CN116371403A - Supported noble metal oxide and preparation method thereof - Google Patents
Supported noble metal oxide and preparation method thereof Download PDFInfo
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- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 52
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000006185 dispersion Substances 0.000 claims abstract description 71
- 239000003054 catalyst Substances 0.000 claims abstract description 59
- 239000007788 liquid Substances 0.000 claims abstract description 48
- 239000002243 precursor Substances 0.000 claims abstract description 37
- 239000000843 powder Substances 0.000 claims abstract description 33
- 229910052751 metal Inorganic materials 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 29
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 23
- 239000002184 metal Substances 0.000 claims abstract description 22
- 238000000498 ball milling Methods 0.000 claims abstract description 16
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 239000002245 particle Substances 0.000 claims abstract description 13
- 230000001105 regulatory effect Effects 0.000 claims abstract description 11
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 10
- 238000000713 high-energy ball milling Methods 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 83
- 239000000243 solution Substances 0.000 claims description 79
- 238000000227 grinding Methods 0.000 claims description 40
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 30
- 235000019441 ethanol Nutrition 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 239000008367 deionised water Substances 0.000 claims description 23
- 229910021641 deionized water Inorganic materials 0.000 claims description 23
- 239000002904 solvent Substances 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 229910021645 metal ion Inorganic materials 0.000 claims description 10
- 238000009210 therapy by ultrasound Methods 0.000 claims description 10
- 239000000969 carrier Substances 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- YNJJJJLQPVLIEW-UHFFFAOYSA-M [Ir]Cl Chemical compound [Ir]Cl YNJJJJLQPVLIEW-UHFFFAOYSA-M 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 150000002736 metal compounds Chemical class 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 claims description 2
- 229940005991 chloric acid Drugs 0.000 claims description 2
- 238000009826 distribution Methods 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 229910052755 nonmetal Inorganic materials 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 claims description 2
- 229910003446 platinum oxide Inorganic materials 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- FBEIPJNQGITEBL-UHFFFAOYSA-J tetrachloroplatinum Chemical compound Cl[Pt](Cl)(Cl)Cl FBEIPJNQGITEBL-UHFFFAOYSA-J 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 3
- SMVPNBSENDTIEH-UHFFFAOYSA-M [Ir]Br Chemical compound [Ir]Br SMVPNBSENDTIEH-UHFFFAOYSA-M 0.000 claims 1
- KFIKNZBXPKXFTA-UHFFFAOYSA-N dipotassium;dioxido(dioxo)ruthenium Chemical compound [K+].[K+].[O-][Ru]([O-])(=O)=O KFIKNZBXPKXFTA-UHFFFAOYSA-N 0.000 claims 1
- 239000003002 pH adjusting agent Substances 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 238000011068 loading method Methods 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 238000005245 sintering Methods 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 description 11
- 230000008569 process Effects 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 239000012876 carrier material Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000012855 volatile organic compound Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000002082 metal nanoparticle Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910000457 iridium oxide Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 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
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229910002058 ternary alloy Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/468—Iridium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
- C25B11/093—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one noble metal or noble metal oxide and at least one non-noble metal oxide
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Catalysts (AREA)
Abstract
A supported noble metal oxide and a preparation method thereof, wherein the method comprises the following steps: s1, preparing carrier dispersion liquid A; s2, adjusting the pH value of the carrier dispersion liquid A obtained in the step S1; s3, preparing a precursor solution B; s4, carrying out high-energy ball milling and mixing on the carrier dispersion liquid A and the precursor solution B; s5, synthesizing a catalyst precursor C; s6, synthesizing a high-dispersion powder catalyst D; s7, synthesizing metal or metal oxide with a super-dispersed structure; the oxide is obtained by the preparation method; according to the invention, after the carrier is pretreated, the carrier is fully contacted with the precursor solution through mechanical ball milling, the carrier is uniformly dispersed, the coverage amount is regulated through regulating the stirring time, and meanwhile, the oxide particle size can be controlled through regulating the temperature and time of the later sintering, so that the simple synthesis of the noble metal supported nano oxide with high loading capacity and high dispersity is realized, and the method has the characteristics of simplicity in operation and cost saving.
Description
Technical Field
The invention belongs to the technical field of preparation of membrane electrode catalysts, and particularly relates to a supported noble metal oxide and a preparation method thereof.
