CN105597753A - Three-dimensional ordered macroporous lanthanum manganite supported platinum tin nanometer catalyst, and preparation method and application thereof - Google Patents
Three-dimensional ordered macroporous lanthanum manganite supported platinum tin nanometer catalyst, and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- FHMDYDAXYDRBGZ-UHFFFAOYSA-N platinum tin Chemical compound [Sn].[Pt] FHMDYDAXYDRBGZ-UHFFFAOYSA-N 0.000 title abstract 3
- BQENXCOZCUHKRE-UHFFFAOYSA-N [La+3].[La+3].[O-][Mn]([O-])=O.[O-][Mn]([O-])=O.[O-][Mn]([O-])=O Chemical compound [La+3].[La+3].[O-][Mn]([O-])=O.[O-][Mn]([O-])=O.[O-][Mn]([O-])=O BQENXCOZCUHKRE-UHFFFAOYSA-N 0.000 title abstract 2
- 229910002846 Pt–Sn Inorganic materials 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000002105 nanoparticle Substances 0.000 claims abstract description 20
- 230000003197 catalytic effect Effects 0.000 claims abstract description 10
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims abstract description 9
- 239000004926 polymethyl methacrylate Substances 0.000 claims abstract description 9
- 239000013078 crystal Substances 0.000 claims abstract description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 50
- 239000011943 nanocatalyst Substances 0.000 claims description 29
- 239000007864 aqueous solution Substances 0.000 claims description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 12
- 239000003292 glue Substances 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- 229910052718 tin Inorganic materials 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 6
- 239000011572 manganese Substances 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 3
- 238000005352 clarification Methods 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000005457 ice water Substances 0.000 claims description 3
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 claims description 3
- LTUDISCZKZHRMJ-UHFFFAOYSA-N potassium;hydrate Chemical compound O.[K] LTUDISCZKZHRMJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 240000007594 Oryza sativa Species 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 2
- 230000005587 bubbling Effects 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000001802 infusion Methods 0.000 claims description 2
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 claims description 2
- 235000009566 rice Nutrition 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 2
- 229910002328 LaMnO3 Inorganic materials 0.000 abstract description 8
- 239000011148 porous material Substances 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 239000002245 particle Substances 0.000 abstract description 5
- 229910001128 Sn alloy Inorganic materials 0.000 abstract description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 abstract 1
- 238000000746 purification Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 235000013339 cereals Nutrition 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 229910002847 PtSn Inorganic materials 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- HBAGRTDVSXKKDO-UHFFFAOYSA-N dioxido(dioxo)manganese lanthanum(3+) Chemical compound [La+3].[La+3].[O-][Mn]([O-])(=O)=O.[O-][Mn]([O-])(=O)=O.[O-][Mn]([O-])(=O)=O HBAGRTDVSXKKDO-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000006424 Flood reaction Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910002248 LaBO3 Inorganic materials 0.000 description 1
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 1
- 229910006854 SnOx Inorganic materials 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000002468 redox effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
Classifications
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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
- B01J23/54—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
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/656—Manganese, technetium or rhenium
- B01J23/6562—Manganese
-
- 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
-
- 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
-
- B01J35/40—
-
- B01J35/60—
-
- B01J35/613—
-
- 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
-
- 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
Abstract
A three-dimensional ordered macroporous lanthanum manganite supported platinum tin nanometer catalyst, and preparation method and application thereof belong to the technical field of automobile exhaust purification. The pore walls of a perovskite oxide LaMnO3 with a three-dimensional ordered macroporous structure is loaded with Pt-Sn nanoparticles in uniform size. The preparation method is as below: preparing a 3DOM LaMnO3 carrier by using a citrate assisted PMMA colloidal crystal template method, then loading platinum-tin alloy nanoparticles on the LaMnO3 surface by using an acid-modified PVA protection reduction method to obtain Pty-Sn / 3DOM LaMnO3. The catalyst has good three-way catalytic properties, and can effectively remove CO, HC and NOx in a reaction system. The present invention has the characteristics of cheap and readily available raw materials, simple preparation process, controllable morphology, particle size and pore size of the product and excellent catalytic performance.
Description
Technical field
The present invention relates to a kind of lanthanum manganate Supported Pt Nanoparticles tin nanocatalyst with three-dimensional ordered macroporous structure, also relate to thisPt-Sn/3DOMLaMnO3The preparation method of nanocatalyst, the invention still further relates to this nanocatalyst clean at vehicle exhaustThe application in change field, belongs to purifying vehicle exhaust technical field.
