CN101112683A - Cerium zirconium aluminum composite oxides sosoloid with a mesopore structure and method for preparing the same - Google Patents
Cerium zirconium aluminum composite oxides sosoloid with a mesopore structure and method for preparing the same Download PDFInfo
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- CN101112683A CN101112683A CNA2007100577610A CN200710057761A CN101112683A CN 101112683 A CN101112683 A CN 101112683A CN A2007100577610 A CNA2007100577610 A CN A2007100577610A CN 200710057761 A CN200710057761 A CN 200710057761A CN 101112683 A CN101112683 A CN 101112683A
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- aluminum composite
- composite oxides
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Abstract
The invention relates to a preparation method for the cerium-zirconium-aluminum composite oxide solid solution material with mesopore structure. The mesopore Ce1-x-yZrxAlyO2 (x is equal to 0.10-0.45; y is equal to 0.10-0.45) solid solution with high specific surface (200m2/g through 250m2/g) is prepared for one step by adopting the simple surface active agent (CTMACI) method, the hole diameter ranges from 2.5 nm to 3.4 nm, the worm-shaped channel structure with narrow distribution of hole diameter, and the invention can be used for high activity catalyst or catalyst carrier. In the preparation process, the operation is simple, the raw material is easy to be obtained and the invention is suitable for the industrial enlarged production.
Description
Technical field
The present invention relates to a kind of catalysis material, particularly have the preparation of the cerium zirconium aluminum composite oxides sosoloid material of meso-hole structure, belong to the synthetic field of inorganic material.
Background technology
Cerium oxide is a kind of very important functional material because its valence state changeability has the oxygen of storing function, is widely used in catalyst, solid fuel cell, UV Absorption, glass polishing material etc.Doping ZrO
2After can effectively improve CeO
2Oxygen storage capacity, redox property and heat endurance.CeO with meso-hole structure
2-ZrO
2Compound is because shape is selected, the catalytic performance that can be enhanced in its high-ratio surface and duct.Document New J.Chem.2005,29,237 have reported with the KLE macromolecule and have prepared mesoporous Ce as template
0.5Zr
0.5O
2Document J.Am.Chem.Soc.2007,129,6698 have reported the order mesoporous Ce of crystallization wall
1-xZr
xO
2(x=0.4-0.8) solid solution.
Though cerium zirconium sosoloid at high temperature can keep good storage oxygen performance, the heat endurance of texture is relatively poor, and specific surface is lower, and the cubic phase zirconium dioxide that easily dissociates under higher temperature makes single cube to be transformed into heterogeneous coexistence mutually.In order to make its catalytic performance reach best, the texture of cerium zirconium sosoloid and the heat endurance of structure have much room for improvement.Chinese patent CN1449863A discloses a kind of nano cerium zirconium based compound oxide, make with the method for hydrogen peroxide and ammoniacal liquor co-precipitation, but its specific surface is lower, imporosity.Chinese patent CN1695798A discloses a kind of Ce-Zr-Al based oxide solid solution, but needs to add stabilizing agent in its preparation, selects at least a used as stabilizers in lanthana, yittrium oxide and the alkaline earth oxide for use, and its preparation method complexity.Chinese patent CN1935359A and CN1962051A also disclose the preparation of Ce-Zr based composite oxide material.The above most specific surface of reporting of these cerium zirconium base oxide solid solution is not high, and imporosity, complicated process of preparation, and catalytic activity is lower when being used for catalyst carrier.
We adopt a kind of easy method, and a step synthesizes the meso-hole structure cerium zirconium aluminum composite oxides sosoloid material with high-ratio surface.The solid solution permeability that is synthesized is big, crystalline phase is single, the specific surface height, and catalyst list dispersion amount is big during as catalyst carrier, and is active high, has very high actual application value.
Summary of the invention
The object of the present invention is to provide a kind of meso-hole structure cerium zirconium aluminum composite oxides sosoloid preparation methods of high-ratio surface.The mesoporous cerium zirconium aluminum composite oxides sosoloid that adopts simple surfactant method to prepare has single cubic fluorite crystalline phase, and the specific surface of sample is up to 250m after 450 ℃ of high-temperature roastings
2/ g, average pore size is 2.5～3.4nm, pore size distribution is narrow, pore volume 0.3cm
3More than/the g.It is simple, easy and simple to handle to test used instrument, and raw material is easy to get.
It is as follows that one-step method prepares the concrete grammar of meso-hole structure cerium zirconium aluminum composite oxides sosoloid among the present invention:
Under the room temperature, take by weighing certain amount of surfactant CTAB and be dissolved in the deionized water, add Ce (NO under the vigorous stirring by a certain percentage
3)
3, Zr (NO
3)
4And Al (NO
3)
3, continue to stir a period of time, add the NaOH solution of 0.2M, stir the suspension 3～12h that obtains, 90 ℃ of aging 3～5h, hot wash, suction filtration, 90～120 ℃ of drying 4～8h, 300～800 ℃ of roasting 3～5h prepare meso-pore Ce
1-x-yZr
xAl
yO
2(x=0.10-0.45, y=0.1-0.45) solid-solution powder sample.