Background
Proton Exchange Membrane (PEM) electrolyzed water hydrogen production is currently the most interesting hydrogen production process, where the oxygen evolution reaction is the bottleneck reaction of PEM electrolyzed water. Oxygen evolution overpotential is a main factor affecting reaction efficiency, and anode catalysts are required to have higher catalytic activity, and noble metals such as Ir, ru and the like and oxides thereof are generally adopted as catalysts to obtain higher catalytic activity, however, the reserves of the metal elements are low, the price is high, and the requirements of PEM mass production application cannot be met, so that supported noble metals become important points of research. The ideal oxygen evolution electrocatalyst should have high specific surface area and porosity, high electron conductivity, good electrocatalytic performance, long-term mechanical and electrochemical stability, small bubble effect, low cost availability, no toxicity and the like, so noble metals/oxides such as Ir, ru and the like with a load structure and binary and ternary alloy/mixed oxides based on the noble metals/oxides are ideal catalyst materials.
The solution method is used as a traditional method for synthesizing a metal supported catalyst, and the idea is to uniformly disperse a metal precursor and a carrier material with high specific surface area and then load a reduced metal nano structure on a substrate. In fact, conventional solution methods do not allow for uniform adhesion of metal precursors to the support surface, while the metal or oxide on the support surface is not adequately covered, thus increasing the effective catalytic active area.
Chinese patent CN111569867a discloses a method for preparing supported noble metal VOCs degradation catalyst by ball milling, the catalyst prepared by the method of the present invention is an inert material (such as Al) with high surface area and porosity 2 O 3 Cordierite, etc.) and transition metal oxides (Co 3 O 4 、MnO 2 、Fe 3 O 4 TiO 2 Etc.) as carrier, loading noble metal single atoms such as noble metal Pt, rh, pd, au, etc. by ball milling methodClusters or nanoparticles, for preparing catalysts for the catalytic oxidation of VOCs. Firstly preparing carrier dispersion solution A with a certain concentration, adding noble metal precursor solution B after uniform dispersion, adding the solution B into the solution A, uniformly stirring and adsorbing, placing the solution B into a planetary ball mill for liquid-phase ball milling, and carrying out suction filtration, drying and recycling to obtain the catalyst. Different kinds of supported noble metal catalysts can be obtained by controlling the types of carriers, the concentration of noble metal precursors and the ball milling process parameters. The method is suitable for VOCs catalysts with porous structures, but because the common solid phase particles generally have lower surface energy, the combination of two phases is not easy to realize through physical adsorption, the catalyst is unevenly distributed on the carrier particles due to simple mechanical grinding, and meanwhile, the loading capacity of the catalyst is limited by the surface morphology of the carrier, so that the improvement of the activity of the catalyst is not facilitated.
Chinese patent CN104741118A discloses a preparation method of a high-dispersion noble metal alloy catalyst, specifically a one-step synthesis of mesoporous silica supported Au-Pt, au-Ru noble metal alloy catalyst. The method has simple synthesis process and avoids pollution and resource waste in the complex synthesis process. The prepared noble metal alloy catalyst has the advantages of good dispersity of noble metal nano particles (average particle diameter is approximately equal to 3.0 nm) and developed mesoporous channels, and meanwhile, the noble metal nano particles are partially embedded on the pore wall of the mesoporous silica carrier, so that the stability of the catalyst can be greatly improved, and the service life of the catalyst can be prolonged. However, the simple stirring method cannot realize a large-scale uniform load, and the condition of uneven load still occurs in the process of preparing the supported catalyst in batches.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a supported noble metal oxide and a preparation method thereof, wherein the loading capacity of a catalyst on the surface of a carrier is improved by adopting a pH regulator to regulate the chemical potential of the surface of the carrier; in addition, the invention makes the carrier fully disperse by using a mechanical ball milling method, and simultaneously promotes the interaction between noble metal ions and the carrier through the action of mechanical energy when the active substances are uniformly loaded on the surface of the carrier; in the high-energy ball milling process, part of mechanical energy is converted into internal energy, so that the diffusion effect of metal ions on the surface of a carrier is promoted, a metal-carrier strong interaction layer is formed, and the effect of increasing the catalytic activity of noble metals is achieved; the noble metal catalyst for electrolysis water with uniform load structure and excellent catalytic activity is obtained through ball milling, drying, grinding and sintering steps, and has the characteristics of improving the reaction efficiency, saving the cost and being easy to realize.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the preparation method of the supported noble metal oxide specifically comprises the following steps:
