CN1242844C - Highly specific surface area possessed cerium-zirconium solid solution and its preparing method - Google Patents
Highly specific surface area possessed cerium-zirconium solid solution and its preparing method Download PDFInfo
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- CN1242844C CN1242844C CN 03129432 CN03129432A CN1242844C CN 1242844 C CN1242844 C CN 1242844C CN 03129432 CN03129432 CN 03129432 CN 03129432 A CN03129432 A CN 03129432A CN 1242844 C CN1242844 C CN 1242844C
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- cerium
- zirconium
- surface area
- specific surface
- solid solution
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Abstract
The present invention relates to a cerium zirconium solid solution with a high specific surface area, which is characterized in that the chemical molecular formula of a cerium zirconium solid solution is Ce<x>Zr<1-x>O<2>, and the molar ratio of cerium and zirconium meets the following requirements of Ce=x, Zr=1-x and x=0.1-1.0. The preparation technology of the cerium zirconium solid solution with a high specific surface area comprises: cerous nitrate (Ce (No3) 3 6H2O) and zirconium nitrate (Zr (NO3) 4 5H2O) are used as raw materials, and a proper amount of distilled water is added in the raw materials; the distilled water is heated for dissolving the cerous nitrate and the zirconium nitrate, and then, a cationic surface active agent of certain proportion is added; an obtained solution is dropped in ammonia water under stirring, and the pH value of obtained deposition liquid is regulated by sodium hydroxide; precipitates are aged, washed, dried and calcined to obtain the cerium zirconium solid solution with a high specific surface area. The present invention has the advantages of simple technological process, homogeneous component and large specific surface area.
Description
Technical field
The present invention relates to a kind of cerium zirconium sosoloid and preparation method thereof, particularly prescription of high-specific surface area cerium zirconium sosoloid and preparation method thereof.
Background technology
CeO
2And the research of associated materials is subjected to people and pays close attention to greatly, and relevant studies show that is at CeO
2The middle ZrO that adds
2Form solid solution, can improve it greatly and store oxygen performance and resistance to elevated temperatures.CeO
2Be the good auxiliary agent with oxidation catalyst of fluorite structure, it has higher storage oxygen and discharges the ability of oxygen, and by redox couple Ce
4+/ Ce
3+Carry out redox reaction, to the effect of sky-combustion compared with chemical regulator.When adding ZrO
2After, the portion C e in the former lattice is replaced by Zr, and Zr ionic radius (0.84 ) is less than Ce ionic radius (0.97 ), CeO
2Face-centred cubic structure causes crystal structure to distort because of lattice shrinks, and has produced the face-centered cubic defective, thereby has increased the flowability of negative oxygen ion in the fluorite lattice greatly, and the ability that stores oxygen and discharge oxygen is greatly improved, and has improved catalytic activity.Single CeO
2Experience high temperature (＞1023K) can make sintering own and reduce catalytic action, be not suitable for the use under the hot conditions.Mixing of Zr can the stable cubic fluorite structure, as the coated carrier of catalyst, improves the high-temperature stability of catalyst, and the anti-caking power of auxiliary agent is improved.In addition, different Ce/Zr mole specific energys make Ce
xZr
1-xO
2Solid solution has different structures, with Ce
xZr
1-xO
2Solid solution adopts different template agent, can obtain different high-specific surface areas, though some is reported, but does not have similar research both at home and abroad.As: list of references Catalysis Today is to adopt CeCl on 43 (1998) 79-88
37H
2O and ZrOCl
28H
2O adds surfactant, and the CeZr80 that makes high-specific surface area is through the 723K roasting, and specific area is 230m
2/ g; After the 1173K roasting, specific area then is 40m
2/ g.
The Ce of preparation high-specific surface area
xZr
1-xO
2The meaning of solid solution is, increases Ce
xZr
1-xO
2The specific area of carrier and heat endurance help active component at Ce
xZr
1-xO
2Load on the carrier and dispersion, this has great importance in the environmental protection catalytic reaction of reality.
Summary of the invention
The purpose of this invention is to provide a kind of high-specific surface area cerium zirconium sosoloid and preparation method thereof.
High-specific surface area cerium zirconium sosoloid provided by the invention, described component cerium zirconium is than being Ce=x (x=0.1～1.0), Zr=1-x (mol ratio), wherein Ce
xZr
1-xO
2(during mol ratio x=0.5) has best catalytic performance, and in this ratio, zirconium can increase the defective space to greatest extent, increases the flowability of oxygen to greatest extent.Make catalyst have maximum activity.
