CN114628706A - Catalyst for proton exchange membrane fuel cell and preparation method thereof - Google Patents
Catalyst for proton exchange membrane fuel cell and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 84
- 239000000446 fuel Substances 0.000 title claims abstract description 58
- 239000012528 membrane Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title abstract description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 143
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 69
- 239000006229 carbon black Substances 0.000 claims abstract description 57
- 238000000034 method Methods 0.000 claims abstract description 35
- 239000002262 Schiff base Substances 0.000 claims abstract description 22
- 150000004753 Schiff bases Chemical class 0.000 claims abstract description 22
- 239000002608 ionic liquid Substances 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 131
- 238000003756 stirring Methods 0.000 claims description 127
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 126
- 239000000243 solution Substances 0.000 claims description 90
- 229910052757 nitrogen Inorganic materials 0.000 claims description 65
- 238000011282 treatment Methods 0.000 claims description 54
- 238000005406 washing Methods 0.000 claims description 54
- 238000001035 drying Methods 0.000 claims description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 51
- 239000012018 catalyst precursor Substances 0.000 claims description 48
- 238000006243 chemical reaction Methods 0.000 claims description 47
- 239000002002 slurry Substances 0.000 claims description 45
- 239000011259 mixed solution Substances 0.000 claims description 42
- 235000019441 ethanol Nutrition 0.000 claims description 37
- 238000011049 filling Methods 0.000 claims description 36
- 239000001257 hydrogen Substances 0.000 claims description 33
- 229910052739 hydrogen Inorganic materials 0.000 claims description 33
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- 238000001816 cooling Methods 0.000 claims description 26
- 230000009467 reduction Effects 0.000 claims description 26
- 238000006722 reduction reaction Methods 0.000 claims description 26
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- 239000012498 ultrapure water Substances 0.000 claims description 25
- 238000009210 therapy by ultrasound Methods 0.000 claims description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 23
- 238000001914 filtration Methods 0.000 claims description 19
- 239000002243 precursor Substances 0.000 claims description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 18
- AKGUXECGGCUDCV-UXBLZVDNSA-N [(e)-benzylideneamino]urea Chemical compound NC(=O)N\N=C\C1=CC=CC=C1 AKGUXECGGCUDCV-UXBLZVDNSA-N 0.000 claims description 18
- 229910052799 carbon Inorganic materials 0.000 claims description 18
- 230000035484 reaction time Effects 0.000 claims description 18
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 16
- 229910017604 nitric acid Inorganic materials 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 239000005457 ice water Substances 0.000 claims description 14
- 238000009835 boiling Methods 0.000 claims description 10
- 210000003298 dental enamel Anatomy 0.000 claims description 9
- 238000007710 freezing Methods 0.000 claims description 9
- 230000008014 freezing Effects 0.000 claims description 9
- 150000002431 hydrogen Chemical class 0.000 claims description 9
- CPXYGYOMIMOSCX-YRNVUSSQSA-N [(e)-1-phenylethylideneamino]urea Chemical compound NC(=O)N\N=C(/C)C1=CC=CC=C1 CPXYGYOMIMOSCX-YRNVUSSQSA-N 0.000 claims description 8
- IPILPUZVTYHGIL-UHFFFAOYSA-M tributyl(methyl)azanium;chloride Chemical compound [Cl-].CCCC[N+](C)(CCCC)CCCC IPILPUZVTYHGIL-UHFFFAOYSA-M 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- PDJBCBKQQFANPW-UHFFFAOYSA-L azanide;platinum(2+);dichloride Chemical compound [NH2-].[NH2-].[NH2-].[NH2-].Cl[Pt]Cl PDJBCBKQQFANPW-UHFFFAOYSA-L 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- BRKFQVAOMSWFDU-UHFFFAOYSA-M tetraphenylphosphanium;bromide Chemical compound [Br-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BRKFQVAOMSWFDU-UHFFFAOYSA-M 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- XOTZDSWJKMKAMT-UHFFFAOYSA-M tributyl(ethyl)phosphanium;bromide Chemical compound [Br-].CCCC[P+](CC)(CCCC)CCCC XOTZDSWJKMKAMT-UHFFFAOYSA-M 0.000 claims description 3
- KLFRPGNCEJNEKU-FDGPNNRMSA-L (z)-4-oxopent-2-en-2-olate;platinum(2+) Chemical compound [Pt+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O KLFRPGNCEJNEKU-FDGPNNRMSA-L 0.000 claims description 2
- 238000002525 ultrasonication Methods 0.000 claims 2
- VVKBUFYSWPMDNG-UHFFFAOYSA-N nitroxyl anion platinum(2+) Chemical compound N(=O)[Pt]N=O VVKBUFYSWPMDNG-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 15
- 238000011056 performance test Methods 0.000 abstract description 4
- 230000003993 interaction Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 20
- 238000003917 TEM image Methods 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- 229910021397 glassy carbon Inorganic materials 0.000 description 5
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910001260 Pt alloy Inorganic materials 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- NOWPEMKUZKNSGG-UHFFFAOYSA-N azane;platinum(2+) Chemical compound N.N.N.N.[Pt+2] NOWPEMKUZKNSGG-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- MBUJACWWYFPMDK-UHFFFAOYSA-N pentane-2,4-dione;platinum Chemical compound [Pt].CC(=O)CC(C)=O MBUJACWWYFPMDK-UHFFFAOYSA-N 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
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Classifications
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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
- H01M4/90—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)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Inert Electrodes (AREA)
Abstract
The invention discloses a catalyst for a proton exchange membrane fuel cell and a preparation method thereof, the catalyst for the proton exchange membrane fuel cell comprises a carbon black carrier and metal platinum loaded on the carbon black carrier, and the mass percentage of the platinum in the catalyst is 40-60%. In addition, the invention also provides a method for preparing the catalyst, the method for preparing the catalyst for the proton exchange membrane fuel cell obtains the catalyst for the proton exchange membrane fuel cell by the interaction of the carbon black treated by the Schiff base and the platinum complex dispersed by the ionic liquid, and the catalyst for the proton exchange membrane fuel cell has the mass specific activity of more than 0.2A/mg and the electrochemical active area of 60m in the electrochemical performance test2More than g, the attenuation rate after circulating for 30000 circles is within 10 percent, and the electrochemical activity and the stability are high.
Description
Technical Field
The invention belongs to the technical field of catalysis, and particularly relates to a catalyst for a proton exchange membrane fuel cell and a preparation method thereof.
Background
The main energy of the hydrogen fuel cell automobile is hydrogen energy, and due to the high energy density of the hydrogen fuel cell automobile, the proton exchange membrane fuel cell has the outstanding advantages of high energy conversion efficiency, environmental friendliness, high starting speed at room temperature, small volume, no electrolyte loss, easiness in water drainage, long service life, high specific power and specific energy and the like, and is the preferred choice for the power new energy battery for the automobile at present. The catalyst is considered to be a key factor affecting activation polarization of the hydrogen fuel cell, however, activity and stability of the catalyst for proton exchange membrane fuel cells are greatly affected due to corrosion.
