CN116722158A - Fuel cell catalyst composite carrier and preparation method and application thereof - Google Patents
Fuel cell catalyst composite carrier and preparation method and application thereof Download PDFInfo
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- CN116722158A CN116722158A CN202310994995.7A CN202310994995A CN116722158A CN 116722158 A CN116722158 A CN 116722158A CN 202310994995 A CN202310994995 A CN 202310994995A CN 116722158 A CN116722158 A CN 116722158A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 71
- 239000002131 composite material Substances 0.000 title claims abstract description 70
- 239000000446 fuel Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000010438 heat treatment Methods 0.000 claims abstract description 34
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 31
- 239000000843 powder Substances 0.000 claims abstract description 25
- 238000002156 mixing Methods 0.000 claims abstract description 21
- 239000002243 precursor Substances 0.000 claims abstract description 20
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 19
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 19
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 239000012046 mixed solvent Substances 0.000 claims abstract description 17
- 230000001681 protective effect Effects 0.000 claims abstract description 14
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 40
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- NGCRLFIYVFOUMZ-UHFFFAOYSA-N 2,3-dichloroquinoxaline-6-carbonyl chloride Chemical compound N1=C(Cl)C(Cl)=NC2=CC(C(=O)Cl)=CC=C21 NGCRLFIYVFOUMZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 9
- 239000011261 inert gas Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000006229 carbon black Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000011282 treatment Methods 0.000 claims description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 32
- 239000001301 oxygen Substances 0.000 abstract description 22
- 229910052760 oxygen Inorganic materials 0.000 abstract description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 20
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 abstract description 15
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 5
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 abstract description 5
- 229910001936 tantalum oxide Inorganic materials 0.000 abstract description 5
- 238000009210 therapy by ultrasound Methods 0.000 abstract description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 107
- 239000010936 titanium Substances 0.000 description 64
- 230000000694 effects Effects 0.000 description 22
- 239000002245 particle Substances 0.000 description 20
- 239000000243 solution Substances 0.000 description 17
- 238000002484 cyclic voltammetry Methods 0.000 description 11
- 229910052697 platinum Inorganic materials 0.000 description 10
- DJCDXWHFUVBGLR-UHFFFAOYSA-N CCO[Ta] Chemical compound CCO[Ta] DJCDXWHFUVBGLR-UHFFFAOYSA-N 0.000 description 9
- OHDRQQURAXLVGJ-HLVWOLMTSA-N azane;(2e)-3-ethyl-2-[(e)-(3-ethyl-6-sulfo-1,3-benzothiazol-2-ylidene)hydrazinylidene]-1,3-benzothiazole-6-sulfonic acid Chemical compound [NH4+].[NH4+].S/1C2=CC(S([O-])(=O)=O)=CC=C2N(CC)C\1=N/N=C1/SC2=CC(S([O-])(=O)=O)=CC=C2N1CC OHDRQQURAXLVGJ-HLVWOLMTSA-N 0.000 description 9
- 229910010413 TiO 2 Inorganic materials 0.000 description 8
- 239000002105 nanoparticle Substances 0.000 description 8
- 239000003642 reactive oxygen metabolite Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- CSLZEOQUCAWYDO-UHFFFAOYSA-N [O-2].[Ti+4].[Ta+5] Chemical compound [O-2].[Ti+4].[Ta+5] CSLZEOQUCAWYDO-UHFFFAOYSA-N 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 229910044991 metal oxide Inorganic materials 0.000 description 7
- 150000004706 metal oxides Chemical class 0.000 description 7
- 230000010287 polarization Effects 0.000 description 7
- 238000013112 stability test Methods 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 230000007062 hydrolysis Effects 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- 230000001976 improved effect Effects 0.000 description 6
- 230000002829 reductive effect Effects 0.000 description 6
- 230000027756 respiratory electron transport chain Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229910001260 Pt alloy Inorganic materials 0.000 description 5
- CDXSJGDDABYYJV-UHFFFAOYSA-N acetic acid;ethanol Chemical compound CCO.CC(O)=O CDXSJGDDABYYJV-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 229910001069 Ti alloy Inorganic materials 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000004108 freeze drying Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- -1 oxygen ions Chemical class 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 238000012430 stability testing Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- 230000003313 weakening effect Effects 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 238000004873 anchoring Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 2
- 230000001939 inductive effect Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000008213 purified water Substances 0.000 description 2
- 238000004729 solvothermal method Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- 238000004224 UV/Vis absorption spectrophotometry Methods 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- QKUSRAKPUWQSJS-UHFFFAOYSA-N diazanium 3-ethyl-2H-1,3-benzothiazole-6-sulfonate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)C1=CC=C2N(CC)CSC2=C1.[O-]S(=O)(=O)C1=CC=C2N(CC)CSC2=C1 QKUSRAKPUWQSJS-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000010977 jade Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
Classifications
-
- 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
- H01M4/8803—Supports for the 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a fuel cell catalyst composite carrier, a preparation method and application thereof, relating to the technical field of fuel cells, comprising the following steps: adding a carbon-based material into an ethanol solution of polyvinylpyrrolidone, and performing ultrasonic treatment to obtain a first mixed system; mixing ethanol and acetic acid according to a preset proportion to form a mixed solvent, adding a preset amount of precursor into the mixed solvent, and performing ultrasonic treatment to obtain a second mixed system; dropping the second mixed system into the first mixed system, and performing ultrasonic treatment to obtain a third mixed system; placing the third mixed system in a reaction kettle, heating for a preset time, cooling and washing to obtain first powder; and (3) placing the first powder in a protective atmosphere for heat treatment to obtain the composite carrier. According to the invention, the titanium oxide and/or the tantalum oxide are/is formed on the carbon-based material to form the composite carrier, so that the generation of hydrogen peroxide can be weakened, and active oxygen free radicals can be eliminated, thereby effectively improving the capability of the platinum-carbon catalyst for resisting the active oxygen free radicals and ensuring the stability of the performance of the platinum-carbon catalyst.
