CN114220979B - Catalyst carrier, preparation method thereof, catalyst and fuel cell - Google Patents
Catalyst carrier, preparation method thereof, catalyst and fuel cell Download PDFInfo
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- CN114220979B CN114220979B CN202111343421.0A CN202111343421A CN114220979B CN 114220979 B CN114220979 B CN 114220979B CN 202111343421 A CN202111343421 A CN 202111343421A CN 114220979 B CN114220979 B CN 114220979B
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- cerium
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- trifluoride
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- 239000003054 catalyst Substances 0.000 title claims abstract description 213
- 239000000446 fuel Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title abstract description 22
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 72
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 72
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims abstract description 59
- QCCDYNYSHILRDG-UHFFFAOYSA-K cerium(3+);trifluoride Chemical compound [F-].[F-].[F-].[Ce+3] QCCDYNYSHILRDG-UHFFFAOYSA-K 0.000 claims abstract description 59
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 59
- 239000002086 nanomaterial Substances 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 36
- 238000003682 fluorination reaction Methods 0.000 claims abstract description 26
- 230000008569 process Effects 0.000 claims abstract description 18
- 239000012298 atmosphere Substances 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims description 40
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 37
- 239000002073 nanorod Substances 0.000 claims description 27
- 229910052684 Cerium Inorganic materials 0.000 claims description 25
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 23
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 20
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 19
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 15
- 239000003513 alkali Substances 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 11
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 8
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 8
- 150000001785 cerium compounds Chemical class 0.000 claims description 6
- -1 hydrogen urea fluoride Chemical class 0.000 claims description 6
- 238000005530 etching Methods 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000012670 alkaline solution Substances 0.000 claims description 3
- CEBDXRXVGUQZJK-UHFFFAOYSA-N 2-methyl-1-benzofuran-7-carboxylic acid Chemical compound C1=CC(C(O)=O)=C2OC(C)=CC2=C1 CEBDXRXVGUQZJK-UHFFFAOYSA-N 0.000 claims description 2
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-diisopropylethylamine Substances CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 2
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 2
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 claims description 2
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 2
- DAANAKGWBDWGBQ-UHFFFAOYSA-N difluoromethyl trifluoromethanesulfonate Chemical compound FC(F)OS(=O)(=O)C(F)(F)F DAANAKGWBDWGBQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 229910000510 noble metal Inorganic materials 0.000 abstract description 31
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 20
- 239000001301 oxygen Substances 0.000 abstract description 20
- 229910052760 oxygen Inorganic materials 0.000 abstract description 20
- 239000002082 metal nanoparticle Substances 0.000 abstract description 15
- 239000002245 particle Substances 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 11
- 239000013078 crystal Substances 0.000 abstract description 9
- 230000007547 defect Effects 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 38
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 34
- 239000002105 nanoparticle Substances 0.000 description 33
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- 239000007864 aqueous solution Substances 0.000 description 21
- 239000000047 product Substances 0.000 description 21
- 230000003197 catalytic effect Effects 0.000 description 19
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 18
- 239000011259 mixed solution Substances 0.000 description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 16
- CFQCIHVMOFOCGH-UHFFFAOYSA-N platinum ruthenium Chemical compound [Ru].[Pt] CFQCIHVMOFOCGH-UHFFFAOYSA-N 0.000 description 16
- 229910052763 palladium Inorganic materials 0.000 description 15
- 239000007788 liquid Substances 0.000 description 14
- 238000011068 loading method Methods 0.000 description 14
- 238000003756 stirring Methods 0.000 description 14
- 238000012360 testing method Methods 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 239000000725 suspension Substances 0.000 description 12
- 238000005406 washing Methods 0.000 description 12
- 238000002441 X-ray diffraction Methods 0.000 description 11
- 238000007254 oxidation reaction Methods 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 8
- 235000019253 formic acid Nutrition 0.000 description 8
- 238000001291 vacuum drying Methods 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 238000002484 cyclic voltammetry Methods 0.000 description 7
- 230000002349 favourable effect Effects 0.000 description 7
- 239000007791 liquid phase Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 6
- 238000009210 therapy by ultrasound Methods 0.000 description 6
- 238000003917 TEM image Methods 0.000 description 5
- 229910052573 porcelain Inorganic materials 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- JIDUBFKLNRRLDT-UHFFFAOYSA-N [Ru].[Pt].[C] Chemical compound [Ru].[Pt].[C] JIDUBFKLNRRLDT-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000543 intermediate Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000011144 upstream manufacturing Methods 0.000 description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- 229910021642 ultra pure water Inorganic materials 0.000 description 3
- 239000012498 ultrapure water Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 150000002222 fluorine compounds Chemical group 0.000 description 2
- 229910021397 glassy carbon Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000004627 transmission electron microscopy Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004334 fluoridation Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- VAKIVKMUBMZANL-UHFFFAOYSA-N iron phosphide Chemical compound P.[Fe].[Fe].[Fe] VAKIVKMUBMZANL-UHFFFAOYSA-N 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- FBMUYWXYWIZLNE-UHFFFAOYSA-N nickel phosphide Chemical compound [Ni]=P#[Ni] FBMUYWXYWIZLNE-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000002468 redox effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- ITDRVJXDQOONPC-UHFFFAOYSA-N urea;hydrofluoride Chemical compound F.NC(N)=O ITDRVJXDQOONPC-UHFFFAOYSA-N 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
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
-
- 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
- H01M4/8817—Treatment of supports before application 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
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
-
- 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)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Catalysts (AREA)
Abstract
The application belongs to the technical field of catalysts, and particularly relates to a catalyst carrier and a preparation method thereof, a catalyst and a fuel cell. Wherein, the preparation method of the catalyst carrier comprises the following steps: preparing cerium oxide nano material; and (3) carrying out fluorination treatment on the cerium oxide nano material in an inert atmosphere to obtain a catalyst carrier, wherein the catalyst carrier comprises cerium oxide and cerium trifluoride. According to the preparation method of the catalyst carrier, the cerium oxide nano material is subjected to fluorination treatment, and when cerium oxide is converted into cerium trifluoride in the fluorination treatment process, lattice oxygen can be consumed to generate oxygen vacancies, more surface defects are generated, and the conductivity and the specific surface area of the material are improved. The obtained catalyst carrier comprises cerium dioxide and cerium trifluoride, wherein crystal faces with high surface energy of the cerium dioxide are reserved, and meanwhile, a unique interface is formed between the cerium dioxide and cerium trifluoride particles, so that the dispersion of noble metal nano particles is facilitated, and the catalyst utilization rate is improved.