Background technology
Motor-vehicle tail-gas is one of Air Pollutant Discharge source, and it mainly comprises carbon monoxide (CO), hydrocarbon (HC)And nitrogen oxide (NOx). Three-way catalyst is to remove at present the most effective catalyst of motor-vehicle tail-gas, it be by Pt, Ph,Pd contour active metal particles loads on and makes on metal oxide carrier. Because noble metal is expensive, how to improve expensiveMetal utilization ratio is eternal problem. Recently, support type Pt-Sn material causes researcher's interest widely because of excellent performance.For example PtSn/Al2O3Nanometer sheet is for preparing propylene by dehydrogenating propane reaction, compared with Pt/Al2O3Show more excellent conversion ratio and selectionProperty (A.H.Lu, etal., Angew.Chem.Int.Ed.2015,54:1 – 6); In hydrogen rich gas atmosphere CO preferential reaction, loadType PtSn nanocatalyst show higher selective and double Pt catalyst conversion ratio (J.L.G.Fierro, etal.,AppliedCatalysisB.2000,24:193 – 205); In addition, Fierro etc. prepares silicon dioxide carried PtSn nanometer and urgesAgent is applied to CO oxidation, finds oxidation state SnOxShow better CO catalytic oxidation performance (J.L.G. compared with metallic state SnFierro, etal., Chem.Mater.1998,10:1333 – 1342). The introducing of Sn can not only improve the catalytic performance of Pt, simultaneouslyEffectively improve the utilization rate of Pt in supported Pt catalysts, reduce catalyst cost.
Perofskite type oxide because of its good redox ability, store oxygen ability and anti-caking power, and at catalyst and urgingAgent carrier aspect is widely applied. At a series of LaBO3In (B=Co, Mn, andFe) material, LevasseurDeng discovery LaMnO3Show best catalysis methanol oxidation susceptibility (B.Levasseur, S.Kaliaguine, Appl.Catal.A2008,343:29-38). Loose structure catalyst is because having higher specific area, larger pore volume and flourishing pore structureAnd it is had great application prospect in physics and chemistry fields such as electricity, magnetic, absorption and catalysis. Macroporous structure can reduce mass transferResistance and impel guest molecule to arrive active sites, meso-hole structure can significantly improve specific area, thereby is conducive to reactant moleculeAbsorption and diffusion, and the catalyst that simultaneously has macropore and mesoporous bimodulus pore structure concurrently will have more excellent performance. In the past severalNian Li, Chinese scholars has been carried out the preparation of three-dimensional ordered macroporous (3DOM-meso) structural material with mesoporous wallResearch widely. Chinese patent (CN201010241853.6) discloses a kind of three-dimensional ordered large-hole manganese with mesoporous wallThe bimodulus plate preparation method of acid lanthanum, adopts taking polymethyl methacrylate (PMMA) microballoon as hard template, with 1B orTriblock copolymer P123 is soft template, taking PEG400 as additive, taking first alcohol and water as solvent, will contain aboveAfter the mixed solution dipping PMMA hard template of soft template, additive, solvent and soluble metallic salt, adopt two one-step baking methods,Prepare 3DOM-mesoLaMnO3。
Due to excellent redox property and larger specific area, 3DOMLaMnO3Be a kind of desirable catalyst or carryBody. If more appropriate Pt-Sn nano particle is supported to 3DOMLaMnO3On carrier, can further improve catalytic performance.In Pt, introduce Sn element, not only will reduce noble metal dosage, will be conducive to improve the redox (Redox) of Pt simultaneouslyPerformance, thus be conducive to the raising of catalytic activity. Up to now, there is no document and patent report crosses and utilizes citric acid auxiliaryThe polyvinyl alcohol protection reducing process that PMMA glue crystal template method and acid are modified is prepared three-dimensional ordered macroporous Pt-Sn/3DOMLaMnO3Catalyst. Therefore, research and development preparation has the LaMnO of three-dimensional ordered macroporous structure3Carried noble metal Pt-Sn catalyst has heavilyWant meaning.
Summary of the invention
The object of the present invention is to provide a kind of lanthanum manganate Supported Pt Nanoparticles tin nanocatalyst with three-dimensional ordered macroporous structure andPreparation method.