Description
Technical Field
The invention relates to the technical field of fuel cells, in particular to a fuel cell catalyst composite carrier, a preparation method and application thereof.
Background
The fuel cell is a power generation device which directly converts chemical energy of fuel into electric energy in an electrochemical reaction mode without burning, and has the advantages of high energy density, quick starting, high energy conversion efficiency and the like, wherein the proton exchange membrane fuel cell technology is an efficient and clean energy conversion device, has wide application prospect in the fields of electric automobiles, portable power sources, fixed power stations and the like, and is one of research hotspots in the energy field at present.
Noble metal platinum is the most effective and mature catalyst for proton exchange membrane fuel cells at present, but traditional commercial platinum carbon catalysts face serious performance decay problems. In the electrochemical reaction process of the proton exchange membrane fuel cell, the two-electron oxygen reduction reaction generated on the cathode side and the gas cross generated on the anode side can cause the generation of hydrogen peroxide, the hydrogen peroxide brings about a great negative effect on the catalytic layer of the proton exchange membrane fuel cell due to the strong oxidation characteristic of the hydrogen peroxide, the hydrogen peroxide can cause the generation of active oxygen free Radicals (ROS) such as hydroxyl free radicals (∙ OH), and the active oxygen free radicals attack the platinum-carbon catalyst, so that the platinum-carbon catalyst is degraded, and the performance of the platinum-carbon catalyst is quickly attenuated.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides a fuel cell catalyst composite carrier, a preparation method and application thereof.
The invention provides a preparation method of a fuel cell catalyst composite carrier, which comprises the following steps:
adding a carbon-based material into an ethanol solution of polyvinylpyrrolidone, and uniformly mixing by ultrasonic waves to obtain a first mixed system;
mixing ethanol and acetic acid according to a preset proportion to form a mixed solvent, adding a preset amount of precursor into the mixed solvent, and uniformly mixing by ultrasonic to obtain a second mixed system; wherein the precursor is one or two of titanium isopropoxide and tantalum ethoxide;
dripping the second mixed system into the first mixed system, and uniformly mixing by ultrasonic to obtain a third mixed system;
placing the third mixed system in a reaction kettle, heating for a preset time, cooling and washing to obtain first powder;
placing the first powder in a protective atmosphere for heat treatment to obtain a composite carrier; wherein, the composition gas of the protective atmosphere is one or more of reducing gas and inert gas.
Specifically, the carbon-based material comprises one or more of carbon black, activated carbon, mesoporous carbon, carbon nanotubes and graphene;
the reducing gas is one or more of hydrogen, carbon monoxide and ammonia;
the inert gas is one or more of argon, nitrogen and helium.
Specifically, the mass concentration of the ethanol solution of polyvinylpyrrolidone is 0.1-20%, wherein the molecular weight of polyvinylpyrrolidone is 8000-70000.
Specifically, the ratio of the polyvinylpyrrolidone to the carbon-based material is 1:0.1 to 100.
Specifically, in the mixed solvent, the ratio of ethanol to acetic acid is 1: 100-100: 1.
specifically, in the second mixed system, the concentration of the titanium isopropoxide is 0-50 mu L/mL, and the concentration of the tantalum ethoxide is 0-50 mu L/mL.
Specifically, the volume ratio of the first mixed system to the second mixed system is 100:1 to 1:1.
specifically, the third mixed system is placed in a reaction kettle and is heated for 0.1 to 24 hours at the temperature of 60 to 200 ℃;
and placing the first powder in a protective atmosphere to perform heat treatment at 60-1100 ℃.
The invention also provides a fuel cell catalyst composite carrier, which is prepared by the preparation method.
The invention also provides application of the fuel cell catalyst composite carrier in preparing a fuel cell catalyst.