The chinese patent application, published as 2016, 11, 16, and CN 106129424B, discloses a method for preparing a catalyst for a fuel cell in a high-efficiency and batch manner, and specifically discloses a process for preparing a catalyst for a proton exchange membrane fuel cell by mixing a platinum source solution with a carrier treated by organic weak acid, heating the mixture by microwave under a certain pH condition, and using concentrated hydrochloric acid as a precipitator. Chinese patent application publication No. CN 110444781 a, published as 11/12/2019, discloses a method for preparing a fuel cell catalyst and discloses a fuel cell catalyst prepared by mixing a carrier and a platinum source, adjusting pH, performing a spray reaction, filtering, and performing spray drying, but the electrochemical activity of the catalyst still cannot meet the technical requirements. The Chinese patent application with the publication number of CN 112259752B, 10 and 19 in 2020, discloses a preparation method of a platinum alloy fuel cell catalyst and discloses a process for preparing a proton exchange membrane platinum alloy fuel cell catalyst by mixing a carrier and amino acid for heat treatment, adding a reducing agent solution and a platinum source into an auxiliary agent metal salt solution and then carrying out high-pressure reaction, wherein the activity of the alloy catalyst is higher, but after circulating for 30000 circles, the mass specific activity and the attenuation of the electrochemical activity area are both about 15 percent, and the defect of poor stability exists.
Disclosure of Invention
The technical problem to be solved by the present invention is to provide a catalyst for a proton exchange membrane fuel cell and a preparation method thereof, aiming at the defects of the prior art. Preparation of proton conjugates of the inventionThe method for changing the catalyst for the membrane fuel cell obtains the catalyst for the proton exchange membrane fuel cell by the interaction of the carbon black treated by Schiff base and the platinum complex dispersed by the ionic liquid, and the catalyst has the mass specific activity of more than 0.2A/mg and the electrochemical active area of 60m in the electrochemical performance test2More than g, the attenuation rate after circulating for 30000 circles is within 10 percent, and the electrochemical activity and the stability are high.
In order to solve the technical problems, the invention adopts the technical scheme that: the catalyst for the proton exchange membrane fuel cell is characterized by comprising a carbon black carrier and metal platinum loaded on the carbon black carrier, wherein the mass percentage of the platinum in the catalyst is 40-60%.
In addition, the present invention also provides a method for preparing the catalyst for a proton exchange membrane fuel cell, which is characterized by comprising:
firstly, carrying out ultrasonic treatment and boiling on a carbon black carrier, washing the boiled carrier, and drying;
dissolving Schiff base in absolute ethyl alcohol to obtain an ethanol solution of Schiff base;
step three, under the microwave condition, placing the dried carrier in the step one into the ethanol solution of the Schiff base in the step two, treating for 40-120 min, washing, and drying to obtain a treated carbon black carrier;
dispersing the ionic liquid in an ethanol solution to obtain a mixed solution A;
dissolving the platinum complex in a solvent, and performing ultrasonic treatment under the ice-water bath condition to obtain a mixed solution B;
step six, under the stirring condition, dropwise adding the mixed solution A obtained in the step four into the mixed solution B obtained in the step five, and continuously stirring after dropwise adding is finished to obtain a platinum precursor solution;
seventhly, placing the carbon black carrier treated in the step three in methanol, and uniformly stirring to obtain carbon slurry;
step eight, under the condition of water bath stirring, dropwise adding the platinum precursor solution obtained in the step six into the carbon slurry obtained in the step seven, continuously stirring after dropwise adding is finished, and standing to obtain slurry;
step nine, reducing the slurry obtained in the step eight, cooling, filtering, washing, freezing and drying to obtain a catalyst precursor;
step ten, dispersing the catalyst precursor in the step nine into a nitric acid solution to obtain a catalyst precursor system;
step eleven, stirring the catalyst precursor system for 30min under the water bath condition, and then carrying out post-treatment to obtain the catalyst for the proton exchange membrane fuel cell;
the method is characterized in that in the step one, the ultrasonic treatment is carried out by putting the carbon black carrier into an acid solution for ultrasonic treatment, wherein the acid solution is a nitric acid solution or a sulfuric acid solution, and the carbon black carrier comprises XC-72R, EC-300J or BP-2000; step one, washing is carried out by using ultrapure water until the pH value is more than 6.
The method is characterized in that the mass percentage of the Schiff base in the ethanol solution of the Schiff base in the step two is 5-20%, and the Schiff base comprises benzaldehyde semicarbazone or acetophenone semicarbazone; and step three, the mass of the Schiff base is 0.5-2 times of that of the dried carrier, and the washing in step three is to wash the Schiff base with ultrapure water until the conductivity is less than 4 delta/cm.
The method is characterized in that in the mixed solution A in the fourth step, the mass percentage of the ionic liquid is 5% -20%, and the ionic liquid is tributyl methyl ammonium chloride, tributyl ethyl phosphonium bromide or tetraphenyl phosphonium bromide.
The method is characterized in that the platinum complex in the fifth step comprises tetraammineplatinum dichloride, dinitroso diammineplatinum or acetylacetone platinum, the solvent is N-N dimethylformamide, water or an ammonia water solution, and the mass percentage of the platinum complex in the mixed solution B is 2-5%; fifthly, the temperature of the ice-water bath is 0-5 ℃; in the sixth step, the mass of the ionic liquid is 1.5 times of that of the platinum; and sixthly, the stirring speed and the continuous stirring speed are both 800 rpm-1500 rpm.
The method is characterized in that the stirring speed and the continuous stirring speed in the step eight are both 2000rpm, and the temperature of the water bath is 5-15 ℃.
The method described above, wherein the reduction in step nine comprises: and (2) placing the slurry in a high-pressure reaction kettle, filling nitrogen to replace air, then replacing nitrogen with hydrogen, and filling hydrogen to react, wherein in the reaction process, the hydrogen pressure is 4-7 MPa, the temperature is 200-300 ℃, the stirring speed is 1000-2000 rpm, and the reaction time is 3-5 h.
The method described above, wherein the mass of the nitric acid solution in the step ten is 50 to 150 times the mass of the catalyst precursor.
The method is characterized in that in the eleventh step, the water bath temperature is 5-15 ℃, and the stirring speed is 10000 rpm; step eleven, the post-treatment specifically comprises high-pressure nitrogen treatment, temperature reduction, filtration, washing and cooling drying; the high-pressure nitrogen treatment comprises the following steps: placing the catalyst precursor system after water bath stirring in a high-pressure reaction kettle with an enamel lining, filling nitrogen to replace air, and continuously filling nitrogen, wherein in the reaction process, the pressure of the nitrogen in the kettle is kept between 3 and 5MPa, the temperature is between 300 and 450 ℃, the stirring speed is between 1000 and 2000rpm, and the reaction time is between 4 and 8 hours.
