CN107456973A - Hierarchical self-assembly perovskite micro-sphere structure preparation method and products thereof and application - Google Patents
Hierarchical self-assembly perovskite micro-sphere structure preparation method and products thereof and application Download PDFInfo
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- CN107456973A CN107456973A CN201710650547.XA CN201710650547A CN107456973A CN 107456973 A CN107456973 A CN 107456973A CN 201710650547 A CN201710650547 A CN 201710650547A CN 107456973 A CN107456973 A CN 107456973A
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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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- 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
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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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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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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Abstract
The present invention relates to a kind of Hierarchical self-assembly perovskite micro-sphere structure preparation method and products thereof and application, a kind of Hierarchical self-assembly LaFe is specifically disclosed0.65Co0.35O3The preparation method of perovskite micro-sphere structure, using water miscible salt as the presoma for preparing Hierarchical self-assembly RE perovskite micro-sphere structure, template is added, the hydroxide of component is generated after hexa addition, reheating processing generation RE perovskite, it is not necessary to the course of reaction of long period.By controlling the dosage of hexa to can be obtained by the Hierarchical self-assembly RE perovskite micro-sphere structure of different-shape.The present invention is simple to operate, and reaction temperature is relatively low, prepares RE perovskite micro-sphere structure even size distribution, structure-controllable.Classification prepared by the invention independently fills RE perovskite micro-sphere structure available for vehicle maintenance service etc..
Description
Technical field
It is prepared by RE perovskite technology of preparing of the present invention, especially a kind of Hierarchical self-assembly perovskite micro-sphere structure
Method and products thereof and application, in particular to a kind of Hierarchical self-assembly LaFe0.65Co0.35O3Perovskite micro-sphere structure preparation method
And products thereof and application.
Background technology
China is currently one of area of atmosphere pollution most serious in the world, and more ground PM2.5 indexes are throughout the year more than 100, far
Exceed well over WHO standard（Year average 10）.In recent years, the situation is tense for China's atmosphere pollution, and more ground haze weather in the whole nation takes place frequently,
With inhalable particulate matter, fine particles thing（PM2.5）The pollution problem that nitrogen oxides is characterized becomes increasingly conspicuous.And the nitrogen in air
Oxide, although maximum source is thermal power generation, next to that industry and traffic and transportation sector, contribute to 40%, 23% and respectively
20%, but automobile is pollution sources the most serious to individual palpation for utilization rate per capita.Therefore, country and local such as Beijing, Shanghai
Recently the environmental protection policy regulation formulated, some areas are first from strict regulations, particularly 2016 year April has all been made to motor vehicle emission
The more strict discharge standard of state five is first carried out, the car of state four standard stops registering the license or transferring ownership.These all illustrate that automobile is arranged
Put the importance that control is administered to air.Harmless treatment to pollutants such as NOx, CO and HC, while environment is improved,
The harm to the mankind's particularly Susceptible population such as children and old man health is reduced, this is also recessive huge society's effect
Benefit.
Controlled for motor vehicle exhaust emission, development one kind has self-regeneration characteristic, to tri- kinds of main pollutions of NOx/CO/HC
Constituent element is simultaneously effective, and perovskite-based rare earth oxide catalyst is used only, in the same of guarantee catalytic efficiency and stability
When reduce rare precious metal dosage.
The content of the invention
For overcome the deficiencies in the prior art, it is an object of the invention to provide a kind of Hierarchical self-assembly perovskite micro-sphere structure system
Preparation Method
Another object of the present invention is：The product that above-mentioned preparation method obtains is provided.
A further object of the present invention is：The application that above-mentioned preparation method obtains product is provided.
The object of the invention is realized by following proposal：A kind of Hierarchical self-assembly perovskite micro-sphere structure preparation method, to divide
Level self assembly LaFe0.65Co0.35O3Perovskite micro-sphere structure preparation method, comprises the following steps：
（1）The salt of cobalt, iron, lanthanum is dissolved in deionized water and forms mixed solution, the mol ratio of the various salt of cobalt, iron, lanthanum is La2+:
Fe3+:Co3+=1:0.65:0.35, after stirring, add template；
（2）In step（1）Pregnancy urotropine is added dropwise in obtained solution makes lanthanum, iron, cobalt formation hydroxide sink as precipitating reagent
Form sediment；
（3）By step（2）Obtained lanthanum, iron, cobalt precipitation use deionized water centrifuge washing 3 times, after oven drying 24 hours, put
Enter Muffle furnace 700oC burns 5 ~ 10 hours, obtains the RE perovskite pure phase of microballoon.