Compared with the prior art, the invention has the beneficial effects that:
adding carbon-based materials into ethanol solution of polyvinylpyrrolidone to ultrasonically form a uniform first mixed system, adding titanium isopropoxide and/or ethoxytantalum into ethanol acetic acid mixed solvent to ultrasonically form a uniform second mixed system, and then dropwise adding the second mixed system into the first mixed system to ultrasonically form a uniform third mixed system; the third mixed system is subjected to heat treatment in a reaction kettle, ethanol acetic acid is subjected to esterification reaction to generate a small amount of water, titanium isopropoxide and/or tantalum ethoxide are subjected to mild hydrolysis to generate metal oxide particles (with uniform particle size and nano-scale particle size) which are uniformly dispersed on a carbon-based material; then, placing the obtained first powder in a protective atmosphere for heat treatment, inducing generation of oxygen vacancies and enhancing the stability of the material structure;
the titanium and tantalum oxides have the functions of weakening the generation of hydrogen peroxide and removing active oxygen free radicals, nano-scale particles are uniformly dispersed and supported on a carbon-based material to form a composite carrier, and when the composite carrier is applied to a platinum-carbon catalyst, the capability of the platinum-carbon catalyst for resisting the active oxygen free radicals can be effectively improved, and the stability of the performance of the platinum-carbon catalyst is ensured.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings which are required in the description of the embodiments or the prior art will be briefly described, it being obvious that the drawings in the description below are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a flow chart of a method of preparing a fuel cell catalyst composite support in an embodiment of the invention;
FIG. 2 is a diagram of Ti obtained in example 1 0.7 Ta 0.3 O 2 Transmission electron micrograph of C (500 ℃ C.):
FIG. 3 is an XRD contrast pattern of the composite carrier obtained in example 1 and the composite carrier obtained in comparative example 1;
FIG. 4 is a Pt/Ti alloy obtained in example 2 0.7 Ta 0.3 O 2 -C transmission electron micrographs of the catalyst;
FIG. 5 is a graph comparing CV curves of a composite supported Pt catalyst and commercial Pt/C obtained in example 2;
FIG. 6 is a graph of ECSA area contrast for the composite supported Pt catalyst and commercial Pt/C obtained in example 2;
FIG. 7 is a graph comparing ORR polarization curves of the composite supported Pt catalyst and commercial Pt/C obtained in example 2;
FIG. 8 is a graph comparing Mass Activity (MA) and area activity (SA) of the composite supported Pt catalyst and commercial Pt/C obtained in example 2;
FIG. 9 is a schematic diagram of the reaction of ABTS with ROS;
FIG. 10 is ABTS+H in comparative example 2 2 O 2 And ABTS+H 2 O 2 +Ti 0.7 Ta 0.3 O 2 An ultraviolet-visible spectrum of (a);
FIG. 11 is a graph comparing ORR polarization curves of the composite supported Pt catalyst and commercial Pt/C obtained in example 3;
FIG. 12 is a graph comparing CV curves of a composite supported Pt catalyst and commercial Pt/C obtained in example 3;
FIG. 13 is a graph showing hydrogen peroxide yield and electron transfer number comparisons of the composite supported Pt catalyst and commercial Pt/C obtained in example 3;
FIG. 14 is a CV plot of stability testing for commercial Pt/C over 13000 cycles;
FIG. 15 is a polarization graph of a stability test of commercial Pt/C for 13000 cycles;
FIG. 16 is a graph of Pt/Ti in example 3 0.7 Ta 0.3 O 2 (25%) -C CV curve for stability test with 13000 cycles;
FIG. 17 is a Pt/Ti alloy of example 3 0.7 Ta 0.3 O 2 (25%) -C polarization profile of stability test for 13000 cycles;
FIG. 18 is a Pt/Ti alloy of example 3 0.7 Ta 0.3 O 2 (40%) -C CV curve for stability test with 13000 cycles;
FIG. 19 is a Pt/Ti alloy of example 3 0.7 Ta 0.3 O 2 (40%) -C polarization profile of stability test for 13000 cycles;
FIG. 20 is a graph comparing ORR polarization curves of the composite supported Pt catalyst and commercial Pt/C obtained in example 4;
FIG. 21 is a graph comparing CV curves of a composite supported Pt catalyst and commercial Pt/C obtained in example 4;
FIG. 22 is a graph showing the hydrogen peroxide yield and electron transfer number of the composite supported Pt catalyst obtained in example 4;
FIG. 23 is a graph showing hydrogen peroxide yields and electron transfer numbers of the composite supported Pt catalyst and commercial Pt/C obtained in example 5.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Fig. 1 shows a flowchart of a method for preparing a fuel cell catalyst composite carrier according to an embodiment of the present invention, including the steps of:
s1, adding a carbon-based material into an ethanol solution of polyvinylpyrrolidone, and uniformly mixing by ultrasonic to obtain a first mixed system;
the carbon-based material mainly refers to a material taking carbon as a main body, is commonly used as a carrier of a catalyst, can provide electron conduction and serves as an anchor point of platinum or platinum alloy catalyst particles, and specifically comprises one or more of carbon black, activated carbon, mesoporous carbon, carbon nano tubes and graphene.
The ethanol solution of polyvinylpyrrolidone contains no water, has good dispersion effect on carbon-based materials, can activate the carbon-based materials to make the carbon-based materials more easily accept and carry metal oxides, and specifically, the mass concentration of the ethanol solution of polyvinylpyrrolidone is 0.1-20%, wherein the molecular weight of polyvinylpyrrolidone is 8000-70000; further, the ratio of the polyvinylpyrrolidone to the carbon-based material is 1:0.1 to 100.
In addition, the ultrasonic mixing is beneficial to promoting the dispersion of the carbon-based material and accelerating the activation of the carbon-based material.
S2, mixing ethanol and acetic acid according to a preset proportion to form a mixed solvent, adding a preset amount of precursor into the mixed solvent, and carrying out ultrasonic mixing uniformly to obtain a second mixed system;
specifically, in the mixed solvent, the ratio of ethanol to acetic acid is 1: 100-100: 1, the mixed solvent does not contain moisture, a good dispersing environment is created for the precursor, the precursor is uniformly dispersed, in addition, the ethanol and the acetic acid can also provide moisture for the hydrolysis of the precursor through the esterification reaction in the subsequent step, and meanwhile, the acetic acid provides an acidic environment for the hydrolysis of the precursor.