Three-dimensional ordered macroporous Pt-Sn/3DOMLaMnO3Nanocatalyst, is characterized in that, has three-dimensional ordered macroporous structurePerofskite type oxide LaMnO3Hole wall on load have the Pt-Sn nano particle of size homogeneous. Pt and Sn can be by appointingMeaning ratio, the load capacity of Pt-Sn nano particle does not have particular/special requirement yet.
As the three-dimensional ordered macroporous Pt-Sn/3DOMLaMnO of the present invention3Preferred version, wherein a Pt-Sn of nanocatalystIn nano particle, the mol ratio y of Pt and Sn is (0～12): 1 or Sn be 0 and contain Pt. Three-dimensional ordered macroporous as the present inventionPt-Sn/3DOMLaMnO3The further preferred version of nanocatalyst, wherein the total load amount of Pt-Sn nano particle is notBe greater than 0.5% (mass fraction).
As the three-dimensional ordered macroporous Pt-Sn/3DOMLaMnO of the present invention3Another preferred version of nanocatalyst, Qi ZhongsanThe perofskite type oxide LaMnO of dimension ordered big hole structure3Macropore diameter be 155nm～175nm. As three-dimensional of the present inventionOrdered big hole Pt-Sn/3DOMLaMnO3The further preferred version of nanocatalyst, wherein three-dimensional ordered macroporous structurePerofskite type oxide LaMnO3Hole wall on to have mesoporous, mesoporous aperture be 9nm～15nm. As three-dimensional of the present inventionOrdered big hole Pt-Sn/3DOMLaMnO3The further preferred version of nanocatalyst, three-dimensional ordered macroporousPt-Sn/3DOMLaMnO3The specific area of nanocatalyst is 25.2m2/g～30.0m2/g。
The present invention also provides one to prepare three-dimensional ordered macroporous Pt-Sn/3DOMLaMnO3The method of nanocatalyst, its spyLevy and be, adopt the PVA protection reducing process that the auxiliary PMMA hard template method of citric acid is modified in conjunction with acid to prepare respectively 3DOMLaMnO3And Pt-Sn/3DOMLaMnO3; Specifically comprise the following steps:
(1)3DOMLaMnO3The preparation of carrier: get lanthanum nitrate hexahydrate and monohydrate potassium join absolute methanol andIn the aqueous solution of ethylene glycol, wherein preferred absolute methanol: ethylene glycol: the volume ratio 7.5:1.5:7 of water, after dissolution of solid,Add manganese nitrate (preferably 50wt% manganese nitrate aqueous solution), after stirring at room temperature is even, add PMMA template, wherein La (NO3)3:Citric acid: Mn (NO3)3: the ratio of absolute methanol is 10mmol:10mmol:10mmol:7.5mL, floods extremely in room temperatureFew 4h, filtration, drying at room temperature obtain 3DOMLaMnO after roasting3Carrier, calcination steps and condition are followed successively by:(a) at N2Under atmosphere, be warming up to 300 DEG C with 1 DEG C/min speed by room temperature, and keep 3h, be naturally down to subsequently room temperature; (b)Under air atmosphere, be warming up to 300 DEG C with 1 DEG C/min speed by room temperature, keep 2h, rise to 1 DEG C/min speed subsequently650 DEG C, keep being naturally down to room temperature after 4h;
(2) under ice-water bath condition, a certain amount of platinum chloride and the stannic chloride aqueous solution are joined in the aqueous solution of PVA, addAppropriate hydrochloric acid, uniform stirring, adds rapidly NaBH subsequently4The aqueous solution rapid stirring, make Pt-Sn nanometre glue after 1h;
(3) adopt bubbling reducing process and the infusion process of PVA protection to prepare Pt-Sn/3DOMLaMnO3Nanocatalyst: pressAccording to Pt-Sn/3DOMLaMnO3Load capacity in nanocatalyst, to the 3DOM that adds step (1) in Pt-Sn nanometre glueLaMnO3Carrier adsorbs under gas sparging is auxiliary, after colloidal solution clarification, filters, washing at 110 DEG CDry 12h, makes Pt-Sn/3DOMLaMnO3Nanocatalyst.
