CN1270398C - Method for preparing methanol poisoning resistant cathode catalyst of fuel cell - Google Patents
Method for preparing methanol poisoning resistant cathode catalyst of fuel cell Download PDFInfo
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- CN1270398C CN1270398C CNB2004100868932A CN200410086893A CN1270398C CN 1270398 C CN1270398 C CN 1270398C CN B2004100868932 A CNB2004100868932 A CN B2004100868932A CN 200410086893 A CN200410086893 A CN 200410086893A CN 1270398 C CN1270398 C CN 1270398C
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Abstract
The present invention relates to a method for preparing methanol poisoning resistant cathode catalyst (carbon carrying nanometer platinum-bismuth alloy / intermetallic compound catalyst) for fuel cells. In the method, chloroplatinic acid and bismuth trichloride are dissolved in 1-3 mol/L of hydrochloric acid according to the mol ratio of 1-5: 1; PVP is added into the mixture, and the molar ratio of PVP to the sum of the chloroplatinic acid and the bismuth trichloride is 15: 1; sodium borohydride is added into the mixture and stirred, wherein the molar ratio of the sodium borohydride to the sum of the chloroplatinic acid and the bismuth trichloride is 20: 1, and sol is obtained by stirring for 2-3 hours; the sol is boiled for one hour, and is filtered and dried according to the proportion that 10 ml of acetone is added into 1g of carbon powder; 6 mol/L of HNO3 solution is added into the sol according to the proportion that 10 ml of HNO3 solution is added into 1g of carbon powder, the mixture is boiled for one hour, filtered and washed to neutral, and is dried to obtain preprocessed carbon powder; the carbon powder is added into sol and is stirred for 5-8 hours, wherein the quality ratio of the carbon powder to the sum of the chloroplatinic acid and the bismuth trichloride is 4: 1; after the sample is dried by rotation in low pressure, the sample is washed and dried in vacuum. The catalyst prepared by the present invention has high methanol resistance, and has good electrocatalysis reduction by oxygen at the same time.
Description
Technical field
The present invention relates to a kind of cathode catalyst for fuel cell of anti methanol toxication---carbon-supported nano platinum bismuth alloy/intermetallic compound Preparation of catalysts method belongs to fuel cell material science and technology field and electro-catalysis technical field.
Background technology
Proton Exchange Membrane Fuel Cells (PEMFC) is a kind of device that directly chemical energy is converted to electric energy, because it is not subjected to the restriction of Carnot cycle, has very high energy conversion efficiency.Employing hydrogen acts as a fuel, and oxygen or air are as oxidant, and primary product is a water, is the friendly energy conversion technique of ideal environment.Caused the research boom of direct methanol fuel cell (DMFC) in the nineties.Compare with the fuel cell of other types, the development of DMFC is faced with an obstacle---" methyl alcohol penetrate " problem.This be because, the Nafion film that DMFC generally uses has higher methanol permeability, methyl alcohol can pass dielectric film from anode and enter into negative electrode, because negative electrode generally uses Pt/C to make catalyst, hydrogen reduction and methanol oxidation can take place simultaneously, therefore produce " mixed potential ", seriously reduce the power output of battery and the utilance of methyl alcohol.In addition, the intermediate product of methyl alcohol and oxide thereof can make conventional Pt/C catalyst take place to poison and inactivation causes the power output of battery to reduce significantly.One of method that addresses this problem is the good electrocatalyst for cathode of development selectivity, and promptly catalyst only has activity to hydrogen reduction, and to methanol oxidation non-activity or active little.
Because Pt costs an arm and a leg, therefore resource-constrained will realize the commercialization of fuel cell, must further reduce the use amount of platinum, and improve catalytic performance.Studies show that in a large number, the activity of Pt alloy catalyst is than monomer Pt height, stability might as well, (A K Shukla such as Shukla, M Neergat.J.Electroanal.Chem., 2001,504 (1): 111-119) negative electrode that Pt-Co/C, Pt-Cr/C, Pt-Ni/C, Pt-Co-Cr/C, Pt-Co-Ni/C is applied to DMFC finds that the activity of alloy catalyst all is higher than independent Pt/C.Introduce in platinum catalyst that other metallic element forms alloy or intermetallic compound can influence its electronic factor, thereby change it to methanol oxidation with to the cathode reduction process of oxygen.