Description
Technical Field
The application belongs to the technical field of catalysts, and particularly relates to a catalyst carrier and a preparation method thereof, a catalyst and a fuel cell.
Background
The liquid fuel cell uses liquid fuel such as formic acid, methanol and the like as fuel, can directly convert chemical energy into electric energy, and has the advantages of high energy density, high energy conversion efficiency, safety, environmental protection and the like. Compared with an oxyhydrogen fuel cell using hydrogen as fuel, the preparation of the liquid fuel is more environment-friendly, is easy to transport and store, and greatly reduces the generation of safety problems, so that the liquid fuel cell is considered as an alternative energy source for automobiles and small-sized equipment in the future. However, the main problem faced by the current liquid fuel cell is that the oxidation reaction process occurring at the anode is relatively complex and slow, and a highly efficient and stable catalyst is lacking. In addition, the platinum carbon and platinum ruthenium carbon catalysts which realize commercial production at present belong to precious metal scarce resources, have high production cost and are easy to be poisoned by intermediates in the reaction process to cause the reduction of catalytic stability. Therefore, the current research on the anode catalyst of the liquid fuel cell is mainly focused on how to reduce the catalyst loading, improve the utilization efficiency of the catalyst and enhance the catalytic activity and stability of the catalyst.
Supported noble metal nanocatalysts are considered as effective methods for reducing catalyst cost and increasing catalyst activity and stability. By loading a small amount of noble metal catalyst on a carrier with lower cost, various advantages of the carrier, such as high conductivity, large specific surface area, electronic effect with noble metal and the like, can be fully utilized while the cost is reduced, the utilization rate of the catalyst is improved, and the stability of the catalyst is enhanced. Currently, commonly used catalyst supports include carbon materials such as carbon black, carbon nanotubes, graphene, and the like; transition metal phosphides such as nickel phosphide, iron phosphide, and the like, and various metal oxides such as titanium dioxide, manganese dioxide, cerium oxide, and the like. Among them, ceria has proved to be an excellent carrier for noble metals because of its abundant lattice oxygen content, good redox properties, and many oxygen vacancies. However, the conductivity of the ceria serving as a metal oxide is poor, the exposed crystal faces of the ceria nano materials with different morphologies are different, the binding energy is also different, and the capability of promoting catalysis as a catalyst carrier is strong or weak. In addition, ceria nanorods that expose more high surface energy crystal planes are generally larger in size, easily causing agglomeration of noble metal nanoparticles, and are unfavorable for the catalytic reaction. Therefore, in order to realize the large-scale application of the catalyst as a noble metal catalyst carrier, the defects of the catalyst need to be overcome while the advantages of the catalyst are expanded.
Disclosure of Invention
The application aims to provide a catalyst carrier, a preparation method thereof, a catalyst and a fuel cell, and aims to solve the technical problems that the stability of a cerium oxide carrier in a fuel cell anode catalyst is poor, the conductivity is poor and the catalytic effect of the catalyst is improved to an undesirable degree.
In order to achieve the purposes of the application, the technical scheme adopted by the application is as follows:
in a first aspect, the present application provides a method for preparing a catalyst support, comprising the steps of:
preparing cerium oxide nano material;
and (3) carrying out fluorination treatment on the cerium oxide nano material in an inert atmosphere to obtain a catalyst carrier, wherein the catalyst carrier comprises cerium oxide and cerium trifluoride.
In a second aspect, the present application provides a catalyst support made by the above method comprising ceria and cerium trifluoride.
In a third aspect, the present application provides a catalyst comprising the above catalyst support and a catalyst supported in the catalyst support.
In a fourth aspect, the present application provides a fuel cell comprising the catalyst described above.
According to the preparation method of the catalyst carrier, in the process of carrying out fluorination treatment on the cerium oxide nano material, on one hand, cerium oxide is converted into cerium trifluoride, lattice oxygen can be consumed to generate more oxygen vacancies, more surface defects are generated, the increase of the oxygen vacancies can improve the conductivity of the catalyst carrier material, the electronic structure of the noble metal nano particle catalyst can be regulated, more active hydroxyl groups can be generated by reaction with surrounding adsorbed water, and the removal of toxic intermediates on the active sites of the catalyst is facilitated. On the other hand, the cerium oxide nano material is continuously etched and crushed in the fluorination treatment process, cerium trifluoride is generated, the overall size of the material is greatly reduced, the specific surface area of the catalyst carrier is improved, and the catalyst carrier is more favorable for loading noble metal nano particles and other catalysts. In addition, due to incomplete fluorination, the crystal face with high surface energy of the cerium oxide is reserved, and a unique interface is formed between the cerium oxide and cerium trifluoride particles, so that the loading uniformity of the noble metal nanoparticles in the carrier is further improved, and the utilization rate of the catalyst is further improved.
The catalyst carrier provided by the second aspect of the application comprises cerium dioxide and cerium trifluoride, and is prepared by the method, and through fluoridation treatment of the cerium dioxide nano material, the conductivity of the catalyst carrier is improved, and the combination stability and the catalytic effect of the carrier and the noble metal and other catalysts are improved; and the activity specific surface area of the catalyst carrier is increased, meanwhile, the crystal face with high surface energy of the cerium oxide is reserved, and a unique interface is formed between the cerium oxide and cerium trifluoride particles, so that the catalyst carrier is favorable for loading and dispersing of catalysts such as noble metals and the like, and the catalyst utilization rate is improved.
The catalyst provided in the third aspect of the application comprises the catalyst carrier and the catalyst loaded in the catalyst carrier, and the catalyst carrier has excellent conductive performance, large specific surface area and good structural stability, so that the loading effect of the catalyst such as noble metal nano particles in the carrier is improved, and the catalytic activity and stability of the catalyst are improved.