step S1, preparing carrier dispersion liquid A: weighing a certain amount of carrier powder, adding the carrier powder into an alcohol solution, and uniformly stirring to obtain a carrier dispersion liquid A with the mass-volume concentration of 0.25-0.5 mg/mL; the alcohol solution can be one or a mixture of more than two of absolute ethyl alcohol, isopropanol, deionized water and ethylene glycol; the carrier is metal oxide, nonmetal oxide, g-C with good solubility or dispersibility 3 N 4 Any ratio mixture of one or more than two of open hollow carbon spheres, nano porous carbon and conductive carbon black XC 72R;
step S2, adjusting the pH value of the carrier dispersion liquid A obtained in the step S1: adding a pH regulator into the carrier dispersion liquid A, regulating the pH of the carrier dispersion liquid A to be less than or equal to 6, regulating the charge distribution on the surface of the carrier, and putting the carrier into an ultrasonic environment with the ultrasonic frequency of 25-40 Hz and the temperature of 40-50 ℃ for ultrasonic treatment for 20-60 minutes;
step S3, preparing a precursor solution B: dissolving noble metal compound in alcohol solution to form dispersion liquid with metal ion concentration of 0.4-1.2 mmol/L, namely precursor solution B, wherein the alcohol solution can be one or more than two of absolute ethyl alcohol, isopropanol, deionized water and ethylene glycol in any ratio;
step S4, carrying out high-energy ball milling mixing on the carrier dispersion liquid A obtained in the step S2 and the precursor solution B obtained in the step S3: mixing the carrier dispersion liquid A obtained in the step S2 and the precursor solution B obtained in the step S3 according to the ratio of the mass of the metal element to the mass of the carrier of 20% -50%, pouring the solution with uniform components after stirring into a ball grinding tank, feeding according to the ball ratio of 1 (1-6), wherein the ball diameter is 1-8 mm, adding grinding balls with different diameters in equal proportion, the rotating speed is 800-1000 r/min, and ball grinding for 6-16 h;
step S5, synthesizing a catalyst precursor C: drying the ball-milled product in an oven at 80-110 ℃ and grinding to obtain a catalyst precursor C;
step S6, synthesizing a high-dispersion powder catalyst D: placing the catalyst precursor C obtained in the step S5 into a crucible, placing the crucible into a muffle furnace, heating to 450-550 ℃ at the speed of 2-5 ℃/min, preserving heat for 1-4 h, and cooling along with the furnace to obtain the high-dispersion powder catalyst D with a carrier structure;
step S7, synthesizing a metal or metal oxide catalyst with a super-dispersed structure: and (3) adopting a centrifugal machine, and sequentially using deionized water and absolute ethyl alcohol to centrifugally clean and dry the powder catalyst for a plurality of times to finally obtain the metal or metal oxide with the super-dispersed structure.
The pH regulator in the step S2 is one or a mixture of more than two of oxalic acid, formic acid, acetic acid, nitric acid, sulfuric acid, sulfurous acid, hydrochloric acid, perchloric acid, chloric acid, hypochlorous acid, phosphoric acid, sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonia water, potassium carbonate, potassium bicarbonate, sodium carbonate and sodium bicarbonate.
The noble metal compound in the step S3 is at least one of chloroiridic acid, iridium trichloride, bromoiridic acid, chloroplatinic acid, platinum tetrachloride, platinum oxide, ruthenium trichloride, chlororuthenic acid, potassium chlororuthenate, sodium chlororuthenate and ammonium chlororuthenate.
A supported noble metal oxide is obtained by the above preparation method.
The beneficial effects of the invention are as follows:
1. a supported noble metal oxide and a preparation method thereof, wherein the step S2 is used for preprocessing a carrier with high specific surface area by adjusting the pH value of the carrier dispersion liquid A obtained in the step S1, and the step S4 is used for fully contacting the carrier with the precursor solution through mechanical ball milling, so that the noble metal and the carrier form a strong interaction layer and then are uniformly dispersed on the surface interface of the carrier, thereby playing the role of adjusting the electronic structure of the catalyst and having the characteristic of enhancing the catalytic activity.
2. In the step S4, the materials are added according to the ball ratio of 1 (1-6), the ball diameter is 1-8 mm, grinding balls with different diameters are added in equal proportion, the rotating speed is 800-1000 r/min, ball milling is carried out for 6-16 h, the covering amount is regulated by regulating the stirring time, meanwhile, the catalyst particle size can be controlled by regulating the temperature and time of the later sintering in the step S5-S7, the simple synthesis of the noble metal supported nano catalyst with high loading capacity and high dispersity is realized, and the method has the characteristic of easy realization.
In summary, the invention regulates the surface charge of the carrier material to make the carrier material have the property of adsorbing noble metal ions; the high-energy ball milling method is adopted to carry out mechanical reaction on the carrier and the noble metal precursor ions, so that the metal active components are distributed more uniformly in the carrier holes and on the surfaces, and when the powder catalyst is calcined in the step S7, deionized water and absolute ethyl alcohol are sequentially used to carry out centrifugal cleaning and drying for a plurality of times, so that the valence state of the metal oxide is relatively rich, and the method has the characteristics of simplicity in operation and cost saving.
