CN105833862A - Preparation method and application of nanometer platinum oxide catalyst - Google Patents
Preparation method and application of nanometer platinum oxide catalyst Download PDFInfo
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- CN105833862A CN105833862A CN201610199715.3A CN201610199715A CN105833862A CN 105833862 A CN105833862 A CN 105833862A CN 201610199715 A CN201610199715 A CN 201610199715A CN 105833862 A CN105833862 A CN 105833862A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 62
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910003446 platinum oxide Inorganic materials 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 114
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 52
- 239000000243 solution Substances 0.000 claims abstract description 52
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims abstract description 37
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 33
- 229940049964 oleate Drugs 0.000 claims abstract description 23
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 22
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 21
- 150000003057 platinum Chemical class 0.000 claims abstract description 17
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims abstract description 14
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims abstract description 14
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000005642 Oleic acid Substances 0.000 claims abstract description 14
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 14
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 239000011259 mixed solution Substances 0.000 claims abstract description 11
- 239000000843 powder Substances 0.000 claims abstract description 8
- 239000012266 salt solution Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 16
- 239000000084 colloidal system Substances 0.000 claims description 14
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 12
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 claims description 12
- RCFVMJKOEJFGTM-UHFFFAOYSA-N cerium zirconium Chemical compound [Zr].[Ce] RCFVMJKOEJFGTM-UHFFFAOYSA-N 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 8
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 229910052593 corundum Inorganic materials 0.000 claims description 7
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical group [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 claims description 7
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 13
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 238000005245 sintering Methods 0.000 abstract description 5
- 238000003756 stirring Methods 0.000 abstract description 5
- 238000010438 heat treatment Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 12
- 239000007789 gas Substances 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 4
- 239000010970 precious metal Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000000576 coating method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 229910001868 water Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000002341 toxic gas Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 1
- 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 description 1
- 229910019020 PtO2 Inorganic materials 0.000 description 1
- 230000010757 Reduction Activity Effects 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- -1 Therefore Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- YKIOKAURTKXMSB-UHFFFAOYSA-N adams's catalyst Chemical compound O=[Pt]=O YKIOKAURTKXMSB-UHFFFAOYSA-N 0.000 description 1
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910002064 alloy oxide Inorganic materials 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- HRHBQGBPZWNGHV-UHFFFAOYSA-N azane;bromomethane Chemical compound N.BrC HRHBQGBPZWNGHV-UHFFFAOYSA-N 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- PXXKQOPKNFECSZ-UHFFFAOYSA-N platinum rhodium Chemical compound [Rh].[Pt] PXXKQOPKNFECSZ-UHFFFAOYSA-N 0.000 description 1
- 229910000923 precious metal alloy Inorganic materials 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9445—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC]
- B01D53/945—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC] characterised by a specific catalyst
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/01—Engine exhaust gases
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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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- 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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/10—Internal combustion engine [ICE] based vehicles
- Y02T10/12—Improving ICE efficiencies
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Abstract
The invention discloses a preparation method and application of a nanometer platinum oxide catalyst. The preparation method comprises the following concrete steps: heating a platinum salt solution to about 65 DEG C; then rapidly adding an oleate solution (a mixed solution of oleic acid and excess sodium hydroxide) and carrying out rapid stirring for 10 to 15 min so as to obtain a mixed platinic hydroxide solution; adding cetyl trimethyl ammonium bromide and hydrogen peroxide with a concentration of 30% into the solution and stopping a reaction in 30 to 40 min so as to obtain a nanometer platinum oxide colloidal solution, wherein nanometer platinum oxide are uniformly dispersed in the solution due to existence of oleate and cetyl trimethyl ammonium bromide; and adding materials like AC100, RC25 and RC35 into the nanometer platinum oxide colloidal solution, then carrying out mixing and drying; and then carrying out sintering to 550 DEG C so as to prepare nanometer platinum oxide catalyst powder. According to the invention, the specific surface area of platinum oxide in the catalyst material is increased through preparation of nanometer platinum oxide, so the distribution rate and usage efficiency of platinum in the catalyst are improved; and thus, the purposes of thorough utilization and improvement of catalytic activity of platinum oxide are achieved.
Description
Technical field
The invention belongs to catalytic field, particularly relate to the preparation side of a kind of nano oxidized platinum catalyst
Method and application.