The fuel cell provided in the fourth aspect of the application contains the catalyst, and the catalyst has good catalytic activity and stability, and shows higher catalytic activity and stability and good anti-poisoning capability when catalyzing the oxidation reaction of liquid fuel such as formic acid and methanol in the fuel cell, especially in the liquid fuel cell. The method can effectively improve the activity of the anodic oxidation reaction of the liquid fuel cell, thereby improving the electrochemical performance of the fuel cell and solving the problems of high cost, low catalytic activity, poor stability and the like of the anode catalyst of the liquid fuel cell.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the following description will briefly introduce the drawings that are needed in the embodiments or the description of the prior art, it is obvious that the drawings in the following description are only some embodiments of the present application, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an XRD pattern of the catalyst supports prepared in example 1, comparative examples 1 and 2 of the present application;
FIG. 2 is a TEM image of the catalyst supports prepared in example 1, comparative examples 1 and 2 of the present application;
FIG. 3 is an XRD pattern of noble metal-supported catalysts prepared in example 2, comparative examples 3 and 4 of the present application;
FIG. 4 is a TEM spectrum of the noble metal-supported catalyst prepared in example 2, comparative examples 3 and 4 of the present application;
FIG. 5 is an XRD pattern of noble metal-supported catalysts prepared in example 3, comparative examples 5 and 6 of the present application;
FIG. 6 is a TEM spectrum of noble metal-supported catalysts prepared in example 3, comparative examples 5 and 6 of the present application;
FIG. 7 is a cyclic voltammogram (a) and chronoamperometric test curve (b) for use in catalyzing formic acid oxidation reactions for supported palladium nanoparticle catalysts, and palladium on carbon catalysts prepared in example 2, comparative examples 3 and 4 herein;
fig. 8 is a cyclic voltammogram (a) and a chronoamperometric test curve (b) for use in catalyzing methanol oxidation reactions in an acidic electrolyte for supported platinum ruthenium nanoparticle catalysts prepared in example 3, comparative examples 5 and 6, and for commercial platinum ruthenium carbon catalysts of the present application.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved by the present application more clear, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the present application.
In this application, the term "and/or" describes an association relationship of an association object, which means that there may be three relationships, for example, a and/or B may mean: a alone, a and B together, and B alone. Wherein A, B may be singular or plural. The character "/" generally indicates that the context-dependent object is an "or" relationship.
In the present application, "at least one" means one or more, and "a plurality" means two or more. "at least one of" or the like means any combination of these items, including any combination of single item(s) or plural items(s). For example, "at least one (individual) of a, b, or c," or "at least one (individual) of a, b, and c" may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, c may be single or multiple, respectively.
It should be understood that, in various embodiments of the present application, the sequence number of each process does not mean that the sequence of execution is sequential, and some or all of the steps may be executed in parallel or sequentially, where the execution sequence of each process should be determined by its functions and internal logic, and should not constitute any limitation on the implementation process of the embodiments of the present application.
The terminology used in the embodiments of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in this application in the examples and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The weights of the relevant components mentioned in the embodiments of the present application may refer not only to specific contents of the components, but also to the proportional relationship between the weights of the components, and thus, any ratio of the contents of the relevant components according to the embodiments of the present application may be enlarged or reduced within the scope disclosed in the embodiments of the present application. Specifically, the mass in the specification of the embodiment of the present application may be a mass unit well known in the chemical industry field such as μ g, mg, g, kg.
The terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated for distinguishing between objects such as substances from each other. For example, a first XX may also be referred to as a second XX, and similarly, a second XX may also be referred to as a first XX, without departing from the scope of embodiments of the present application. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature.
A first aspect of the embodiments of the present application provides a method for preparing a catalyst carrier, including the steps of:
s10, preparing a cerium oxide nano material;
s20, carrying out fluorination treatment on the cerium oxide nano material in an inert atmosphere to obtain a catalyst carrier, wherein the catalyst carrier comprises cerium oxide and cerium trifluoride.
According to the preparation method of the catalyst carrier provided by the first aspect of the embodiment of the application, after the cerium oxide nano material is prepared, the cerium oxide nano material is subjected to fluorination treatment, so that the food catalyst carrier comprising cerium oxide and cerium trifluoride is obtained. In the process of carrying out fluorination treatment on the cerium oxide nano material, on one hand, the cerium oxide is converted into cerium trifluoride, so that lattice oxygen can be consumed to generate more oxygen vacancies and more surface defects are generated, the increase of the oxygen vacancies can improve the conductivity of the catalyst carrier material, the electronic structure of the noble metal nano particle catalyst can be regulated, more active hydroxyl groups can be generated by reaction with surrounding adsorbed water, and the removal of toxic intermediates on the active sites of the catalyst is facilitated. On the other hand, the cerium oxide nano material is continuously etched and crushed in the fluorination treatment process, cerium trifluoride is generated, the overall size of the material is greatly reduced, the specific surface area of the catalyst carrier is improved, and the catalyst carrier is more favorable for loading noble metal nano particles and other catalysts. In addition, due to incomplete fluorination, the crystal face with high surface energy of the cerium oxide is reserved, and a unique interface is formed between the cerium oxide and cerium trifluoride particles, so that the loading uniformity of the noble metal nanoparticles in the carrier is further improved, and the utilization rate of the catalyst is further improved. The preparation method of the catalyst carrier is simple in process and suitable for industrial large-scale production and application. The prepared catalyst carrier comprising cerium dioxide and cerium trifluoride has excellent conductivity, large specific surface area and good structural stability, can improve the loading effect of the noble metal nano-particles and other catalysts in the carrier, and improves the catalytic activity and stability of the catalyst.
In some embodiments, in the step S10, the step of preparing the cerium oxide nanomaterial includes:
s11, mixing a solution containing a cerium compound with alkali liquor, performing hydrothermal reaction, and separating to obtain a hydrothermal product;
s12, calcining the hydrothermal product to obtain the cerium dioxide nanorod.
The step of the cerium oxide nanomaterial of the embodiment of the application comprises the steps of firstly mixing a solution containing a cerium compound with an alkali solution, performing a hydrothermal reaction, and mixing 3-valent cerium ions and OH - Ion complexation to form Ce (OH) 3 The Ce (OH) produced 3 The core is first dissolved into nanoparticles during the hydrothermal reaction. Then, anions are used as CeO 2 The capping agent in the nanomaterial formation process forms a surface layer that alters the free energy of the surface by selectively adsorbing on a specific plane. Thus, the growth rate of the specific plane will be controlled, thereby generating a rod-shaped nano-structure, and the rod-shaped Ce (OH) obtained by the hydrothermal reaction 3 I.e. the hydrothermal product. Calcining the hydrothermal product to obtain rod-shaped Ce (OH) 3 Oxidized to CeO by heat treatment in air 2 The nano rod is the cerium dioxide nano rod. The cerium dioxide with the rod-shaped structure prepared by the embodiment of the application has larger specific surface area, is beneficial to subsequent fluorination treatment and is also beneficial to improving the activity specific surface area of the catalyst carrier.