Compared with the prior art, the invention has the following advantages:
1. the invention provides a catalyst for a proton exchange membrane fuel cell and a preparation method thereof, the method comprises the step of interacting carbon black treated by Schiff base with a platinum complex dispersed by ionic liquid to obtain the catalyst for the proton exchange membrane fuel cell, and the catalyst has the mass specific activity of more than 0.2A/mg and the electrochemical active area of 60m in an electrochemical performance test2More than g, the attenuation rate after circulating for 30000 circles is within 10 percent, and the electrochemical activity and the stability are high.
2. Preferably, the preparation method comprises the steps of treating the carbon black by ultrasonic treatment, boiling and ethanol solution of Schiff base under microwave conditions, so that impurities in the carbon black can be effectively removed, the Schiff base is uniformly adsorbed on the carrier, and the adsorption and dispersion of the metal platinum in the subsequent platinum adsorption process are promoted.
3. Preferably, the preparation method comprises the step of stirring the platinum complex subjected to ultrasonic treatment under the ice-water bath condition and the ionic liquid at a high speed to obtain a platinum precursor, wherein the platinum complex is used as an active metal source to interact with the ionic liquid, and has the characteristic of higher platinum component dispersibility.
4. Preferably, the preparation method of the invention comprises the steps of dispersing the catalyst precursor in nitric acid under the water bath condition and performing post-treatment comprising high-pressure nitrogen treatment and cooling and drying, so that the impurities such as organic matters and the like can be effectively removed, and the catalyst with higher purity can be obtained.
5. The preparation method of the invention has reliable principle, practical method and wide popularization and application value.
The technical solution of the present invention is further described in detail with reference to the accompanying drawings and embodiments.
Drawings
FIG. 1 is a transmission electron micrograph of the catalyst of example 1.
Fig. 2 is a transmission electron micrograph of the catalyst of comparative example 1.
FIG. 3 is a transmission electron micrograph of the catalyst of example 2.
Fig. 4 is a transmission electron micrograph of the catalyst of comparative example 3.
Fig. 5 is a transmission electron micrograph of the catalyst of comparative example 4.
Detailed Description
Example 1
The embodiment provides a catalyst for a proton exchange membrane fuel cell, which comprises a carbon black carrier and metal platinum loaded on the carbon black carrier, wherein the mass percentage of the platinum in the catalyst is 40%.
The present embodiment also provides a method for preparing the catalyst for a proton exchange membrane fuel cell, including:
step one, ultrasonically dispersing 10g of XC-72R carbon black carrier in 100ml of sulfuric acid solution with the mass percentage of 10% for 30min, boiling for 30min, taking out, naturally cooling to room temperature, washing with ultrapure water until the pH value is more than 6, and drying at the temperature of 120 ℃ to constant weight; the ultrasonic power is 200W, the frequency is 40KHz, and the room temperature is 20-25 ℃;
dissolving 2.5g of benzaldehyde semicarbazone in 50g of absolute ethyl alcohol to obtain an ethanol solution of the benzaldehyde semicarbazone;
step three, placing 5g of the dried carrier in the step one in the ethanol solution of the benzaldehyde semicarbazone in the step two, performing microwave treatment in a microwave reactor for 120min, washing with ultrapure water until the conductivity is less than 4 delta/cm, and drying to obtain a treated carbon black carrier; the temperature of the microwave treatment can be 80 ℃, and the power can be 500W; the drying may be drying in a vacuum rotary evaporator;
dissolving 2.4g of tributylmethylammonium chloride in 48g of ethanol solution, uniformly stirring, and performing ultrasonic treatment for 30min to obtain a mixed solution A; the power of the ultrasonic wave is 400W, and the frequency is 40 KHz; the volume ratio of the absolute ethyl alcohol to the water in the ethyl alcohol solution is 1: 1;
step five, dissolving 2.74g of tetramine platinum dichloride in 137.04g of pure water, uniformly stirring, and carrying out ultrasonic treatment for 30min under the condition of ice-water bath at the temperature of 0-5 ℃ to obtain a mixed solution B; the power of the ultrasonic wave is 200W, and the frequency is 40 KHz; the ultrasonic wave under the ice-water bath condition can be as follows: taking an ice-water mixture as an ultrasonic medium, placing a container filled with a system of tetrammine platinum dichloride and pure water in the ultrasonic medium, and treating by utilizing ultrasonic waves;
step six, under the stirring condition, dropwise adding the mixed solution A in the step four into the mixed solution B in the step five within 30min, and continuously stirring for 30min after dropwise adding is finished to obtain a platinum precursor solution; the stirring speed is 800 rpm;
seventhly, placing 2.4g of the carbon black carrier treated in the step three in 240g of methanol, and uniformly stirring to obtain carbon slurry;
step eight, under the condition of stirring in a water bath at 5 ℃, dropwise adding the platinum precursor solution obtained in the step six into the carbon slurry obtained in the step seven for 50min, continuously stirring for 30min after the dropwise adding is finished, and standing for 12h to obtain slurry; the stirring speed is 2000 rpm;
step nine, reducing the slurry obtained in the step eight, cooling, filtering, washing, freezing and drying to obtain a catalyst precursor; the reduction is carried out in a 1L high-pressure reaction kettle; the reduction comprises the following steps: placing the slurry in a high-pressure reaction kettle, filling nitrogen to replace air, then replacing nitrogen with hydrogen, and filling hydrogen to react, wherein in the reaction process, the hydrogen pressure is 7MPa, the temperature is 200 ℃, the stirring speed is 1000rpm, and the reaction time is 5 h;
step ten, dispersing 3g of the catalyst precursor in the step nine in 150g of 0.3mol/L nitric acid solution to obtain a catalyst precursor system;
step eleven, stirring the catalyst precursor system for 30min under the condition of water bath at the temperature of 5 ℃, and then carrying out post-treatment to obtain the catalyst for the proton exchange membrane fuel cell; the stirring speed is 10000 rpm; the post-treatment comprises high-pressure nitrogen treatment, temperature reduction, filtration, washing, cooling and drying; the high-pressure nitrogen treatment comprises the following steps: placing the catalyst precursor system after water bath stirring in a high-pressure reaction kettle with an enamel lining, filling nitrogen to replace air, and continuously filling nitrogen, wherein in the reaction process, the pressure of the nitrogen in the kettle is kept at 3MPa, the temperature is 450 ℃, the stirring speed is 1200pm, and the reaction time is 8 h; the temperature is reduced to room temperature, and the room temperature is 20-25 ℃; the washing is alternately washing by using ultrapure water and absolute ethyl alcohol until the conductivity is less than 4 delta/cm.
As shown in fig. 1, a transmission electron micrograph of the catalyst for a proton exchange membrane fuel cell according to the present example shows, from fig. 1, that the platinum particles in the catalyst according to the present example are uniformly dispersed on the surface of the support.
Comparative example 1
This comparative example is the same as example 1 except that no benzaldehyde semicarbazone was added in step two.
The transmission electron micrograph of the catalyst for proton exchange membrane fuel cell of this comparative example is shown in fig. 2, and it is known from fig. 2 that the platinum particles are not uniformly dispersed on the surface of the carrier and serious agglomeration occurs.