The present invention uses sol-gel process, synthesizes Hierarchical self-assembly microballoon in aqueous using chemical solution method, improves
The contact area of perovskite catalyst, so as to improve catalytic efficiency.Can be by changing containing for hexa in reaction system
The final pattern of amount regulation and control perovskite, reacts 100oBelow C is carried out, and the reaction time is short, then handles mixture at high temperature
Become perovskite single phase.
On the basis of such scheme, the cobalt salt for being dissolved in water is one kind of cobalt chloride or cobalt oxalate, and molysite is iron chloride or nitre
One kind of sour iron, lanthanum salt are lanthanum nitrate.
Preferably, step（1）In, stirring condition is：It is 200 ~ 600rpm, time 60min that speed, which is stirred at room temperature,.
Preferably, step（1）Described template is carbon dust or molecular sieve, with La2+Mol ratio be 3 ~ 6:1, add solution
Middle stirring 2h.
Preferably, step（2）The mol ratio of middle pregnancy urotropine and three metal ion species summations is 4 ~ 2:1, add above-mentioned
In 60-90 in solutionoC reacts 0.5 ~ 3h, obtains brown precipitate.
The present invention provides a kind of Hierarchical self-assembly LaFe obtained according to any of the above-described preparation method0.65Co0.35O3Calcium
Titanium ore micro-sphere structure product matter.
The present invention provides also a kind of above-mentioned Hierarchical self-assembly LaFe0.65Co0.35O3Perovskite micro-sphere structure is used for vehicle exhaust
The application of improvement.
The present invention is advantageous in that：Preparation method is simple to operate, and reaction temperature is relatively low, prepares RE perovskite microballoon
Physical dimension is evenly distributed, structure-controllable.Classification prepared by the invention independently fills RE perovskite micro-sphere structure and can be used for automobile
Vent gas treatment etc..
Embodiment
Embodiment 1
The lanthanum nitrate for weighing 0.01mol is dissolved in 100ml deionized waters and forms La2+Solution, by La2+:Fe3+:Co3+Ratio is 1:
0.65:0.35 continues to weigh iron chloride and cobalt chloride, is mixed into 200rpm in above-mentioned solution and stirs 60min；Add 0.03mol carbon
Powder, continue to stir 2h, metal ion is fully contacted with carbon dust；Then, 0.08mol pregnancy urotropine is added as precipitating reagent
Hydroxide precipitation is formed, 60oC reacts 0.5h, obtains tan precipitate.Sediment deionized water centrifuge washing 3 times,
80oC oven drying is put into Muffle furnace 700 after 24 hoursoC burns 5 hours, obtains flower-shaped perovskite self-assembly microspheres.
Embodiment 2
The lanthanum nitrate for weighing 0.01mol is dissolved in 100ml deionized waters and forms La2+Solution, by La2+:Fe3+:Co3+Ratio is 1:
0.65:0.35 continues to weigh iron chloride and cobalt chloride, is mixed into 400rpm in above-mentioned solution and stirs 60min.Add 0.12mol point
Son sieve, continue to stir 2h, metal ion is fully contacted with carbon dust, add 0.04mol pregnancy urotropine as precipitation dosage form
Hydrate precipitates, 90oC reacts 3h, obtains tan precipitate.Sediment deionized water centrifuge washing 3 times, 80oC
Oven drying after 24 hours, be put into Muffle furnace 700oC burns 10 hours, obtains spherical perovskite self-assembly microspheres.
Embodiment 3
The lanthanum nitrate for weighing 0.01mol is dissolved in 100ml deionized waters and forms La2+Solution, by La2+:Fe3+:Co3+Ratio is 1:
0.65:0.35 continues to weigh iron chloride and cobalt chloride, is mixed into 600rpm in above-mentioned solution and stirs 60min.Add 0.10mol point
Son sieve, continue to stir 2h, metal ion is fully contacted with carbon dust, add 0.06mol pregnancy urotropine as precipitation dosage form
Hydrate precipitates, 75oC reacts 1.5h, obtains tan precipitate.Sediment deionized water centrifuge washing 3 times,
80oC oven drying is put into Muffle furnace 700 after 24 hoursoC burns 7 hours, obtains spherical flower-shaped perovskite self-assembly microspheres.
Gas is included into CO, NO and C3H8 mixture by catalyst phase, air inlet and outlet are detected with gaseous mass analyzer
Three kinds of gas concentrations of mouth, draw the data of gas conversion ratio.