In some embodiments, in step S11, the step of mixing the solution of the cerium-containing compound with the lye includes: and (3) dropwise adding the alkali liquor into the solution containing the cerium compound, and then mixing for 30-60 minutes. In some embodiments, the cerium-containing compound and the alkaline substance are dissolved in water to obtain an aqueous solution of the cerium-containing compound and an alkaline solution, respectively; then, the prepared alkali solution is dropwise added into the aqueous solution of the cerium-containing compound. After the completion of the dropwise addition, stirring was continued for half an hour to obtain a mixed solution. In the embodiment of the application, alkali liquor is dripped into the solution of the cerium-containing compound, and the pH value in the solution is regulated by the alkali liquor to prevent local OH in the solution - The concentration is too high, the shape of the hydrothermal reaction product is affected, and the alkali liquor is slowly dripped into the solution containing the cerium compound. In addition, in order to make 3-valent cerium ions and OH in the solution - Fully complexing ions, dripping alkali liquor into the solution containing cerium compound, and mixing for 30-60 minutes. In some embodiments, the rate of addition may be 10 to 15 seconds per drop; further, a constant pressure dropping funnel may be used to control the droppingIs a function of the speed of the machine. If the alkali liquor dropping speed is too high or too low, the final appearance of the product can be influenced.
In some embodiments, the molar ratio of cerium-containing compound to alkaline material in the lye is 1: (50-100); the proportion can enable the alkaline substance to provide OH - The ion is fully complexed with 3-valence cerium ion in the cerium-containing compound to finally form rod-shaped Ce (OH) 3 . If the alkaline substance content is too low, i.e. the alkali concentration is low, ceO will be formed finally 2 Nanoparticles rather than rod-like morphology.
In some embodiments, the cerium-containing compound is selected from: cerium nitrate Ce (NO) 3 ) 3 ·6H 2 O, cerium chloride CeCl 3 ·7H 2 O, cerium acetate Ce (CH) 3 COO) 3 ·xH 2 O, cerium sulfate Ce 2 (SO 4 ) 3 ·8H 2 At least one of O; the cerium-containing compounds have better solubility and are easy to dissociate into 3-valent cerium ions in solution.
In some embodiments, the alkaline material in the lye is selected from the group consisting of: at least one of sodium hydroxide and potassium hydroxide, which have good solubility and dissociate OH in the solution - Ion complexing of 3-valent cerium ions, and finally forming rod-shaped Ce (OH) 3 。
In some embodiments, in step S11, the conditions of the hydrothermal reaction include: reacting for 24-26 hours at the temperature of 80-120 ℃; . In some embodiments, the hydrothermal product is obtained by mixing a solution of the cerium-containing compound with an alkaline solution, performing a hydrothermal reaction, centrifuging the hydrothermal product, and washing the hydrothermal product to remove impurity components. The conditions of the hydrothermal reaction in the examples herein are related to the size of the ceria nanorods, and the higher the hydrothermal temperature, the longer the ceria nanorods become widened. The method is characterized in that when the temperature of the hydrothermal reaction is 40 ℃, the diameter of the finally prepared cerium oxide nano rod is about 8nm, and the length is about 50nm; when the temperature of the hydrothermal reaction is 60 ℃, the diameter of the finally prepared cerium oxide nano rod is about 10nm, and the length is about 70nm; when the temperature of the hydrothermal reaction is 80 ℃, the diameter and the length of the finally prepared cerium oxide nano rod are about 13nmAbout 105nm; when the temperature of the hydrothermal reaction is 100 ℃, the diameter of the finally prepared cerium oxide nano rod is about 25nm, and the length is about 300nm. When the hydrothermal reaction temperature is 80-120 ℃, the obtained cerium oxide nanorod has relatively large size, can ensure certain morphology in the subsequent etching process, and is favorable for loading noble metal nanoparticles, so that the embodiment of the application prefers the hydrothermal reaction temperature of 80-120 ℃. In addition, the hydrothermal reaction time is ensured to be all Ce (OH) 3 Conversion of nanoparticles to rod-like Ce (OH) 3 The method comprises the steps of carrying out a first treatment on the surface of the If the reaction time is too short, ce (OH) is obtained 3 The preferred reaction of the examples of the present application for 24-26 hours is a mixture of nanoparticles and nanorods, which is sufficient to ensure Ce (OH) 3 Conversion of nanoparticles to rod-like Ce (OH) 3 。
In some embodiments, in the step S12, the conditions of the calcination treatment include: reacting for 2-4 hours at 400-600 ℃. Washing and drying a product obtained after the hydrothermal reaction is finished to obtain the rod-shaped Ce (OH) 3 Calcining for 2-4 hours at 400-600 ℃, wherein oxygen in the air promotes Ce (OH) in the calcining process 3 Conversion of nanorods to CeO 2 Nanorods, the calcination conditions ensuring Ce (OH) 3 Sufficient conversion of nanorods to CeO 2 The nano rod improves the stability of the material. If the temperature is too low or the calcination time is too short, the conversion effect is insufficient; if the temperature is too high or the calcination time is too long, the rod-like morphology may be destroyed.
In some embodiments, the prepared lye is added dropwise to an aqueous solution of a cerium-containing compound. After the dripping is finished, stirring is continued for half an hour, and then the mixed solution is transferred into a reaction kettle for hydrothermal reaction. After the hydrothermal reaction is finished, centrifugally separating, washing with water to remove impurity components, and drying to obtain yellow solid powder, namely a hydrothermal product. And (3) placing the hydrothermal product in a tube furnace, and calcining in air to obtain the cerium oxide nanorod.
In some embodiments, the ceria nanorods have a diameter of 13 to 30nm and a length of 100 to 500nm; the cerium dioxide nano rod with the size is relatively large in size and large in specific surface, can ensure certain morphology in the subsequent etching process, is stable in structure and is favorable for loading noble metal nano particles.