A patent application: a kind of direct methanol fuel cell negative electrode tolerant catalyst, (number of patent application: 2003101103480), in the method that relates to melting prepare body phase platinum bismuth intermetallic compound, have the effect of good anti methanol toxication.If use it in the actual fuel cell, satisfy electrocatalysis characteristic and the requirement that reduces cost, must prepare nanocatalyst, improve the decentralization of platinum bismuth, reduce catalyst loadings.Reach these requirements, carbon supported catalyst is one of main path.
At present relevant Pt intermetallic compound catalyst is also at the early-stage as the research of DMFC electrocatalyst for cathode.Prepare nanometer Pt alloy and carbon carries by sol method, the anti methanol toxication catalyst of this method preparation will be to the practicability that promotes DMFC and theoretical research all with significant.
Summary of the invention
The objective of the invention is to propose the preparation method of a kind of direct methanol fuel cell with the carbon-supported nano platinum bismuth alloy/intermetallic compound eelctro-catalyst of anti methanol toxication.
The Bi of carbon-supported nano platinum bismuth alloy/intermetallic compound of the present invention: the Pt mol ratio is 1～5: 1
The preparation method of the cathode catalyst for fuel cell of a kind of anti methanol toxication that the present invention proposes is characterized in that, is made up of following each step:
With bismuth chloride and chloroplatinic acid by 1～5: 1 mol ratio is dissolved in the hydrochloric acid of 1～3mol/L, add polyvinylpyrrolidone, be PVP, cook protective agent, wherein the mol ratio of polyvinylpyrrolidone and chloroplatinic acid and bismuth chloride sum is 15: 1, add sodium borohydride under stirring condition, wherein the mol ratio of sodium borohydride and chloroplatinic acid and bismuth chloride sum is 20: 1, stirs to prepare nanometer platinum bismuth alloy and nanometer platinum bismuth intermetallic compound colloidal sol in 2-3 hour;
2. in the ratio that adds the 1g carbon dust in the 10ml acetone, boil 1h, filter, drying is pressed 10ml HNO again
3The ratio that adds the 1g carbon dust in the solution adds 6mol/L HNO
3Solution boils 1h, filters, and the distilled water cyclic washing is to neutral, and drying obtains through pretreated carbon dust;
3. the pretreated carbon dust of above-mentioned process is joined in the colloidal sol and stirred 5-8 hour, wherein the mass ratio of carbon dust and chloroplatinic acid and bismuth chloride sum is 4: 1, behind the low pressure rotary furnace drying sample, with distilled water and acetone washing, vacuumize, obtain the cathode catalyst for fuel cell of anti methanol toxication of the present invention, i.e. carbon-supported nano platinum bismuth alloy/intermetallic compound catalyst.
The cathode catalyst for fuel cell of the anti methanol toxication that the present invention makes, it is the size that carbon-supported nano platinum bismuth alloy/intermetallic compound catalyst adopts nanometer platinum bismuth alloy/intermetallic compound in the transmission electron microscope observing catalyst, what transmission electron microscope used is JEM-2010 (NEC), operating voltage 200KV; Adopt X-ray diffraction (XRD) to carry out the nanocrystalline structure analysis, XRD is to use D8ADVANCE (U.S. Bruker), and light source is the Cu radiographic source, and 2 θ scopes are 10-90 °, and step-length is 0.02 °; Catalyst performance evaluation adopts three-electrode system, carries out the cyclic voltammetry scan test, and data are by the Potentiostat/Galvanostat model 263A record of U.S. Princeton applied research company.The work electrode preparation method: take by weighing the 5mg catalyst, add the ethanol of 1ml and the 5%Nafion solution of 50 μ l, ultrasonic wave is dispersed into the ink shape, gets 5 μ l with microsyringe and drips on the GC electrode, oven dry.Reference electrode is Hg/Hg
2SO
4Electrode; To electrode is smooth platinized platinum.Containing the H of methyl alcohol by contrast
2SO
4Its anti methanol toxication performance and hydrogen reduction electrocatalysis characteristic are estimated in the variation of the cyclic voltammetry curve of catalyst in the solution.Electrode face is long-pending for the area of glass-carbon electrode head among the present invention, is about 0.2cm
2, do not adopt current density value to carry out catalyst performance evaluation in the present invention, but this does not influence anti methanol toxication performance and the oxygen reduction electro-catalyst performance of judging carbon-supported nano platinum bismuth alloy catalyst and carbon-supported nano platinum bismuth intermetallic compound catalyst.
