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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- chloroplatinic acid
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- 239000003054 catalyst Substances 0.000 title claims abstract description 49
- 239000000446 fuel Substances 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title claims abstract description 14
- 208000021251 Methanol poisoning Diseases 0.000 title abstract 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 108
- 229910000765 intermetallic Inorganic materials 0.000 claims abstract description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910001152 Bi alloy Inorganic materials 0.000 claims abstract description 27
- 239000002253 acid Substances 0.000 claims abstract description 24
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims abstract description 24
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 12
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 8
- 230000007935 neutral effect Effects 0.000 claims abstract description 3
- ZOKDWBDDYVCACM-UHFFFAOYSA-N bismuth platinum Chemical compound [Pt].[Bi] ZOKDWBDDYVCACM-UHFFFAOYSA-N 0.000 claims description 37
- 229910052799 carbon Inorganic materials 0.000 claims description 28
- 238000002360 preparation method Methods 0.000 claims description 17
- 239000000428 dust Substances 0.000 claims description 16
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 14
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 14
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 14
- 230000036228 toxication Effects 0.000 claims description 13
- 239000012153 distilled water Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000003223 protective agent Substances 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
- 239000001301 oxygen Substances 0.000 abstract description 4
- 238000001291 vacuum drying Methods 0.000 abstract 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 21
- 239000002245 particle Substances 0.000 description 7
- 229910052697 platinum Inorganic materials 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 229920000557 Nafion® Polymers 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 239000010411 electrocatalyst Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910001260 Pt alloy Inorganic materials 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910020630 Co Ni Inorganic materials 0.000 description 1
- 229910002440 Co–Ni Inorganic materials 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical class COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- 229910002845 Pt–Ni Inorganic materials 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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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
本发明涉及一种抗甲醇中毒的燃料电池用阴极催化剂(碳载纳米铂铋合金/金属间化合物催化剂)的制备方法。将氯铂酸和氯化铋按1～5∶1摩尔比溶于1～3mol/L的盐酸中，加入与氯铂酸和氯化铋之和的摩尔比为15∶1的PVP，搅拌加入硼氢化钠，其中硼氢化钠与氯铂酸和氯化铋之和的摩尔比为20∶1，搅拌2-3小时得到溶胶；按10ml丙酮中加入1g碳粉比例，煮沸1h，过滤，干燥，再按10ml HNO3溶液中加入1g碳粉的比例加入6mol/LHNO3溶液，煮沸1h，过滤，洗涤至中性，干燥，得到经过预处理的碳粉；将碳粉加入到溶胶中搅拌5-8小时，其中碳粉与氯铂酸和氯化铋之和的质量比为4∶1，低压旋转烘干样品后，洗涤，真空干燥。本发明制备的催化剂具有优异的抗甲醇性能，同时具有良好的氧还原电催化性能。
The invention relates to a method for preparing a methanol poisoning-resistant fuel cell cathode catalyst (carbon-supported nano-platinum-bismuth alloy/intermetallic compound catalyst). Dissolve chloroplatinic acid and bismuth chloride in a molar ratio of 1 to 5:1 in hydrochloric acid of 1 to 3 mol/L, add PVP with a molar ratio of 15:1 to the sum of chloroplatinic acid and bismuth chloride, and stir to add Sodium borohydride, wherein the molar ratio of sodium borohydride to the sum of chloroplatinic acid and bismuth chloride is 20:1, stir for 2-3 hours to obtain a sol; add 1g of carbon powder to 10ml of acetone, boil for 1h, filter, and dry , and then add 6mol/L HNO 3 solution according to the ratio of adding 1g carbon powder to 10ml HNO 3 solution, boil for 1h, filter, wash until neutral, and dry to obtain pretreated carbon powder; add carbon powder to the sol and stir for 5 -8 hours, wherein the mass ratio of carbon powder to the sum of chloroplatinic acid and bismuth chloride is 4:1, after drying the sample under low pressure, washing and vacuum drying. The catalyst prepared by the invention has excellent methanol resistance performance and good oxygen reduction electrocatalysis performance.
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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| 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 | Electrocatalyst Pt for fuel cell1Bi1Method for preparing intermetallic compound |
| 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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