In some embodiments, in the step S20, the step of fluorination treatment includes: and (3) simultaneously placing the cerium oxide nano material and fluoride in an inert atmosphere for thermal reaction to obtain the catalyst carrier. In the fluorination treatment process, fluorine atoms consume cerium oxide nano material lattice oxygen to generate more oxygen vacancies, the increase of the oxygen vacancies can improve the conductivity of the material, adjust the electronic structure of noble metal nano particles in the catalyst, and can react with surrounding adsorbed water to generate more active hydroxyl groups, so that the removal of toxic intermediates on the active sites of the catalyst is facilitated. In addition, the cerium oxide nano material is continuously etched and crushed in the fluorination treatment process, cerium trifluoride is generated, and the overall size of the material is greatly reduced; meanwhile, due to incomplete fluorination, the crystal face with high surface energy of the cerium oxide is reserved, and a unique interface is formed between the cerium oxide and cerium trifluoride particles, so that the dispersion of noble metal nano particles is facilitated, and the utilization rate of the catalyst is improved.
In some embodiments, to avoid introducing impurity components into the catalyst support product, the ceria nanomaterial is separated from the fluoride and simultaneously placed in an inert atmosphere for thermal reaction, and in the reaction system, the ceria nanomaterial is placed separately from the fluoride, and the hydrogen fluoride gas generated by thermal decomposition of the fluoride performs etching fluorination treatment on the ceria nanomaterial. In some embodiments, the fluoride and ceria nanomaterials are placed upstream and downstream of the porcelain boat, respectively, i.e., along the flow direction of the air flow, with the fluoride placed upstream and the ceria nanomaterial placed downstream. Meanwhile, in order to ensure that the generated hydrogen fluoride and cerium oxide fully react, the porcelain boat is wrapped by aluminum foil paper to provide a closed environment, and then the porcelain boat is placed in a tube furnace to be subjected to heat treatment under inert atmosphere such as nitrogen, helium and the like, so as to obtain a cerium oxide and cerium trifluoride mixture.
In some embodiments, the conditions of the thermal reaction include: reacting for 1-3 hours in an inert atmosphere with the temperature of 200-300 ℃; under the temperature condition, the fluoride is heated and decomposed to generate hydrogen fluoride with high efficiency, the reaction time is long enough to ensure that the hydrogen fluoride gas decomposed by the fluoride fully reacts with the cerium oxide nano material, and the cerium oxide nano material is verified to obtain the catalyst carrier containing cerium oxide and cerium trifluoride.
In some embodiments, the fluoride is selected from at least one of ammonium fluoride, N-diisopropylethylamine tri-hydrofluoric acid salt, difluoromethyl triflate, urea hydrogen fluoride, iodine pentafluoride; the fluorides can be heated to decompose to generate hydrogen fluoride gas, and the cerium oxide nano material is etched through the hydrogen fluoride gas to generate a catalyst carrier containing cerium oxide and cerium trifluoride.
In some embodiments, the mass ratio of ceria nanomaterial to fluoride is (1-2): (1-5). The ratio of the cerium oxide nanomaterial to the fluoride in the embodiment of the application influences the fluorination degree of the cerium oxide nanomaterial, and the more the fluoride is, the higher the fluorination degree of the cerium oxide is. When fluoride is excessive, the ceria may be completely converted to cerium trifluoride. In the embodiment of the application, the cerium oxide is etched by utilizing the hydrogen fluoride generated by fluoride, so that more oxygen vacancies are created while cerium trifluoride is generated. However, the content of lattice oxygen in the ceria material is ensured while the oxygen vacancies are increased, and the lattice oxygen in the oxide support plays an important role in the catalytic process. Therefore, the amount of fluoride is proper, and the mass ratio of the cerium oxide nano material to the fluoride is (1-2): (1-5) to ensure that the resulting catalyst support contains both ceria and cerium trifluoride. In some embodiments, the mass ratio of ceria nanomaterial to fluoride can be 1:1, 2: 1. 2:3, 2:5, etc., preferably 2:1, which is more advantageous in ensuring a relative balance of oxygen vacancies and lattice oxygen content.
In a second aspect, embodiments of the present application provide a catalyst support made by the above method, comprising ceria and cerium trifluoride.
The catalyst carrier provided by the second aspect of the embodiment of the application comprises cerium dioxide and cerium trifluoride, and is prepared by the method, and through the fluorination treatment of the cerium dioxide nano material, the conductivity of the catalyst carrier is improved, and the combination stability and the catalytic effect of the carrier and the noble metal and other catalysts are improved; and the activity specific surface area of the catalyst carrier is increased, meanwhile, the crystal face with high surface energy of the cerium oxide is reserved, and a unique interface is formed between the cerium oxide and cerium trifluoride particles, so that the catalyst carrier is favorable for loading and dispersing of catalysts such as noble metals and the like, and the catalyst utilization rate is improved.
In some embodiments, the mass ratio of ceria to cerium trifluoride in the catalyst support is (0.8-1): 1, the ratio is favorable for forming a unique interface between the cerium oxide and the cerium trifluoride while retaining a crystal face with high surface energy of the cerium oxide, and optimizing the activity specific surface area of the catalyst carrier.
A third aspect of embodiments of the present application provides a catalyst comprising the above-described catalyst carrier and a catalyst supported in the catalyst carrier.
The catalyst provided in the third aspect of the embodiment of the present application includes the above catalyst carrier and a catalyst supported in the catalyst carrier, and because the above catalyst carrier has excellent conductive performance, large specific surface area and good structural stability, the loading effect of the catalyst such as noble metal nanoparticles in the carrier is improved, thereby improving the catalytic activity and stability of the catalyst.
In some embodiments, the method of preparing the catalyst includes, but is not limited to, dispersing a catalyst support and a noble metal salt into a solution, uniformly loading the noble metal salt into the catalyst support, and then subjecting the noble metal salt to a reduction treatment to form a noble metal simple substance uniformly loaded in the catalyst support. In some embodiments, the step of reducing the noble metal salt comprises: the preparation method of the catalyst comprises, but is not limited to, dispersing a catalyst carrier and noble metal salt into a solution to form a uniform mixed solution, adding alkaline substances such as potassium hydroxide, sodium hydroxide and the like to adjust the pH value of the mixed solution to 9-12, then carrying out solid-liquid phase microwave synthesis, and separating to obtain the catalyst loaded with noble metal simple substances.
A fourth aspect of the embodiments of the present application provides a fuel cell, which includes the above catalyst.
The fuel cell provided in the fourth aspect of the present application includes the above catalyst, and the catalyst has good catalytic activity and stability, and shows higher catalytic activity and stability and good poisoning resistance when catalyzing the oxidation reaction of liquid fuel such as formic acid and methanol in the fuel cell, especially in the liquid fuel cell. The method can effectively improve the activity of the anodic oxidation reaction of the liquid fuel cell, thereby improving the electrochemical performance of the fuel cell and solving the problems of high cost, low catalytic activity, poor stability and the like of the anode catalyst of the liquid fuel cell.