Drawings
FIG. 1 is a scanning electron microscope image of a powder catalyst prepared by a mechanical ball milling method according to example 1 of the present invention.
FIG. 2 is a scanning electron microscope image of a powder catalyst prepared by a mechanical ball milling method according to example 2 of the present invention.
FIG. 3 is a scanning electron microscope image of a powder catalyst prepared by a mechanical ball milling method according to example 3 of the present invention.
FIG. 4 is a scanning electron microscope image of a comparative example preparation powder catalyst of the present invention.
Fig. 5 is a polarization graph of inventive example 1 and comparative example 1.
FIG. 6 is a cyclic voltammogram of example 1 and comparative example 1 of the present invention.
Detailed Description
The invention is described in further detail below with reference to the accompanying drawings.
Example 1
The preparation method of the supported noble metal oxide specifically comprises the following steps:
step S1, preparing carrier dispersion liquid A:20mL of 0.5mg/mL of TiO with a particle size of 1 μm 2 The solution is ethanol;
step S2, adding 40 mu L of acetic acid and 20 mu L of deionized water into the carrier dispersion liquid A obtained in the step S1, putting into the ultrasonic environment with the ultrasonic frequency of 28Hz and the temperature of 45 ℃ for ultrasonic treatment for 40min, and uniformly dispersing the carrier in a solvent to obtain an adjusted carrier dispersion liquid A with the pH value of 5.5;
step S3, preparing a precursor solution B: the noble metal precursor solution B is prepared from Ir metal ions and Ru metal ions according to a ratio of 1:1 mol ratio of mixed solution with concentration of 1mmol/L, and ethanol as solvent;
s4, mixing the carrier dispersion liquid A obtained in the step S2 with the precursor solution B obtained in the step S3 according to the proportion of 50% of the mass of metal elements to the mass of carriers, pouring the solution with uniform components after stirring into a ball grinding tank, feeding according to the ball ratio of 1:2, adding grinding balls with different diameters according to the ball diameter of 1 mm-8 mm in equal proportion, rotating at 800r/min, and ball grinding for 16h;
s5, placing the ball-milled product in a 100 ℃ oven for drying, and grinding to obtain a catalyst precursor C;
step S6, placing the catalyst precursor C obtained in the step S5 into a crucible, placing into a muffle furnace, heating to 500 ℃ at a speed of 5 ℃/min, preserving heat for 2 hours, and cooling along with the furnace to obtain the high-dispersion powder catalyst Ir with a carrier structure 0.5 Ru 0.5 O 2 @TiO 2 ；
And S7, adopting a centrifugal machine, and sequentially using deionized water and absolute ethyl alcohol to centrifugally clean and dry the powder catalyst for a plurality of times to finally obtain the metal or metal oxide with the super-dispersed structure.
Example 2
The preparation method of the supported noble metal oxide specifically comprises the following steps:
step S1, preparing a carrier dispersion solution A:20mL of 0.5mg/mL SiO with particle size of 200nm 2 The solution is ethanol;
step S2, adding 40 mu L of acetic acid and 20 mu L of deionized water into the carrier dispersion liquid A obtained in the step S1, and placing the mixture into an ultrasonic environment with the ultrasonic frequency of 40Hz and the temperature of 40 ℃ for ultrasonic treatment for 20min to uniformly disperse the carrier in a solvent to obtain an adjusted carrier dispersion liquid A with the pH value of 6;
step S3, preparing a precursor solution B:1mmol/L chloroiridium acid solution, wherein the solvent is ethanol;
s4, mixing the carrier dispersion liquid A obtained in the step S2 with the precursor solution B obtained in the step S3 according to the proportion of 50% of the mass of metal elements to the mass of carriers, pouring the solution with uniform components after stirring into a ball grinding tank, feeding according to the ball ratio of 1:2, adding grinding balls with different diameters according to the ball diameter of 1 mm-8 mm in equal proportion, rotating at 900r/min, and ball grinding for 6h;
s5, placing the ball-milled product in a 100 ℃ oven for drying, and grinding to obtain a catalyst precursor C;
step S6, placing the catalyst precursor C obtained in the step S5 into a crucible, placing into a muffle furnace, heating to 500 ℃ at a speed of 5 ℃/min, preserving heat for 2 hours, and cooling along with the furnace to obtain the high-dispersion powder catalyst IrO with a carrier structure 2 /SiO 2 ；
And S7, adopting a centrifugal machine, and sequentially using deionized water and absolute ethyl alcohol to centrifugally clean and dry the powder catalyst for a plurality of times to finally obtain the metal or metal oxide with the super-dispersed structure.
