CN108963273B - Branch-shaped platinum electrocatalyst and preparation method and application thereof - Google Patents
Branch-shaped platinum electrocatalyst and preparation method and application thereof Download PDFInfo
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 204
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 102
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000000243 solution Substances 0.000 claims abstract description 27
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 25
- 239000002243 precursor Substances 0.000 claims abstract description 25
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 20
- 239000011259 mixed solution Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000446 fuel Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 239000008139 complexing agent Substances 0.000 claims abstract description 10
- 239000012528 membrane Substances 0.000 claims abstract description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 20
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 235000019253 formic acid Nutrition 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 9
- 239000004280 Sodium formate Substances 0.000 claims description 9
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 9
- 235000019254 sodium formate Nutrition 0.000 claims description 9
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 7
- 229960003975 potassium Drugs 0.000 claims description 7
- 229910052700 potassium Inorganic materials 0.000 claims description 7
- 239000011591 potassium Substances 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 239000001509 sodium citrate Substances 0.000 claims description 6
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 6
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- 239000001508 potassium citrate Substances 0.000 claims description 4
- 229960002635 potassium citrate Drugs 0.000 claims description 4
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 claims description 4
- 235000011082 potassium citrates Nutrition 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 abstract description 15
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 5
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- 239000013078 crystal Substances 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 description 35
- 238000006722 reduction reaction Methods 0.000 description 18
- 230000000694 effects Effects 0.000 description 12
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 238000000227 grinding Methods 0.000 description 6
- 230000010718 Oxidation Activity Effects 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 238000000840 electrochemical analysis Methods 0.000 description 5
- 239000012065 filter cake Substances 0.000 description 5
- 229920005862 polyol Polymers 0.000 description 5
- 150000003077 polyols Chemical class 0.000 description 5
- 238000012430 stability testing Methods 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
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- 238000003917 TEM image Methods 0.000 description 2
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- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000012694 precious metal precursor Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229910001252 Pd alloy Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000000851 scanning transmission electron micrograph Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Catalysts (AREA)
- Inert Electrodes (AREA)
Abstract
The invention belongs to the technical field of proton exchange membrane fuel cells, and discloses a branch-shaped platinum electrocatalyst, a preparation method and application thereof. The method comprises the following steps: (S1) dissolving a platinum precursor and a complexing agent in water to obtain a mixed solution; mixing a reducing agent with the mixed solution, and standing to obtain a platinum sol solution; (S2) uniformly mixing the solution of the platinum sol with the carbon carrier, and performing subsequent treatment to obtain the branch-shaped platinum electrocatalyst; or mixing the platinum precursor, the complexing agent, the carbon carrier and water to obtain a mixed solution containing the carbon carrier; and mixing the reducing agent with the mixed solution of the carbon-containing carrier, standing, and performing subsequent treatment to obtain the branch-shaped platinum electrocatalyst. The platinum electrocatalyst is a branch-shaped platinum electrocatalyst, has rich high-index active crystal faces, and simultaneously has high stability and high catalytic activity; the method is simple, green and environment-friendly, low in energy consumption and low in cost, and batch industrial production of the electrocatalyst is easy to realize.
Description
Technical Field
The invention belongs to the field of proton exchange membrane fuel cell electro-catalysts, and particularly relates to a branch-shaped platinum electro-catalyst, and a preparation method and application thereof. The branch-shaped platinum electrocatalyst is applied to a proton exchange membrane fuel cell to catalyze methanol oxidation and oxygen reduction of the proton exchange membrane fuel cell.
Background
In fuel cells, electrocatalysts play the role of "factories" of electrochemical reactions and are the core materials of the cells, and the development of electrocatalysts is one of the key parts of fuel cells. The noble metals platinum, palladium or platinum-palladium alloy have very high catalytic activity for the oxidation reaction and oxygen reduction reaction of fuel molecules such as hydrogen, formic acid, methanol, ethanol and the like, so most of the commercial and practical electrocatalysts at present are carbon-supported platinum or carbon-supported palladium electrocatalysts. The main goal of electrocatalyst development is to improve catalytic activity and stability, neither of which is necessary.