Example 2
The embodiment provides a catalyst for a proton exchange membrane fuel cell, which comprises a carbon black carrier and metal platinum loaded on the carbon black carrier, wherein the mass percentage of the platinum in the catalyst is 60%.
The present embodiment also provides a method for preparing the catalyst for a proton exchange membrane fuel cell, including:
step one, ultrasonically dispersing 10g of EC-300J carbon black carrier in 100ml of nitric acid solution with the mass percentage of 10% for 30min, boiling for 30min, taking out, naturally cooling to room temperature, washing with ultrapure water until the pH value is more than 6, and drying at the temperature of 120 ℃ to constant weight; the ultrasonic power is 200W, the frequency is 40KHz, and the room temperature is 20-25 ℃;
dissolving 10g of acetophenone semicarbazone in 50g of absolute ethanol to obtain an ethanol solution of the acetophenone semicarbazone;
step three, placing 5g of the dried carrier in the step one in the ethanol solution of the acetophenone semicarbazone in the step two, performing microwave treatment in a microwave reactor for 40min, washing with ultrapure water until the conductivity is less than 4 delta/cm, and drying to obtain a treated carbon black carrier; the temperature of the microwave treatment can be 80 ℃, and the power can be 500W; the drying may be drying in a vacuum rotary evaporator;
dissolving 3.6g of tributyl methyl ammonium chloride in 72g of ethanol solution, uniformly stirring, and performing ultrasonic treatment for 30min to obtain a mixed solution A; the power of the ultrasonic wave is 400W, and the frequency is 40 KHz; the volume ratio of the absolute ethyl alcohol to the water in the ethyl alcohol solution is 1: 1;
step five, dissolving 3.95g of tetramine dichloride platinum in 79.03g of aqueous solution of ammonia water with the mass percentage of 30%, uniformly stirring, and carrying out ultrasonic treatment for 30min under the condition of ice-water bath at the temperature of 0-5 ℃ to obtain a mixed solution B; the power of the ultrasonic wave is 200W, and the frequency is 40 KHz;
step six, under the stirring condition, dropwise adding the mixed solution A obtained in the step four into the mixed solution B obtained in the step five within 30min, and continuously stirring for 30min after dropwise adding is finished to obtain a platinum precursor solution; the stirring speed is 1500 rpm;
seventhly, placing 1.6g of the carbon black carrier treated in the step three in 160g of methanol, and uniformly stirring to obtain carbon slurry;
step eight, under the condition of stirring in a water bath at 15 ℃, dropwise adding the platinum precursor solution obtained in the step six into the carbon slurry obtained in the step seven for 50min, continuously stirring for 30min after the dropwise adding is finished, and standing for 12h to obtain slurry; the stirring speed is 2000 rpm;
step nine, reducing the slurry obtained in the step eight, cooling, filtering, washing, freezing and drying to obtain a catalyst precursor; the reduction is carried out in a 1L high-pressure reaction kettle; the reduction comprises the following steps: placing the slurry in a high-pressure reaction kettle, filling nitrogen to replace air, then replacing nitrogen with hydrogen, and filling hydrogen to react, wherein in the reaction process, the hydrogen pressure is 4MPa, the temperature is 300 ℃, the stirring speed is 2000rpm, and the reaction time is 3 h;
step ten, dispersing 3g of the catalyst precursor in the step nine in 450g of 0.3mol/L nitric acid solution to obtain a catalyst precursor system;
step eleven, stirring the catalyst precursor system for 30min under the condition of water bath at 15 ℃, and then carrying out post-treatment to obtain the catalyst for the proton exchange membrane fuel cell; the stirring speed is 10000 rpm; the post-treatment specifically comprises high-pressure nitrogen treatment, temperature reduction, filtration, washing and cooling drying; the high-pressure nitrogen treatment comprises the following steps: placing the catalyst precursor system after water bath stirring in a high-pressure reaction kettle with an enamel lining, filling nitrogen to replace air, and continuously filling nitrogen, wherein in the reaction process, the pressure of the nitrogen in the kettle is kept at 5MPa, the temperature is 300 ℃, the stirring speed is 1500pm, and the reaction time is 4 hours; the temperature reduction is to be carried out to room temperature, and the room temperature is 20-25 ℃; the washing is alternately washing by using ultrapure water and absolute ethyl alcohol until the conductivity is less than 4 delta/cm.
As shown in fig. 3, it can be seen from the transmission electron micrograph of the catalyst for a proton exchange membrane fuel cell of the present example that the particle size of the metal platinum particles in the catalyst of the present example is uniform and the particles are uniformly dispersed, according to fig. 3.
Comparative example 2
This comparative example is the same as example 2 except that in step two, the microwave treatment and vacuum spin-drying were not performed, and oven-drying was performed at 80 ℃.
Example 3
The embodiment provides a catalyst for a proton exchange membrane fuel cell, which comprises a carbon black carrier and metal platinum loaded on the carbon black carrier, wherein the mass percentage of the platinum in the catalyst is 50%.
The present embodiment also provides a method for preparing the catalyst for a proton exchange membrane fuel cell, including:
step one, ultrasonically dispersing 10g of BP-2000 carbon black carrier in 100ml of sulfuric acid solution with the mass percentage of 10% for 30min, boiling for 30min, taking out, naturally cooling to room temperature, washing with ultrapure water until the pH value is more than 6, and drying at the temperature of 120 ℃ to constant weight; the ultrasonic power is 200W, the frequency is 40KHz, and the room temperature is 20-25 ℃;
dissolving 5g of benzaldehyde semicarbazone in 50g of absolute ethyl alcohol to obtain an ethanol solution of the benzaldehyde semicarbazone;
step three, placing 5g of the dried carrier obtained in the step one in the ethanol solution of the benzaldehyde semicarbazone obtained in the step two, performing microwave treatment in a microwave reactor for 60min, washing with ultrapure water until the conductivity is less than 4 delta/cm, and drying to obtain a treated carbon black carrier; the temperature of the microwave treatment can be 80 ℃, and the power can be 500W; the drying may be drying in a vacuum rotary evaporator;
dissolving 3g of tetraphenylphosphonium bromide in 60g of ethanol solution, uniformly stirring, and performing ultrasonic treatment for 30min to obtain a mixed solution A; the power of the ultrasonic wave is 400W, and the frequency is 40 KHz; the volume ratio of the absolute ethyl alcohol to the water in the ethyl alcohol solution is 1: 1;
dissolving 4.03g of platinum acetylacetonate in 134.43g N-N dimethylformamide, uniformly stirring, and performing ultrasonic treatment for 30min under the condition of ice-water bath at the temperature of 0-5 ℃ to obtain a mixed solution B; the power of the ultrasonic wave is 200W, and the frequency is 40 KHz;
step six, under the stirring condition, dropwise adding the mixed solution A obtained in the step four into the mixed solution B obtained in the step five within 30min, and continuously stirring for 30min after dropwise adding is finished to obtain a platinum precursor solution; the stirring speed is 1000 rpm;
seventhly, placing 2g of the carbon black carrier treated in the step three in 200g of methanol, and uniformly stirring to obtain carbon slurry;
step eight, under the condition of stirring in water bath at the temperature of 8 ℃, dropwise adding the platinum precursor solution obtained in the step six into the carbon slurry obtained in the step seven for 50min, continuously stirring for 30min after the dropwise adding is finished, and standing for 12h to obtain slurry; the stirring speed is 2000 rpm;
step nine, reducing the slurry obtained in the step eight, cooling, filtering, washing, freezing and drying to obtain a catalyst precursor; the reduction is carried out in a 1L high-pressure reaction kettle; the reduction comprises the following steps: placing the slurry in a high-pressure reaction kettle, filling nitrogen to replace air, then replacing nitrogen with hydrogen, and filling hydrogen to react, wherein in the reaction process, the pressure of the hydrogen is 6MPa, the temperature is 250 ℃, the stirring speed is 1800rpm, and the reaction time is 4 h;
step ten, dispersing 3g of the catalyst precursor in the step nine in 400g of 0.3mol/L nitric acid solution to obtain a catalyst precursor system;
step eleven, stirring the catalyst precursor system for 30min under the condition of 8 ℃ water bath, and then carrying out post-treatment to obtain the catalyst for the proton exchange membrane fuel cell; the stirring speed is 10000 rpm; the post-treatment comprises high-pressure nitrogen treatment, temperature reduction, filtration, washing, cooling and drying; the high-pressure nitrogen treatment comprises the following steps: placing the catalyst precursor system after water bath stirring in a high-pressure reaction kettle with an enamel lining, filling nitrogen to replace air, and continuously filling nitrogen, wherein in the reaction process, the pressure of the nitrogen in the kettle is kept at 4MPa, the temperature is 400 ℃, the stirring speed is 1000pm, and the reaction time is 6 h; the temperature is reduced to room temperature, and the room temperature is 20-25 ℃; the washing is alternately washing by using ultrapure water and absolute ethyl alcohol until the conductivity is less than 4 delta/cm.