As the three-dimensional ordered macroporous Pt-Sn/3DOMLaMnO of the present invention3Preparation method's a preferred version, in step (2)Pt and Sn gross mass/PVA mass ratio=1.0:1.8. As another preferred version of said method, Pt/HCl in step (2)Mol ratio=1:5. As the further preferred version of said method, Pt and total mole/NaBH of Sn in step (2)4MoleRatio=1:5.
The catalyst of different mol ratio Pt/Sn is called Pty-Sn/3DOMLaMnO3，Pty-Sn/3DOMLaMnO3Middle Pt/SnMol ratio is y (as y=12,6,0), and preferably the total load amount of the Pt-Sn of institute is 0.5% (mass fraction), Pt-Sn nanometerGrain particle diameter is in 5.0nm left and right, and catalyst aperture is 160nm left and right, and specific area is 28m2/ g left and right.
The features such as it is low that the present invention has bullion content, and preparation process is simple, and products therefrom pattern, particle diameter and aperture are controlled.
Pt prepared by the present inventiony-Sn/3DOMLaMnO3(y=12,6,0) have binary metal and three-dimensional ordered macroporous structureFeature and excellent catalytic activity, have a good application prospect in catalytic cleaning of car tail gas field.
Utilize D8ADVANCE type X-ray diffractometer (XRD), ZEISSSUPRA55 type SEM (SEM),The instrumental characterizing gained targets such as JEOL-2010 type transmission electron microscope (TEM) and FEIG280-200/Chemi-STEMCrystal structure, particle morphology, particle structure and the pore structure of product, XPS measures material surface element valence. Result shows,According to the prepared Pt of the inventive methody-Sn/3DOMLaMnO3Catalyst presents 3DOM structure even on large hole wallLoad has Pty-Sn alloy nanoparticle, and Pty-Sn nano particle diameter is in 5.0nm left and right.
Brief description of the drawings
Fig. 1 is obtained Pt/3DOMLaMnO3, and Pty-Sn/3DOMLaMnO3The XRD spectra of (y=12,6,0) catalyst,Wherein curve LMO is LaMnO3The XRD spectra of carrier, (a), (b), (c), (d) be respectively embodiment 1, embodiment 2,The XRD spectra of embodiment 3 and embodiment 4 catalyst.
Fig. 2 is prepared Pt6The HADDF of-Sn nano particle and element scanned photograph.
Fig. 3 is prepared Pt/3DOMLaMnO3And Pty-Sn/3DOMLaMnO3The TEM photo of catalyst, wherein figure (I)(II) is the TEM photo of embodiment 1 catalyst, and (III) and (IV) is the TEM photo of embodiment 3 catalyst.
Fig. 4 is prepared Pt/3DOMLaMnO3And Pty-Sn/3DOMLaMnO3The catalytic activity of (y=12,6,0) catalyst,Wherein (a), (b), (c) and (d) be respectively embodiment 1, embodiment 2, embodiment 3 and embodiment 4 catalyst in CO concentrationBe 1.6%, HC concentration is 0.05% (concentration ratio of propane and propylene is 1:3), NOxConcentration is 0.1%, O2Concentration is1.0％、H2Concentration is 0.23%, N2Balance, air speed is the three-effect catalysis activity curve under 600,000mL/ (gh) condition.
Detailed description of the invention
The following example, just for describing the present invention in detail, does not limit the scope of the invention.
Embodiment 1:
(1)3DOMLaMnO3The preparation of carrier: get 4.33g lanthanum nitrate hexahydrate and 2.10g monohydrate potassium addsIn the mixed solution of 7.5mL absolute methanol, 1.5mL ethylene glycol and 7mL deionized water, after dissolution of solid, add3.58g50wt% manganese nitrate aqueous solution, after stirring at room temperature is even, adds 2gPMMA template, in room temperature dipping 4h, mistakeFilter, drying at room temperature 48h obtain 3DOMLaMnO after roasting3Carrier, calcination steps and condition are followed successively by: (a)At N2Under atmosphere, be warming up to 300 DEG C with 1 DEG C/min speed by room temperature, and keep 3h, be naturally down to subsequently room temperature; (b) existUnder air atmosphere, be warming up to 300 DEG C with 1 DEG C/min speed by room temperature, keep 2h, rise to 650 with 1 DEG C/min speed subsequentlyDEG C, keep being naturally down to room temperature after 4h;
(2) under ice-water bath condition, get 5.13mLH2PtCl6The aqueous solution (1.5mmol/L) joins 1.35mLPVAThe aqueous solution (2.0mg/mL) in, add the 0.38mLHCl aqueous solution (0.1mol/L), uniform stirring 30min (Pt/PVAMass ratio=1.0:1.8, Pt/HCl mol ratio=1:5), add rapidly subsequently 0.73mLNaBH4The aqueous solution (2.0mg/mL)And rapid stirring (Pt/NaBH4Mol ratio=1:5), after 1h, make Pt nanometre glue;
(3) in the Pt nanometre glue making to (2), add 300mg3DOMLaMnO3Carrier, at N2Gas sparging is auxiliaryUnder adsorb, after glue clarification (i.e. absorption is completely), filter, also dry 12h at 110 DEG C of washing, makePt/3DOMLaMnO3Nanocatalyst, aperture is about 160～170nm, and Pt nano particle average grain diameter is 5.1nm.