In order that the details and operations of the foregoing implementation of the present application may be clearly understood by those skilled in the art, and that the catalyst carrier, the preparation method thereof and the advanced performance of the catalyst according to the embodiments of the present application are significantly embodied, the foregoing technical solutions are exemplified by a plurality of embodiments below.
Example 1
A catalyst support comprising ceria and cerium trifluoride, the preparation of which comprises the steps of:
(1) 870 mg of cerium nitrate hexahydrate and 4.8 g of sodium hydroxide solids were each dissolved in 10 ml of ultrapure water. After complete dissolution, dropwise adding a sodium hydroxide solution into a cerium nitrate solution at a speed of 13 seconds under stirring, and continuing stirring for 30 minutes after the dropwise addition is finished;
(2) transferring the mixed solution into a 50 ml reaction kettle, reacting for 24 hours at 100 ℃, centrifuging the product after the hydrothermal reaction is finished, washing the product with deionized water, and vacuum drying for 12 hours at 60 ℃ to obtain yellow powder, namely a hydrothermal product;
(3) placing the yellow powder into a tube furnace, and calcining for 3 hours in an air atmosphere at 500 ℃ to obtain a cerium dioxide nano rod;
(4) and (3) respectively placing 100 mg of ammonium fluoride solid and 50 mg of cerium dioxide nanorod at the upstream and downstream of a porcelain boat, wrapping with aluminum foil paper, placing in a tube furnace, and performing heat treatment at 250 ℃ for 2 hours in a nitrogen atmosphere to obtain the catalyst carrier comprising cerium dioxide and cerium trifluoride.
Example 2
A catalyst, the preparation of which comprises the steps of:
(5) 30mg of the catalyst support comprising cerium oxide and cerium trifluoride prepared in example 1 was added to 50 ml of ethylene glycol solution, followed by 333. Mu.l of an aqueous solution of chloropalladac acid (the content of palladium in the aqueous solution was 30 mg/ml); magnetically stirring for 30 minutes, and carrying out ultrasonic treatment for 30 minutes to form uniform suspension;
(6) dropwise adding potassium hydroxide solution into the suspension until the pH value of the solution reaches 10; transferring into a solid-liquid phase microwave synthesizer with the power of 800W, reacting for 3 minutes, and naturally cooling to room temperature; and (3) carrying out suction filtration, repeatedly washing the sample with ethanol and deionized water for at least 3 times, and vacuum drying at 60 ℃ overnight to obtain the catalyst with palladium nano particles supported in the cerium oxide and cerium trifluoride catalyst carrier.
Example 3
A catalyst, the preparation of which comprises the steps of:
(5) 25mg of the catalyst support comprising cerium oxide and cerium trifluoride prepared in example 1 was added to 50 ml of ethylene glycol solution, followed by addition of 330. Mu.l of an aqueous solution of chloroplatinic acid (the content of platinum in the aqueous solution being 30 mg/ml) and 250. Mu.l of an aqueous solution of ruthenium trichloride (the content of ruthenium in the aqueous solution being 20 mg/ml); magnetically stirring for 30 minutes, and carrying out ultrasonic treatment for 30 minutes to form uniform suspension;
(6) dropwise adding potassium hydroxide solution into the suspension until the pH value of the solution reaches 10; transferring into a solid-liquid phase microwave synthesizer with the power of 800W, reacting for 3 minutes, and naturally cooling to room temperature; and (3) carrying out suction filtration, repeatedly washing the sample with ethanol and deionized water for at least 3 times, and vacuum drying at 60 ℃ overnight to obtain the catalyst with platinum ruthenium nano particles supported in the cerium oxide and cerium trifluoride catalyst carrier.
Comparative example 1
A ceria catalyst support, the preparation comprising the steps of:
(1) 870 mg of cerium nitrate hexahydrate and 4.8 g of sodium hydroxide solids were each dissolved in 10 ml of ultrapure water. After complete dissolution, dropwise adding a sodium hydroxide solution into a cerium nitrate solution at a speed of 13 seconds under stirring, and continuing stirring for 30 minutes after the dropwise addition is finished;
(2) transferring the mixed solution into a 50 ml reaction kettle, reacting for 24 hours at 100 ℃, centrifuging the product after the hydrothermal reaction is finished, washing the product with deionized water, and vacuum drying for 12 hours at 60 ℃ to obtain yellow powder, namely a hydrothermal product;
(3) the yellow powder is placed in a tube furnace and calcined for 3 hours in an air atmosphere at 500 ℃ to obtain the cerium dioxide nano rod, namely the catalyst carrier.
Comparative example 2
A cerium trifluoride catalyst support, the preparation of which comprises the steps of:
(1) 870 mg of cerium nitrate hexahydrate and 4.8 g of sodium hydroxide solids were each dissolved in 10 ml of ultrapure water. After complete dissolution, dropwise adding a sodium hydroxide solution into a cerium nitrate solution at a speed of 13 seconds under stirring, and continuing stirring for 30 minutes after the dropwise addition is finished;
(2) transferring the mixed solution into a 50 ml reaction kettle, reacting for 24 hours at 100 ℃, centrifuging the product after the hydrothermal reaction is finished, washing the product with deionized water, and vacuum drying for 12 hours at 60 ℃ to obtain yellow powder, namely a hydrothermal product;
(3) placing the yellow powder into a tube furnace, and calcining for 3 hours in an air atmosphere at 500 ℃ to obtain a cerium dioxide nano rod;
(4) and (3) respectively placing 250 mg of ammonium fluoride solid and 50 mg of cerium dioxide nanorod at the upstream and downstream of a porcelain boat, wrapping with aluminum foil paper, placing in a tube furnace, and performing heat treatment at 250 ℃ for 2 hours in a nitrogen atmosphere to obtain the cerium trifluoride catalyst carrier.
Comparative example 3
A catalyst, the preparation of which comprises the steps of:
(5) 30mg of the ceria catalyst support prepared in comparative example 1 was added to 50 ml of an ethylene glycol solution, followed by 333. Mu.l of an aqueous solution of chloropalladac acid (the content of palladium in the aqueous solution is 30 mg/ml); magnetically stirring for 30 minutes, and carrying out ultrasonic treatment for 30 minutes to form uniform suspension;
(6) dropwise adding potassium hydroxide solution into the suspension until the pH value of the solution reaches 10; transferring into a solid-liquid phase microwave synthesizer with the power of 800W, reacting for 3 minutes, and naturally cooling to room temperature; and (3) carrying out suction filtration, repeatedly washing the sample with ethanol and deionized water for at least 3 times, and vacuum drying at 60 ℃ overnight to obtain the catalyst with palladium nano particles loaded in the cerium oxide catalyst carrier.