Example 3
The preparation method of the supported noble metal oxide specifically comprises the following steps:
step S1, preparing a carrier dispersion solution A:20mL of 0.25mg/mL conductive carbon black XC72R solution, wherein the solvent is ethanol;
step S2, adding 20 mu L of hydrogen peroxide, 20 mu L of acetic acid and 20 mu L of deionized water into the carrier dispersion liquid A obtained in the step S1, and placing the mixture into an ultrasonic environment with the ultrasonic frequency of 28Hz and the temperature of 50 ℃ for ultrasonic treatment for 30min to uniformly disperse the carrier in a solvent to obtain an adjusted carrier dispersion liquid A with the pH value of 6;
step S3, preparing a precursor solution B:1mmol/L chloroplatinic acid solution, wherein the solvent is ethanol;
s4, mixing the carrier dispersion liquid A obtained in the step S2 with the precursor solution B obtained in the step S3 according to the proportion of 20% of the mass of metal elements to the mass of carriers, pouring the solution with uniform components after stirring into a ball grinding tank, feeding according to the ball ratio of 1:1, adding grinding balls with different diameters in equal proportion, wherein the ball diameter is 1-8 mm, the rotating speed is 1000r/min, and ball grinding is carried out for 10h;
s5, placing the ball-milled product in a 100 ℃ oven for drying, and grinding to obtain a catalyst precursor C;
step S6, placing the catalyst precursor C obtained in the step S5 into a crucible, placing into a muffle furnace, heating to 550 ℃ at a speed of 5 ℃/min, preserving heat for 2 hours, and cooling along with the furnace to obtain the high-dispersion powder catalyst Pt/C with a carrier structure;
and S7, adopting a centrifugal machine, and sequentially using deionized water and absolute ethyl alcohol to centrifugally clean and dry the powder catalyst for a plurality of times to finally obtain the metal or metal oxide with the super-dispersed structure.
Example 4
The preparation method of the supported noble metal oxide specifically comprises the following steps:
step S1, preparing a carrier dispersion solution A:20mL of 0.4mg/mL of TiO with particle size of 1 μm 2 The solution is ethanol;
step S2, adding 40 mu L of acetic acid and 20 mu L of deionized water into the carrier dispersion liquid A obtained in the step S1, and placing the mixture into an ultrasonic environment with the ultrasonic frequency of 40Hz and the temperature of 45 ℃ for ultrasonic treatment for 60min to uniformly disperse the carrier in a solvent to obtain an adjusted carrier dispersion liquid A with the pH value of 5.5;
step S3, preparing a precursor solution B:1mmol/L chloroiridium acid solution, wherein the solvent is ethanol;
s4, mixing the carrier dispersion liquid A obtained in the step S2 with the precursor solution B obtained in the step S3 according to the proportion of 50% of the mass of metal elements to the mass of carriers, pouring the solution with uniform components after stirring into a ball mill tank, feeding according to the ball ratio of 1:4, adding grinding balls with different diameters according to the ball diameter of 1 mm-8 mm in equal proportion, rotating at 1000r/min, and ball milling for 10h;
s5, placing the ball-milled product in a 100 ℃ oven for drying, and grinding to obtain a catalyst precursor C;
step S6, placing the catalyst precursor C obtained in the step S5 into a crucible, placing into a muffle furnace, heating to 450 ℃ at a speed of 5 ℃/min, preserving heat for 1h, and cooling along with the furnace to obtain the high-dispersion powder catalyst IrO with a carrier structure 2 @TiO 2 ；
And S7, adopting a centrifugal machine, and sequentially using deionized water and absolute ethyl alcohol to centrifugally clean and dry the powder catalyst for a plurality of times to finally obtain the metal or metal oxide with the super-dispersed structure.
Comparative example 1
First, a carrier dispersion solution a is prepared: 20mL of 0.5mg/mL of TiO with a particle size of 1 μm 2 The solution is ethanol; the noble metal precursor solution B is prepared from Ir metal ions and Ru metal ions according to a ratio of 1:1 mol ratio of mixed solution with concentration of 1mmol/L, and ethanol as solvent; the solution a and the solution B were mixed in a ratio of 50% by mass of the metal element to the carrier. Stirring for 30min by a magnetic stirrer, drying at 100 ℃, grinding, placing in a muffle furnace, heating to 500 ℃ at a speed of 5 ℃/min, preserving heat for 2h, and cooling along with the furnace to obtain a powder catalyst Ir 0.5 Ru 0.5 O 2 @TiO 2 。
As can be seen from the comparison of FIGS. 1 and 4, the invention adds the ball milling process, adopts a planetary ball mill in the embodiment, so that the catalyst particles are distinct and agglomeration is avoided; meanwhile, a chemical pretreatment method of the carrier is utilized, namely, firstly, carrier dispersion liquid A is prepared, then the pH value of the carrier dispersion liquid A obtained in the step S1 is regulated, and finally, precursor solution B is prepared, so that iridium oxide is fully loaded on spherical TiO 2 The surface plays a positive role in increasing the effective active area.