Embodiment 2:
Prepare Pt/3DOMLaMnO by the method identical with embodiment 13Nanocatalyst, difference is to get 4.89mLH2PtCl6The aqueous solution (1.5mmol/L) and 0.41mLSnCl4The aqueous solution (1.5mmol/L) joins 1.35mLPVAThe aqueous solution (2.0mg/mL) in, add the 0.37mLHCl aqueous solution (0.1mol/L), add rapidly subsequently 0.75mLNaBH4The aqueous solution (2.0mg/mL) rapid stirring, finally make Pt12-Sn/3DOMLaMnO3, aperture is about 155～165nm,Pt12-Sn nano particle average grain diameter is 4.9nm.
Embodiment 3:
Prepare Pt/3DOMLaMnO by the method identical with embodiment 13Nanocatalyst, difference is to get 4.65mLH2PtCl6The aqueous solution (1.5mmol/L) and 0.77mLSnCl4The aqueous solution (1.5mmol/L) joins 1.35mLPVAThe aqueous solution (2.0mg/mL) in, add the 0.35mLHCl aqueous solution (0.1mol/L), add rapidly subsequently 0.77mLNaBH4The aqueous solution (2.0mg/mL) rapid stirring, finally make Pt6-Sn/3DOMLaMnO3, aperture is about 165～175nm,Pt6-Sn nano particle average grain diameter is 5.2nm.
Embodiment 4:
Prepare Pt/3DOMLaMnO by the method identical with embodiment 13Nanocatalyst, difference is to get 8.33mLSnCl4The aqueous solution (1.5mmol/L) joins in the aqueous solution (2.0mg/mL) of 1.35mLPVA, adds rapidly subsequently1.19mLNaBH4The aqueous solution (2.0mg/mL) rapid stirring, finally make Sn/3DOMLaMnO3, aperture is about160～170nm, Sn nano particle average grain diameter is 5.3nm.
Claims (9)
1. a three-dimensional ordered macroporous Pt-Sn/3DOMLaMnO3Nanocatalyst, is characterized in that, has three-dimensionalThe perofskite type oxide LaMnO of ordered big hole structure3Hole wall on load have the Pt-Sn nano particle of size homogeneous.
2. according to three-dimensional ordered macroporous Pt-Sn/3DOMLaMnO claimed in claim 13Nanocatalyst, its spyLevy and be, in Pt-Sn nano particle, the mol ratio y of Pt and Sn is (0～12): 1 or only contain Pt.
3. according to three-dimensional ordered macroporous Pt-Sn/3DOMLaMnO claimed in claim 23Nanocatalyst, its spyLevy and be, the total load amount of Pt-Sn nano particle is not more than 0.5% (mass fraction).
4. according to three-dimensional ordered macroporous Pt-Sn/3DOMLaMnO claimed in claim 13Nanocatalyst, its spyLevy and be, the perofskite type oxide LaMnO of three-dimensional ordered macroporous structure3Macropore diameter be 155nm～175nm.
