of the reducing agent for uniform impregnation, and then vacuum-drying at 90° C. for 3 to 5 hours; the mass volume concentration of the aqueous solution of the reducing agent is 70 to 200 g/L; The molar ratio of the metal salt precursor to the reducing agent is 1:1-10; (4)将步骤(3)制得的物料研磨后,放入陶瓷舟中,在氮气保护下140~160℃还原反应2~5h,继续通氮气冷却至室温;(4) After grinding the material obtained in step (3), put it into a ceramic boat, and perform a reduction reaction at 140-160° C. for 2-5 hours under the protection of nitrogen, and continue cooling to room temperature with nitrogen; (5)将步骤(4)中所制得的物料水洗至无氯离子检出,然后真空干燥,即制得用于燃料电池的铂碳类催化剂。(5) washing the material prepared in step (4) with water until no chlorine ions are detected, and then drying in vacuum to obtain a platinum-carbon catalyst for fuel cells. 2、根据权利要求1所述的用于燃料电池的铂碳类催化剂的固相还原制备方法,其特征在于:所述金属盐前驱体为H2PtCl6·6H2O和RuCl3的混合物,Pt:Ru物质的量比为1∶1。2. The solid-phase reduction preparation method for platinum-carbon catalysts for fuel cells according to claim 1, characterized in that: the metal salt precursor is a mixture of H 2 PtCl 6 ·6H 2 O and RuCl 3 , The molar ratio of Pt:Ru species is 1:1. 3、根据权利要求1所述的用于燃料电池催化剂的固相还原制备方法,其特征在于:所述络合剂为柠檬酸钠、乙二胺四乙酸二钠或酒石酸钠。3. The solid-phase reduction preparation method for fuel cell catalysts according to claim 1, characterized in that: the complexing agent is sodium citrate, disodium edetate or sodium tartrate. 4、根据权利要求1所述的用于燃料电池的铂碳类催化剂的固相还原制备方法,其特征在于:所述溶剂为水,或者是水与丙酮的混合溶液,或者是水与异丙醇的混合溶液。4. The solid-phase reduction preparation method for platinum-carbon catalysts for fuel cells according to claim 1, characterized in that: the solvent is water, or a mixed solution of water and acetone, or water and isopropyl Alcohol mixed solution. 5、根据权利要求4所述的用于燃料电池的铂碳类催化剂的固相还原制备方法,其特征在于:所述水与丙酮体积比为3:1,水与异丙醇体积比为3:1。5. The solid-phase reduction preparation method of platinum-carbon catalysts for fuel cells according to claim 4, characterized in that: the volume ratio of water to acetone is 3:1, and the volume ratio of water to isopropanol is 3 :1. 6、根据权利要求1所述的用于燃料电池的铂碳类催化剂的固相还原制备方法,其特征在于:步骤(1)中,将催化剂的金属盐前驱体与络合剂加入到溶剂中,超声使其完全溶解后,再添加固态促进剂硅钼酸;继续超声10min;所述金属盐前驱体与固态促进剂的物质的量比为1~10:1。6. The solid-phase reduction preparation method for platinum-carbon catalysts for fuel cells according to claim 1, characterized in that: in step (1), the metal salt precursor of the catalyst and the complexing agent are added to the solvent , after ultrasonically dissolving it completely, then add the solid accelerator silicomomolybdic acid; continue ultrasonication for 10 minutes; the ratio of the metal salt precursor to the solid accelerator is 1-10:1. 7、根据权利要求1所述的用于燃料电池的铂碳类催化剂的固相还原制备方法,其特征在于:所述还原剂为甲酸钠、葡萄糖、亚硫酸钠或硫代硫酸钠。7. The solid-phase reduction preparation method of platinum-carbon catalysts for fuel cells according to claim 1, wherein the reducing agent is sodium formate, glucose, sodium sulfite or sodium thiosulfate. 8、根据权利要求1所述的用于燃料电池的铂碳类催化剂的固相还原制备方法,其特征在于:所述碱性物质为摩尔浓度为2mol/L的NaOH水溶液。8. The solid-phase reduction preparation method of platinum-carbon catalysts for fuel cells according to claim 1, characterized in that: the alkaline substance is an aqueous NaOH solution with a molar concentration of 2 mol/L. 9、根据权利要求1所述的用于燃料电池的铂碳类催化剂的固相还原制备方法,其特征在于:所述碳载体为XC-72R碳黑或者纳米碳管。9. The solid-phase reduction preparation method of platinum-carbon catalysts for fuel cells according to claim 1, characterized in that: the carbon carrier is XC-72R carbon black or carbon nanotubes. 10、根据权利要求1所述的用于燃料电池的铂碳类催化剂的固相还原制备方法,其特征在于:所述步骤(4)所采用的还原反应为固相还原反应,还原过程在固相中进行。10. The solid-phase reduction preparation method for platinum-carbon catalysts for fuel cells according to claim 1, characterized in that: the reduction reaction used in the step (4) is a solid-phase reduction reaction, and the reduction process is carried out in the solid state. in phase.
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