Further, the precursor is one or two of titanium isopropoxide and ethoxytantalum, in the second mixed system, the concentration of the titanium isopropoxide is 0-50 mu L/mL, the concentration of the ethoxytantalum is 0-50 mu L/mL, at least one of the titanium isopropoxide and the ethoxytantalum exists, the titanium isopropoxide and the ethoxytantalum are both liquid, the titanium isopropoxide can be hydrolyzed to generate titanium oxide, the ethoxytantalum can be hydrolyzed to generate tantalum oxide, and the titanium oxide and the tantalum oxide have the functions of weakening hydrogen peroxide and scavenging active oxygen free radicals.
In addition, the ultrasonic mode is used for mixing, so that the precursor is promoted to be uniformly distributed in the mixed solvent, and oxide agglomeration formed during subsequent hydrolysis of the precursor is avoided.
S3, dripping the second mixed system into the first mixed system, and uniformly mixing by ultrasonic to obtain a third mixed system;
gradually dissolving a second mixed system containing the precursor into a first mixed system containing the carbon-based material in a dropwise adding mode, so that aggregation of the precursor and the carbon-based material is avoided; and then uniformly mixing in an ultrasonic mode to promote the precursor and the carbon-based material to be fully and uniformly dispersed, so that the oxide formed by the precursor can be uniformly loaded on the carbon-based material during the subsequent heating treatment.
Specifically, the volume ratio of the first mixed system to the second mixed system is 100:1 to 1:1, ensuring that the precursor can be fully dispersed, and preventing the oxide agglomeration formed by the precursor after the subsequent heating treatment.
S4, placing the third mixed system in a reaction kettle, heating for a preset time, cooling and washing to obtain first powder;
specifically, the third mixed system is placed in a reaction kettle, heating is carried out for 0.1-24 h at 60-200 ℃, the carbon-based material, titanium isopropoxide and/or ethoxyl tantalum, ethanol and acetic acid are subjected to solvothermal reaction in the reaction kettle, the ethanol acetic acid is subjected to esterification reaction to generate a small amount of water, the titanium isopropoxide and/or the ethoxyl tantalum are subjected to mild hydrolysis to generate metal oxide particles (with uniform particle size and nano-scale) and uniformly disperse on the carbon-based material, a primary composite carrier product is formed, and the primary composite carrier product is washed clean by purified water, ethanol and the like after cooling, so as to obtain first powder.
In some embodiments, the first powder is subjected to freeze-drying treatment, which can remove ethanol and water remained during washing, thereby being beneficial to improving the efficiency of subsequent heat treatment.
S5, placing the first powder in a protective atmosphere for heat treatment to obtain a composite carrier;
the first powder is heat treated under the protection of a protective atmosphere to induce oxygen vacancies, which refers to the escape of oxygen atoms (oxygen ions) in the crystal lattice in the metal oxide or other oxygen-containing compound, resulting in oxygen deficiency, and the formation of vacancies, simply referred to as defects left by the escape of oxygen ions from its crystal lattice. Oxygen vacancies can optimize the adsorption energy of reactants on the catalyst surface, thereby reducing the reaction energy barrier, promoting molecular activation, and acting synergistically with nearby active metal sites in the catalyst.
Moreover, the first powder is subjected to heat treatment under a protective atmosphere, so that the bonding strength of the metal oxide particles and the carbon-based material is enhanced, and the stability of the composite carrier structure is improved.
Specifically, the first powder is placed in a protective atmosphere for heat treatment at 60-1100 ℃, the temperature has important influence on the dispersion uniformity, particle size and the like of the metal oxide particles, and the reasonable heat treatment temperature is beneficial to promoting the titanium oxide and/or tantalum oxide particles to form good distribution on the carbon-based material, improving the resistance of the composite carrier to active oxygen free radicals and improving the catalytic activity of the composite carrier after platinum is carried.
Further, the composition gas of the protective atmosphere is one or more of reducing gas and inert gas, and the reducing gas is one or more of hydrogen, carbon monoxide and ammonia; the inert gas is one or more of argon, nitrogen and helium, and the reducing gas and the inert gas can be mixed for use.
Adding carbon-based materials into ethanol solution of polyvinylpyrrolidone to ultrasonically form a uniform first mixed system, adding titanium isopropoxide and/or ethoxytantalum into ethanol acetic acid mixed solvent to ultrasonically form a uniform second mixed system, and then dropwise adding the second mixed system into the first mixed system to ultrasonically form a uniform third mixed system; the third mixed system is subjected to heat treatment in a reaction kettle, ethanol acetic acid is subjected to esterification reaction to generate a small amount of water, titanium isopropoxide and/or tantalum ethoxide are subjected to mild hydrolysis to generate metal oxide particles (with uniform particle size and nano-scale particle size) which are uniformly dispersed on a carbon-based material; then, placing the obtained first powder in a protective atmosphere for heat treatment, inducing generation of oxygen vacancies and enhancing the stability of the material structure; the oxide of titanium and tantalum has the functions of weakening the generation of hydrogen peroxide and removing active oxygen free radicals, nano-scale particles are uniformly dispersed and supported on a carbon-based material to form a composite carrier, and when the composite carrier is applied to a platinum-carbon catalyst, the capability of the platinum-carbon catalyst for resisting the active oxygen free radicals can be effectively improved, the stability of the performance of the platinum-carbon catalyst is ensured, and the catalytic activity of the platinum-carbon catalyst is improved.