The material of preparation gained is used XRD, nitrogen adsorption desorption analysis, TEM, TG-DTA, H respectively
2-TPR etc. characterize its structure and performance, and the result invests Fig. 1～Fig. 3.XRD analysis has formed single cubic fluorite crystalline phase Ce after showing 400-500 ℃ of roasting
1-x-yZr
xAl
yO
2Solid solution.The mesoporous aperture size 2.6-2.8nm of material (calculating of BJH method), the vermiform pore passage structure, specific surface is up to 200-250m
2/ g, pore volume 0.2-0.3cm
3/ g.
Characteristics of the present invention are: adopting surfactant hexadecyltrimethylammonium chloride (CTMACl) is the template agent, and simple one-step method is prepared meso-pore Ce
1-x-yZr
xAl
yO
2Solid solution, gained sample specific surface height, mesoporous aperture are narrow respectively, oxygen storage capacity is high and Heat stability is good, is suitable for use as high activated catalyst or catalyst carrier, are applied in the catalyst system and catalyzings such as purifying vehicle exhaust, catalytic combustion.This method preparation technology and equipment are simple, and is simple to operate, and raw material is easy to get, and great industrial production prospects is arranged.
Description of drawings
Fig. 1 is the meso-pore Ce that the present invention prepares
0.7Zr
0.2Al
0.1O
2X-ray diffraction spectrogram after 450 ℃ of roastings of solid solution shows that sample has single cubic fluorite crystalline phase.
Fig. 2 is the meso-pore Ce that the present invention prepares
0.7Zr
0.2Al
0.1O
2Nitrogen adsorption-desorption isotherm figure after 450 ℃ of roastings of solid solution shows that the solid solution of preparing possesses typical meso-hole structure.
Fig. 3 is the meso-pore Ce that the present invention prepares
0.7Zr
0.2Al
0.1O
2Transmission electron microscope photo after 450 ℃ of roastings of solid solution demonstrates the meso-hole structure of wormhole shape.
The specific embodiment
Under the room temperature, take by weighing 6mmol CTMACl, be dissolved in the 200mL deionized water, vigorous stirring added the Ce (NO of amount of calculation after 15 minutes in solution
3)
36H
2O, Zr (NO
3)
45H
2O and Al (NO
3)
36H
2O (mol ratio 3.5: 1.0: 0.5) continues to stir 30 minutes, and NaOH solution to the pH value that adds 0.2M is 10, the suspension that stirring obtains 12 hours, 90 ℃ were worn out hot wash, suction filtration 3 hours, 110 ℃ of dryings 6 hours, the meso-pore Ce of mesoporous preparation is prepared in 450 ℃ of roastings 4 hours
0.7Zr
0.2Al
0.1O
2Solid solution, its XRD, nitrogen adsorption desorption analysis, tem analysis are as Figure 1-3.
Mixed solution among the embodiment 1 is regulated system pH value 9 with NaOH, and other is all with embodiment 1.The meso-pore Ce of preparing
0.7Zr
0.2Al
0.1O
2The XRD of solid solution sample and nitrogen adsorption desorption analysis are shown in Fig. 1-2.
Change the mol ratio of Ce/Zr/Al in the reaction solution among the embodiment 1 into 3: 1: 1, other all with embodiment 1, prepares meso-pore Ce
0.6Zr
0.2Al
0.2O
2The solid solution sample.Its XRD, nitrogen adsorption, transmission electron microscope picture is similar to Fig. 1-3.
Embodiment 4
Change the mol ratio of Ce/Zr/Al in the reaction solution among the embodiment 1 into 4: 0.5: 0.5, other all with embodiment 1, prepares meso-pore Ce
0.8Zr
0.1Al
0.1O
2The solid solution sample.Its XRD, nitrogen adsorption, transmission electron microscope picture is similar to Fig. 1-3.
Embodiment 5
Change the mol ratio of Ce/Zr/Al in the reaction solution among the embodiment 1 into 2.5: 1.5: 1, other all with embodiment 1, prepares meso-pore Ce
0.5Zr
0.3Al
0.2O
2The solid solution sample.Its XRD, nitrogen adsorption, transmission electron microscope picture is similar to Fig. 1-3.
Claims (9)
1. meso-hole structure cerium zirconium aluminum composite oxides sosoloid, it is characterized in that: the composition of this compound mainly contains aluminium oxide, cerium oxide and zirconia, exists with homogeneous solid solution structure form, can chemical general formula " Ce
1-x-yZr
xAl
yO
2" expression, wherein x=0.10-0.45; Y=0.10-0.45.
2. the described a kind of meso-hole structure cerium zirconium aluminum composite oxides sosoloid of claim 1 is characterized in that it has single cube fluorite crystalline phase, high-ratio surface (200-250m
2/ g), narrow mesoporous distribution (2.5-3.4nm), large pore volume (0.2-0.3cm
3/ g), the vermiform pore passage structure can be used as high activated catalyst or catalyst carrier.