Comparative example 3
This comparative example is the same as example 3 except that no tetraphenylphosphonium bromide was added in step three.
A transmission electron micrograph of the catalyst for a proton exchange membrane fuel cell of this comparative example is shown in fig. 4, and it can be seen from fig. 4 that the dispersion of platinum particles in the carrier is extremely uneven and the platinum particles are agglomerated seriously.
Example 4
The embodiment provides a catalyst for a proton exchange membrane fuel cell, which comprises a carbon black carrier and metal platinum loaded on the carbon black carrier, wherein the mass percentage of the platinum in the catalyst is 55%.
The present embodiment also provides a method for preparing the catalyst for a proton exchange membrane fuel cell, including:
step one, ultrasonically dispersing 10g of XC-72R carbon black carrier in 100ml of nitric acid solution with the mass percentage of 10% for 30min, boiling for 30min, taking out, naturally cooling to room temperature, washing with ultrapure water until the pH value is more than 6, and drying at the temperature of 120 ℃ to constant weight; the ultrasonic power is 200W, the frequency is 40KHz, and the room temperature is 20-25 ℃;
step two, dissolving 8g of acetophenone semicarbazone in 50g of absolute ethyl alcohol to obtain an ethyl alcohol solution of acetophenone semicarbazone;
step three, placing 5g of the dried carrier in the step one in the ethanol solution of the acetophenone semicarbazone in the step two, performing microwave treatment for 80min in a microwave reactor, washing with ultrapure water until the conductivity is less than 4 delta/cm, and drying to obtain a treated carbon black carrier; the temperature of the microwave treatment can be 80 ℃, and the power can be 500W; the drying may be drying in a vacuum rotary evaporator;
step four, dissolving 3.3g of tributyl methyl ammonium chloride in 66g of ethanol solution, uniformly stirring, and performing ultrasonic treatment for 30min to obtain a mixed solution A; the power of the ultrasonic wave is 400W, and the frequency is 40 KHz; the volume ratio of the absolute ethyl alcohol to the water in the ethyl alcohol solution is 1: 1;
step five, dissolving 3.77g of tetraammineplatinum dichloride in 94.21g of pure water, uniformly stirring, and carrying out ultrasonic treatment for 30min under the condition of ice-water bath at the temperature of 0-5 ℃ to obtain a mixed solution B; the power of the ultrasonic wave is 200W, and the frequency is 40 KHz;
step six, under the stirring condition, dropwise adding the mixed solution A in the step four into the mixed solution B in the step five within 30min, and continuously stirring for 30min after dropwise adding is finished to obtain a platinum precursor solution; the stirring speed is 800 rpm;
seventhly, placing 1.8g of the carbon black carrier treated in the step three in 180g of methanol, and uniformly stirring to obtain carbon slurry;
step eight, under the condition of water bath stirring at 12 ℃, dropwise adding the platinum precursor solution obtained in the step six into the carbon slurry obtained in the step seven within 50min, continuously stirring for 30min after the dropwise adding is finished, and standing for 12h to obtain slurry; the stirring speed is 2000 rpm;
step nine, reducing the slurry obtained in the step eight, cooling, filtering, washing, freezing and drying to obtain a catalyst precursor; the reduction is carried out in a 1L high-pressure reaction kettle; the reduction comprises the following steps: placing the slurry in a high-pressure reaction kettle, filling nitrogen to replace air, then replacing nitrogen with hydrogen, and filling hydrogen to react, wherein in the reaction process, the hydrogen pressure is 5MPa, the temperature is 280 ℃, the stirring speed is 1500rpm, and the reaction time is 4.5 h;
step ten, dispersing 3g of the catalyst precursor in the step nine in 300g of 0.3mol/L nitric acid solution to obtain a catalyst precursor system;
step eleven, stirring the catalyst precursor system for 30min under the condition of water bath at the temperature of 12 ℃, and then carrying out post-treatment to obtain the catalyst for the proton exchange membrane fuel cell; the stirring speed is 10000 rpm; the post-treatment specifically comprises high-pressure nitrogen treatment, temperature reduction, filtration, washing and cooling drying; the high-pressure nitrogen treatment comprises the following steps: placing the catalyst precursor system after water bath stirring in a high-pressure reaction kettle with an enamel lining, filling nitrogen to replace air, and continuously filling nitrogen, wherein in the reaction process, the pressure of the nitrogen in the kettle is kept at 3.5MPa, the temperature is 420 ℃, the stirring speed is 1200pm, and the reaction time is 5 hours; the temperature is reduced to room temperature, and the room temperature is 20-25 ℃; the washing is alternately washing by using ultrapure water and absolute ethyl alcohol until the conductivity is less than 4 delta/cm.
Comparative example 4
This comparative example is the same as example 4 except that tetraamineplatinum dichloride in step four was replaced with chloroplatinic acid of the same platinum content.
A transmission electron micrograph of the catalyst for a pem fuel cell of this comparative example is shown in fig. 5, and it can be seen from fig. 5 that the platinum particles are highly aggregated and have a large difference in particle size.
