CN116632258A - Batch controllable preparation method of high-dispersion low-platinum alloy catalyst - Google Patents
Batch controllable preparation method of high-dispersion low-platinum alloy catalyst Download PDFInfo
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- CN116632258A CN116632258A CN202310334286.6A CN202310334286A CN116632258A CN 116632258 A CN116632258 A CN 116632258A CN 202310334286 A CN202310334286 A CN 202310334286A CN 116632258 A CN116632258 A CN 116632258A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 104
- 239000006185 dispersion Substances 0.000 title claims abstract description 100
- 238000002360 preparation method Methods 0.000 title claims abstract description 47
- 229910001260 Pt alloy Inorganic materials 0.000 title claims abstract description 34
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 160
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 125
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 95
- 238000010438 heat treatment Methods 0.000 claims abstract description 75
- 239000002245 particle Substances 0.000 claims abstract description 62
- 238000000498 ball milling Methods 0.000 claims abstract description 60
- 238000003756 stirring Methods 0.000 claims abstract description 50
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 42
- 238000009826 distribution Methods 0.000 claims abstract description 29
- 230000008569 process Effects 0.000 claims abstract description 26
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 238000012544 monitoring process Methods 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims description 69
- 239000000243 solution Substances 0.000 claims description 60
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- 239000000843 powder Substances 0.000 claims description 44
- 239000007788 liquid Substances 0.000 claims description 41
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 claims description 32
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- 238000004140 cleaning Methods 0.000 claims description 23
- 238000001816 cooling Methods 0.000 claims description 22
- 239000002131 composite material Substances 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- 239000012298 atmosphere Substances 0.000 claims description 15
- 239000006229 carbon black Substances 0.000 claims description 15
- 238000012216 screening Methods 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 238000001291 vacuum drying Methods 0.000 claims description 11
- 238000001514 detection method Methods 0.000 claims description 10
- 235000019441 ethanol Nutrition 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 230000007704 transition Effects 0.000 claims description 10
- 229910052723 transition metal Inorganic materials 0.000 claims description 10
- 150000003624 transition metals Chemical class 0.000 claims description 10
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- 239000002270 dispersing agent Substances 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- 239000012266 salt solution Substances 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 239000002041 carbon nanotube Substances 0.000 claims description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 4
- LDMNYTKHBHFXNG-UHFFFAOYSA-H disodium;platinum(4+);hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Na+].[Na+].[Pt+4] LDMNYTKHBHFXNG-UHFFFAOYSA-H 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 230000002572 peristaltic effect Effects 0.000 claims description 4
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000007873 sieving Methods 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- NOWPEMKUZKNSGG-UHFFFAOYSA-N azane;platinum(2+) Chemical compound N.N.N.N.[Pt+2] NOWPEMKUZKNSGG-UHFFFAOYSA-N 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 238000013461 design Methods 0.000 abstract description 23
- 239000002002 slurry Substances 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 9
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- 238000004062 sedimentation Methods 0.000 description 16
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 13
- 229910021641 deionized water Inorganic materials 0.000 description 13
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 6
- 239000000956 alloy Substances 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 229910002837 PtCo Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000000265 homogenisation Methods 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 239000011163 secondary particle Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910001339 C alloy Inorganic materials 0.000 description 3
- 229940011182 cobalt acetate Drugs 0.000 description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 238000009775 high-speed stirring Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- FXXMDJFRMDVSCF-RXSVEWSESA-N (2r)-2-[(1s)-1,2-dihydroxyethyl]-3,4-dihydroxy-2h-furan-5-one;hydrate Chemical compound O.OC[C@H](O)[C@H]1OC(=O)C(O)=C1O FXXMDJFRMDVSCF-RXSVEWSESA-N 0.000 description 1
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- CLBRCZAHAHECKY-UHFFFAOYSA-N [Co].[Pt] Chemical compound [Co].[Pt] CLBRCZAHAHECKY-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 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
-
- 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
- H01M4/921—Alloys or mixtures with metallic elements
-
- 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)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Catalysts (AREA)
- Inert Electrodes (AREA)
Abstract
The application provides a batch controllable preparation method of a high-dispersion low-platinum alloy catalyst, which comprises the following steps: firstly, preliminary crushing and high-solid-content dispersion of carbon powder are carried out through step-by-step wet ball milling; then transferring the carbon carrier slurry into stirring equipment, and successfully realizing kilogram-level dispersion of the carbon carrier by multi-step homogenate design and on-line monitoring of viscosity and particle size distribution of the carbon carrier slurry, and monitoring and solving the problems of uneven mixing and local particle agglomeration of the carbon carrier slurry in real time; secondly, the platinum source solution feeding process design with the temperature higher than hundred liters is adopted, and the temperature rising design of respective heating and mixed heating is adopted for different materials, so that the problem of poor consistency of a local concentration field and a temperature field of the catalyst reaction materials is remarkably solved; thirdly, the technological process design can monitor and accurately control corresponding reaction parameters in real time, a structural design of high dispersion of catalyst particles on a carbon carrier is constructed, and consistency of kilogram-level preparation of the platinum alloy catalyst is realized.
Description
Technical Field
The application belongs to the technical field of nano powder preparation and fuel cell catalysts, and particularly relates to a batch controllable preparation method of a high-dispersion low-platinum alloy catalyst.
Background
The fuel cell catalyst mainly comprises platinum-based noble metal catalyst particles and a carbon carrier. For batch preparation of catalysts, whether platinum-based noble metal particles can be highly dispersed on the surface of a support is a key factor in batch preparation of catalysts. In many fuel catalyst preparation patents and literature reports, the laboratory pilot stage of gram-scale platinum carbon or platinum alloy catalysis is often involved, the batch preparation process of catalyst hundred gram/kilogram level is not basically involved, and particularly the problems of dispersion consistency of batch carbon carriers, local concentration difference of reactants, local temperature difference of a reactor, temperature rising rate control of batch solvents and the like are not well solved. The batch preparation process parameters specifically relate to the type of carbon carrier, the reaction temperature, the reaction time, the mixing mode, the feeding mode, the drying mode, the heat treatment equipment, the real-time monitoring of the process parameters and the like.
At present, the commonly used carbon carriers mainly comprise carbon black, carbon nano tubes, active carbon and the like. For the carbon black support used primarily, its primary particles are typically below 100nm, but the primary particles are typically connected to one another to form the morphology of the secondary particles. Therefore, the difference in the secondary particle structure and the surface properties of the carbon support affects the dispersion state and the interaction of the noble metal particles during the catalyst preparation process. In particular, dispersion and state evaluation of carbon powder of hundred gram/kg level in a solution has become one of the keys of controllable preparation of catalysts in batches.