3. according to the preparation method of claim 1 and 2 described mesoporous cerium zirconium aluminum composite oxides sosoloids, it is characterized in that adopting the preparation of surfactant hexadecyltrimethylammonium chloride (CTMACl) one-step method, simple to operate in the preparation process, raw material is easy to get.
4. the preparation method of the described solid solution of claim 3 is characterized in that comprising the following steps: a certain amount of CTMACl is dissolved in the deionized water, adds the Ce (NO of amount of calculation
3)
3, Zr (NO
3)
4And Al (NO
3)
3, the NaOH solution of adding 0.2M stirs the suspension that obtains after stirring a period of time, and is aging, hot wash, and oven dry, mesoporous cerium zirconium aluminum composite oxides powder is prepared in roasting.
5. the preparation method of solid solution according to claim 4, it is characterized in that: the mol ratio of CTMACl and cerous nitrate is 1: 2～2: 1; The mol ratio of cerous nitrate and zirconium nitrate is 4: 1～1: 1; The mol ratio of cerous nitrate and aluminum nitrate is 4: 1～1: 1.
6. the preparation method of solid solution according to claim 4 is characterized in that: the mixing time of mixing suspension is 3～12 hours; The aging temperature that mixes suspension is 90 ℃, and ageing time is 3～5 hours.
7. the preparation method of solid solution according to claim 4 is characterized in that: the pH value of mixing suspension is 8.5～11.
8. the preparation method of solid solution according to claim 4, it is characterized in that: bake out temperature is 90～120 ℃, drying time is 4～8h.
9. the preparation method of solid solution according to claim 4, it is characterized in that: the sintering temperature of solid solution is 300～800 ℃, roasting time is 3～5h.
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|---|---|---|---|
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101429028B (en) * | 2008-11-28 | 2012-01-25 | 同济大学 | Method for producing Zr0.30Ce0.45Al0.25O1.87sosoloid nano-particle |
| CN102407164A (en) * | 2011-10-09 | 2012-04-11 | 南京大学 | Cerium zirconium aluminum nanometer composite with mesoporous structure and preparation method and use thereof |
| CN102824904A (en) * | 2012-09-20 | 2012-12-19 | 上海华明高纳稀土新材料有限公司 | Composite aluminium, cerium and zirconium oxide catalytic material and method for producing same |
| CN102962047A (en) * | 2012-11-12 | 2013-03-13 | 上海华明高纳稀土新材料有限公司 | Aluminum-cerium-zirconium based composite oxide catalytic material and preparation method thereof |
| CN103623835B (en) * | 2013-11-08 | 2016-05-04 | 北京龙宝科技发展有限公司 | A kind of tail gas catalytic purification absorbing material, preparation technology and purification method |
| CN105709841A (en) * | 2016-01-18 | 2016-06-29 | 张玲 | Preparation of n-butene skeletal isomerization catalyst |
| CN106964332A (en) * | 2011-07-01 | 2017-07-21 | 特莱巴赫工业有限公司 | Cerium oxide zirconia alumina composition with enhanced heat endurance |
| CN109964349A (en) * | 2016-11-24 | 2019-07-02 | 罗伯特·博世有限公司 | Method for the anode of fuel cell and for manufacturing anode |
-
2007
- 2007-06-27 CN CNA2007100577610A patent/CN101112683A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101429028B (en) * | 2008-11-28 | 2012-01-25 | 同济大学 | Method for producing Zr0.30Ce0.45Al0.25O1.87sosoloid nano-particle |
| CN106964332A (en) * | 2011-07-01 | 2017-07-21 | 特莱巴赫工业有限公司 | Cerium oxide zirconia alumina composition with enhanced heat endurance |
| CN102407164A (en) * | 2011-10-09 | 2012-04-11 | 南京大学 | Cerium zirconium aluminum nanometer composite with mesoporous structure and preparation method and use thereof |
| CN102824904A (en) * | 2012-09-20 | 2012-12-19 | 上海华明高纳稀土新材料有限公司 | Composite aluminium, cerium and zirconium oxide catalytic material and method for producing same |
| CN102824904B (en) * | 2012-09-20 | 2015-09-02 | 上海华明高纳稀土新材料有限公司 | Aluminium cerium zirconium compound oxide catalysis material and preparation method thereof |
| CN102962047A (en) * | 2012-11-12 | 2013-03-13 | 上海华明高纳稀土新材料有限公司 | Aluminum-cerium-zirconium based composite oxide catalytic material and preparation method thereof |
| CN102962047B (en) * | 2012-11-12 | 2014-10-08 | 上海华明高纳稀土新材料有限公司 | Aluminum-cerium-zirconium based composite oxide catalytic material and preparation method thereof |
| CN103623835B (en) * | 2013-11-08 | 2016-05-04 | 北京龙宝科技发展有限公司 | A kind of tail gas catalytic purification absorbing material, preparation technology and purification method |
| CN105709841A (en) * | 2016-01-18 | 2016-06-29 | 张玲 | Preparation of n-butene skeletal isomerization catalyst |
| CN109964349A (en) * | 2016-11-24 | 2019-07-02 | 罗伯特·博世有限公司 | Method for the anode of fuel cell and for manufacturing anode |
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Open date: 20080130 |