As can be seen from the combination of the graphs in FIGS. 1 to 5, the preparation method of the coordination compound containing the Schiff base treatment carrier, the ionic liquid and the platinum can effectively promote the uniform dispersion of the platinum particles on the carbon black carrier.
Example 5
The embodiment provides a catalyst for a proton exchange membrane fuel cell, which comprises a carbon black carrier and platinum metal loaded on the carbon black carrier, wherein the mass percentage of the platinum in the catalyst is 45%.
The present embodiment also provides a method for preparing the catalyst for a proton exchange membrane fuel cell, including:
step one, ultrasonically dispersing 10g of EC-300J carbon black carrier in 100ml of sulfuric acid solution with the mass percentage of 10% for 30min, boiling for 30min, taking out, naturally cooling to room temperature, washing with ultrapure water until the pH value is more than 6, and drying at the temperature of 120 ℃ until the weight is constant; the ultrasonic power is 200W, the frequency is 40KHz, and the room temperature is 20-25 ℃;
dissolving 4g of benzaldehyde semicarbazone in 50g of absolute ethanol to obtain an ethanol solution of the benzaldehyde semicarbazone;
step three, placing 5g of the dried carrier in the step one in the ethanol solution of the benzaldehyde semicarbazone in the step two, performing microwave treatment in a microwave reactor for 100min, washing with ultrapure water until the conductivity is less than 4 delta/cm, and drying to obtain a treated carbon black carrier; the temperature of the microwave treatment can be 80 ℃, and the power can be 500W; the drying may be drying in a vacuum rotary evaporator;
step four, dissolving 2.7g of tributyl ethyl phosphonium bromide in 54g of ethanol solution, uniformly stirring, and performing ultrasonic treatment for 30min to obtain a mixed solution A; the power of the ultrasonic wave is 400W, and the frequency is 40 KHz; the volume ratio of the absolute ethyl alcohol to the water in the ethyl alcohol solution is 1: 1;
dissolving 2.96g of dinitroso diammine platinum in 118.55g of pure water solution of 30% ammonia water by mass percent, uniformly stirring, and carrying out ultrasonic treatment for 30min under the condition of ice-water bath at the temperature of 0-5 ℃ to obtain a mixed solution B; the power of the ultrasonic wave is 200W, and the frequency is 40 KHz;
step six, under the stirring condition, dropwise adding the mixed solution A obtained in the step four into the mixed solution B obtained in the step five within 30min, and continuously stirring for 30min after dropwise adding is finished to obtain a platinum precursor solution; the stirring speed is 1500 rpm;
seventhly, placing 2.2g of the carbon black carrier treated in the step three in 220g of methanol, and uniformly stirring to obtain carbon slurry;
step eight, under the condition of stirring in a water bath at 10 ℃, dropwise adding the platinum precursor solution obtained in the step six into the carbon slurry obtained in the step seven for 50min, continuously stirring for 30min after the dropwise adding is finished, and standing for 12h to obtain slurry; the stirring speed is 2000 rpm;
step nine, reducing the slurry obtained in the step eight, cooling, filtering, washing, freezing and drying to obtain a catalyst precursor; the reduction is carried out in a 1L high-pressure reaction kettle; the reduction comprises the following steps: placing the slurry in a high-pressure reaction kettle, filling nitrogen to replace air, then replacing nitrogen with hydrogen, and filling hydrogen to perform reaction, wherein in the reaction process, the pressure of the hydrogen is 6Mpa, the temperature is 230 ℃, the stirring speed is 1300rpm, and the reaction time is 3.5 h;
step ten, dispersing 3g of the catalyst precursor in the step nine in 200g of 0.3mol/L nitric acid solution to obtain a catalyst precursor system;
step eleven, stirring the catalyst precursor system for 30min under the condition of water bath at 10 ℃, and then carrying out post-treatment to obtain a catalyst for the proton exchange membrane fuel cell; the stirring speed is 10000 rpm; the post-treatment specifically comprises high-pressure nitrogen treatment, temperature reduction, filtration, washing and cooling drying; the high-pressure nitrogen treatment comprises the following steps: placing the catalyst precursor system after water bath stirring in a high-pressure reaction kettle with an enamel lining, filling nitrogen to replace air, and continuously filling nitrogen, wherein in the reaction process, the pressure of the nitrogen in the kettle is kept at 4.5MPa, the temperature is 350 ℃, the stirring speed is 1800pm, and the reaction time is 7 h; the temperature reduction is to be carried out to room temperature, and the room temperature is 20-25 ℃; the washing is alternately washing by using ultrapure water and absolute ethyl alcohol until the conductivity is less than 4 delta/cm.
Comparative example 5
This comparative example is the same as example 5 except that there is no acid treatment in step eight.
Example 6
The embodiment provides a catalyst for a proton exchange membrane fuel cell, which comprises a carbon black carrier and metal platinum loaded on the carbon black carrier, wherein the mass percentage of the platinum in the catalyst is 40%.
The present embodiment also provides a method for preparing the catalyst for a proton exchange membrane fuel cell, including:
step one, ultrasonically dispersing 10g of XC-72R carbon black carrier in 100ml of sulfuric acid solution with the mass percentage of 10% for 30min, boiling for 30min, taking out, naturally cooling to room temperature, washing with ultrapure water until the pH value is more than 6, and drying at the temperature of 120 ℃ to constant weight; the ultrasonic power is 200W, the frequency is 40KHz, and the room temperature is 20-25 ℃;
dissolving 2.5g of benzaldehyde semicarbazone in 50g of absolute ethyl alcohol to obtain an ethanol solution of the benzaldehyde semicarbazone;
step three, placing 5g of the dried carrier in the step one in the ethanol solution of the benzaldehyde semicarbazone in the step two, performing microwave treatment in a microwave reactor for 120min, washing with ultrapure water until the conductivity is less than 4 delta/cm, and drying to obtain a treated carbon black carrier; the temperature of the microwave treatment can be 80 ℃, and the power can be 500W; the drying may be drying in a vacuum rotary evaporator;
dissolving 2.4g of tributylmethylammonium chloride in 21.6g of ethanol solution, uniformly stirring, and performing ultrasonic treatment for 30min to obtain a mixed solution A; the power of the ultrasonic wave is 400W, and the frequency is 40 KHz; the volume ratio of the absolute ethyl alcohol to the water in the ethyl alcohol solution is 1: 1;
step five, dissolving 2.74g of tetramine platinum dichloride in 137.04g of pure water, uniformly stirring, and carrying out ultrasonic treatment for 30min under the condition of ice-water bath at the temperature of 0-5 ℃ to obtain a mixed solution B; the power of the ultrasonic wave is 200W, and the frequency is 40 KHz;
step six, under the stirring condition, dropwise adding the mixed solution A obtained in the step four into the mixed solution B obtained in the step five within 30min, and continuously stirring for 30min after dropwise adding is finished to obtain a platinum precursor solution; the stirring speed is 1000 rpm;
seventhly, placing 2.4g of the carbon black carrier treated in the step three in 240g of methanol, and uniformly stirring to obtain carbon slurry;
step eight, under the condition of water bath stirring at 15 ℃, dropwise adding the platinum precursor solution obtained in the step six into the carbon slurry obtained in the step seven within 50min, continuously stirring for 30min after the dropwise adding is finished, and standing for 12h to obtain slurry; the stirring speed is 2000 rpm;
step nine, reducing the slurry obtained in the step eight, cooling, filtering, washing, freezing and drying to obtain a catalyst precursor; the reduction is carried out in a 1L high-pressure reaction kettle; the reduction comprises the following steps: placing the slurry in a high-pressure reaction kettle, filling nitrogen to replace air, then replacing nitrogen with hydrogen, and filling hydrogen to react, wherein in the reaction process, the hydrogen pressure is 7MPa, the temperature is 200 ℃, the stirring speed is 1000rpm, and the reaction time is 5 h;
step ten, dispersing 3g of the catalyst precursor in the step nine in 150g of 0.3mol/L nitric acid solution to obtain a catalyst precursor system;
step eleven, stirring the catalyst precursor system for 30min under the condition of water bath at 15 ℃, and then carrying out post-treatment to obtain the catalyst for the proton exchange membrane fuel cell; the stirring speed is 10000 rpm; the post-treatment specifically comprises high-pressure nitrogen treatment, temperature reduction, filtration, washing and cooling drying; the high-pressure nitrogen treatment comprises the following steps: placing the catalyst precursor system after water bath stirring in a high-pressure reaction kettle with an enamel lining, filling nitrogen to replace air, and continuously filling nitrogen, wherein in the reaction process, the pressure of the nitrogen in the kettle is kept at 3MPa, the temperature is 450 ℃, the stirring speed is 1200pm, and the reaction time is 8 h; the temperature is reduced to room temperature, and the room temperature is 20-25 ℃; the washing is alternately washing by using ultrapure water and absolute ethyl alcohol until the conductivity is less than 4 delta/cm.