The methods for preparing platinum catalysts by chemical reduction are numerous, and the most common methods are impregnation reduction and polyol reduction. The solid-phase dipping reduction method comprises the steps of dipping a precious metal precursor and a carbon carrier, drying and grinding the precious metal precursor and the carbon carrier, and introducing hydrogen into a tubular furnace for reduction at high temperature (generally more than 200 ℃), wherein the method has high energy consumption and the precious metal is unevenly distributed on the carbon carrier; the liquid phase dipping reduction method is that firstly, a noble metal precursor and a carbon carrier are dipped, and then a strong reducing agent is added for room temperature reduction, although the method is simple, rapid and has no energy consumption, the prepared electro-catalyst has large grain diameter and uneven grain diameter distribution. The most common polyol reduction method is that glycol and other polyols are used as a solvent and a reducing agent at the same time, the noble metal precursor is reduced into the electrocatalyst by heating (120-160 ℃) for 3-8 hours, and the electrocatalyst prepared by the method has small particle size and uniform dispersion because the polyols play a role of a protective agent at the same time, and has the defects of high energy consumption, incapability of recycling and high cost due to the oxidation of the glycol and other polyols in the reaction process. In addition, the platinum catalysts prepared by the chemical reduction methods are all platinum particles, and the catalysts are easy to age and grow in the using process and have poor stability.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the invention aims to provide a branch-shaped platinum electrocatalyst and a preparation method thereof. The method has the advantages of low energy consumption, simplicity, low cost and easy realization of the batch industrial production of the electrocatalyst. The prepared electro-catalyst is a branch-shaped platinum electro-catalyst and has high stability and high catalytic activity.
The invention also aims to provide the application of the branch-shaped platinum electrocatalyst. The branch-shaped platinum electrocatalyst is applied to a proton exchange membrane fuel cell, and particularly catalyzes methanol oxidation and oxygen reduction of the proton exchange membrane fuel cell.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a branch-shaped platinum electrocatalyst comprises the following steps:
(S1) dissolving a platinum precursor and a complexing agent in water to obtain a mixed solution; mixing a reducing agent with the mixed solution, and standing to obtain a platinum sol solution; the complexing agent is more than one of citric acid, sodium citrate or potassium citrate; the reducing agent is more than one of formaldehyde, formic acid or sodium formate; (S2) uniformly mixing the solution of the platinum sol with the carbon carrier, and performing subsequent treatment to obtain the branch-shaped platinum electrocatalyst;
or
(P1) mixing the platinum precursor, the complexing agent, the carbon carrier and water to obtain a mixed solution containing the carbon carrier; mixing the reducing agent with the mixed solution of the carbon-containing carrier, standing, and performing subsequent treatment to obtain a branch-shaped platinum electrocatalyst; the complexing agent is more than one of citric acid, sodium citrate or potassium citrate; the reducing agent is more than one of formaldehyde, formic acid or sodium formate.
The step (S1) of standing is at room temperature; and standing at room temperature for 24-96 hours.
The uniformly mixing in the step (S2) is to soak the carbon carrier in the platinum sol solution or to perform ultrasonic dispersion treatment on the platinum sol solution and the carbon carrier; the time for ultrasonic dispersion is preferably 0.5-2 h;
the post-treatment in the step (S2) is to filter, wash and dry the mixed product.
Standing at room temperature in the step (P1); the standing time at room temperature is 24-96 hours.
The subsequent treatment in the step (P1) is ultrasonic dispersion after standing, and then the product is filtered, washed and dried. The time of ultrasonic dispersion is preferably 0.5-2 h.
In the steps (S1) and (P1), the platinum precursor is a water-soluble platinum precursor, preferably one or more of chloroplatinic acid, potassium chloroplatinite, chloroplatinic acid, sodium chloroplatinite, potassium chloroplatinate, and sodium chloroplatinate;
in the steps (S1) and (P1), the molar ratio of the complexing agent to the platinum precursor is (0.5-5): 1;
the molar ratio of the reducing agent to the platinum precursor in the steps (S1) and (P1) is (10-200): 1; preferably, when the reducing agent is formaldehyde, the molar ratio of the formaldehyde to the platinum precursor is 10: 1-100: 1; when the reducing agent is formic acid, the molar ratio of the formic acid to the platinum precursor is 50: 1-200: 1; when the reducing agent is sodium formate, the molar ratio of the sodium formate to the platinum precursor is 20: 1-100: 1.
The amounts of the carbon carrier and the platinum precursor used in the steps (S2) and (P1) satisfy the following condition: the platinum accounts for 20-60% of the total mass of the platinum and the carbon carrier, namely the loading capacity of the platinum in the branch-shaped platinum electrocatalyst is 20-60%.
The relationship between the amount of the platinum precursor and the amount of water in the steps (S1) and (P1) satisfies the following condition: the molar volume concentration of the platinum precursor in water is 0.05-0.001 mol/L.
The carbon carrier in steps (S2) and (P1) may be carbon black, activated carbon, carbon nanotubes, carbon fibers, graphene, or the like.
The branch-shaped platinum electrocatalyst is prepared by the method.