Electrochemical performance measurement of catalyst at 0.5mol/L H in electrolyte 2 SO 4 Electrochemical reaction at room temperatureOn a workstation. Catalyst coated Glass Carbon (GC) electrode (diameter: 3 mm), ag/AgCl electrode and platinum sheet were used as working electrode, reference electrode and counter electrode, respectively. 4mg of the catalyst powder was added to a mixed solution containing 200. Mu.L of ethanol and 200. Mu.L of aqueous solution of LNafion (5 vol%, ethanol as solvent), and dispersed by ultrasonic waves for 15 minutes to form a uniform ink, which was uniformly coated on the GC to form a working electrode.
As can be seen from the polarization curve of FIG. 5, according to the method of the present invention, after the carrier is subjected to surface treatment, the noble metal solution is uniformly dispersed on the surface of the carrier in the ball milling process, and interacts with the carrier under the mechanical action to form a noble metal-carrier strong interaction layer, and the formation of the structure effectively improves the catalytic activity of the noble metal oxide to 50mA/cm -2 The electrolysis voltage required for the current density is reduced from 1.58V to 1.48V.
Meanwhile, the CV diagram shown in FIG. 6 shows that the invention effectively increases the effective active area of the oxide and obtains better catalytic activity.
In conclusion, the high-energy ball milling method with the rotating speed of 800-1000 r/min is adopted, so that the dispersing capability of effective catalytic ions is improved, meanwhile, the surface ions of the carrier are effectively modified, the adsorption capability of the carrier on metal ions is improved, and the loading capacity of effective catalytic components on the carrier is increased. By this method, an electrolyzed water oxygen evolution oxide having high electron conductivity and good electrocatalytic performance is prepared.
The foregoing is merely exemplary of embodiments of the present invention to enable those skilled in the art to understand or practice the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention.
Claims (8)
1. The preparation method of the supported noble metal oxide is characterized by comprising the following steps of:
step S1, preparing carrier dispersion liquid A: weighing a certain amount of carrier powder, adding into alcohol solution, stirringUniformly obtaining carrier dispersion liquid A with the mass-volume concentration of 0.25-0.5 mg/mL; the alcohol solution can be one or a mixture of more than two of absolute ethyl alcohol, isopropanol, deionized water and ethylene glycol; the carrier is metal oxide, nonmetal oxide, g-C with good solubility or dispersibility 3 N 4 Any ratio mixture of one or more than two of open hollow carbon spheres, nano porous carbon and conductive carbon black XC 72R;
step S2, adjusting the pH value of the carrier dispersion liquid A obtained in the step S1: adding a pH regulator into the carrier dispersion liquid A, regulating the pH of the carrier dispersion liquid A to be less than or equal to 6, regulating the charge distribution on the surface of the carrier, and putting the carrier into an ultrasonic environment with the ultrasonic frequency of 25-40 Hz and the temperature of 40-50 ℃ for ultrasonic treatment for 20-60 minutes;
step S3, preparing a precursor solution B: dissolving noble metal compound in alcohol solution to form dispersion liquid with metal ion concentration of 0.4-1.2 mmol/L, namely precursor solution B, wherein the alcohol solution can be one or more than two of absolute ethyl alcohol, isopropanol, deionized water and ethylene glycol in any ratio;
step S4, carrying out high-energy ball milling mixing on the carrier dispersion liquid A obtained in the step S2 and the precursor solution B obtained in the step S3: mixing the carrier dispersion liquid A obtained in the step S2 and the precursor solution B obtained in the step S3 according to the ratio of the mass of the metal element to the mass of the carrier of 20% -50%, pouring the solution with uniform components after stirring into a ball grinding tank, feeding according to the ball ratio of 1 (1-6), wherein the ball diameter is 1-8 mm, adding grinding balls with different diameters in equal proportion, the rotating speed is 800-1000 r/min, and ball grinding for 6-16 h;
step S5, synthesizing a catalyst precursor C: drying the ball-milled product in an oven at 80-110 ℃ and grinding to obtain a catalyst precursor C;
step S6, synthesizing a high-dispersion powder catalyst D: placing the catalyst precursor C obtained in the step S5 into a crucible, placing the crucible into a muffle furnace, heating to 450-550 ℃ at the speed of 2-5 ℃/min, preserving heat for 1-4 h, and cooling along with the furnace to obtain the high-dispersion powder catalyst D with a carrier structure;
step S7, synthesizing a metal or metal oxide catalyst with a super-dispersed structure: and (3) adopting a centrifugal machine, and sequentially using deionized water and absolute ethyl alcohol to centrifugally clean and dry the powder catalyst for a plurality of times to finally obtain the metal or metal oxide with the super-dispersed structure.
