CN1257570C - Method of preparing direct methanol fuel sell anode catalyst by sub-stannic acid method - Google Patents

Method of preparing direct methanol fuel sell anode catalyst by sub-stannic acid method Download PDF

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CN1257570C
CN1257570C CNB2004100044167A CN200410004416A CN1257570C CN 1257570 C CN1257570 C CN 1257570C CN B2004100044167 A CNB2004100044167 A CN B2004100044167A CN 200410004416 A CN200410004416 A CN 200410004416A CN 1257570 C CN1257570 C CN 1257570C
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catalyst
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direct methanol
methanol fuel
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CN1560946A (en
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王新东
张红飞
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University of Science and Technology Beijing USTB
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University of Science and Technology Beijing USTB
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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
    • 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
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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Abstract

The present invention provides a method for the preparation of a catalyst of the anode of a direct methanol fuel cell by a stannous method, which relates to the preparation of a carbon carrying catalyst of the anode of a direct methanol fuel cell. In the present invention, a stannous method is proposed to be adopted to control the existence mode of Pt so that all the valence states of Pt in a prepared catalyst are well distributed; the pH value which changes a preparation system is first considered, NaHSnO2 /Na2 SnO2 is selected as a reductive agent, and H2 PtCl6 is selected as a precursor for Pt; through the adjustment of the rotio of the reductive agent to the precursor, the ratio of the reductive agent to OH<->, reaction temperature and time, the concentration of the preparation system, the adding mode of the precursor, etc., the distribution of the valence states of Pt is controlled so that the prepared Pt/C catalyst has excellent catalytic activity for the electrooxidation of methanol under the condition that no other auxiliary catalyst is introduced. Products prepared by the present invention not only can be used as a catalyst of the anode of a direct methanol fuel cell and can also be used as a catalyst of the cathodes and the anodes of other fuel cells. In addition, the present invention can also be used in many fields, such as gas reformation, organic fragmentation, pollutant combustion, organic synthesis, etc.