In view of the above, the application mainly aims to solve the problem of dispersion of kilogram-level carbon powder as a break-through, and provides a batch controllable preparation method of a high-dispersion low-platinum alloy catalyst from the viewpoints of breaking, surface modification, uniform dispersion and state evaluation of the carbon powder, corresponding reaction parameters are monitored and accurately controlled in real time through the design of a technological process, and the structural design of high dispersion of catalyst particles on a carbon carrier is constructed, so that the consistency of kilogram-level preparation of a platinum-based catalyst is realized.
Disclosure of Invention
The application provides a batch controllable preparation method of a high-dispersion low-platinum alloy catalyst, which comprises the following steps: firstly, solving the problem of difficult dispersion of heck-level/kilogram-level carbon powder by adopting a sectional type homogenizing process, and firstly, finishing preliminary crushing and high-solid-content dispersion of the carbon powder by step-by-step wet ball milling; then transferring the carbon carrier slurry into high-speed stirring equipment, and monitoring and solving the problems of uneven internal mixing and local particle agglomeration of the carbon carrier slurry in real time through multi-step homogenization mode design and on-line monitoring of the viscosity and the particle size distribution of the carbon carrier slurry, so that kilogram-level dispersion of the carbon carrier is successfully realized; secondly, on the basis of kilogram-level dispersion of the carbon carrier, a platinum source solution feeding process design with more than hundred liters is adopted, and a heating design of heating and mixing heating is adopted for different materials, so that the problem of poor consistency of a local concentration field and a temperature field of a catalyst reaction material is remarkably solved; thirdly, the technological process design can monitor and accurately control corresponding reaction parameters in real time, a structural design of high dispersion of catalyst particles on a carbon carrier is constructed, and consistency of kilogram-level preparation of the platinum alloy catalyst is realized.
The aim of the application is realized by the following technical scheme:
in a first aspect, the present application provides a batch controllable preparation method of a high dispersion low platinum alloy catalyst, comprising the steps of:
(1) Mixing carbon powder and a first solvent for ball milling, performing primary dispersion on the carbon powder, adding the first solvent or a dispersing agent in batches, and continuing ball milling to form a carbon carrier dispersion liquid;
(2) Transferring the carbon carrier dispersion liquid into a reactor, adding a dilute acid solution, uniformly stirring, monitoring the particle size and particle size distribution of the carbon carrier in real time, and obtaining the carbon carrier suspension liquid after the particle size distribution detection value is in a proper range;
(3) Slowly adding the platinum source solution into the carbon carrier suspension which is preheated and kept at the temperature under stirring, and heating and keeping the temperature of the reactor for a period of time; then cooling and settling, and then cleaning to obtain a mixture; the platinum source solution is prepared from at least one of chloroplatinic acid, sodium chloroplatinate, potassium chloroplatinate, sodium hexahydroxyplatinate, tetraamineplatinum acetate and platinum nitrate;
(4) Vacuum drying the mixture obtained in the step (3) to obtain mixture powder; then carrying out heat treatment on the mixture powder, ball milling, screening and obtaining a platinum-carbon catalyst;
(5) Mixing a platinum carbon catalyst with a second solvent, and dispersing to obtain a platinum carbon catalyst dispersion; adding a transition metal salt solution into the platinum-carbon catalyst dispersion liquid, heating, drying and ball milling to obtain transition metal-platinum-carbon catalyst powder;
(6) Heat treating transition metal-platinum carbon catalyst powder to obtain a composite material; dealloying the composite material, filtering, drying, ball milling and sieving to obtain the high-dispersion low-platinum alloy catalyst.
The step (1) comprises the following steps:
mixing carbon powder with a first solvent, ball milling for 2-36 hours at a rotating speed of 50-400rpm, and primarily dispersing the carbon powder; then adding the first solvent or dispersing agent in batches, continuously ball milling for 1-36 hours at a rotating speed of 100-500rpm, and adjusting the viscosity to 50-20000mpas to form the carbon carrier dispersion liquid with high solid content.
The carbon powder is at least one of carbon black, conductive graphite, active carbon, carbon fiber, carbon nanotube, graphene and mesoporous carbon;
the first solvent comprises at least one of water, ethanol, isopropanol, acetone, dimethyl sulfoxide, N-methyl dipyrrolidone and N, N-dimethylformamide;
the dispersing agent comprises one or more of ethylene glycol, propylene glycol, glycerol, polyethylene glycol, polyacrylic acid, acrylonitrile, polyvinyl alcohol, polyvinylpyrrolidone and carboxymethyl cellulose.
The step (2) comprises the following steps:
transferring the carbon carrier dispersion liquid into a reactor with stirring and heating constant temperature functions, adding a dilute acid solution, and stirring for 0.5-24 hours at 50-1000rpm to prepare a carbon carrier primary suspension; continuously stirring the primary suspension of the carbon carrier at a rotating speed of 50-500rpm, preheating and preserving heat at 30-60 ℃ for 1-12 h, simultaneously monitoring the particle size and the particle size distribution of the carbon carrier in real time, and obtaining the suspension of the carbon carrier when the detected value of the particle size distribution respectively meets D10<200nm, D50<500nm and D90<5000 nm;
wherein the reactor comprises at least one of a jacketed heating reaction kettle, a high-capacity heat collection type stirring device system, a microwave chemical reactor and other high-capacity vessels.
The step (3) is specifically as follows:
preparing a solution containing a platinum source, and slowly adding the platinum source solution into the preheated and heat-preserving carbon carrier suspension at a speed of 10ml/min-900ml/min through a peristaltic pump at a continuous rotating speed of 50-500 rpm; after the platinum source solution is completely added, heating the reactor to 70-120 ℃, preserving heat for 2-12 h, stopping stirring and heating, cooling and settling to obtain a mixture; the temperature inside the reactor is monitored in real time in the heating process, and the temperature difference between the central temperature and each point position close to the inner wall of the reactor is controlled to be +/-2-5 ℃; in the heat preservation process, the temperature difference between the center temperature and each point position close to the inner wall of the reactor is controlled to be +/-1-5 ℃.
The step (4) is specifically as follows: vacuum drying the mixture obtained in the step (3) at 50-100 ℃ for 3-48 h to obtain mixture powder; and then placing the mixture powder in a heat treatment device for heat treatment for 1-12 h under the hydrogen atmosphere, wherein the gas flow rate is 0.1L/min-10L/min, and then carrying out circulating water cooling, ball milling and 50-200 mesh vibration screening to obtain the platinum-carbon catalyst.
The step (5) comprises the following steps: dispersing the platinum-carbon catalyst and the second solvent in a mode of combining ball milling and stirring, firstly ball milling for 1h to 24h at a rotating speed of 50rpm to 400rpm, and stirring for 1h to 24h at a rotating speed of 50rpm to 1000rpm to obtain platinum-carbon catalyst dispersion liquid; adding a transition metal salt solution into a platinum-carbon catalyst dispersion liquid, heating at 30-100 ℃ for 1-24 h, then drying at 60-120 ℃ for 6-72 h, and ball milling at a rotating speed of 10-500rpm for 0.5-12 h to obtain transition metal-platinum-carbon catalyst powder;
the second solvent comprises at least one of water, ethanol, isopropanol, acetone, dimethyl sulfoxide, N-methyl dipyrrolidone, and N, N-dimethylformamide.