Comparative example 4
A catalyst, the preparation of which comprises the steps of:
(5) 30mg of the cerium trifluoride catalyst carrier prepared in comparative example 2 was added to 50 ml of an ethylene glycol solution, followed by 333. Mu.l of an aqueous solution of chloropalladac acid (the content of palladium in the aqueous solution was 30 mg/ml); magnetically stirring for 30 minutes, and carrying out ultrasonic treatment for 30 minutes to form uniform suspension;
(6) dropwise adding potassium hydroxide solution into the suspension until the pH value of the solution reaches 10; transferring into a solid-liquid phase microwave synthesizer with the power of 800W, reacting for 3 minutes, and naturally cooling to room temperature; and (3) carrying out suction filtration, repeatedly washing the sample with ethanol and deionized water for at least 3 times, and drying in vacuum at 60 ℃ overnight to obtain the catalyst with palladium nano particles supported in the cerium trifluoride catalyst carrier.
Comparative example 5
A catalyst, the preparation of which comprises the steps of:
(5) 25mg of the ceria catalyst support prepared in comparative example 1 was added to 50 ml of ethylene glycol solution, followed by addition of 330. Mu.l of an aqueous solution of chloroplatinic acid (the content of platinum in the aqueous solution being 30 mg/ml) and 250. Mu.l of an aqueous solution of ruthenium trichloride (the content of ruthenium in the aqueous solution being 20 mg/ml); magnetically stirring for 30 minutes, and carrying out ultrasonic treatment for 30 minutes to form uniform suspension;
(6) dropwise adding potassium hydroxide solution into the suspension until the pH value of the solution reaches 10; transferring into a solid-liquid phase microwave synthesizer with the power of 800W, reacting for 3 minutes, and naturally cooling to room temperature; and (3) carrying out suction filtration, repeatedly washing the sample with ethanol and deionized water for at least 3 times, and carrying out vacuum drying at 60 ℃ overnight to obtain the catalyst with platinum ruthenium nano particles loaded in the cerium oxide catalyst carrier.
Comparative example 6
A catalyst, the preparation of which comprises the steps of:
(5) 25mg of the cerium trifluoride catalyst carrier prepared in comparative example 2 was added to 50 ml of ethylene glycol solution, followed by addition of 330. Mu.l of an aqueous solution of chloroplatinic acid (the content of platinum in the aqueous solution was 30 mg/ml) and 250. Mu.l of an aqueous solution of ruthenium trichloride (the content of ruthenium in the aqueous solution was 20 mg/ml); magnetically stirring for 30 minutes, and carrying out ultrasonic treatment for 30 minutes to form uniform suspension;
(6) dropwise adding potassium hydroxide solution into the suspension until the pH value of the solution reaches 10; transferring into a solid-liquid phase microwave synthesizer with the power of 800W, reacting for 3 minutes, and naturally cooling to room temperature; and (3) carrying out suction filtration, repeatedly washing the sample with ethanol and deionized water for at least 3 times, and carrying out vacuum drying at 60 ℃ overnight to obtain the catalyst with platinum ruthenium nano particles supported in the cerium trifluoride catalyst carrier.
Further, to verify the advancement of the examples of the present application, the following performance tests were performed on the examples and comparative examples, respectively:
1. the catalyst supports prepared in example 1 and comparative examples 1 and 2 were subjected to an X-ray diffraction test and a transmission electron microscope test, respectively; the XRD pattern is shown in figure 1, and the TEM pattern is shown in figure 2.
As can be seen from fig. 1 and 2, the ceria nanorods prepared in example 1 of the present application and the ceria catalyst support prepared in comparative example 1 are pure phase ceria, and have a width of about 10nm and a length of several hundred nm. Comparative example 2 the cerium trifluoride catalyst carrier obtained by complete fluorination exhibited irregular particles with a particle diameter of about 30 nm. Whereas the catalyst support comprising ceria and cerium trifluoride obtained after the partial fluorination treatment of example 1 exhibited particles of different particle sizes, XRD contained diffraction peaks belonging to both ceria and cerium trifluoride.
2. The noble metal-supported catalysts prepared in example 2, comparative examples 3 and 4 were respectively subjected to X-ray diffraction test, and XRD patterns are shown in fig. 3; and transmission electron microscopy test was performed on example 2, and a TEM image is shown in fig. 4.
As can be seen from fig. 3 and 4, the diffraction peaks of cerium oxide and cerium trifluoride in the XRD pattern were reduced, and the average particle size of the material particles was increased, indicating that example 2 successfully supported palladium nanoparticles. The palladium nanoparticles were uniformly dispersed on the surface of the mixture of cerium oxide and cerium trifluoride as seen by TEM images.
3. The noble metal-supported catalysts prepared in example 3, comparative examples 5 and 6 were respectively subjected to X-ray diffraction test, and XRD patterns are shown in fig. 5; and transmission electron microscopy test was performed on example 3, and a TEM image is shown in fig. 6.
As can be seen from fig. 5 and 6, the diffraction peaks of the cerium oxide and cerium trifluoride in the XRD pattern were reduced, and the average particle diameter of the material particles was increased, which indicates that the platinum ruthenium nanoparticles were successfully supported on the cerium oxide and cerium trifluoride catalyst supports of example 3. It can be seen from the TEM image that the platinum ruthenium nanoparticles are uniformly dispersed on the surface of the mixture of ceria and cerium trifluoride.
4. The supported palladium nanoparticle catalysts prepared in example 2, comparative examples 3 and 4 were applied to catalytic formic acid oxidation:
4 mg of the supported palladium nanoparticle catalyst prepared in example 2, comparative examples 3 and 4 and 1 mg of carbon black were added to 950. Mu.l of ethanol and 50. Mu.l of Nafion mixed solution, respectively, and dispersed uniformly by ultrasonic. 10 microliters of the mixed solution is dripped on the surface of a glassy carbon electrode to serve as a working electrode, a carbon rod serves as a counter electrode, a Saturated Calomel Electrode (SCE) serves as a reference electrode, the mixed solution is placed in a sulfuric acid mixed solution containing 0.5mol/L formic acid and 0.5mol/L sulfuric acid, cyclic voltammetry is adopted to carry out cyclic voltammetry scanning between-0.2 and 1V at a scanning speed of 50mV/s, and constant current timing test is carried out for 1 hour under the potential of 0.1V.