Background technology
Automobile exhaust gas purifying catalyst divides oxidation catalyst and reduction one oxidation catalyst (ternary
Catalyst, Three WayCatalyst) two kinds.The seventies uses oxidation catalyst in a large number,
Entering large-scale popularization application three-way catalyst after the eighties, by 1988, three-way catalyst accounted for
80%～90%.Oxidation catalyst is with platinum or platinum palladium as active component, and carrier is γ-Al203 ball
Or added with γ-Al203.The ceramic honeycomb body of coating, its function is by the nuisance CO in aerofluxus
It is converted into CO2 and water with HC.Three-way catalyst with platinum rhodium as active component, carrier be added with
The ceramic honeycomb of γ-Al203 coating, its function is by three kinds of nuisances (CO, HC in aerofluxus
And NOx) eliminate, it is changed into CO2, H2O and N2. simultaneously.
Catalytic performance that precious metal oxide catalyst can not be substituted due to it and selectivity,
The fields such as oil, chemical industry, medicine, pesticide, the energy there is extremely important status.Particularly
In recent years, national economy develops rapidly, freeway net all-round construction, and Living Water mean pole
Big raising, automobile gradually incorporates in the middle of people's daily life, is bringing the most easily for society
Meanwhile, also bringing a series of social problem, the discharge environmental pollution such as vehicle exhaust is tight
Weight, restricts the national economic development, that harm health of the masses becomes impact society is steady to a certain extent
Fixed harmonious key factor.Become increasingly conspicuous with people to environmental conservation pay attention to day by day in environmental problem
Under the new situation, motor vehicle exhaust emission problem increasingly causes society's attention, therefore uses your gold
Belong to oxide as catalyst cleaning vehicle exhaust, the discharge of minimizing toxic gas, protection crowd
Health, the development that promotes social harmony is particularly important.Platinum oxide is as one your gold typical
Belong to oxide catalyst, there is the catalytic performance of excellence, car tail can be reduced to a great extent
Toxic gas in gas discharge, causes increasing attention, becomes vehicle maintenance service accessory
In indispensable material.Traditional platinum oxide as one of the main material of catalyst, by
Relatively big in granule, the platinum oxide of equivalent distribution specific surface area in the catalyst is smaller, with gas
The area of body contact is relatively fewer, there is the phenomenon of waste.Nano oxidized platinum exists due to its yardstick
Nanometer scale, has bigger specific surface area energy and higher catalysis activity, therefore prepares and receive
Rice platinum oxide can preferably reduce catalyst cost, saves more Precious Metals Resources for country.
It is to make an addition to a certain amount of platinum salt by catalyst coat powder that traditional platinum-oxide catalyst makes
Expect in the slurry with weakly acidic aqueous solution mixed preparing and be coated on catalyst support surface, then will
The carrier being coated with catalyst is heated to 500 DEG C of sintering carried out above.In sintering process, slurry
Oxidized being changed into of platinum salt in material is attached to catalyst support surface and has catalytic action
Platinum oxide particle, prepares nano oxidized platinum catalyst.The platinum oxide preparation method that presently, there are is
By chloroplatinic acid (H2PtCl6) or ammonium chloroplatinate [(NH4) 2PtCl6] and sodium nitrate when 500 DEG C altogether
Found standby.Prepared by Luo Jie Adams and his student V.Voorhees the earliest.Mr. in this method
Becoming platinum nitrate, the latter decomposes to give off nitrogen oxides and oxygen again, obtains platinum oxide, this method system
The platinum oxide gone out not nanoscale, the characteristic of many nano materials cannot in catalyst material body
Reveal to come.
Platinum oxide particle prepared by traditional method is formed under the high temperature in sintering process, different platinum
Between particle, atom is susceptible to diffusion, the oxygen in the catalyst support coatings that therefore prepared by the method
Change platinum is relatively large in diameter due to mutually bonding particle, the most hundreds of nanometers to tens micron, Er Qieke
Bigger alloy body can be formed with other precious metal elements (such as rhodium) sintering, so be formed
Precious metal alloys Catalytic active phase to more weak, the most this alloy and metal oxide containing precious metals due to
Grain compared with big, specific surface area is relatively small, the noble metal that will cause granule inner core part cannot be with
Exhaust gas component directly contacts, reduce effectively the making full use of of noble metal, cause noble metal to use
Waste.