Description

A kind of sub-stannic acid method prepares the method for direct methanol fuel cell anode catalyst
Technical field
The present invention relates to the liquid phase preparation process of fuel-cell catalyst, relate to the preparation of direct methanol fuel cell anode carbon carried catalyst.
Background technology
In known metal simple-substance, Pt is the highest to the electro-oxidizing-catalyzing activity of methyl alcohol.In order to increase the surface area of Pt, also be in order to reduce the battery cost, generally all Pt to be carried on the inertia conductive carrier of high-specific surface area, making so-called Pt/C catalyst simultaneously.In known direct methanol fuel cell anode Pt/C method for preparing catalyst, generally adopt acidity or alkalescent system, Pt is generally single composition in the catalyst of preparing, as Pt (0) or Pt (IV).More typical preparation method has colloid method and infusion process, the preparation process of colloid method is, as United States Patent (USP) 4,004,193, at first chloroplatinic acid is reduced the divalence complex anion that forms a kind of Pt with sodium hydrogensulfite, and then in the pH=4-5 scope, carry out oxidation with hydrogen peroxide, the final product that forms is the hydrate of platinum dioxide, further with reducing agents such as hydrogen product is reduced into simple substance platinum again; Infusion process, as document Srinvasans, Ticianelli EA, Derouin CR, et.al., Advances:in solidpolymer electrolyte fuel cell technology With low platinum loading electrodes, report adopts reducing agent reduction chloroplatinic acids such as formaldehyde or formic acid among the J.Power Sources 22 (1988) 359., add surfactants such as alcohol simultaneously and improve the wetability of carbon black, the product of formation is a simple substance platinum.Many researchs are as document A.S.Arico, et.al., Effect of Pt-Ru alloy composition on high-temperaturemethanol electro-oxidation, the catalytic oxidation of methyl alcohol on Electrochimica.Acta.47 (2002) 3723. and Pt/C-SPE and the PtRu/C-SPE membrane electrode. electrochemistry, show in 4 (1995) 397., single Pt species, single Pt valence state is not the best to the electro-oxidizing-catalyzing activity of methyl alcohol, its key issue is the surface that the intermediate product CO of methanol electro-oxidizing is adsorbed on Pt easily, repelled the absorption to active oxygen, promptly so-called Pt poisons; This problem is solved the conventional method that is adopted, as document A.J.Dickinson, L.P.L.Carrette, et.al., Preparation of a Pt-Ru/C catalyst from carbonyl complexes for fuel cellapplications, Electrochimica.Acta., 47 (2002) 3733. and B.Rajesh, et.al., Pt-WO 3Supported on carbon nanotubes as possible anodes for direct methanol fuel cells, (2002) 2177. reports of Fuel81, be in catalyst, to add other one or more metals or nonmetal composition such as Ru, W etc., these methods can only improve activity of such catalysts at normal temperatures limitedly, so the methanol electro-oxidizing electric current of catalyst is still lower.
Summary of the invention
The carbon that purpose of the present invention is intended to prepare highly active single Pt species carries type Pt/C catalyst, propose to adopt sub-stannic acid method, the existence form of control Pt makes that each valence state of Pt has a good distribution in the catalyst that makes, and set about selection NaHSnO from the pH value that changes the preparation system 2/ Na 2SnO 2As reducing agent, select H 2PtCl 6As the presoma of Pt, by adjusting ratio, reducing agent and the OH of reducing agent and presoma -Ratio, reaction temperature and time, the concentration of preparation system and the adding mode of presoma wait the control that reaches the Pt valence distribution, make prepared Pt/C catalyst under the situation of not introducing other cocatalyst, just can have excellent catalytic activity to the electroxidation of methyl alcohol.
Preparation process of the present invention:
1, according to SnCl 22H 2The amount of substance of O is more than or equal to H 2PtCl 66 times of amount of substance, less than H 2PtCl 6The addition of 30 times of amount of substance and strong alkaline substance NaOH or KOH is greater than SnCl 22H 26 times of the amount of substance of O, less than SnCl 22H 230 times ratio of the amount of substance of O is with SnCl 22H 2O places NaOH or KOH, and according to the difference of ultrasonic power, ultrasonic wave dissolving 5-30 minute makes inferior stannic acid solution.
2, carbon black XC-72 or other inertia high surface area carrier were handled 10 minutes to 1 hour in 550--620 ℃ of air atmosphere, place the inferior stannic acid solution that has prepared then, ultrasonic wave disperseed 5-30 minute, with carbon black or other inertia high specific surface carrier high degree of dispersion, form the suspended substance of homogeneous.
3, above-mentioned suspended substance is heated to 20--85 ℃, then with H 2PtCl 6Under stationary temperature, drip continuously in or directly be added in the suspension of above-mentioned high-speed stirred, in the dropping process, evaporation of water in the continuous post-reactor of the water in the dropping liquid remains in the 0.02-0.1M scope total concentration that contains the Sn species.1-2 hour dropping time, after dropwising again constant temperature stirred 1--5 hour, replenish evaporation of water simultaneously.
4, after reaction finishes, filter, drying makes the Pt/C catalyst.
The present invention mainly is that the stannous chloride that utilizes alkaline medium will have strong reducing property changes the inferior stannic acid with week reduction into, the inferior stannic acid that utilization has week reduction reduces to chloroplatinic acid, numerous intermediate steps in slower reduction process, occurs, cause the generation of numerous intermediate products simultaneously; Be not reduced to preceding the carrying out of cessation reaction in time of Pt (0) as yet fully at chloroplatinic acid, then intermediate product has constituted final product jointly in company with the Pt (0) that has formed.Prepared product mainly is Pt (0)/C, and the intermediate product that intermediate steps generates mainly contains Pt (OH) 2, form such as PtOH, exactly because Pt has had multiple existence form just to make prepared Pt/C catalyst that the electroxidation of methyl alcohol is had excellent catalytic activity.
The prepared product of the present invention not only can be used for the direct methanol fuel cell anode catalyst, simultaneously can also be used for other fuel cell cathode and anode catalyst, and gas reforming, organic substance cracking, pollutant burning, and organic many fields such as synthetic.
Description of drawings