The transition metal comprises at least one of cobalt, nickel, manganese, iron, copper, palladium, iridium and ruthenium; in the transition metal-platinum carbon catalyst powder, the atomic ratio of transition metal to platinum is 1:1-10. The step (6) is specifically as follows: transferring the transition metal-platinum carbon catalyst powder into a heat treatment device, and performing heat treatment for 1-12 h at 400-1100 ℃ in a mixed atmosphere of 5% -50% hydrogen and argon, wherein the gas flow rate is 0.1-10L/min, so as to obtain a composite material; the composite material J is arranged at a temperature of between 0.1 and 2MHNO 3 Dealloying for 2-72 h at 50-80 ℃ in the solution, filtering, drying, ball milling and vibrating and sieving with 50-200 meshes to obtain the high-dispersion low-platinum alloy catalyst.
The high-dispersion low-platinum alloy catalyst prepared by the preparation method belongs to the protection scope of the application.
As an embodiment of the present application, the batch controllable preparation method of the high dispersion low platinum alloy catalyst comprises the following steps:
(1) Mixing carbon powder with a first solvent for ball milling, performing primary dispersion on the carbon powder, adding the first solvent or the dispersant mixed solution in batches, continuing ball milling, and adjusting the viscosity to 50-20000mpas to form a carbon carrier dispersion liquid A;
(2) Transferring the carbon carrier dispersion liquid A to a reactor (with the volume of 5L-500L), adding a dilute acid solution, and stirring to obtain a carbon carrier suspension liquid B;
(3) Continuously stirring the carbon carrier suspension B, and preheating and preserving heat; simultaneously, the particle size and the particle size distribution of the carbon carrier are monitored in real time; after the particle size distribution detection value is in a proper range, obtaining a suspension C of the carbon carrier; sampling in time, and visually measuring the dispersion stability of carbon powder according to the observation of the sedimentation speed of particles by combining a sampling sedimentation method;
(4) Preparing a platinum source solution D, and slowly adding the platinum source solution D into the preheated and heat-preserving carbon carrier suspension C at a continuous rotating speed of 50-500 rpm; the platinum source solution D is a solution prepared from at least one of chloroplatinic acid, sodium chloroplatinate, potassium chloroplatinate, sodium hexahydroxyplatinate, tetraamineplatinum acetate and platinum nitrate; (5) After the platinum source solution D is completely added, the temperature of the reactor is continuously raised to 70-120 ℃, the temperature is kept for 2-12 hours, stirring and heating are stopped, cooling and sedimentation are carried out, and the reactor is transferred into dispersing, cleaning, redispersing and cleaning integrated circulating equipment for rapid cleaning and collecting treatment, thus obtaining a mixture E;
(6) Vacuum drying the mixture E in the step (5) to obtain mixture powder F; then carrying out heat treatment on the mixture powder F, and carrying out circulating water cooling, ball milling and vibration screening to obtain a platinum-carbon catalyst G;
(7) Mixing a platinum carbon catalyst G with a second solvent, and dispersing in a ball milling and stirring combined mode to obtain a dispersion liquid H;
(8) Adding a stoichiometric calculated transition metal salt solution to dispersion H, the atomic ratio of transition metal to platinum being 1: (1-10), heating at 25-100 ℃ for 1-24 h; and then drying and ball milling to obtain the catalyst powder I.
(9) Transferring the catalyst powder I into a heat treatment device, and performing heat treatment under a hydrogen-argon mixed atmosphere to obtain a composite material J;
(10) And (3) dealloying the composite material J, filtering, drying, ball milling and vibrating and screening to obtain the alloy catalyst K.
Compared with the prior art, the application has the following beneficial effects:
1. the application develops a batch controllable preparation method of a high-dispersion low-platinum alloy catalyst, firstly, a sectional type homogenization process design is provided, the problem of difficult dispersion of hundred-gram-level/kilogram-level carbon powder is solved, and preliminary crushing and high-solid-content dispersion of the carbon powder are completed through step-by-step wet ball milling; then transferring the carbon carrier slurry into high-speed stirring equipment, and monitoring and solving the problems of uneven internal mixing and local particle agglomeration of the carbon carrier slurry in real time through multi-step homogenization mode design and on-line monitoring of the viscosity and the particle size distribution of the carbon carrier slurry, so that kilogram-level dispersion of the carbon carrier is successfully realized;
2. the application adopts the design of the feeding process of platinum source solution with the concentration of hundreds of liters on the basis of the kilogram level dispersion of the carbon carrier, and adopts the design of heating up by heating and mixing the materials respectively, thereby remarkably solving the problem of poor consistency of the local concentration field and the temperature field of the catalyst reaction materials.
In summary, the technical process design can monitor and accurately control corresponding reaction parameters in real time, a structural design of high dispersion of catalyst particles on a carbon carrier is constructed, and consistency of kilogram-level preparation of the platinum alloy catalyst is realized.
Drawings
Other features, objects and advantages of the present application will become more apparent upon reading of the detailed description of non-limiting embodiments, given with reference to the accompanying drawings in which:
FIG. 1 is a TEM photograph of the PtCo/C alloy catalyst obtained in example 1 of the present application;
FIG. 2 is a TEM photograph of the Pt/C catalyst prepared in example 2 of the present application;
FIG. 3 is a TEM photograph of the PtCo/C catalyst obtained in example 4 of the present application.
Detailed Description
The present application will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the present application, but are not intended to limit the application in any way. It should be noted that variations and modifications could be made by those skilled in the art without departing from the inventive concept. These are all within the scope of the present application.