Summary of the invention
For solving the problems referred to above, the invention provides the preparation side of a kind of nano oxidized platinum catalyst
Method and application.The present invention improves platinum oxide at catalyst material by preparing nanoscale platinum
In specific surface area, and then improve platinum distributive law in the catalyst and service efficiency, reach
Make full use of and improve the purpose of platinum oxide catalysis activity.
For reaching above-mentioned technique effect, the technical scheme is that
The preparation method of a kind of nano oxidized platinum catalyst, comprises the steps: platinum salt and oleic acid
Saline solution reaction generates platinic hydroxide mixed solution, adds 16 in platinic hydroxide mixed solution
Alkyl trimethyl ammonium bromide and hydrogen peroxide carry out oxidation reaction and prepare nano oxidized Pt colloids solution.
Further improving, described oleate solution is the mixed solution of oleic acid and sodium hydroxide,
PH >=10 of oleate solution.
Further improve, comprise the steps:
Step one, platinum salt is dissolved in deionized water obtains platinum salt solution, platinum salt solution is heated to
About 65 DEG C；
Step 2, prepare oleate solution: added by sodium hydroxide in deionized water and fully dissolve then
Add oleic acid, make oleic acid fully dissolve and obtain oleate solution；The wherein PH of oleate solution
>=10, described oleate solution is sodium oleate solution；
Step 3, sodium oleate solution is added platinum salt solution reaction obtain platinic hydroxide solution；
Step 4, in platinic hydroxide solution, add cetyl trimethylammonium bromide and hydrogen peroxide solution
Carry out oxidation reaction and prepare nano oxidized Pt colloids solution；Wherein cetyl trimethylammonium bromide
Final concentration of 0.01mol/L-0.05mol/L；
Step 5, in nano oxidized Pt colloids solution add cerium zirconium compound oxide, mixing dry system
Obtain nano oxidized platinum catalyst powder.
Further improving, in described step one, platinum salt is platinum nitrate.
Further improve, in described step 4, the final concentration of 5%-10% of hydrogen peroxide.
Further improve, in described step 5, cerium zirconium compound oxide include AC100,
RC25 and RC35；The mass ratio of AC100, RC25 and RC35 is: 2:1:1；Cerium zirconium is combined
Oxide with the mass ratio of nano oxidized platinum is: 100:1；Wherein, AC100 includes 96%Al2O3
And 4%La2O3；RC25 includes 5%La2O3, 5%Y2O3, 60%CeO2And 30%ZrO2；RC35 bag
Include 5%La2O3, 5%Y2O3, 30%CeO2And 60%ZrO2。
Further improving, in described step 5, the temperature of drying is 550 DEG C.
Further improving, described nano oxidized platinum is used as three-way catalyst.
The use of the nano oxidized platinum that the preparation method of a kind of above-mentioned nano oxidized platinum catalyst prepares
On the way, it is characterised in that described nano oxidized platinum is used as three-way catalyst.
Advantages of the present invention:
1. platinum oxide prepared by is nanoscale, and therefore specific surface area is relatively big, and catalytic performance is stronger；
Oleate and cetyl trimethylammonium bromide (CTAB) in the most nano oxidized platinum preparation process
Mixing add and be possible to prevent the gathering of nano-particle, the effective size controlling nano-particle,
Therefore, platinum distributive law in the catalyst and service efficiency can be improved, thus fully improve your gold
Belong to the service efficiency of platinum.
Accompanying drawing explanation
Fig. 1 is the microgram of nano oxidized platinum precipitation；
Fig. 2 is the 550 DEG C of TPR experimental result contrasts of nano oxidized platinum and common platinum-oxide catalyst.
Detailed description of the invention
Below by way of detailed description of the invention and combine accompanying drawing to technical scheme make have
Body explanation.