The branch-shaped platinum electrocatalyst is applied to a proton exchange membrane fuel cell, in particular to the application of the branch-shaped platinum electrocatalyst in catalyzing methanol oxidation and oxygen reduction of the proton exchange membrane fuel cell.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the platinum electrocatalyst is a branch-shaped platinum electrocatalyst, is not a platinum particle, has rich high-index active crystal faces, and simultaneously has high stability and high catalytic activity;
(2) the invention takes water as solvent, thus being green and environment-friendly; the reaction process is room temperature, so that the energy consumption is saved; the method is simple, low in cost and easy to realize the batch industrial production of the electrocatalyst.
Drawings
FIG. 1 is a scanning transmission electron micrograph of a branched platinum sol prepared in example 1;
fig. 2 is a transmission electron micrograph of the branched platinum electrocatalyst supported on the carbon support prepared in example 1.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
Example 1
(1) Adding 8ml of chloroplatinic acid solution with the concentration of 0.038mol/L into 100ml of water, and then adding 448mg of sodium citrate for dissolving to obtain a mixed solution; adding 0.0598mol of formic acid into the mixed solution, and standing for 96 hours at room temperature to obtain a branch-shaped platinum sol solution;
(2) adding 90mg of carbon powder (carbon black) into the platinum sol solution, ultrasonically dispersing for 1h, performing suction filtration, washing a filter cake with deionized water, performing vacuum drying, and grinding to obtain the carbon-supported platinum catalyst, namely the branched platinum electrocatalyst, wherein the mass percent of platinum in the electrocatalyst is 40%.
Fig. 1 is a scanning transmission electron microscope image of the branched platinum sol (branched platinum in the sol) prepared in this example. As can be seen from fig. 1, platinum is in the form of distinct multiple branches. Fig. 2 is a transmission electron micrograph of the branched platinum electrocatalyst (branched platinum electrocatalyst supported on a carbon support) prepared in this example. As can be seen from fig. 2, most of the platinum is branched and uniformly distributed on the carbon support.
Electrochemical tests found that the catalyst prepared in this example had an electrochemically active area of 58m2·g-1(ii) a At 0.5mol · L-1 H2SO4In solution at 50mV s-1The scan speed of (2) was scanned for 2000 revolutions, and then the electrochemically active area decay of the catalyst was calculated. It was found that the catalyst, after stability testing, had 58% electrochemically active area remaining, while the same type of commercial catalyst had 25% electrochemically active area remaining under the same testing conditions. The catalyst prepared in this example had an oxygen reduction mass activity of 140A g at 0.9V (vs. standard hydrogen electrode)-1The mass activity of the catalyst is 150 percent higher than that of a commercial catalyst. At 0.5mol · L-1 H2SO4+0.5mol·L-1 CH3The catalyst was tested for methanol oxidation activity in OH solution and mass activity was 850A g-1The mass activity of the catalyst is 180 percent higher than that of a commercial catalyst.
Example 2
(1) Adding 8ml of chloroplatinic acid solution with the concentration of 0.038mol/L into 100ml of water, and then adding 150mg of sodium citrate for dissolving to obtain a mixed solution; adding 0.0156mol of formic acid into the mixed solution, and standing for 24 hours at room temperature to obtain a branch-shaped platinum sol solution;
(2) adding 40mg of carbon powder into the platinum sol solution, ultrasonically soaking for 1h, carrying out suction filtration, washing a filter cake with water, drying in vacuum, and grinding to obtain the carbon-supported platinum catalyst, namely the branched platinum electrocatalyst, wherein the mass percent of platinum in the electrocatalyst is 60%. Electrochemical tests show that the electrochemical active area of the catalyst is 52m2·g-1(ii) a The catalyst was found to have 45% electrochemically active area remaining after stability testing. At 0.9V (vs. standard hydrogen electrode), the oxygen reduction mass activity of the catalyst was 120A g-1. At 0.5mol · L-1 H2SO4+0.5mol·L-1 CH3In OH solutionThe catalyst was tested for methanol oxidation activity and mass activity was 650A g-1。
Example 3
(1) Adding 8ml of potassium chloroplatinite with the concentration of 0.038mol/L into 100ml of water, and then adding 220mg of citric acid for dissolving to obtain a mixed solution; adding 413mg of sodium formate into the mixed solution, and standing for 48 hours at room temperature to obtain a branch-shaped platinum sol solution;