Example 1
The batch controllable preparation method of the high-dispersion low-platinum alloy catalyst comprises the following steps:
(1) Weighing 500g of carbon black and deionized water with the volume of 3L, ball milling for 12 hours at the rotating speed of 120rpm by a horizontal ball mill, and primarily dispersing the carbon black; then adding mixed solution of ethanol with the volume of 2L and deionized water with the volume of 3L in batches, continuously ball-milling for 12 hours at the rotating speed of 200rpm, and adjusting the viscosity to 5000mpas by a viscometer to form carbon carrier dispersion liquid A with higher solid content;
(2) Transferring the carbon carrier dispersion liquid A into a reactor (with the volume of 100L) with the functions of stirring and heating at constant temperature, adding 20L of dilute nitric acid solution, and stirring at the speed of 200rpm for 6 hours at room temperature to prepare a carbon carrier suspension liquid B;
(3) Continuously stirring the carbon carrier suspension B at a rotating speed of 200rpm, and preheating and preserving heat for 3 hours at 60 ℃; meanwhile, monitoring the particle size and particle size distribution (D10, D50 and D90) of the carbon carrier in real time by a nano particle size analyzer, and obtaining a suspension C of the carbon carrier after the particle size distribution detection values D10<200nm, D50<500nm and D90<5000 nm; then, sampling in time, and visually measuring the dispersion stability of the carbon powder according to the observation of the sedimentation speed of the particles by combining a sampling sedimentation method;
(4) Preparing a platinum source solution D of 2.56mol of chloroplatinic acid and 0.26mol of sodium hydroxide (the molar concentrations of the chloroplatinic acid and the sodium hydroxide are 0.256mol/L and 0.026mol/L respectively), and slowly adding the platinum source solution D into the preheated and insulated carbon carrier suspension C at a speed of 80ml/min through a peristaltic pump at a continuous rotating speed of 200rpm so as to prevent splashing, wall hanging and the like in the adding process of the platinum source solution;
(5) After the platinum source solution D is completely added, the temperature of the reactor is continuously raised for 2 to 90 ℃ and kept for 8 hours, stirring and heating are stopped, and after cooling and sedimentation, a mixture is obtained; the temperature inside the reactor is monitored in real time in the heating process, and the temperature difference between the central temperature and each point position close to the inner wall of the reactor cannot exceed +/-2 ℃; in the heat preservation process, the temperature difference between the center temperature and each point position close to the inner wall of the reactor cannot exceed +/-2 ℃, and if the temperature difference exceeds the temperature difference range, a special temperature alarm device configured in the reactor gives a prompt;
transferring the obtained mixture into dispersing, cleaning, redispersing and cleaning integrated circulation equipment for rapid cleaning and collecting treatment, and limiting the treatment of the mixture to be completed within 24 hours to prepare a mixture E;
(6) Vacuum drying the mixture E in the step (5) at 80 ℃ for 24 hours to obtain mixture powder F; then placing the mixture powder F in a box-type furnace with the volume of 200L, carrying out heat treatment for 6 hours at the temperature of 300 ℃ in a hydrogen atmosphere, wherein the gas flow rate is 0.5L/min, and carrying out circulating water cooling, planetary ball milling, 200-mesh vibration screening and weighing to obtain a platinum carbon catalyst G;
(7) Taking 500G of platinum carbon catalyst G and 5L of deionized water and ethanol mixed solution (the volume ratio of water to ethanol is 1:1), dispersing by a ball milling and stirring combined mode, firstly ball milling for 12 hours at a rotating speed of 120rpm, and stirring for 12 hours at a rotating speed of 200rpm to obtain 30L of dispersion liquid H;
(8) Adding a cobalt nitrate solution (volume is 15L, atomic ratio Pt: co=4.5:1) with calculated stoichiometric ratio into the dispersion liquid H to disperse, and starting heating at 90 ℃ for 12H; then transferring the mixture into an oven to dry for 12 hours at 60 ℃, and performing planetary ball milling treatment for 3 hours at a rotating speed of 50rpm to obtain catalyst powder I;
(9) The catalyst powder I was transferred to a box furnace having a volume of 50L and heat-treated at 900℃for 6 hours under a mixed atmosphere of 30% hydrogen and argon at a gas flow rate of 0.8L/min to obtain a composite material J.
(10) The composite J is then continued at 1M HNO 3 Dealloying in the solution at 80 ℃ for 24 hours, filtering, drying, ball milling and 100-mesh vibration screening to obtain the alloy catalyst K.
FIG. 1 is a TEM photograph of the PtCo/C alloy catalyst prepared in example 1 of the present application, and it is evident that platinum cobalt alloy particles are uniformly dispersed on the surface of a carbon support, and the average particle diameter is 3.5-4nm. The particle size distribution results of the carbon support suspension B in example 1 are shown in table 1, and the carbon support particles are highly dispersed to achieve the intended effect.
Example 2
The batch controllable preparation method of the high-dispersion low-platinum alloy catalyst comprises the following steps:
(1) Weighing 180g of carbon black, 20g of carbon nanotube mixture, and a mixed solution of deionized water with the volume of 1L and ethanol with the volume of 0.5L, ball milling for 8 hours at the rotating speed of 150rpm by a planetary ball mill, and primarily dispersing the carbon black; then adding polyethylene glycol aqueous solution with the volume of 2L (the mass ratio of the dispersing agent to the carbon powder is 0-2:1000) in batches, continuously ball-milling for 12 hours at the rotating speed of 150rpm, and adjusting the viscosity to 2000mpas by a viscometer to form carbon carrier dispersion liquid A with higher solid content;
(2) Transferring the carbon carrier dispersion liquid A into a high-capacity heat-collecting type stirring device system, adding 10L of dilute hydrochloric acid solution, and stirring at the room temperature for 9 hours at the speed of 150rpm to prepare a carbon carrier suspension liquid B;
(3) Continuously stirring the carbon carrier suspension B at a rotating speed of 120rpm, and preheating and preserving heat for 3 hours at 50 ℃; meanwhile, monitoring the particle size and particle size distribution (D10, D50 and D90) of the carbon carrier in real time by a nano particle size analyzer, and obtaining a suspension C of the carbon carrier after the particle size distribution detection values D10<200nm, D50<500nm and D90<5000 nm; then, sampling in time, and visually measuring the dispersion stability of the carbon powder according to the observation of the sedimentation speed of the particles by combining a sampling sedimentation method;
(4) Preparing a platinum source solution D containing 1.0mol of chloroplatinic acid and 0.12mol of potassium hydroxide (the molar concentrations of the chloroplatinic acid and the potassium hydroxide are 0.33mol/L and 0.04mol/L respectively), and slowly adding a preheated and insulated carbon carrier suspension C into the platinum source solution D at a speed of 100ml/min through a liquid feeder at a continuous rotation speed of 250rpm so as to prevent splashing, wall hanging and the like existing in the adding process of the carbon carrier suspension C;
(5) After the carbon carrier suspension C is completely added, continuously heating the reactor for 3 hours to 100 ℃, preserving heat for 12 hours, stopping stirring and heating, cooling and settling to obtain a mixture; the temperature inside the reactor is monitored in real time in the heating process, and the temperature difference between the central temperature and each point position close to the inner wall of the reactor cannot exceed +/-5 ℃; in the heat preservation process, the temperature difference between the center temperature and each point position close to the inner wall of the reactor cannot exceed +/-5 ℃, and if the temperature difference exceeds the temperature difference range, a special temperature alarm device configured in the reactor gives a prompt; transferring the obtained mixture into dispersing, cleaning, redispersing and cleaning integrated circulation equipment for rapid cleaning and collecting treatment to obtain the mixture, and completing the treatment of the mixture within 48 hours to prepare a mixture E; (6) Vacuum drying the mixture E in the step (5) at 90 ℃ for 48 hours to obtain mixture powder F; then placing the mixture powder F in a box-type furnace with the volume of 100L, carrying out heat treatment for 6 hours at 400 ℃ in a hydrogen atmosphere, wherein the gas flow rate is 0.6L/min, and carrying out circulating water cooling, planetary ball milling, 200-mesh vibration screening and weighing to obtain a platinum-carbon catalyst G;
(7) 400G of platinum carbon catalyst G and 3L of deionized water and ethanol mixed solution (the volume ratio of water to ethanol is 2:1) are taken, dispersed in a ball milling and stirring combined mode, ball milling is carried out for 24 hours at a rotating speed of 100rpm, and stirring is carried out for 24 hours at a rotating speed of 150rpm, so that 20L of dispersion liquid H is obtained;
(8) Cobalt chloride and manganese chloride solutions (volume 10L, atomic ratio Pt: co: ni=5:0.8:0.2) were added to the above dispersion H in stoichiometric proportions, and heating was started at 100 ℃ for 12H. Then transferring the mixture into an oven to be dried for 24 hours at 80 ℃, and performing planetary ball milling treatment for 2 hours at a rotating speed of 100rpm to obtain catalyst powder I;
(9) The catalyst powder I was transferred to a box furnace having a volume of 100L and heat-treated at 800℃for 12 hours under a mixed atmosphere of 10% hydrogen and argon at a gas flow rate of 1L/min to obtain a composite material J.