Embodiment 1
Weigh 1.5g platinum nitrate powder to put in 250mL deionized water, be allowed to fully dissolve,
To platinum nitrate solution；Weigh 4g sodium hydroxide, put in the beaker of the deionized water filling 50ml,
It is sufficiently stirred for, obtains sodium hydroxide solution；4mL is added in the sodium hydroxide solution configured
Oleic acid, and be placed in beaker in ultrasonic cleaner to be stirred vigorously and make oleic acid fully dissolve, (molten
Till liquid does not has block oleic acid), obtain sodium oleate solution (oleate solution), (add NaOH
Amount need keep sodium oleate solution PH >=10)；By molten for 250ml platinum nitrate good for above-mentioned configuration
Liquid is heated to about 65 DEG C (also can room temperature carry out), and then stirring platinum nitrate solution limit in limit adds rapidly
Enter the sodium oleate solution of preparation, i.e. can get platinic hydroxide and oleate mixed solution, persistently stir
Mix 10min, make reaction be more uniformly distributed；Platinic hydroxide solution successively adds
50ml (0.1mol/L) cetyl trimethylammonium bromide (CTAB) [the wherein final concentration of CTAB
Be maintained at (between 0.01mol/L-0.05mol/L] and 30% hydrogen peroxide solution of 100ml
[between the final concentration 5%-10% to be maintained at of hydrogen peroxide], stopped reaction after 30min, it is thus achieved that receive
Rice platinum oxide colloid solution, now can pass through absolute ethanol washing, centrifugal acquisition nano oxidized
Platinum precipitation (see Fig. 1), is dried and seals preservation, and in addition, nano oxidized platinum is the most uniform
It is dispersed in colloid solution, in colloid solution, adds cerium zirconium compound oxide, it may be assumed that
50gAC-100 (96%Al2O3, 4%La2O3), 25gRC-25 (5%La2O3, 5%Y2O3, 60%CeO2、
30%ZrO2), 25gRC-35 (5%La2O3, 5%Y2O3, 30%CeO2, 60%ZrO2) three kinds of materials,
After being sufficiently stirred for, dry, be sintered to 550 DEG C, prepare nano oxidized platinum catalyst powder, wherein
Cerium zirconium compound oxide with the mass ratio of nano oxidized platinum is: 100:1.This method prepares
Nano oxidized platinum catalyst can preferably be distributed in catalyst carrier, it is thus achieved that optimal catalytic effect.
The platinum oxide material nano oxidized platinum catalyst material made and ordinary sinter prepared is respectively
Carrying out TPR experiment (reaction of catalyst temperature programmed reduction), TPR experiment unified parameters sets:
Material weight scope: between 0.28-0.32g, reducing gas: 5%H2+95%Ar, degassing gas
Body: 70%He+30%N2 (should use nitrogen or helium can), removes temperature 350 DEG C,
1.5 hours degassing time, gas flow is set as that 80,30 DEG C/min of the rate of heat addition, decay shelves adjust
To 64, sensor bridge stream IA is set to 150, He and H2 gas pressure is all adjusted to 0.07Mpa.
Experimental result Fig. 2 shows, nano oxidized platinum catalyst TPR tests (catalyst temperature programming
Reduction reaction) reduction peak area be significantly greater than the reduction peak of common platinum-oxide catalyst, it is seen then that
Catalyst reduction activity is apparently higher than common Platinum Nanoparticles.
Additionally, the nano oxidized platinum of the present invention to the tolerance degree of high temperature substantially than common platinum oxide
The tolerance degree of catalyst is high.
The present invention uses the sedimentation method to prepare nano oxidized platinum, for the oxidation overcoming the sedimentation method to prepare
Platinum easily forms the phenomenon of aggregate, adds oleate and cetyl trimethylammonium bromide
(CTAB), the nano oxidized platinum particles of monodisperse system is prepared, concrete steps: first that platinum salt is molten
Liquid is heated to about 65 DEG C, is then rapidly added oleate solution (oleic acid and the hydroxide of excess
Sodium mixed solution), quickly stir 10-15min, it is thus achieved that platinic hydroxide mixed solution, more molten toward this
Liquid adds cetyl trimethylammonium bromide (CTAB) and the hydrogen peroxide of 30%, 30-40min
Rear stopped reaction, prepares nano oxidized Pt colloids solution, due to oleate and cetyl front three
The existence of base ammonium bromide (CTAB) surfactant, nano oxidized platinum is uniformly dispersed in colloid
In solution, absolute ethanol washing, the centrifugal nano oxidized platinum precipitation that obtains can be passed through, dry close
Envelope preserves, it is possible to directly add AC100, RC25, RC35 in nano oxidized Pt colloids solution
Dry etc. material mixing, be sintered to 550 DEG C, prepare nano oxidized platinum catalyst powder.