(2) adding 120mg of carbon powder into the platinum sol solution, collecting the platinum catalyst, ultrasonically dispersing for 1h, performing suction filtration, washing a filter cake with deionized water, performing vacuum drying, and grinding to obtain the carbon-supported platinum catalyst, namely the branched platinum electrocatalyst, wherein the mass percent of platinum in the electrocatalyst is 20%. Electrochemical tests show that the electrochemical active area of the catalyst is 135m2g-1(ii) a The catalyst was found to have 40% electrochemically active area remaining after stability testing. At 0.9V (vs. standard hydrogen electrode), the oxygen reduction mass activity of the catalyst was 90A g-1. At 0.5mol · L-1 H2SO4+0.5mol·L-1 CH3The catalyst was tested for methanol oxidation activity in OH solution and had a mass activity of 520A g-1。
Example 4
(1) Adding 8ml of potassium chloroplatinite with the concentration of 0.038mol/L into 100ml of water, and then adding 49mg of potassium citrate for dissolving to obtain a mixed solution; adding 2050mg of sodium formate into the mixed solution, and standing for 48 hours at room temperature to obtain a branch-shaped platinum sol solution;
(2) adding 120mg of carbon powder into the platinum sol solution, ultrasonically dispersing for 1h, performing suction filtration, washing a filter cake with deionized water, drying in vacuum, and grinding to obtain the carbon-supported platinum catalyst, namely the branched platinum electrocatalyst, wherein the mass percent of platinum in the electrocatalyst is 20%. Electrochemical tests show that the electrochemical active area of the catalyst is 125m2·g-1(ii) a The catalyst was found to have 45% electrochemically active area remaining after stability testing. At 0.9V (relative to a standard hydrogen electrode), the oxygen reduction mass activity of the catalyst was 80A g-1. At 0.5mol · L-1 H2SO4+0.5mol·L-1 CH3The catalyst was tested for methanol oxidation activity in OH solution with a mass activity of 450A g-1。
Example 5
(1) Adding 8ml of potassium chloroplatinite with the concentration of 0.038mol/L into 100ml of water, and then adding 260mg of sodium citrate for dissolving to obtain a mixed solution; adding 20ml of formaldehyde into the mixed solution, and standing for 48 hours at room temperature to obtain a branch-shaped platinum sol solution;
(2) adding 120mg of carbon powder into the platinum sol solution, ultrasonically soaking for 1h, performing suction filtration, washing a filter cake with deionized water, drying in vacuum, and grinding to obtain the carbon-supported platinum catalyst, wherein the mass ratio of platinum in the electrocatalyst is 20%. Electrochemical tests show that the electrochemical active area of the catalyst is 140m2·g-1(ii) a The catalyst was found to have 38% electrochemically active area remaining after stability testing. At 0.9V (vs. standard hydrogen electrode), the oxygen reduction mass activity of the catalyst was 85A g-1. At 0.5mol · L-1 H2SO4+0.5mol·L-1 CH3The catalyst was tested in OH solution for methanol oxidation activity with a mass activity of 800A g-1。
Claims (2)
1. The application of a branch-shaped platinum electrocatalyst in catalyzing methanol oxidation and oxygen reduction of a proton exchange membrane fuel cell is characterized in that: the preparation method of the branch-shaped platinum electrocatalyst comprises the following steps:
(S1) dissolving a platinum precursor and a complexing agent in water to obtain a mixed solution; mixing a reducing agent with the mixed solution, and standing to obtain a platinum sol solution; the complexing agent is more than one of citric acid, sodium citrate or potassium citrate; the reducing agent is more than one of formaldehyde, formic acid or sodium formate; (S2) uniformly mixing the solution of the platinum sol with the carbon carrier, and performing subsequent treatment to obtain the branch-shaped platinum electrocatalyst;
the step (S1) of standing is at room temperature; in the step (S1), the platinum precursor is a water-soluble platinum precursor, specifically, one or more of chloroplatinic acid, potassium chloroplatinite, chloroplatinic acid, sodium chloroplatinite, potassium chloroplatinate, and sodium chloroplatinate;
standing at room temperature for 24-96 hours;
the amounts of the carbon carrier and the platinum precursor used in the step (S2) satisfy the following condition: the platinum accounts for 20-60% of the total mass of the platinum and the carbon carrier;
in the step (S1), the molar ratio of the complexing agent to the platinum precursor is (0.5-5): 1;
in the step (S1), the molar ratio of the reducing agent to the platinum precursor is (10-200): 1; when the reducing agent is formaldehyde, the molar ratio of the formaldehyde to the platinum precursor is 10: 1-100: 1; when the reducing agent is formic acid, the molar ratio of the formic acid to the platinum precursor is 50: 1-200: 1; when the reducing agent is sodium formate, the molar ratio of the sodium formate to the platinum precursor is 20: 1-100: 1;
the post-treatment in the step (S2) is to filter, wash and dry the mixed product.
2. Use according to claim 1, characterized in that:
the mixing in the step (S2) is to soak the carbon support in the platinum sol solution or to perform ultrasonic dispersion treatment on the platinum sol solution and the carbon support.
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