Fig. 1 is the anodic oxidation of methanol steady-state polarization of embodiment 1 product.
Fig. 2 is the anodic oxidation of methanol steady-state polarization of embodiment 2 products.
Fig. 3 is the anodic oxidation of methanol steady-state polarization of embodiment 3 products.
Fig. 4 is the anodic oxidation of methanol steady-state polarization of the PtRu/C of E-TEK company catalyst.
Fig. 5 is the anodic oxidation of methanol steady-state polarization of carbonyl complex method PtRu/C catalyst.
Fig. 6 is the X-ray diffraction spectrogram of embodiment 3 products.
Fig. 7 is the transmission electron microscope shape appearance figure of embodiment 3 product I.
Fig. 8 is the electron diffraction pattern of embodiment 3 product I.
Embodiment
Embodiment 1:
Get 6.2mmol SnCl 22H 2O places 20 ℃ the capable ultrasonic oscillation of 50ml 1.25M NaOH solution 10 minutes, after treating that it dissolves fully, add carbon black XC-720.8g again, and then ultrasonic oscillation 20 minutes, make the carbon black high degree of dispersion, add deionized water again, suspended substance is diluted to 250ml, then disposable adding 25.6ml H in high-speed stirred 2PtCl 6Solution was 20 ℃ of following high-speed stirred 5 hours.Outwell liquid after placing layering, filter then.Again earlier with 1.25M NaOH washing filter residue, back hot deionized water cyclic washing.Filtration washing finishes, and filter residue was placed 80 ℃ of baking ovens dry 24 hours.
The present embodiment product labelling is A, and thermogravimetric analysis shows that the Pt yield is more than 98%.
At 1MH 2SO 4In cyclic voltammetry experiment show that its electrochemistry particle diameter is 8.61nm.At 1MH 2SO 4+ 1MCH 3The steady-state polarization of OH as Fig. 1, shows the active 47.55mA mg of being of its methanol electro-oxidizing-catalyzing when 0.5Vvs.SCE -1(Pt).The electro-chemical test temperature is 25 ℃, and the dead weight capacity of each valence state Pt is 2mgcm in the electrode -2
Embodiment 2:
Press the step of the inferior stannic acid of embodiment 1 preparation, get five parts of 12.29mmolSnCl 22H 2O is dissolved in the inferior stannic acid of preparation among 90ml, 110ml, 130ml, 150ml, the 170ml 1.25M NaOH respectively, adds 0.8g XC-72 more respectively, all dilutes after the ultrasonic dispersion to be 280ml, and is warming up to 80 ℃.Get five parts of 25.6ml0.04M H then respectively 2PtCl 6Solution, and be diluted to 80ml.In 1 hour with the H that is prepared 2PtCl 6Solution dropwises, and keeps stirring at a high speed in the dropping process, after dropwising, keeps 1 hour under 80 ℃ of high-speed stirred conditions again, replenishes evaporation of water simultaneously.Outwell liquid after placing layering, filter then.Earlier wash filter residue again, back hot deionized water cyclic washing with 1.25MNaOH.Filtration washing finishes, and filter residue was placed 80 ℃ of baking ovens dry 24 hours.
Products obtained therefrom is labeled as B, C, D, E, F respectively according to the order that the NaOH addition increases, and thermogravimetric analysis shows, the yield of Pt is all more than 98% in five products.
At 1MH 2SO 4In cyclic voltammetry experiment show that its electrochemistry particle diameter is respectively 11.79,5.21,7.66,4.53,6.88nm, at 1MH 2SO 4+ 1MCH 3The steady-state polarization of OH as Fig. 2, shows that its methanol electro-oxidizing-catalyzing activity when 0.5Vvs.SCE is respectively 40.58,55.44,76.66,70,77.5mAmg -1(Pt).The electrochemistry temperature conditions is 25 ℃, and the dead weight capacity of each valence state Pt is 2mg cm in each electrode -2
Embodiment 3:
Get three parts of 12.29mmolSnCl 22H 2O is dissolved in respectively among 90ml, 110ml, the 130ml 1.25M NaOH.Except the dropping process is 2 hours, other implementation process is with embodiment 2.
Products obtained therefrom is labeled as G, H, I respectively according to the order that the NaOH addition increases.Thermogravimetric analysis shows that the yield of Pt is more than 98% among product G and the H, and the yield of Pt is 67% in the product I.
At 1MH 2SO 4In cyclic voltammetry experiment show that the electrochemistry particle diameter of product G, H, I is respectively 9.42,10.53,9.63nm, at 1MH 2SO 4+ 1MCH 3The steady-state polarization of OH as Fig. 3, shows that its methanol electro-oxidizing-catalyzing activity when 0.5V vs.SCE is respectively 180,154.5,176mAmg -1(Pt).The electro-chemical test temperature is 25 ℃, and the dead weight capacity of each valence state Pt is 1mg cm in each electrode -2
The properties of product of the embodiment of the invention 3 can give comparative illustration by the steady-state polarization of Fig. 4, Fig. 5.
Under the room temperature, the PtRu/C of E-TEK company catalyst is at 1MH 2SO 4+ 1MCH 3When 0.5Vvs.SCE, be 82mAmg among the OH to the methanol electro-oxidizing-catalyzing activity -1(Pt).The PtRu/C of E-TEK company catalyst is at 1MH 2SO 4+ 1MCH 3Steady-state polarization among the OH as shown in Figure 4, its condition determination is: the mensuration temperature is a room temperature, the Pt carrying capacity is 0.49mg cm -2, Pt: Ru=1: 1 (atm%).
Under 25 ℃, carbonyl complex method PtRu/C catalyst is at 1MH 2SO 4+ 1MCH 3Be 60mA cm during 0.5Vvs.SCE among the OH to the methanol electro-oxidizing-catalyzing activity -2Carbonyl complex method PtRu/C catalyst is at 1MH 2SO 4+ 1MCH 3Steady-state polarization among the OH as shown in Figure 5, Pt carrying capacity the unknown in the electrode, Pt: Ru=1: 1 (atm%).
By the product of the embodiment of the invention 3 and E-TEK company and carbonyl complex method PtRu/C catalyst at 1MH 2SO 4+ 1MCH 3The contrast of the steady-state polarization among the OH can see, the prepared Pt/C catalyst of the present invention has high catalytic activity to the electro-oxidizing-catalyzing of methyl alcohol, and it just can have excellent catalytic performance under the condition of not introducing other cocatalyst.
Fig. 6 is the XRD figure of product G, H, I, and Pt is face-centred cubic structure, and the granular size of using the calculating of Scherrer formula is respectively 13.03nm, 13.85nm, 10.51nm.Fig. 7 is the TEM photo of product I, and multiplication factor is 100,000 times, also can see from Fig. 7, and the size of Pt particle is also about 10nm, and high degree of dispersion has produced great active area to carbon black.Fig. 8 is the electron diffraction pattern of product I, and as seen from Figure 8, the diffraction ring weave in of the diffraction spot of Pt and carbon has illustrated that also Pt and carbon black evenly and closely are distributed in together.The nanometer of Pt particle and to distribute highly uniformly on carbon black be the micro-foundation that the prepared Pt/C catalyst of the present invention has excellent methanol electro-oxidizing-catalyzing activity.