(10) The composite J was then continued at 1.5M HNO 3 Dealloying in the solution at 80 ℃ for 12 hours, filtering, drying, ball milling and 100-mesh vibration screening to obtain the alloy catalyst K.
Example 3
The preparation method of the batch controllable preparation method of the high-dispersion platinum-carbon catalyst comprises the following technical steps:
(1) Weighing 50g of carbon black and deionized water with the volume of 2L, treating for 2 hours at the rotating speed of 300rpm through a homogenizing device, and primarily dispersing the carbon black; then adding N-methyl dipyrrolidone with the volume of 0.5L and deionized water with the volume of 0.2L in batches, continuously treating for 2 hours at the rotating speed of 300rpm, and adjusting the viscosity to 1000mpas by a viscometer to form carbon carrier dispersion A with higher solid content;
(2) Transferring the carbon carrier dispersion liquid A into a jacketed heating reaction kettle (with the volume of 20L), adding 5L of mixed solution of dilute nitric acid and dilute sulfuric acid, and stirring at 100rpm for 2 hours at room temperature to prepare carbon carrier suspension liquid B;
(3) The carbon support suspension B was stirred continuously at 100rpm and was kept warm at 45℃for 2 hours with preheating. Meanwhile, the particle size and the particle size distribution (D10, D50, D90) of the carbon support were monitored in real time by a nano-particle sizer. And obtaining the suspension C of the carbon carrier after the particle size distribution detection values D10<200nm, D50<500nm and D90<5000 nm. And then, sampling in time, and visually measuring the dispersion stability of the carbon powder according to the observation of the sedimentation speed of the particles by combining a sampling sedimentation method.
(4) Preparing a mixed aqueous solution D of 0.26mol of sodium hexahydroxy platinate and 0.03mol of sodium carbonate (the molar concentration of the mixed aqueous solution D is 0.09mol/L and 0.01mol/L respectively), and slowly adding the platinum source solution D into the preheated and insulated carbon carrier suspension C at a speed of 60ml/min by a liquid quantitative controller under a continuous rotating speed of 120rpm, wherein the phenomena of splashing, wall hanging and the like in the adding process of the platinum source solution are prevented;
(5) After the platinum source solution D is completely added, the temperature of the reactor is continuously raised to 120 ℃, the temperature is kept for 6 hours, stirring and heating are stopped, and the mixture E is obtained after cooling and sedimentation; the temperature inside the reactor is monitored in real time in the heating process, and the temperature difference between the central temperature and each point position close to the inner wall of the reactor cannot exceed +/-3 ℃; in the heat preservation process, the temperature difference between the center temperature and each point position close to the inner wall of the reactor cannot exceed +/-3 ℃, and if the temperature difference exceeds the temperature difference range, a special temperature alarm device configured in the reactor gives a prompt;
(6) Transferring the obtained mixture E into dispersing, cleaning, redispersing and cleaning integrated circulation equipment for rapid cleaning and collecting, and completing the treatment of the mixture within 24h to obtain the mixture E
(7) Vacuum drying the mixture obtained in the step (6) at 100 ℃ for 48 hours to obtain mixture powder F; then placing the mixture powder F in a box-type furnace with the volume of 40L, carrying out heat treatment for 2 hours at the temperature of 450 ℃ in a hydrogen atmosphere, wherein the gas flow rate is 0.2L/min, and carrying out circulating water cooling, ball milling by a roller mill, vibration screening by 200 meshes and weighing to obtain a platinum carbon catalyst G;
FIG. 2 is a TEM photograph of the Pt/C catalyst prepared in example 2 of the present application, and it is apparent that platinum particles are uniformly dispersed on the surface of a carbon support, and the average particle diameter is 3 to 3.5nm. The particle size distribution results of the carbon support suspension B in example 3 are shown in table 1, and the carbon support particles are highly dispersed to achieve the desired effect.
Example 4
The preparation method of the batch controllable preparation method of the high-dispersion low-platinum alloy catalyst comprises the following technical steps:
(1) 300g of carbon black and deionized water with the volume of 3L are weighed, and are treated for 6 hours at the speed of 1000rpm by a stirrer, so that the carbon black is primarily dispersed; then adding N, N-dimethylformamide with the volume of 0.4L and deionized water with the volume of 0.1L in batches, continuously treating for 6 hours at the speed of 2000rpm, and adjusting the viscosity to 5000mpas by a viscometer to form carbon carrier dispersion A with higher solid content;
(2) Transferring the carbon carrier dispersion liquid A into a jacketed heating reaction kettle (with the volume of 100L), adding 15L of dilute sulfuric acid solution, and stirring at the room temperature for 1h at the speed of 120rpm to prepare a carbon carrier suspension liquid B;
(3) The carbon support suspension B was stirred continuously at 120rpm and was kept at a temperature of 70℃for 1 hour by preheating.