。
Claims (7)
- A kind of 1. Hierarchical self-assembly perovskite micro-sphere structure preparation method, it is characterised in that Hierarchical self-assembly LaFe0.65Co0.35O3 Prepared by perovskite micro-sphere structure comprises the following steps：（1）The salt of cobalt, iron, lanthanum is dissolved in deionized water and forms mixed solution, the mol ratio of the various salt of cobalt, iron, lanthanum is La2+: Fe3+:Co3+=1:0.65:0.35, after stirring, add template；（2）In step（1）Pregnancy urotropine is added dropwise in obtained solution makes lanthanum, iron, cobalt formation hydroxide sink as precipitating reagent Form sediment；（3）By step（2）Obtained lanthanum, iron, cobalt precipitation use deionized water centrifuge washing 3 times, after oven drying 24 hours, put Enter Muffle furnace 700oC burns 5 ~ 10 hours, obtains the RE perovskite pure phase of microballoon.
- 2. the Hierarchical self-assembly perovskite micro-sphere structure preparation method as described in claim 1, it is characterised in that be dissolved in the cobalt salt of water For one kind of cobalt chloride or cobalt oxalate, molysite is one kind of iron chloride or ferric nitrate, and lanthanum salt is lanthanum nitrate.
- 3. the Hierarchical self-assembly perovskite micro-sphere structure preparation method as described in claim 1, it is characterised in that step（1）In room The lower mixing speed of temperature is 200 ~ 600rpm, time 60min.
- 4. the Hierarchical self-assembly perovskite micro-sphere structure preparation method as described in claim 1, it is characterised in that step（1）It is described Template be carbon dust or molecular sieve, with La2+Mol ratio be 3 ~ 6:1, add in solution and stir 2h.
- 5. press the Hierarchical self-assembly perovskite micro-sphere structure preparation method of claim 1 or 2, it is characterised in that step（2）In The mol ratio of pregnancy urotropine and three metal ion species summations is 4 ~ 2:1, add in above-mentioned solution in 60-90oC reactions 0.5 ~ 3h, obtain brown precipitate.
- A kind of 6. Hierarchical self-assembly LaFe obtained according to any preparation methods of claim 1-50.65Co0.35O3Perovskite Micro-sphere structure product.
- A kind of 7. Hierarchical self-assembly LaFe according to claim 60.65Co0.35O3Perovskite micro-sphere structure product is used for automobile The application for the treatment of tail gas.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5380692A (en) * | 1991-09-12 | 1995-01-10 | Sakai Chemical Industry Co., Ltd. | Catalyst for catalytic reduction of nitrogen oxide |
| WO1999064377A1 (en) * | 1998-06-05 | 1999-12-16 | Rhodia Chimie | Method for dehydrogenating an organic compound using a catalyst comprising a perovskite |
| CN105720277A (en) * | 2016-04-12 | 2016-06-29 | 华中科技大学 | Three-dimensional porous perovskite catalyst La<x>Sr(1-x)Co<y>Fe<1-y>O<3> and preparation method thereof |
-
2017
- 2017-08-02 CN CN201710650547.XA patent/CN107456973A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5380692A (en) * | 1991-09-12 | 1995-01-10 | Sakai Chemical Industry Co., Ltd. | Catalyst for catalytic reduction of nitrogen oxide |
| WO1999064377A1 (en) * | 1998-06-05 | 1999-12-16 | Rhodia Chimie | Method for dehydrogenating an organic compound using a catalyst comprising a perovskite |
| CN105720277A (en) * | 2016-04-12 | 2016-06-29 | 华中科技大学 | Three-dimensional porous perovskite catalyst La<x>Sr(1-x)Co<y>Fe<1-y>O<3> and preparation method thereof |
Non-Patent Citations (6)
| Title |
|---|
| G.C. MONDRAGÓN RODRÍGUEZ等: ""Pd-integrated perovskites for TWC applications: Synthesis, microstructure and N2O-selectivity"", 《CATALYSIS TODAY》 * |
| YONGXIA WANG等: ""High surface area mesoporous LaFexCo1−xO3 oxides:synthesis and electrocatalytic property for oxygen reduction"", 《DALTON TRANS》 * |
| 姚儒霖等: ""碳微球为模板制备LaCoxFe1-xO3催化剂及其催化甲烷燃烧性能研究"", 《化学通报》 * |
| 李丽著: "《汽车尾气净化催化剂铁基稀土钙钛矿的结构和性能研究》", 31 December 2007, 黑龙江大学出版社 * |
| 杨雨晴等: ""共沉淀法制备LaFexCo1−xO3钙钛矿的研究"", 《自然科学》 * |
| 蒙衍强等: ""稀土钙钛矿型复合氧化物在汽车尾气净化中的应用"", 《广西化工》 * |
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