2. The method for preparing a supported noble metal oxide according to claim 1, wherein the pH adjuster in step S2 is one or a mixture of two or more of oxalic acid, formic acid, acetic acid, nitric acid, sulfuric acid, sulfurous acid, hydrochloric acid, perchloric acid, chloric acid, hypochlorous acid, phosphoric acid, sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonia water, potassium carbonate, potassium bicarbonate, sodium carbonate, and sodium bicarbonate.
3. The method for preparing a supported noble metal oxide according to claim 1, wherein the noble metal compound in the step S3 is at least one of iridium chloride, iridium trichloride, bromoiridium, chloroplatinic acid, platinum tetrachloride, platinum oxide, ruthenium trichloride, ruthenic acid, potassium ruthenate chloride, sodium ruthenate chloride, and ammonium ruthenate chloride.
4. The preparation method of the supported noble metal oxide is characterized by comprising the following steps of:
step S1, preparing carrier dispersion liquid A:20mL of 0.5mg/mL of TiO with a particle size of 1 μm 2 The solution is ethanol;
step S2, adding 40 mu L of acetic acid and 20 mu L of deionized water into the carrier dispersion liquid A obtained in the step S1, putting into the ultrasonic environment with the ultrasonic frequency of 28Hz and the temperature of 45 ℃ for ultrasonic treatment for 40min, and uniformly dispersing the carrier in a solvent to obtain an adjusted carrier dispersion liquid A with the pH value of 5.5;
step S3, preparing a precursor solution B: the noble metal precursor solution B is prepared from Ir metal ions and Ru metal ions according to a ratio of 1:1 mol ratio of mixed solution with concentration of 1mmol/L, and ethanol as solvent;
s4, mixing the carrier dispersion liquid A obtained in the step S2 with the precursor solution B obtained in the step S3 according to the proportion of 50% of the mass of metal elements to the mass of carriers, pouring the solution with uniform components after stirring into a ball grinding tank, feeding according to the ball ratio of 1:2, adding grinding balls with different diameters according to the ball diameter of 1 mm-8 mm in equal proportion, rotating at 800r/min, and ball grinding for 16h;
s5, placing the ball-milled product in a 100 ℃ oven for drying, and grinding to obtain a catalyst precursor C;
step S6, placing the catalyst precursor C obtained in the step S5 into a crucible, placing into a muffle furnace, heating to 500 ℃ at a speed of 5 ℃/min, preserving heat for 2 hours, and cooling along with the furnace to obtain the high-dispersion powder catalyst Ir with a carrier structure 0.5 Ru 0.5 O 2 @TiO 2 ；
And S7, adopting a centrifugal machine, and sequentially using deionized water and absolute ethyl alcohol to centrifugally clean and dry the powder catalyst for a plurality of times to finally obtain the metal or metal oxide with the super-dispersed structure.
5. The preparation method of the supported noble metal oxide is characterized by comprising the following steps of:
step S1, preparing a carrier dispersion solution A:20mL of 0.5mg/mL SiO with particle size of 200nm 2 The solution is ethanol;
step S2, adding 40 mu L of acetic acid and 20 mu L of deionized water into the carrier dispersion liquid A obtained in the step S1, and placing the mixture into an ultrasonic environment with the ultrasonic frequency of 40Hz and the temperature of 40 ℃ for ultrasonic treatment for 20min to uniformly disperse the carrier in a solvent to obtain an adjusted carrier dispersion liquid A with the pH value of 6;
step S3, preparing a precursor solution B:1mmol/L chloroiridium acid solution, wherein the solvent is ethanol;
s4, mixing the carrier dispersion liquid A obtained in the step S2 with the precursor solution B obtained in the step S3 according to the proportion of 50% of the mass of metal elements to the mass of carriers, pouring the solution with uniform components after stirring into a ball grinding tank, feeding according to the ball ratio of 1:2, adding grinding balls with different diameters according to the ball diameter of 1 mm-8 mm in equal proportion, rotating at 900r/min, and ball grinding for 6h;
s5, placing the ball-milled product in a 100 ℃ oven for drying, and grinding to obtain a catalyst precursor C;
step S6, placing the catalyst precursor C obtained in the step S5 into a crucible, placing into a muffle furnace, heating to 500 ℃ at a speed of 5 ℃/min, preserving heat for 2 hours, and cooling along with the furnace to obtain the high-dispersion powder catalyst IrO with a carrier structure 2 /SiO 2 ；
And S7, adopting a centrifugal machine, and sequentially using deionized water and absolute ethyl alcohol to centrifugally clean and dry the powder catalyst for a plurality of times to finally obtain the metal or metal oxide with the super-dispersed structure.