(4) Preparing a mixed aqueous solution D of 1.54mol of potassium chloroplatinate and 0.2mol of ammonia water (the molar concentrations of the potassium chloroplatinate and the ammonia water are respectively 0.385mol/L and 0.05 mol/L), and slowly adding a platinum source solution D into a preheated and heat-preserving carbon carrier suspension C through a long-neck funnel at a speed of 200ml/min under a continuous rotating speed of 200rpm, wherein the phenomena of splashing, wall hanging and the like in the adding process of the platinum source solution are prevented;
(5) After the platinum source solution D is completely added, the temperature of the reactor is continuously raised for 2 to 70 ℃ and kept for 5 hours, stirring and heating are stopped, and after cooling and sedimentation, a mixture E is obtained; the temperature inside the reactor is monitored in real time in the heating process, and the temperature difference between the central temperature and each point position close to the inner wall of the reactor cannot exceed +/-5 ℃; in the heat preservation process, the temperature difference between the center temperature and each point position close to the inner wall of the reactor cannot exceed +/-5 ℃, and if the temperature difference exceeds the temperature difference range, a special temperature alarm device configured in the reactor gives a prompt;
(6) Transferring the obtained mixture E into dispersing, cleaning, redispersing and cleaning integrated circulation equipment for rapid cleaning and collecting, and limiting the treatment of the mixture to be completed within 24 hours to prepare the mixture E;
(7) Vacuum drying the mixture obtained in the step (6) at 120 ℃ for 8 hours to obtain mixture powder F; then placing the mixture powder F in a box-type furnace with the volume of 100L, carrying out heat treatment for 6 hours at the temperature of 350 ℃ in a hydrogen atmosphere, wherein the gas flow rate is 0.8L/min, and carrying out circulating water cooling, planetary ball milling, 200-mesh vibration screening and weighing to obtain a platinum carbon catalyst G;
(8) Taking 500G of platinum carbon catalyst G and 5L of deionized water, dispersing by stirring, firstly treating for 3 hours at 500rpm, and then treating for 3 hours at 2000rpm to obtain 20L of dispersion liquid H;
(9) A cobalt acetate solution (volume 8L, atomic ratio Pt: co=6:1) of calculated stoichiometric ratio was added to the above dispersion H to disperse, and heating at 120 ℃ was started for 5H. Then transferring the mixture into an oven to dry for 12 hours at 60 ℃, and performing planetary ball milling treatment for 2 hours at a rotating speed of 200rpm to obtain catalyst powder I;
(8) The catalyst powder I was transferred to a box furnace having a volume of 40L and heat-treated at 950℃for 3 hours under a mixed atmosphere of 10% hydrogen and argon at a gas flow rate of 0.4L/min to obtain a composite material J.
(9) The composite J was then continued at 0.5M HNO 3 Dealloying in the solution at 60 ℃ for 12 hours, filtering, drying, ball milling and 100-mesh vibration screening to obtain the alloy catalyst K.
FIG. 3 is a TEM photograph of the PtCo/C alloy catalyst obtained in example 4 of the present application;
example 5
The preparation method of the batch controllable preparation method of the high-dispersion low-platinum alloy catalyst comprises the following technical steps:
(1) Weighing 45g of conductive graphite and 5g of graphene composite and 8L of deionized water, ball milling for 3 hours at 200rpm by a planetary ball mill, and primarily dispersing carbon powder; then adding 500ml of acetone in batches, continuously ball-milling for 4 hours at a rotating speed of 100rpm, and adjusting the viscosity to 500mpas by a viscometer to form a carbon carrier dispersion liquid A with higher solid content;
(2) The carbon carrier dispersion A was transferred to a microwave chemical reactor (volume: 10L), and 1L of a diluted hydrochloric acid solution was added thereto, followed by heating at 80℃for 2 hours.
(3) Preparing a mixed aqueous solution D of 0.256mol of chloroplatinic acid and 0.1mol of potassium hydroxide (the molar concentration of the chloroplatinic acid and the potassium hydroxide are respectively 0.256mol/L and 0.1 mol/L), adding the mixed aqueous solution D into a preheated and heat-preserving carbon carrier suspension C, continuously heating the reactor for 0.5 to 120 ℃ and preserving heat for 2 hours, and cooling and settling to obtain a mixture E;
(4) Transferring the obtained mixture E into dispersing, cleaning, redispersing and cleaning integrated circulation equipment for rapid cleaning and collecting, and completing the treatment of the mixture within 24h to obtain the mixture E
(5) Vacuum drying the mixture obtained in the step (6) for 12 hours at 80 ℃ to obtain mixture powder F; then placing the mixture powder F in a box-type furnace with the volume of 40L, carrying out heat treatment for 3 hours at the temperature of 280 ℃ under the hydrogen atmosphere, wherein the gas flow rate is 0.6L/min, and cooling by circulating water to obtain 100G of platinum carbon catalyst G;
(6) Taking 100G of platinum carbon catalyst G, 0.8L deionized water and 0.2L isopropyl alcohol mixed solution, dispersing by an ultrasonic and stirring combined mode, ball milling for 12 hours at a rotating speed of 200rpm, and stirring for 12 hours at a rotating speed of 300rpm to obtain 20L dispersing solution H;
(7) Cobalt acetate and nickel chloride solutions (volume 1L, atomic ratio Pt: co: ni=5:0.9:0.1) were added to the above dispersion H in stoichiometric proportions, and heating was started at 120 ℃ for 6H. Then transferring the mixture into an oven to be dried for 24 hours at 80 ℃, and performing planetary ball milling treatment for 3 hours at a rotating speed of 100rpm to obtain catalyst powder I;
(8) Transferring the catalyst powder I into a box-type furnace with the volume of 50L, and performing heat treatment for 2 hours at 1000 ℃ under a 30% hydrogen-argon mixed atmosphere, wherein the gas flow rate is 1L/min, so as to obtain the composite material J.
(9) The composite J was then continued at 0.3M HNO 3 Dealloying for 72h at 70 ℃ in the solution, filtering, drying and ball milling to obtain the alloy catalyst K.