Claims (1)

1, a kind of sub-stannic acid method prepares the method for direct methanol fuel cell anode catalyst, it is characterized in that, the step of preparation is:
1) according to SnCl 22H 2The amount of substance of O is more than or equal to H 2PtCl 66 times of amount of substance, less than H 2PtCl 6The addition of 30 times of amount of substance and strong alkaline substance NaOH or KOH is greater than SnCl 22H 26 times of the amount of substance of O, less than SnCl 22H 230 times ratio of the amount of substance of O is with SnCl 22H 2O places NaOH or KOH, and according to the difference of ultrasonic power, ultrasonic wave dissolving 5--30 minute makes inferior stannic acid solution;
2) carbon black XC-72 or other inertia high surface area carrier were handled 10 minutes to 1 hour in 550--620 ℃ of air atmosphere, place the inferior stannic acid solution that has prepared then, ultrasonic wave disperseed 5--30 minute, with carbon black or other inertia high specific surface carrier high degree of dispersion, form the suspended substance of homogeneous;
3) above-mentioned suspended substance is heated to 20--85 ℃, then with H 2PtCl 6Under stationary temperature, drip continuously in or directly be added in the suspension of above-mentioned high-speed stirred, in the dropping process, evaporation of water in the continuous post-reactor of the water in the dropping liquid remains in the 0.02-0.1M scope total concentration that contains the Sn species.1-2 hour dropping time, after dropwising again constant temperature stirred 1--5 hour, replenish evaporation of water simultaneously;
4) after reaction finishes, filter drying.
CNB2004100044167A 2004-02-23 2004-02-23 Method of preparing direct methanol fuel sell anode catalyst by sub-stannic acid method Expired - Fee Related CN1257570C (en)

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CN1323450C (en) * 2005-07-05 2007-06-27 北京科技大学 Method of preparing catalyst for anode of fuel cell of direct alcohols
CN100591416C (en) * 2007-01-25 2010-02-24 中国科学院化学研究所 Noble metal carrier catalyst, preparing method and applications thereof
CN101306364B (en) * 2008-07-04 2010-10-06 北京科技大学 Preparation method of direct methanol fuel cell anode catalyst
CN116995254A (en) * 2023-09-25 2023-11-03 华北电力大学 Composite structure catalyst for synthesizing supported Pt-MXene and preparation method and application thereof

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