Example 1
(1) Dispersing 100mg of polyvinylpyrrolidone (PVP) in ethanol to form an ethanol solution of polyvinylpyrrolidone, adding 100mg of EC300 carbon black, and ultrasonically stirring for 30min to obtain a first mixed system;
(2) Mixing 6mL of ethanol and 3mL of acetic acid to form a mixed solvent, adding 56.4 mu L of titanium isopropoxide and 21.2 mu L of tantalum ethoxide into the mixed solvent by a micro-injector, and uniformly mixing by ultrasonic to obtain a second mixed system;
(3) Dropping the second mixed system into the first mixed system, and ultrasonically stirring for 30min to obtain a third mixed system;
(4) Placing the third mixed system into a hydrothermal reaction kettle (using a polytetrafluoroethylene liner), placing the hydrothermal reaction kettle into a muffle furnace for solvothermal reaction at 150 ℃ for 12 hours, after cooling the reaction, centrifugally washing the reaction product with ethanol and purified water for multiple times to obtain purified first powder, and freeze-drying the obtained first powder for 12 hours;
(5) The dried first powder was placed in a tube furnace under a mixed gas of hydrogen and argon (H 2 : ar=5%: 95%) in 500 deg.C for 3 hr to obtain composite carrier Ti 0.7 Ta 0.3 O 2 C (500 ℃ C.), the titanium tantalum oxide physical content is 25% and the atomic molar ratio of Ti/Ta is 7/3, depending on the experimental amount.
For Ti obtained in example 1 0.7 Ta 0.3 O 2 C (500 ℃ C.) was subjected to transmission electron microscopy, and as a result, as shown in FIG. 2, it was found that titanium tantalum oxide particles of small particle size were uniformly distributed on the surface of carbon black, and no large particle titanium tantalum oxide was found.
Comparative example 1
As a control, a plurality of composite carriers were prepared by the method of example 1, and the difference between this control and example 1 is only that:
only titanium isopropoxide is added, and finally the mixture gas of hydrogen and argon (H 2 : ar=5%: 95%) and heat-treating at 500 deg.C for 3 hr to obtain TiO 2 -C（500℃）；
Tantalum ethoxide alone was added, and finally the mixture of hydrogen and argon (H 2 : ar=5%: 95%) and heat-treating at 500 deg.C for 3 hr to obtain Ta 2 O 5 -C（500℃）；
Titanium isopropoxide and tantalum ethoxide are added, and finally the mixture gas of hydrogen and argon (H 2 : ar=5%: 95%) and heat-treating at 700 deg.C for 3 hr to obtain Ti 0.7 Ta 0.3 O 2 -C（700℃）；
Tantalum ethoxide alone was added, and finally the mixture of hydrogen and argon (H 2 : ar=5%: 95%) and heat-treating at 700 deg.C for 3 hr to obtain Ta 2 O 5 -C（700℃）。
The oxide particle size and crystal form of the composite support of example 1 and comparative example 1 were studied by XRD, and the results are shown in FIG. 3, ti 0.7 Ta 0.3 O 2 -C（500℃）、Ti 0.7 Ta 0.3 O 2 -C (700 ℃ C.) and TiO 2 Obvious anatase TiO appearance at-C (500 ℃ C.) 2 Diffraction peak, ta 2 O 5 C (500 ℃ C.) shows no significant diffraction peak, an amorphous structure, indicating Ta at 500 ℃ C 2 O 5 A good crystal form cannot be formed; when the heat treatment temperature is raised to 700 ℃, the crystallinity of the oxide is improved, ta 2 O 5 Appearance of-C (700 ℃ C.) and TiO 2 -C、Ti 0.7 Ta 0.3 O 2 Ta with significantly different C 2 O 5 Diffraction peak, and Ti 0.7 Ta 0.3 O 2 C (700 ℃) is still free of Ta at 700 DEG C 2 O 5 Diffraction peaks, indicating that the Ta element alone did not form an oxide.
By this group of controls, it is demonstrated that Ti during heat treatment 0.7 Ta 0.3 O 2 Ta successful doping to TiO in C 2 In the crystal lattice, and without changing its crystal configuration, generalThe oxide Ti is known by the software calculation of jade 6 0.7 Ta 0.3 O 2 The particle size is about 6 nm.
Example 2
Preparation of Ti as in example 1 0.7 Ta 0.3 O 2 -C，TiO 2 -C and Ta 2 O 5 -C, respectively taking the catalyst as a carrier, and adopting an impregnation-gas phase reduction method to prepare the platinum-carbon catalyst.