Example 6
The preparation method of the batch controllable preparation method of the high-dispersion low-platinum alloy catalyst comprises the following technical steps:
(1) Weighing 250g of carbon black and deionized water with the volume of 3L, ball milling for 6 hours at the rotating speed of 200rpm by a horizontal ball mill, and primarily dispersing the carbon black; then adding 500ml of polyacrylic acid aqueous solution (the mass ratio of the dispersing agent to the carbon powder is 0-5:1000) in batches, continuously ball-milling for 6 hours at the rotating speed of 250rpm, and adjusting the viscosity to 2000mpas by a viscometer to form carbon carrier dispersion liquid A with higher solid content;
(2) Transferring the carbon carrier dispersion liquid A into a high-capacity heat-collecting type stirring device system (with the volume of 60L), adding 1L of a mixed solution of dilute nitric acid and dilute sulfuric acid, and stirring at the room temperature for 3 hours at the speed of 250rpm to prepare a carbon carrier suspension liquid B;
(3) The carbon support suspension B was stirred continuously at 250rpm and was kept warm at 45℃for 2 hours with preheating. Meanwhile, the particle size and the particle size distribution (D10, D50, D90) of the carbon support were monitored in real time by a nano-particle sizer. And obtaining the suspension C of the carbon carrier after the particle size distribution detection value is in a proper range. Then, sampling in time, and visually measuring the dispersion stability of the carbon powder according to the observation of the sedimentation speed of the particles by combining a sampling sedimentation method;
(4) Preparing an aqueous solution D of 1.28mol of chloroplatinic acid and 0.3mol of ammonia water (the molar concentration of the chloroplatinic acid and the ammonia water are respectively 0.32mol/L and 0.075 mol/L), and slowly adding the platinum source solution D into the preheated and heat-preserving carbon carrier suspension C at a speed of 100ml/min through a peristaltic pump under a continuous rotating speed of 150rpm, wherein the phenomena of splashing, wall hanging and the like in the adding process of the platinum source solution are prevented;
(5) After the platinum source solution D is completely added, the temperature of the reactor is continuously raised for 2 hours to 100 ℃, the temperature is kept for 6 hours, stirring and heating are stopped, and the mixture E is obtained after cooling and sedimentation; the temperature inside the reactor is monitored in real time in the heating process, and the temperature difference between the central temperature and each point position close to the inner wall of the reactor cannot exceed +/-2 ℃; in the heat preservation process, the temperature difference between the center temperature and each point position close to the inner wall of the reactor cannot exceed +/-2 ℃, and if the temperature difference exceeds the temperature difference range, a special temperature alarm device configured in the reactor gives a prompt;
(6) Cooling the mixture to room temperature, adding diluted ammonia water solution (volume of 0.5L), regulating pH to 5-12, continuously stirring, adding ascorbic acid water solution (volume of 0.5L, chloroplatinic acid: molar mass ratio of corresponding reducing agent=1 (0-20)), preserving heat at 25-150 ℃ for 1-24 h, standing for ageing, dispersing, cleaning, redispersing, cleaning again, performing rapid cleaning and collecting treatment in integrated circulation equipment, and dehydrating to obtain a platinum-carbon catalyst material G containing water after the pH value is 6-10;
(7) Dispersing the platinum carbon catalyst G and a mixed solution of 2.5L of ionized water and 2.5L of isopropanol by high-speed stirring, and firstly, treating at 1200rpm for 12 hours to obtain 20L of dispersion liquid H;
(9) Cobalt acetate and manganese acetate solutions (volume: 2L, atomic ratio Pt: co=5:0.8:0.2) in the stoichiometric ratio were added to the dispersion H and dispersed therein, and heating was started at 100 ℃ for 8 hours. Then transferring the mixture into an oven to be dried for 24 hours at 80 ℃ to obtain catalyst powder I;
(8) The catalyst powder I was transferred to a box furnace having a volume of 100L and heat-treated at 850℃for 8 hours under a mixed atmosphere of 20% hydrogen and argon at a gas flow rate of 1L/min to obtain a composite material J.
(9) The composite J is then continued at 0.2M HNO 3 Dealloying in the solution at 90 ℃ for 72h, filtering, drying, ball milling and 200-mesh vibration screening to obtain the alloy catalyst K.
Comparative example 1
The comparative example differs from example 1 in that step (1) does not employ a staged homogenization process, and the other steps are essentially the same as in example 1, with the specific preparation process as follows:
(1) 500g of carbon black was weighed, transferred to a reactor (volume 100L) having a constant temperature stirring and heating function, added with 20L of a dilute nitric acid solution, and stirred at 200rpm for 6 hours at room temperature to prepare a carbon support suspension B.
Comparative example 2
The difference between this comparative example and example 1 is that step (3) does not use the design of heating up by heating up the mixture of heating up and heating up, and the other steps are basically the same as example 1, and the specific preparation process of this comparative example is as follows:
(3) Continuously stirring the carbon carrier suspension B at the temperature of 25 ℃ for 3 hours at the rotating speed of 200 rpm; meanwhile, the particle size and the particle size distribution (D10, D50, D90) of the carbon support were monitored in real time by a nano-particle sizer. And after the particle size distribution detection value D10 is less than 200nm, D50 is less than 500nm and D90 is less than 5000nm, obtaining the suspension C of the carbon carrier after the particle size distribution detection value is in a proper range.
Comparative example 3
The difference between this comparative example and example 1 is that step (5) does not monitor the temperature inside the reactor in real time, and the other steps are basically the same as example 1, and the specific preparation process is as follows:
(5) After the platinum source solution D is completely added, the temperature of the reactor is continuously raised for 2 to 90 ℃ and kept for 8 hours, stirring and heating are stopped, and the mixture E is obtained after cooling and sedimentation.
Comparative example 4
The comparative example differs from example 1 in that the hydrogen gas in step (6) is replaced by argon gas, and the other steps are basically the same as in example 1, and the specific preparation process is as follows:
(6) Vacuum drying the mixture E in the step (5) at 80 ℃ for 24 hours to obtain mixture powder F; then placing the mixture powder F in a box-type furnace with the volume of 200L, carrying out heat treatment for 6 hours at 300 ℃ in an argon atmosphere, wherein the gas flow rate is 0.5L/min, and carrying out circulating water cooling, planetary ball milling, 200-mesh vibration screening and weighing to obtain a platinum carbon catalyst G;
performance testing
The effect of the particle size distribution of the carbon secondary particles in the carbon support slurries prepared in examples 1 to 6 and comparative examples 1 to 4 was verified by the following method:
(1) Taking 50ml volume of the carbon carrier suspension B, and adding the carbon carrier suspension B into a test part of a nanometer laser particle sizer; stirring at 100rpm for 15min,
(2) Starting a nano laser particle analyzer for preheating, starting a workstation, and testing;
(3) The test was performed 3 times more, and the average values of D10, D50 and D90 were obtained.
The combined results of D10, D50 and D90 were used to evaluate the dispersion effect, and the experimental results are shown in Table 1.
Table 1 comparative table of particle size distribution of carbon secondary particles in carbon support slurry prepared in examples and comparative examples of the present application
In summary, the application develops a sectional type homogenizing process, solves the problem of difficult dispersion of hundred gram/kilogram carbon powder, and successfully realizes kilogram-level dispersion of the carbon carrier by multi-step homogenizing mode design and on-line monitoring of viscosity and particle size distribution of the carbon carrier slurry, and real-time monitoring and solving the problems of uneven internal mixing and local particle agglomeration of the carbon carrier slurry. In addition, the platinum source solution feeding process with the temperature of hundreds of liters is designed, and the temperature rising design of heating, mixing and heating is adopted for different materials, so that the problem of poor consistency of a local concentration field and a temperature field of the catalyst reaction materials is remarkably solved. The technical process design can monitor and accurately adjust corresponding reaction parameters in real time, constructs a structural design of high dispersion of catalyst particles on a carbon carrier, and realizes consistency of batch preparation of the platinum alloy catalyst.
The foregoing describes specific embodiments of the present application. It is to be understood that the application is not limited to the particular embodiments described above, and that various changes or modifications may be made by those skilled in the art within the scope of the appended claims without affecting the spirit of the application. The embodiments of the application and the features of the embodiments may be combined with each other arbitrarily without conflict.