6. The preparation method of the supported noble metal oxide is characterized by comprising the following steps of:
step S1, preparing a carrier dispersion solution A:20mL of 0.25mg/mL conductive carbon black XC72R solution, wherein the solvent is ethanol;
step S2, adding 20 mu L of hydrogen peroxide, 20 mu L of acetic acid and 20 mu L of deionized water into the carrier dispersion liquid A obtained in the step S1, and placing the mixture into an ultrasonic environment with the ultrasonic frequency of 28Hz and the temperature of 50 ℃ for ultrasonic treatment for 30min to uniformly disperse the carrier in a solvent to obtain an adjusted carrier dispersion liquid A with the pH value of 6;
step S3, preparing a precursor solution B:1mmol/L chloroplatinic acid solution, wherein the solvent is ethanol;
s4, mixing the carrier dispersion liquid A obtained in the step S2 with the precursor solution B obtained in the step S3 according to the proportion of 20% of the mass of metal elements to the mass of carriers, pouring the solution with uniform components after stirring into a ball grinding tank, feeding according to the ball ratio of 1:1, adding grinding balls with different diameters in equal proportion, wherein the ball diameter is 1-8 mm, the rotating speed is 1000r/min, and ball grinding is carried out for 10h;
s5, placing the ball-milled product in a 100 ℃ oven for drying, and grinding to obtain a catalyst precursor C;
step S6, placing the catalyst precursor C obtained in the step S5 into a crucible, placing into a muffle furnace, heating to 550 ℃ at a speed of 5 ℃/min, preserving heat for 2 hours, and cooling along with the furnace to obtain the high-dispersion powder catalyst Pt/C with a carrier structure;
and S7, adopting a centrifugal machine, and sequentially using deionized water and absolute ethyl alcohol to centrifugally clean and dry the powder catalyst for a plurality of times to finally obtain the metal or metal oxide with the super-dispersed structure.
7. The preparation method of the supported noble metal oxide is characterized by comprising the following steps of:
step S1, preparing a carrier dispersion solution A:20mL of 0.4mg/mL of TiO with particle size of 1 μm 2 The solution is ethanol;
step S2, adding 40 mu L of acetic acid and 20 mu L of deionized water into the carrier dispersion liquid A obtained in the step S1, and placing the mixture into an ultrasonic environment with the ultrasonic frequency of 40Hz and the temperature of 45 ℃ for ultrasonic treatment for 60min to uniformly disperse the carrier in a solvent to obtain an adjusted carrier dispersion liquid A with the pH value of 5.5;
step S3, preparing a precursor solution B:1mmol/L chloroiridium acid solution, wherein the solvent is ethanol;
s4, mixing the carrier dispersion liquid A obtained in the step S2 with the precursor solution B obtained in the step S3 according to the proportion of 50% of the mass of metal elements to the mass of carriers, pouring the solution with uniform components after stirring into a ball mill tank, feeding according to the ball ratio of 1:4, adding grinding balls with different diameters according to the ball diameter of 1 mm-8 mm in equal proportion, rotating at 1000r/min, and ball milling for 10h;
s5, placing the ball-milled product in a 100 ℃ oven for drying, and grinding to obtain a catalyst precursor C;
step S6, placing the catalyst precursor C obtained in the step S5 into a crucible, placing into a muffle furnace, heating to 450 ℃ at a speed of 5 ℃/min, preserving heat for 1h, and cooling along with the furnace to obtain the high-dispersion powder catalyst IrO with a carrier structure 2 @TiO 2 ；
And S7, adopting a centrifugal machine, and sequentially using deionized water and absolute ethyl alcohol to centrifugally clean and dry the powder catalyst for a plurality of times to finally obtain the metal or metal oxide with the super-dispersed structure.
8. A supported noble metal oxide, characterized by being obtained by the production method according to any one of claims 1 to 7.
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