The test results are shown in FIG. 7, and FIG. 7 shows a cyclic voltammogram (a) and a chronoamperometric test curve (b) in a mixed solution of 0.5mol/L formic acid and 0.5mol/L sulfuric acid, respectively, for a palladium-on-carbon catalyst (commercial comparative example), a comparative example 3 cerium oxide-supported palladium nanoparticle catalyst, a comparative example 4 cerium trifluoride-supported platinum ruthenium nanoparticle catalyst, and example 2 cerium oxide and cerium trifluoride-supported palladium nanoparticle catalyst. As can be seen from fig. 7, the palladium nanoparticle catalyst supported on the ceria and cerium trifluoride carrier prepared in example 2 of the present application has higher catalytic activity and stability in catalyzing formic acid oxidation reaction, compared to the commercial palladium carbon catalyst and the pure ceria supported palladium nanoparticle catalyst of comparative example 3 and the pure cerium trifluoride supported platinum ruthenium nanoparticle catalyst of comparative example 4.
5. The supported platinum ruthenium nanoparticle catalysts prepared in example 3, comparative examples 5 and 6 were applied to catalytic acid electrolyte methanol oxidation:
4 mg of the supported platinum ruthenium nanoparticle catalyst prepared in example 3, comparative examples 5 and 6 and 1 mg of carbon black were added to 950. Mu.l of ethanol and 50. Mu.l of Nafion mixed solution, respectively, and dispersed uniformly by ultrasonic. And (3) dropwise adding 10 microliters of the mixed solution onto the surface of a glassy carbon electrode to serve as a working electrode, a carbon rod to serve as a counter electrode, and a Saturated Calomel Electrode (SCE) to serve as a reference electrode, placing the mixed solution into a sulfuric acid mixed solution containing 1mol/L of methanol and 0.5mol/L of sulfuric acid, performing cyclic voltammetry scanning between-0.2 and 1V at a scanning speed of 50mV/s, and performing constant current timing test for 2 hours at a potential of 0.5V.
The test results are shown in FIG. 8, which is a cyclic voltammogram (a) and a chronoamperometric test curve (b) in a mixed solution of 1mol/L methanol and 0.5mol/L sulfuric acid for a commercial platinum ruthenium-carbon catalyst (commercial comparative example), a comparative example 5 cerium oxide-supported platinum ruthenium nanoparticle catalyst, a comparative example 6 cerium trifluoride-supported platinum ruthenium nanoparticle catalyst, a catalyst of example 3 cerium oxide and cerium trifluoride support-supported platinum ruthenium nanoparticle. As can be seen from fig. 8, the catalyst of cerium oxide and cerium trifluoride carrier supported platinum ruthenium nanoparticle prepared in example 3 of the present application also has higher catalytic activity and stability in catalyzing acidic methanol oxidation reaction, compared to the commercial platinum ruthenium carbon catalyst, the comparative example 5 cerium oxide supported platinum ruthenium nanoparticle catalyst and the comparative example 6 cerium trifluoride supported platinum ruthenium nanoparticle catalyst.
The foregoing description of the preferred embodiments of the present application is not intended to be limiting, but is intended to cover any and all modifications, equivalents, and alternatives falling within the spirit and principles of the present application.
Claims (9)
1. A method for preparing a catalyst support, comprising the steps of:
preparing cerium oxide nano material;
the mass ratio is (1-2): the cerium dioxide nano material and fluoride in the steps (1-5) are separated and are simultaneously placed in an inert atmosphere for thermal reaction, the fluoride is heated and decomposed to generate hydrogen fluoride gas to carry out etching fluorination treatment on the cerium dioxide nano material, the cerium dioxide nano material is continuously etched and broken in the etching fluorination treatment process to generate cerium trifluoride, and a catalyst carrier is obtained through incomplete fluorination, wherein the catalyst carrier comprises cerium dioxide and cerium trifluoride.
2. The method for preparing a catalyst carrier according to claim 1, wherein the conditions of the thermal reaction include: reacting for 1-3 hours in an inert atmosphere with the temperature of 200-300 ℃;
and/or the fluoride is at least one selected from ammonium fluoride, N-diisopropylethylamine tri-hydrofluoric acid salt, difluoromethyl triflate, hydrogen urea fluoride and iodine pentafluoride.
3. The method for preparing a catalyst support according to any one of claims 1 to 2, wherein the step of preparing the ceria nanomaterial comprises:
mixing a solution containing a cerium compound with an alkali liquor, performing hydrothermal reaction, and separating to obtain a hydrothermal product;
and calcining the hydrothermal product to obtain the cerium dioxide nano rod.
4. The method for preparing a catalyst carrier according to claim 3, wherein the molar ratio of the cerium-containing compound to the alkaline substance in the alkaline solution is 1: (50-100);
and/or, the step of mixing the solution of the cerium-containing compound with the lye comprises: dropwise adding the alkali liquor into the solution of the cerium-containing compound, and then mixing for 30-60 minutes;
and/or, the hydrothermal reaction conditions include: reacting for 15-30 hours at the temperature of 80-120 ℃;
and/or, the conditions of the calcination treatment include: reacting for 2-4 hours at 400-600 ℃.
5. The method for preparing a catalyst carrier according to claim 4, wherein the diameter of the ceria nanorods is 13 to 30nm and the length thereof is 100 to 500nm;
and/or, the cerium-containing compound is selected from: at least one of cerium nitrate, cerium chloride, cerium acetate and cerium sulfate;
and/or, the alkaline substance in the alkali liquor is selected from the group consisting of: at least one of sodium hydroxide and potassium hydroxide.
6. A catalyst support prepared by the method of any one of claims 1 to 5, comprising ceria and cerium trifluoride.
7. The catalyst carrier according to claim 6, wherein in the catalyst carrier, a mass ratio of the ceria to the cerium trifluoride is (0.8 to 1): 1.
8. a catalyst, characterized in that the catalyst comprises the catalyst carrier according to claim 6 or 7 and a catalyst supported in the catalyst carrier.
9. A fuel cell comprising the catalyst according to claim 8.
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