Claims (10)
1. A method for the batch controllable preparation of a high dispersion low platinum alloy catalyst, comprising the steps of:
(1) Mixing carbon powder and a first solvent for ball milling, performing primary dispersion on the carbon powder, adding the first solvent or a dispersing agent in batches, and continuing ball milling to form a carbon carrier dispersion liquid;
(2) Transferring the carbon carrier dispersion liquid into a reactor, adding a dilute acid solution, uniformly stirring, monitoring the particle size and particle size distribution of the carbon carrier in real time, and obtaining the carbon carrier suspension liquid after the particle size distribution detection value is in a proper range;
(3) Slowly adding the platinum source solution into the carbon carrier suspension which is preheated and kept at the temperature under stirring, and heating and keeping the temperature of the reactor for a period of time; cooling and settling, and cleaning to obtain a mixture; the platinum source solution is prepared from at least one of chloroplatinic acid, sodium chloroplatinate, potassium chloroplatinate, sodium hexahydroxyplatinate, tetraamineplatinum acetate and platinum nitrate;
(4) Vacuum drying the mixture obtained in the step (3) to obtain mixture powder; then carrying out heat treatment on the mixture powder, ball milling, screening and obtaining a platinum-carbon catalyst;
(5) Mixing a platinum carbon catalyst with a second solvent, and dispersing to obtain a platinum carbon catalyst dispersion; adding a transition metal salt solution into the platinum-carbon catalyst dispersion liquid, heating, drying and ball milling to obtain transition metal-platinum-carbon catalyst powder;
(6) Heat treating transition metal-platinum carbon catalyst powder to obtain a composite material; dealloying the composite material, filtering, drying, ball milling and sieving to obtain the high-dispersion low-platinum alloy catalyst.
2. The method for the batch controllable preparation of a high dispersion low platinum alloy catalyst according to claim 1, wherein step (1) comprises:
mixing carbon powder with a first solvent, ball milling for 2-36 hours at a rotating speed of 50-400rpm, and primarily dispersing the carbon powder; then adding the first solvent or dispersing agent in batches, continuously ball milling for 1-36 hours at a rotating speed of 100-500rpm, and adjusting the viscosity to 50-20000mpas to form the carbon carrier dispersion liquid with high solid content.
3. A method for the batch controllable preparation of a highly dispersed low platinum alloy catalyst according to claim 2,
the carbon powder is at least one of carbon black, conductive graphite, active carbon, carbon fiber, carbon nanotube, graphene and mesoporous carbon;
the first solvent comprises at least one of water, ethanol, isopropanol, acetone, dimethyl sulfoxide, N-methyl dipyrrolidone and N, N-dimethylformamide;
the dispersing agent comprises one or more of ethylene glycol, propylene glycol, glycerol, polyethylene glycol, polyacrylic acid, acrylonitrile, polyvinyl alcohol, polyvinylpyrrolidone and carboxymethyl cellulose.
4. The method for the batch controllable preparation of a high dispersion low platinum alloy catalyst according to claim 1, wherein step (2) comprises:
transferring the carbon carrier dispersion liquid into a reactor with stirring and heating constant temperature functions, adding a dilute acid solution, and stirring for 0.5-24 hours at 50-1000rpm to prepare a carbon carrier primary suspension; continuously stirring the primary suspension of the carbon carrier at a rotating speed of 50-500rpm, preheating and preserving heat at 30-60 ℃ for 1-12 h, simultaneously monitoring the particle size and the particle size distribution of the carbon carrier in real time, and obtaining the suspension of the carbon carrier when the detection values of the particle size distribution respectively meet D10<200nm, D50<500nm and D90<5000 nm;
wherein the reactor comprises at least one of a jacketed heating reaction kettle, a high-capacity heat collection type stirring device system, a microwave chemical reactor and other high-capacity vessels.
5. The method for the batch controllable preparation of a high dispersion low platinum alloy catalyst according to claim 1, wherein step (3) comprises:
preparing a solution containing a platinum source, and slowly adding the platinum source solution into the preheated and heat-preserving carbon carrier suspension at a speed of 10ml/min-900ml/min through a peristaltic pump at a continuous rotating speed of 50-500 rpm; after the platinum source solution is completely added, heating the reactor to 70-120 ℃, preserving heat for 2-12 h, stopping stirring and heating, cooling and settling to obtain a mixture; the temperature inside the reactor is monitored in real time in the heating process, and the temperature difference between the central temperature and each point position close to the inner wall of the reactor is controlled to be +/-2-5 ℃; in the heat preservation process, the temperature difference between the center temperature and each point position close to the inner wall of the reactor is controlled to be +/-1-5 ℃.
6. The method for the batch controllable preparation of a high dispersion low platinum alloy catalyst according to claim 1, wherein step (4) comprises: vacuum drying the mixture obtained in the step (3) at 50-100 ℃ for 3-48 h to obtain mixture powder; and then placing the mixture powder in a heat treatment device for heat treatment for 1-12 h under the hydrogen atmosphere, wherein the gas flow rate is 0.1L/min-10L/min, and then carrying out circulating water cooling, ball milling and 50-200 mesh vibration screening to obtain the platinum-carbon catalyst.
7. The method for the batch controllable preparation of a high dispersion low platinum alloy catalyst according to claim 1, wherein step (5) comprises: dispersing the platinum-carbon catalyst and the second solvent in a mode of combining ball milling and stirring, firstly ball milling for 1h to 24h at a rotating speed of 50rpm to 400rpm, and stirring for 1h to 24h at a rotating speed of 50rpm to 1000rpm to obtain platinum-carbon catalyst dispersion liquid; adding a transition metal salt solution into a platinum-carbon catalyst dispersion liquid, heating at 30-100 ℃ for 1-24 h, then drying at 60-120 ℃ for 6-72 h, and ball milling at a rotating speed of 10-500rpm for 0.5-12 h to obtain transition metal-platinum-carbon catalyst powder;
the second solvent comprises at least one of water, ethanol, isopropanol, acetone, dimethyl sulfoxide, N-methyl dipyrrolidone, and N, N-dimethylformamide.
8. The method for the batch controllable preparation of a highly dispersed low platinum alloy catalyst according to claim 7, wherein: the transition metal comprises at least one of cobalt, nickel, manganese, iron, copper, palladium, iridium and ruthenium; in the transition metal-platinum carbon catalyst powder, the atomic ratio of transition metal to platinum is 1:1-10.
9. The method for the batch controllable preparation of high dispersion low platinum alloy catalysts according to claim 1, wherein step (6) is specifically: transferring the transition metal-platinum carbon catalyst powder into a heat treatment device, and performing heat treatment for 1-12 h at 400-1100 ℃ in a mixed atmosphere of 5% -50% hydrogen and argon, wherein the gas flow rate is 0.1-10L/min, so as to obtain a composite material; the composite material is treated by the method of 0.1-2M HNO 3 Dealloying for 2-72 h at 50-80 ℃ in the solution, filtering, drying, ball milling and vibrating and sieving with 50-200 meshes to obtain the high-dispersion low-platinum alloy catalyst.
10. The high dispersion low platinum alloy catalyst prepared by the preparation method of any one of claims 1 to 9.
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