Reaction equation is as follows:
Pt(OH)4+4H2O2→PtO2+6H2O+2O2
By platinum salt solution is heated to about 65 DEG C in the present invention, then it was rapidly added
The mixed solution (sodium hydroxide is 8:1 with the mol ratio of oleic acid) of amount sodium hydroxide and oleic acid,
Quickly stir 10min, it is thus achieved that platinic hydroxide and oleate mixed solution, then toward in this solution
Add cetyl trimethylammonium bromide (CTAB) and the hydrogen peroxide (cetyl three of 30%
Methyl bromide ammonium addition is: the final concentration of CTAB to be maintained at (0.01mol/L)-
(0.05mol/L), between, the end reaction concentration of hydrogen peroxide is 5%-10%, 30min
Rear stopped reaction, prepares nano oxidized Pt colloids solution, finally adds in colloid solution
Cerium zirconium compound oxide: AC100 (96%Al2O3, 4%La2O3), RC25 (5%La2O3, 5%Y2O3、
60%CeO2, 30%ZrO2), RC35 (5%La2O3, 5%Y2O3, 30%CeO2, 60%ZrO2) etc.
Material mixing is dried, and is sintered to 550 DEG C, prepares nano oxidized platinum catalyst powder.
Nanometer surfactant oleate and cetyl trimethylammonium bromide (CTAB) mixed
Close and use, make the nano oxidized platinum stable in properties prepared, and it is big preferably to control granule
Little.
Above are only a concrete guiding embodiment of the present invention, but the design concept of the present invention
It is not limited thereto, all changes utilizing this design that the present invention carries out unsubstantiality, all should belong to
In the behavior invading protection scope of the present invention.
Claims (8)
1. the preparation method of a nano oxidized platinum catalyst, it is characterised in that comprise the steps:
Platinum salt and oleate solution are reacted generation platinic hydroxide mixed solution, molten in platinic hydroxide mixing
Liquid adds cetyl trimethylammonium bromide and hydrogen peroxide carries out oxidation reaction and prepares nano oxygen
Change Pt colloids solution.
The preparation method of nano oxidized platinum catalyst the most as claimed in claim 1, it is characterised in that
Described oleate solution is the mixed solution of oleic acid and sodium hydroxide, the PH of oleate solution >=
10。
The preparation method of nano oxidized platinum catalyst the most as claimed in claim 1, it is characterised in that
Comprise the steps:
Step one, platinum salt is dissolved in deionized water obtains platinum salt solution, platinum salt solution is heated to
About 65 DEG C；
Step 2, prepare oleate solution: added by sodium hydroxide in deionized water and fully dissolve then
Add oleic acid, make oleic acid fully dissolve and obtain oleate solution；The wherein PH of oleate solution
>=10, described oleate solution is sodium oleate solution；
Step 3, sodium oleate solution is added platinum salt solution reaction obtain platinic hydroxide solution；
Step 4, in platinic hydroxide solution, add cetyl trimethylammonium bromide and hydrogen peroxide solution
Carry out oxidation reaction and prepare nano oxidized Pt colloids solution；Wherein cetyl trimethylammonium bromide
Final concentration of 0.01mol/L-0.05mol/L；
Step 5, in nano oxidized Pt colloids solution add cerium zirconium compound oxide, mixing dry system
Obtain nano oxidized platinum catalyst powder.
The preparation method of nano oxidized platinum catalyst the most as claimed in claim 3, it is characterised in that
In described step one；Platinum salt is platinum nitrate.
The preparation method of nano oxidized platinum catalyst the most as claimed in claim 3, it is characterised in that
In described step 4, the final concentration of 5%-10% of hydrogen peroxide.
The preparation method of nano oxidized platinum catalyst the most as claimed in claim 3, it is characterised in that
In described step 5, cerium zirconium compound oxide includes AC100, RC25 and RC35；AC100、
The mass ratio of RC25 and RC35 is: 2:1:1；Cerium zirconium compound oxide and nano oxidized platinum
Mass ratio is: 100:1；Wherein, AC100 includes 96%Al2O3And 4%La2O3；RC25 bag
Include 5%La2O3, 5%Y2O3, 60%CeO2And 30%ZrO2；RC35 includes 5%La2O3, 5%Y2O3、
30%CeO2And 60%ZrO2。
The preparation method of nano oxidized platinum catalyst the most as claimed in claim 3, it is characterised in that
In described step 5, the temperature of drying is 550 DEG C.
8. the nanometer that the preparation method of the nano oxidized platinum catalyst described in a claim 1 prepares
The purposes of platinum oxide, it is characterised in that described nano oxidized platinum is used as three-way catalyst.
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