Utilize in the colloidal sol that method of the present invention obtains platinum bismuth alloy/intermetallic compound particle particle diameter in 3-6 nanometer (see figure 5).After carbon carried, on the carbon granules of about 30 nanometers of particle diameter, the particle diameter that distributing was about the platinum bismuth alloy/intermetallic compound particle (see figure 6) of 3-6 nanometer
Through the cyclic voltammetric test, the catalyst that utilizes the inventive method to obtain has excellent anti methanol toxication performance (seeing Fig. 1-4) with respect to nanometer monometallic platinum catalyst.
Description of drawings
Fig. 1 is containing methyl alcohol and is not containing the 0.5MH of methyl alcohol with the existing carbon-supported nano monometallic platinum catalyst of sol method preparation
2SO
4Cyclic voltammetric correlation curve in the solution
Fig. 2 is that the carbon-supported nano platinum bismuth alloy/intermetallic compound catalyst of experimental program one preparation is containing methyl alcohol and do not containing the 0.5MH of methyl alcohol
2SO
4Cyclic voltammetric correlation curve in the solution
Fig. 3 is that the carbon-supported nano platinum bismuth alloy/intermetallic compound catalyst of experimental program two preparation is containing methyl alcohol and do not containing the 0.5MH of methyl alcohol
2SO
4Cyclic voltammetric correlation curve in the solution
Fig. 4 is that the carbon-supported nano platinum bismuth alloy/intermetallic compound catalyst of experimental program three preparation is containing methyl alcohol and do not containing the 0.5MH of methyl alcohol
2SO
4Cyclic voltammetric correlation curve in the solution
Fig. 5 is transmission electron microscope (TEM) photo to the platinum bismuth alloy/intermetallic compound sol particle granularmetric analysis of experimental program two preparations
Fig. 6 carries transmission electron microscope (TEM) photo of platinum bismuth alloy/intermetallic compound sol particle granularmetric analysis to the carbon that experimental program two prepares
Fig. 7 is the XRD figure with the analysis of the existing carbon-supported nano monometallic platinum catalyst crystal structure of sol method preparation
Fig. 8 is that experimental program one preparation carbon carries the XRD figure that platinum bismuth alloy/intermetallic compound catalyst crystal structure is analyzed
Fig. 9 is that experimental program two preparation carbon carry the XRD figure that platinum bismuth alloy/intermetallic compound catalyst crystal structure is analyzed
Figure 10 is that experimental program three preparation carbon carry the XRD figure that platinum bismuth alloy/intermetallic compound catalyst crystal structure is analyzed
Embodiment
Experimental program one:
Chloroplatinic acid and the bismuth chloride mol ratio by 1: 1 is dissolved in the hydrochloric acid of 2mol/L; add polyvinylpyrrolidone (PVP) and cook protective agent; wherein the mol ratio of polyvinylpyrrolidone and chloroplatinic acid and bismuth chloride sum is 15: 1; under stirring condition, add sodium borohydride; wherein the mol ratio of sodium borohydride and chloroplatinic acid and bismuth chloride sum is 20: 1, prepares nanometer platinum bismuth alloy and nanometer platinum bismuth intermetallic compound colloidal sol.The certain amount of pre-treated carbon dust is joined in the colloidal sol stirred for several hour, wherein the mass ratio of carbon dust and chloroplatinic acid and bismuth chloride sum is 4: 1, behind the low pressure rotary furnace drying sample, with distilled water and acetone cyclic washing, vacuumize obtains carbon-supported nano platinum bismuth alloy of the present invention and nanometer platinum bismuth intermetallic compound catalyst.
Experimental program two:
Chloroplatinic acid and the bismuth chloride mol ratio by 1: 2 is dissolved in the hydrochloric acid of 2mol/L; add polyvinylpyrrolidone (PVP) and cook protective agent; wherein the mol ratio of polyvinylpyrrolidone and chloroplatinic acid and bismuth chloride sum is 15: 1; under stirring condition, add sodium borohydride; wherein the mol ratio of sodium borohydride and chloroplatinic acid and bismuth chloride sum is 20: 1, prepares nanometer platinum bismuth alloy and nanometer platinum bismuth intermetallic compound colloidal sol.The certain amount of pre-treated carbon dust is joined in the colloidal sol stirred for several hour, wherein the mass ratio of carbon dust and chloroplatinic acid and bismuth chloride sum is 4: 1, behind the low pressure rotary furnace drying sample, with distilled water and acetone cyclic washing, vacuumize obtains carbon-supported nano platinum bismuth alloy of the present invention and nanometer platinum bismuth intermetallic compound catalyst.