5. according to three-dimensional ordered macroporous Pt-Sn/3DOMLaMnO claimed in claim 43Nanocatalyst, its spyLevy and be, the perofskite type oxide LaMnO of three-dimensional ordered macroporous structure3Hole wall on have mesoporous, mesoporous aperture to be9nm～15nm。
6. according to three-dimensional ordered macroporous Pt-Sn/3DOMLaMnO claimed in claim 53Nanocatalyst, its spyLevy and be, three-dimensional ordered macroporous Pt-Sn/3DOMLaMnO3The specific area of nanocatalyst is 25.2m2/g～30.0m2/g。
7. a three-dimensional ordered macroporous Pt-Sn/3DOMLaMnO who prepares described in claim 1 to 6 any one3ReceiveThe method of rice catalyst, is characterized in that, the PVA that adopts the auxiliary PMMA glue crystal template method of citric acid to modify in conjunction with acidProtection reducing process is prepared respectively 3DOMLaMnO3And Pt-Sn/3DOMLaMnO3; Specifically comprise the following steps:
(1)3DOMLaMnO3The preparation of carrier: get lanthanum nitrate hexahydrate and monohydrate potassium join absolute methanol andIn the aqueous solution of ethylene glycol, wherein preferred absolute methanol: ethylene glycol: the volume ratio 7.5:1.5:7 of water, treats that solid is moltenXie Hou, adds manganese nitrate, after stirring at room temperature is even, adds PMMA template, wherein La (NO3)3: citric acid:Mn(NO3)3: the ratio of absolute methanol is 10mmol:10mmol:10mmol:7.5mL, in room temperature dipping at least 4H, filtration, drying at room temperature obtain 3DOMLaMnO after roasting3Carrier, calcination steps and condition are followed successively by:(a) at N2Under atmosphere, be warming up to 300 DEG C with 1 DEG C/min speed by room temperature, and keep 3h, be naturally down to subsequently room temperature;(b) under air atmosphere, be warming up to 300 DEG C with 1 DEG C/min speed by room temperature, keep 2h, subsequently with 1 DEG C/min speedDegree rises to 650 DEG C, keeps being naturally down to room temperature after 4h;
(2) under ice-water bath condition, a certain amount of platinum chloride and the stannic chloride aqueous solution are joined in the aqueous solution of PVA, addEnter appropriate hydrochloric acid, uniform stirring, adds rapidly NaBH subsequently4The aqueous solution rapid stirring, make Pt-Sn after 1hNanometre glue;
(3) adopt bubbling reducing process and the infusion process of PVA protection to prepare Pt-Sn/3DOMLaMnO3Nanocatalyst: pressAccording to Pt-Sn/3DOMLaMnO3Load capacity in nanocatalyst, to adding step (1) in Pt-Sn nanometre glue 3DOMLaMnO3Carrier adsorbs under gas sparging is auxiliary, after colloidal solution clarification, filters, washsAnd at 110 DEG C, be dried 12h, make Pt-Sn/3DOMLaMnO3Nanocatalyst.
8. according to preparation method claimed in claim 7, it is characterized in that Pt and Sn gross mass in step (2)Mass ratio=1.0:1.8 of/PVA; Mol ratio=1:5 of Pt/HCl; Total molal weight/the NaBH of Pt and Sn4MoleRatio=1:5.
9. the three-dimensional ordered macroporous Pt-Sn/3DOMLaMnO described in claim 1 to 6 any one3NanocatalystApplication in catalytic cleaning of car tail gas field.
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| CN113198495A (en) * | 2021-05-25 | 2021-08-03 | 四川大学 | Fluorine modified lanthanum-manganese composite oxide SCR denitration catalyst and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107046137A (en) * | 2016-02-05 | 2017-08-15 | 天津大学 | Porous LaCr oxides-carbon composite and its synthetic method |
| CN110801828A (en) * | 2019-11-04 | 2020-02-18 | 桂林理工大学 | Catalyst for preparing olefin by oxidative dehydrogenation of ethane chemical chain and application of catalyst in oxidative dehydrogenation reaction of ethane |
| CN113087022A (en) * | 2021-04-07 | 2021-07-09 | 昆明理工大学 | Preparation method and application of lanthanum manganate with three-dimensional ordered porous structure |
| CN113198495A (en) * | 2021-05-25 | 2021-08-03 | 四川大学 | Fluorine modified lanthanum-manganese composite oxide SCR denitration catalyst and preparation method thereof |
| CN113304744A (en) * | 2021-06-10 | 2021-08-27 | 中国科学院城市环境研究所 | Catalyst, preparation method and application thereof |
| CN113304744B (en) * | 2021-06-10 | 2023-03-03 | 中国科学院城市环境研究所 | Catalyst, preparation method and application thereof |
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