With Ti 0.7 Ta 0.3 O 2 For example, 60mg of Ti is weighed 0.7 Ta 0.3 O 2 -C in a 10mL beaker, 775. Mu.L of the solution was measured with a 1mL pipette at a concentration of 51.8mg Pt adding/mL of chloroplatinic acid solution into a beaker, adding 100 mu L of ethanol to improve the dispersibility of the carrier, and adding deionized water until the liquid volume of the beaker reaches 6mL; ultrasonic processing in beaker for 20min to obtain precursor solution and Ti 0.7 Ta 0.3 O 2 Mixing well, placing on a heating plate, stirring at 70 ℃, and carrying out ultrasonic treatment for 5min every 30min until the liquid in the beaker volatilizes to form a viscous slurry; sealing the powder with a preservative film (with air holes), and freeze-drying to obtain a black powder sample; the porcelain boat containing the black powder sample was placed in a tube furnace, and the powder was heated in a mixed gas of hydrogen and argon (H 2 Ar=50%: 50%) in 150 deg.C for 2 hr at a heating rate of 5 deg.C/min to obtain Pt/Ti 0.7 Ta 0.3 O 2 -C catalyst (as shown in figure 4). The Pt/TiO is prepared by the same method 2 -C、Pt/Ta 2 O 5 -C。
For Pt/Ti 0.7 Ta 0.3 O 2 -C、Pt/TiO 2 -C、Pt/Ta 2 O 5 Electrochemical Cyclic Voltammetry (CV) characterization of C and commercial Pt/C (40% JM Pt/C) and calculation of its electrochemical active area (ECSA) and results as shown in FIG. 5 and FIG. 6, the platinum carbon catalyst supported on oxide-carbon composite material was much larger in hydrogen desorption zone area (1.7 times that of commercial Pt/C with the same load) compared to commercial Pt/C due to smaller particle size of Pt nanoparticles per se, more active sites of catalyst at the same load, and overflow effectThe interface formed between them will also provide more catalytically active sites for the ORR reaction; comparing the peak potential of the CV oxygen adsorption peaks, the peak potential of the commercial Pt/C was most positive, indicating that desorption of the oxygen-containing species was easiest, mainly due to the larger particle size of the commercial Pt/C.
For Pt/Ti 0.7 Ta 0.3 O 2 -C、Pt/TiO 2 -C、Pt/Ta 2 O 5 ORR polarization curve test was performed on-C and commercial Pt/C (40% JM Pt/C) and Mass Activity (MA), area activity (SA) at 0.9V were calculated, and the results are shown in FIG. 7, FIG. 8, pt/Ti 0.7 Ta 0.3 O 2 The half-wave potential of C (0.922V) was approximately 20mV higher than that of commercial Pt/C (0.903V), the Mass Activity (MA) was 1.8 times that of Pt/TiO 2 -C and Pt/Ta 2 O 5 C is 0.912V and 0.910V, respectively, from which it can be seen that the multicomponent oxide has a more positive regulating effect on the Pt electronic structure than the single oxide, ta-doped TiO 2 The composite carrier of (2) brings greater catalytic activity advantage, but the pure oxide has very poor conductivity; pt/Ti due to the difference in electrochemically active areas 0.7 Ta 0.3 O 2 The area activity (SA) of C is relatively close to that of commercial Pt/C.
Comparative example 2
The elimination effect of titanium tantalum oxide on reactive oxygen species was verified, and the effect of titanium tantalum oxide on the elimination of ROS was evaluated by uv-vis absorption spectroscopy using 2, 2-diaza-di (3-ethyl-benzothiazole-6-sulfonic acid) diammonium salt (ABTS) as a substrate, as shown in fig. 9, ABTS as a widely used probe was oxidized by Reactive Oxygen Species (ROS), the solution was changed from colorless to blue, and absorbance at 417nm was changed, from which the level of ROS production could be judged.
Since the black color of the composite support affects the UV-visible absorption spectrum test, white titanium tantalum oxide Ti was prepared as in example 1 without the addition of carbon black 0.7 Ta 0.3 O 2 。
Subsequently, ABTS and H 2 O 2 Respectively adding 20mL of 0.1M HClO 4 The concentration in the solution was 2mM and 20mM, respectively, at which time the solution becameBlue. From this two 5mL solutions were taken in two beakers, to one of which was then added 2mg of Ti 0.7 Ta 0.3 O 2 Powders, respectively designated ABTS+H 2 O 2 And ABTS+H 2 O 2 +Ti 0.7 Ta 0.3 O 2 After 5min of reaction, 0.5mL of the supernatant was aspirated with a pipette and 4mL of 0.1M HClO was added 4 Solution dilution and analysis using UV-visible spectrum, results are shown in FIG. 10, ABTS+H 2 O 2 +Ti 0.7 Ta 0.3 O 2 The peak around 417nm was significantly decreased, indicating the addition of Ti 0.7 Ta 0.3 O 2 post-ROS production level is reduced, specifying Ti 0.7 Ta 0.3 O 2 The generation of ROS is reduced.
Example 3
The composite supported Pt catalysts with different oxide contents were prepared, and the synthesis method was the same as in example 2, except that the oxide contents in the composite support were changed by changing the input amounts of titanium isopropoxide and tantalum ethoxide when synthesizing the composite support, so as to prepare composite supported Pt catalysts with oxide contents of 25%, 40%, 60% and 80%, respectively, wherein the Pt contents were 40%, and electrochemical characterization was performed, and the results are shown in fig. 11 and 12.
The half-wave potential of the Pt-carried catalyst on the composite carrier is 0.922V (25%), 0.918V (40%), 0.904V (60%), 0.898V (80%), 0.903V (40% JM Pt/C), and the ORR activity gradually decreases with the increase of the oxide content, and the activity is obviously reduced when 60% is reached, but still slightly higher than that of the commercial Pt/C (40% JM Pt/C); as the oxide content increases, the CV area gradually decreases, because the proportion of the carbon-based material is smaller and smaller, the specific surface area of the composite carrier decreases, the conductivity decreases, and the particle size of the Pt nanoparticles increases; but even Pt/Ti 0.7 Ta 0.3 O 2 (60%) -C still has a larger CV area than commercial Pt/C; the Pt supported composite catalyst has the best ORR performance when the oxide content in the composite support is 25%.