Experimental program three:
Chloroplatinic acid and the bismuth chloride mol ratio by 1: 5 is dissolved in the hydrochloric acid of 2mol/L; add polyvinylpyrrolidone (PVP) and cook protective agent; wherein the mol ratio of polyvinylpyrrolidone and chloroplatinic acid and bismuth chloride sum is 15: 1; under stirring condition, add sodium borohydride; wherein the mol ratio of sodium borohydride and chloroplatinic acid and bismuth chloride sum is 20: 1, prepares nanometer platinum bismuth alloy and nanometer platinum bismuth intermetallic compound colloidal sol.The certain amount of pre-treated carbon dust is joined in the colloidal sol stirred for several hour, wherein the mass ratio of carbon dust and chloroplatinic acid and bismuth chloride sum is 4: 1, behind the low pressure rotary furnace drying sample, with distilled water and acetone cyclic washing, vacuumize obtains carbon-supported nano platinum bismuth alloy of the present invention and nanometer platinum bismuth intermetallic compound catalyst.
The work electrode preparation method: take by weighing the 5mg catalyst, add the ethanol of 1ml and the 5%Nafion solution of 50 μ l, ultrasonic wave is dispersed into the ink shape, gets 5 μ l with microsyringe and drips on the GC electrode, oven dry.Reference electrode is Hg/Hg
2SO
4Electrode; To electrode is smooth platinized platinum.Containing the H of methyl alcohol by contrast
2SO
4Its anti methanol toxication performance and hydrogen reduction electrocatalysis characteristic are estimated in the variation of the cyclic voltammetry curve of catalyst in the solution.
Claims (1)
1, a kind of preparation method of cathode catalyst for fuel cell of anti methanol toxication is characterized in that, is made up of following each step:
1) chloroplatinic acid and bismuth chloride are dissolved in the hydrochloric acid of 1～3mol/L by 1: 1～5 mol ratios, add polyvinylpyrrolidone and cook protective agent, wherein the mol ratio of polyvinylpyrrolidone and chloroplatinic acid and bismuth chloride sum is 15: 1, under stirring condition, add sodium borohydride, wherein the mol ratio of sodium borohydride and chloroplatinic acid and bismuth chloride sum is 20: 1, stirs to prepare nanometer platinum bismuth alloy and nanometer platinum bismuth intermetallic compound colloidal sol in 2-3 hour;
2) in the ratio that adds the 1g carbon dust in the 10ml acetone, boil 1h, filter, drying is pressed 10ml HNO again
3The ratio that adds the 1g carbon dust in the solution adds 6mol/L HNO
3Solution boils 1h, filters, and the distilled water cyclic washing is to neutral, and drying obtains through pretreated carbon dust;
3) the pretreated carbon dust of above-mentioned process is joined in the colloidal sol and to stir 5-8 hour, wherein the mass ratio of carbon dust and chloroplatinic acid and bismuth chloride sum is 4: 1, behind the low pressure rotary furnace drying sample, with distilled water and acetone washing, vacuumize, obtain the cathode catalyst for fuel cell of anti methanol toxication of the present invention, i.e. carbon-supported nano platinum bismuth alloy/intermetallic compound catalyst.
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| CNB2004100868932A CN1270398C (en) | 2004-11-05 | 2004-11-05 | Method for preparing methanol poisoning resistant cathode catalyst of fuel cell |
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| CN100553768C (en) * | 2006-05-12 | 2009-10-28 | 中国科学院大连化学物理研究所 | A kind of loaded and non-supported catalyst and preparation method |
| CN101785999B (en) * | 2010-02-05 | 2012-05-30 | 北京工业大学 | Preparation method of electro-catalyst Pt1Bi1 intermetallic compounds used for fuel batteries |
| CN105903479A (en) * | 2016-04-25 | 2016-08-31 | 中国科学院上海高等研究院 | Carbon-loaded surface platinum-enriched platinum-nickel intermetallic compound and preparation method and application thereof |
| CN113839057B (en) * | 2021-08-31 | 2024-05-14 | 上海大学 | Porous platinum nano dendrite electrocatalyst and preparation method thereof |
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