Example 7
The embodiment provides a catalyst for a proton exchange membrane fuel cell, which comprises a carbon black carrier and metal platinum loaded on the carbon black carrier, wherein the mass percentage of the platinum in the catalyst is 40%.
The present embodiment also provides a method for preparing the catalyst for a proton exchange membrane fuel cell, including:
step one, ultrasonically dispersing 10g of XC-72R carbon black carrier in 100ml of sulfuric acid solution with the mass percentage of 10% for 30min, boiling for 30min, taking out, naturally cooling to room temperature, washing with ultrapure water until the pH value is more than 6, and drying at the temperature of 120 ℃ to constant weight; the ultrasonic power is 200W, the frequency is 40KHz, and the room temperature is 20-25 ℃;
dissolving 2.5g of benzaldehyde semicarbazone in 50g of absolute ethyl alcohol to obtain an ethanol solution of the benzaldehyde semicarbazone;
step three, placing 5g of the dried carrier in the step one in the ethanol solution of the benzaldehyde semicarbazone in the step two, performing microwave treatment in a microwave reactor for 120min, washing with ultrapure water until the conductivity is less than 4 delta/cm, and drying to obtain a treated carbon black carrier; the temperature of the microwave treatment can be 80 ℃, and the power can be 500W; the drying may be drying in a vacuum rotary evaporator;
dissolving 2.4g of tributylmethylammonium chloride in 9.6g of ethanol solution, uniformly stirring, and performing ultrasonic treatment for 30min to obtain a mixed solution A; the power of the ultrasonic wave is 400W, and the frequency is 40 KHz; the volume ratio of the absolute ethyl alcohol to the water in the ethyl alcohol solution is 1: 1;
dissolving 2.74g of tetraammineplatinum dichloride in 137.04g of pure water, uniformly stirring, and carrying out ultrasonic treatment for 30min under the condition of ice-water bath at the temperature of 0-5 ℃ to obtain a mixed solution B; the power of the ultrasonic wave is 200W, and the frequency is 40 KHz;
step six, under the stirring condition, dropwise adding the mixed solution A obtained in the step four into the mixed solution B obtained in the step five within 30min, and continuously stirring for 30min after dropwise adding is finished to obtain a platinum precursor solution; the stirring speed is 800 rpm;
seventhly, placing 2.4g of the carbon black carrier treated in the step three in 240g of methanol, and uniformly stirring to obtain carbon slurry;
step eight, under the condition of stirring in a water bath at 10 ℃, dropwise adding the platinum precursor solution obtained in the step six into the carbon slurry obtained in the step seven for 50min, continuously stirring for 30min after the dropwise adding is finished, and standing for 12h to obtain slurry; the stirring speed is 2000 rpm;
step nine, reducing the slurry obtained in the step eight, cooling, filtering, washing, freezing and drying to obtain a catalyst precursor; the reduction is carried out in a 1L high-pressure reaction kettle; the reduction comprises the following steps: placing the slurry in a high-pressure reaction kettle, filling nitrogen to replace air, then replacing nitrogen with hydrogen, and filling hydrogen to react, wherein in the reaction process, the hydrogen pressure is 7MPa, the temperature is 200 ℃, the stirring speed is 1000rpm, and the reaction time is 5 h;
step ten, dispersing 3g of the catalyst precursor in the step nine in 150g of 0.3mol/L nitric acid solution to obtain a catalyst precursor system;
step eleven, stirring the catalyst precursor system for 30min under the condition of water bath at 10 ℃, and then carrying out post-treatment to obtain the catalyst for the proton exchange membrane fuel cell; the stirring speed is 10000 rpm; the post-treatment comprises high-pressure nitrogen treatment, temperature reduction, filtration, washing, cooling and drying; the high-pressure nitrogen treatment comprises the following steps: placing the catalyst precursor system after water bath stirring in a high-pressure reaction kettle with an enamel lining, filling nitrogen to replace air, and continuously filling nitrogen, wherein in the reaction process, the pressure of the nitrogen in the kettle is kept at 3MPa, the temperature is 450 ℃, the stirring speed is 2000pm, and the reaction time is 8 h; the temperature is reduced to room temperature, and the room temperature is 20-25 ℃; the washing is alternately washing by using ultrapure water and absolute ethyl alcohol until the conductivity is less than 4 delta/cm.
Evaluation of Performance
Electrochemical performance of the catalysts of examples 1 to 7 and comparative examples 1 to 5 was tested using an electrochemical workstation. The test method comprises the following steps: 3mg of the catalysts of examples 1 to 7 and comparative examples 1 to 5 were dissolved in a mixed solution of 0.4mL of isopropyl alcohol and 0.2mL of deionized water, performing ice bath ultrasonic treatment for 10min, measuring 30 μ L of 5 wt% Nafion solution with a pipette, adding into the mixed solution after ultrasonic treatment, continuously performing ultrasonic dispersion for 30min under ice bath condition, coating 6 μ L on glassy carbon electrode with diameter of 5mm, naturally drying to obtain working electrode, a standard hydrogen electrode is taken as a reference electrode, a platinum wire is taken as a counter electrode to form a three-electrode electrochemical system, electrochemical performance tests are respectively carried out in 0.1M perchloric acid solution under the condition of introducing nitrogen and oxygen, wherein, the voltage scanning range is 0V-0.5V under the condition of nitrogen gas introduction, the scanning speed is 20mV/s, the voltage scanning range is 0V-0.5V under the condition of oxygen gas introduction, the scanning speed is 10mV/s, and the test results are shown in Table 1.