The hydrogen peroxide resistance of the Pt catalyst carried by the composite carrier was tested, and the hydrogen peroxide yield and the electron transfer number were obtained by the rotating ring disk electrode test, and the results are shown in fig. 13, it can be seen that as the content of the oxide becomes higher, the hydrogen peroxide yield gradually becomes higher, which indicates that the capability of the titanium tantalum oxide to remove active oxygen free radicals and the capability of the catalyst as a whole to resist hydrogen peroxide are not dependent on the content of the oxide; as the oxide content of the composite support increases, the conductivity of the corresponding catalyst material decreases, and the electron transport capacity decreases, which may lead to an increase in the di-electron oxygen reduction reaction, thus eventually manifesting as an increase in the hydrogen peroxide yield.
Pt catalyst (Pt/Ti) carried on composite carrier with two different oxide contents 0.7 Ta 0.3 O 2 (25%) -C and Pt/Ti 0.7 Ta 0.3 O 2 (40%) -C) stability testing was performed for 13000 cycles and compared with commercial Pt/C (40% JM Pt/C), and as shown in FIGS. 14-19, it was seen that after 13000 cycles, the half-wave potential of 40% JM Pt/C was reduced by 14mV (0.903V. Fwdarw. 0.889V), pt/Ti 0.7 Ta 0.3 O 2 (25%) -C half-wave potential was reduced by 13mV (0.922 V.fwdarw.0.909V) while Pt/Ti 0.7 Ta 0.3 O 2 (40%) -C reduced the half-wave potential by 8mV (0.918 V.fwdarw.0.910V).
After 13000 cycles, a mass activity loss of 40% JM Pt/C was 36% (0.111A/mg Pt →0.071A/mg Pt ) Loss of electrochemically active area 34% (47 m 2 /g Pt →31m 2 /g Pt )；Pt/Ti 0.7 Ta 0.3 O 2 (25%) -C has a mass activity loss of 39% (0.198A/mg) Pt →0.121A/mg Pt ) The electrochemical active area loss was 39% (73 m 2 /g Pt →44m 2 /g Pt )；Pt/Ti 0.7 Ta 0.3 O 2 (40%) -C loss of mass activity 25% (0.177A/mg Pt →0.132A/mg Pt ) Loss of electrochemically active area 24% (64 m 2 /g Pt →49m 2 /g Pt )。
Catalyst Pt/Ti with highest initial activity and highest initial electrochemical activity area 0.7 Ta 0.3 O 2 (25%) -C decays more after stability test, which indicates that although due to the addition of oxide andpt generates strong metal carrier interaction to increase the catalytic activity of Pt, but Pt nano particles with smaller particle size in the catalyst are more likely to be dissolved, migrated and agglomerated due to higher surface energy, while the anchoring effect provided by oxide is limited, so that Pt/Ti is caused 0.7 Ta 0.3 O 2 (25%) -C performs poorly during stability testing. Even so, depending on the higher initial performance, the overall performance is improved compared to commercial Pt/C. Preferably, the oxide content of the composite support is 40%, although a reduction in conductivity is caused, a relative reduction in initial mass activity and electrochemical active area, but Pt/Ti 0.7 Ta 0.3 O 2 The stability test of (40%) -C shows better performance, not only the loss of mass activity and electrochemical activity area is lower than that of the other two catalysts, but also the highest performance is maintained after the test, which benefits from the higher oxide content of the composite support, and the expanded range of anchoring effect reduces the aggregation of Pt nanoparticles.
Example 4
The composite supported Pt catalyst with different Ti/Ta ratios was prepared, and the synthesis method was the same as in example 2, except that the Ti/Ta ratio in the composite support was changed by changing the ratio of titanium isopropoxide and tantalum ethoxide during the synthesis of the composite support, and the Ti/Ta ratio was respectively made to be Ti 0.7 Ta 0.3 O 2 ，Ti 0.55 Ta 0.45 O 2 ，Ti 0.4 Ta 0.6 O 2 Ti and 0.2 Ta 0.8 O 2 as shown in fig. 20 and 21, the half-wave potential of each catalyst is 0.922V (Ti/ta=7/3), 0.917V (Ti/ta=5.5/4.5), 0.911V (Ti/ta=4/6), 0.910V (Ti/ta=2/8) and 0.903V (40% JM Pt/C), and the change of the Ti/Ta ratio directly affects the crystal configuration, electronic structure, conductivity and other properties of the oxide, and then affects the interaction between the oxide and Pt, thereby obtaining different catalytic performances; when Ti/ta=7/3, the catalyst has the best ORR performance. The results are shown in FIG. 21, which shows four composite supported Pt catalystsThe CV area is close.
H obtained by testing composite carrier Pt-supported catalysts with different Ti/Ta ratios through rotating ring disk electrode 2 O 2 Yield and electron transfer number results, as shown in FIG. 22, with the comparative condition being the ratio of Ti/Ta in the oxide (Ti 0.7 Ta 0.3 O 2 ，Ti 0.55 Ta 0.45 O 2 ，Ti 0.4 Ta 0.6 O 2 ，Ti 0.2 Ta 0.8 O 2 ），H 2 O 2 The yield comparison sequence is:
Ti 0.55 Ta 0.45 O 2 <Ti 0.4 Ta 0.6 O 2 ≈Ti 0.7 Ta 0.3 O 2 <Ti 0.2 Ta 0.8 O 2
wherein Pt/Ti 0.55 Ta 0.45 O 2 C has the lowest H 2 O 2 The production level was 3.5% at 0.01V, whereas commercial Pt/C reached 7%; pt/Ti 0.2 Ta 0.8 O 2 H of-C 2 O 2 The yield is highest among them.
Example 5
Preparation of composite Supported Pt catalyst with different Heat treatment temperatures and Heat treatment atmospheres the synthesis method was the same as in example 2, except that when synthesizing composite Supports, heat treatments were performed at different temperatures and atmospheres, respectively, the heat treatment temperature was 300℃and the atmosphere was H 2 Ar; the heat treatment temperature is 500 ℃ and the atmosphere is H 2 Ar (same as in example 2); the heat treatment temperature is 500 ℃ and the atmosphere is Ar; the heat treatment temperature is 700 ℃ and the atmosphere is H 2 Pt catalyst carried by Ar composite carrier and H obtained by rotating ring disk electrode test 2 O 2 Yield and number of electron transfer, the results are shown in FIG. 23.
Composite carrier Pt-carried catalyst (300-H) 2 /Ar，500℃-H 2 /Ar，500℃-Ar，700℃-H 2 Ar) have lower H than commercial Pt/C 2 O 2 Yield, H in the potential range of 0.01V-0.2V 2 O 2 The yield comparison sequence is:
700℃-H 2 /Ar≈500℃-H 2 /Ar<500℃-Ar<300℃-H 2 /Ar
this shows that the high temperature heat treatment of the composite support in an atmosphere containing a reducing gas is advantageous for reducing the catalyst H 2 O 2 Is also advantageous for reducing the catalyst H by increasing the treatment temperature 2 O 2 But the effect increases less significantly after 500 ℃.
The above description is provided for the details of a fuel cell catalyst composite carrier, its preparation method and application, and specific examples should be adopted to illustrate the principles and embodiments of the present invention, and the above description is only for helping to understand the method and core idea of the present invention; meanwhile, as those skilled in the art will have variations in the specific embodiments and application scope in accordance with the ideas of the present invention, the present description should not be construed as limiting the present invention in view of the above.
Claims (10)
1. A method for preparing a fuel cell catalyst composite carrier, comprising the steps of:
adding a carbon-based material into an ethanol solution of polyvinylpyrrolidone, and uniformly mixing by ultrasonic waves to obtain a first mixed system;
mixing ethanol and acetic acid according to a preset proportion to form a mixed solvent, adding a preset amount of precursor into the mixed solvent, and uniformly mixing by ultrasonic to obtain a second mixed system; wherein the precursor is one or two of titanium isopropoxide and tantalum ethoxide;
dripping the second mixed system into the first mixed system, and uniformly mixing by ultrasonic to obtain a third mixed system;
placing the third mixed system in a reaction kettle, heating for a preset time, cooling and washing to obtain first powder;
placing the first powder in a protective atmosphere for heat treatment to obtain a composite carrier; wherein, the composition gas of the protective atmosphere is one or more of reducing gas and inert gas.
2. The method of manufacturing of claim 1, wherein the carbon-based material comprises one or more of carbon black, activated carbon, mesoporous carbon, carbon nanotubes, graphene;
the reducing gas is one or more of hydrogen, carbon monoxide and ammonia;
the inert gas is one or more of argon, nitrogen and helium.
3. The method according to claim 1, wherein the mass concentration of the ethanol solution of polyvinylpyrrolidone is 0.1 to 20%, and wherein the molecular weight of polyvinylpyrrolidone is 8000 to 70000.
4. A production method according to claim 1 or 3, wherein the ratio of the polyvinylpyrrolidone to the carbon-based material is 1 by mass: 0.1 to 100.
5. The method according to claim 1, wherein the ratio of ethanol to acetic acid in the mixed solvent is 1: 100-100: 1.
6. the method according to claim 1, wherein the concentration of titanium isopropoxide in the second mixed system is 0 to 50. Mu.L/mL and the concentration of tantalum ethoxide is 0 to 50. Mu.L/mL.
7. The method of claim 1, wherein the first mixing system and the second mixing system are present in a volume ratio of 100:1 to 1:1.
8. the preparation method according to claim 1, wherein the third mixed system is placed in a reaction kettle and is subjected to heating treatment at 60-200 ℃ for 0.1-24 hours;
and placing the first powder in a protective atmosphere to perform heat treatment at 60-1100 ℃.
9. A fuel cell catalyst composite support, characterized in that it is produced by the production method according to any one of claims 1 to 8.
10. Use of the fuel cell catalyst composite support according to claim 9 for the preparation of a fuel cell catalyst.
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| CN114068949A (en) * | 2021-11-19 | 2022-02-18 | 四川大学 | High-performance titanium-based low-platinum catalyst, preparation method thereof and application thereof in fuel cell |
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| CN106245158A (en) * | 2016-08-15 | 2016-12-21 | 江苏师范大学 | The preparation method of nitrogen-doped carbon/dioxide composite nanofiber carrier |
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