As can be seen from Table 1, the catalyst for proton exchange membrane fuel cell prepared by the method of the invention has the mass specific activity of more than 0.2A/mg and the electrochemical active area of 60m2The catalyst prepared by the method has the advantages that the stability of 30000 circles is obviously higher than that of the comparative example, the attenuation rate after 30000 circles are circulated is within 10 percent, and the attenuation rate is higher than that of the prior art, so that the catalyst has higher electrochemical activity and stability. Compared with the comparative example 5, the catalyst prepared by the method has obviously high stability after 30000 cycles, and the preparation process comprising acid treatment can improve the cycle stability of the catalyst for the proton exchange membrane fuel cell.
TABLE 1 results of electrochemical Performance testing of catalysts
In Table 1, mass specific activity MAThe calculation method comprises the following steps: mA＝IK/[Lpt*Ag]
Wherein: i isK＝Ilim*i/(Ilim-i)；
MA: specific mass activity, unit is A/mg;
IK: kinetic current in units of a;
Lpt: the platinum loading on the glassy carbon electrode; the unit is mgptcm-2In which mgptMass of Pt;
Ag: area of glassy carbon electrode in cm2；
Ilim: limiting current density in units of A;
i: LSV measuring current under given voltage, and the unit is A; the given voltage is 0.9V.
The calculation method of the electrochemical active area ECSA comprises the following steps: ECSA ═ QH*105/[210*Lpt*Ag]
Wherein: and (3) ECSA: electrochemical active area in m2gPt -1；
QH: the adsorption capacity of hydrogen is C;
Lpt: platinum loading on glassy carbon electrode in mgptcm-2In which mgptMass of Pt;
210 is specific charge, in μ C cm-2；
Ag: area of glassy carbon electrode in cm2。
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, changes and equivalent structural changes made to the above embodiment according to the technical spirit of the present invention still fall within the protection scope of the technical solution of the present invention.
Claims (10)
1. The catalyst for the proton exchange membrane fuel cell is characterized by comprising a carbon black carrier and metal platinum loaded on the carbon black carrier, wherein the mass percentage of the platinum in the catalyst is 40-60%.
2. A method of making a catalyst for a proton exchange membrane fuel cell according to claim 1, comprising:
firstly, carrying out ultrasonic treatment and boiling on a carbon black carrier, washing the boiled carrier, and drying;
dissolving Schiff base in absolute ethyl alcohol to obtain an ethanol solution of Schiff base;
step three, under the microwave condition, placing the dried carrier in the step one into the ethanol solution of the Schiff base in the step two, treating for 40-120 min, washing, and drying to obtain a treated carbon black carrier;
dispersing the ionic liquid in an ethanol solution to obtain a mixed solution A;
dissolving the platinum complex in a solvent, and performing ultrasonic treatment under the ice-water bath condition to obtain a mixed solution B;
step six, under the stirring condition, dropwise adding the mixed solution A obtained in the step four into the mixed solution B obtained in the step five, and continuously stirring after dropwise adding is finished to obtain a platinum precursor solution;
seventhly, placing the carbon black carrier treated in the step three in methanol, and uniformly stirring to obtain carbon slurry;
step eight, under the condition of water bath stirring, dropwise adding the platinum precursor solution obtained in the step six into the carbon slurry obtained in the step seven, continuously stirring after dropwise adding is finished, and standing to obtain slurry;
step nine, reducing the slurry obtained in the step eight, cooling, filtering, washing, freezing and drying to obtain a catalyst precursor;
step ten, dispersing the catalyst precursor in the step nine into a nitric acid solution to obtain a catalyst precursor system;
step eleven, stirring the catalyst precursor system in the step eleven for 30min under the water bath condition, and then carrying out post-treatment to obtain the catalyst for the proton exchange membrane fuel cell.
3. The method of claim 2, wherein said ultrasonication of step one is carried out by subjecting said carbon black support to ultrasonication in an acid solution, said acid solution being a nitric acid solution or a sulfuric acid solution, said carbon black support comprising XC-72R, EC-300J or BP-2000; step one, washing is carried out by using ultrapure water until the pH value is more than 6.
4. The method according to claim 2, wherein the ethanol solution of the schiff base in the second step contains 5 to 20 percent of the schiff base by mass, and the schiff base comprises benzaldehyde semicarbazone or acetophenone semicarbazone; and step three, the mass of the Schiff base is 0.5-2 times of that of the dried carrier, and the washing in step three is to wash the Schiff base with ultrapure water until the conductivity is less than 4 delta/cm.
5. The method according to claim 2, wherein in the mixed solution A obtained in the fourth step, the ionic liquid is 5 to 20 mass percent, and the ionic liquid is tributylmethylammonium chloride, tributylethylphosphonium bromide or tetraphenylphosphonium bromide.
6. The method according to claim 2, wherein the platinum complex in the fifth step comprises tetraammineplatinum dichloride, dinitrosoplatinum or platinum acetylacetonate, the solvent is N-N dimethylformamide, water or an ammonia water solution, and the mass percentage of the platinum complex in the mixed solution B is 2-5%; fifthly, the temperature of the ice-water bath is 0-5 ℃; in the sixth step, the mass of the ionic liquid is 1.5 times of that of the platinum; and sixthly, the stirring speed and the continuous stirring speed are both 800 rpm-1500 rpm.
7. The method of claim 2, wherein the stirring and continuing stirring in step eight are both at 2000rpm, and the temperature of the water bath is between 5 ℃ and 15 ℃.
8. The method of claim 2, wherein the reducing of step nine comprises: and (2) placing the slurry in a high-pressure reaction kettle, filling nitrogen to replace air, then replacing nitrogen with hydrogen, and filling hydrogen to react, wherein in the reaction process, the hydrogen pressure is 4-7 MPa, the temperature is 200-300 ℃, the stirring speed is 1000-2000 rpm, and the reaction time is 3-5 h.
9. The method according to claim 2, wherein the mass of the nitric acid solution in the step ten is 50 to 150 times the mass of the catalyst precursor.
10. The method according to claim 2, wherein the water bath temperature in the eleventh step is 5 ℃ to 15 ℃, and the stirring speed is 10000 rpm; step eleven, the post-treatment specifically comprises high-pressure nitrogen treatment, temperature reduction, filtration, washing and cooling drying; the high-pressure nitrogen treatment comprises the following steps: and (3) placing the catalyst precursor system after water bath stirring in a high-pressure reaction kettle with an enamel lining, filling nitrogen to replace air, and continuously filling nitrogen, wherein in the reaction process, the pressure of the nitrogen in the kettle is kept between 3 and 5MPa, the temperature is between 300 and 450 ℃, the stirring speed is between 1000 and 2000rpm, and the reaction time is between 4 and 8 hours.
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