High-specific surface area cerium zirconium sosoloid provided by the invention and preparation method thereof: be with cerous nitrate (Ce (NO
3)
36H
2O) and zirconium nitrate (Zr (NO
3)
45H
2O) presoma is a raw material, press, Ce=x (x=0.1～1.0), Zr=1-x, mol ratio preparation cerium, zirconium mixed aqueous solution, add a certain proportion of cationic surfactant, mix with above-mentioned cerium, aqueous zirconium after being dissolved in water, under agitation the speed of mixed liquor with 60 droplets/minute is added drop-wise in the ammoniacal liquor, the rate of addition of controlling 60 droplets/minute is extremely important, it can make its precipitation (pH 〉=9.5) fully, regulates pH value=11.5 of precipitated liquid then with NaOH, to increase the combination degree of Ce+Zr and surfactant; Sediment changed over to ageing 132～144h in 70～80 ℃ the oil bath, behind the aged substance suction filtration, distilled water with 60～70 ℃ of heat washs earlier, wash with cold distilled water the back, embathe several times with acetone again, remove solution, put into 100～120 ℃ baking oven freeze-day with constant temperature 36h, change 600～650 ℃ of roasting 2h of Muffle furnace over to.
The present invention is by adding the rate of addition of cationic surfactant control material liquid, under alkali condition, utilize the hydrate reaction of cationic surfactant and mixed oxide, make surfactant form electric double layer at particle surface, reduced the surface energy of particle, suppressed the group of particle, surfactant solution and cerium zirconium solution evenly mix, and in precipitation process vigorous stirring, the Ce-Zr-O solid solution pellet is separated each other, suppressed grain growth, interparticle sintering when hindering roasting.In addition, the adding of surfactant can reduce the tension force of water, can mix with the liquid in the porous mass hole, has reduced the surface tension of the energy and the water at interface.It can reduce net when dry and roasting contraction and subside, help the specific area that keeps big.
The cerium zirconium sosoloid crystalline phase homogeneous that the present invention makes, specific area is big.Through the suction one desorption experiment of nitrogen, find that this suction-desorption isotherm belongs to the IV type thermoisopleth in the BDDT classification, be the adsorpting type of mesopore porous mass; It is 29.1 °, 34 ° and 485 ° of characteristic peaks of locating to occur tangible cerium zirconium sosoloid that the XRD determining result is presented at 2 θ; SEM measures the high-specific surface area cerium zirconium sosoloid that also shows employing co-precipitation-constant temperature ageing method preparation and has homogeneous granules, and particle also is difficult for reuniting under the 1073K hot conditions.In addition, the high-specific surface area cerium zirconium sosoloid that adopts the present invention's preparation is through 973K and 1073K roasting, and its specific area is 280.5m
2/ g and 232.6m
2/ g; And after the 1173K roasting, still have 58.7m
2/ g.
The specific embodiment
Embodiment 1:
The preparation of high-specific surface area cerium zirconium sosoloid the steps include:
(1) cerium zirconium sosoloid of high-specific surface area, its chemical molecular formula are Ce
xZr
1-xO
2(wherein x=0.1～1.0).In the ratio of Ce: Zr, Ce=x (x=0.1～1.0), the mol ratio of Zr=1-x is calculated corresponding cerous nitrate (Ce (NO
3)
36H
2O) and zirconium nitrate (Zr (NO
3)
45H
2O) amount is dissolved in water.
(2) take by weighing a certain amount of cerous nitrate (Ce (NO
3)
36H
2O) and zirconium nitrate (Zr (NO
3)
45H
2O), add an amount of distilled water, heating for dissolving adds cationic surfactant C again
16Alkyl trimethyl ammonium bromide, consumption are 70～80% of cerium zirconium precursor body weight, after being dissolved in water, mix the mixed liquor displaing yellow with cerium, aqueous zirconium.In the 600ml beaker, add 125ml ammoniacal liquor (25%) and 125ml distilled water, mix.Under agitation slowly be added drop-wise in ammoniacal liquor with 60 droplets/minute speed mixed liquor with certain speed, the rate of addition of controlling 60 droplets/minute makes its precipitation (pH 〉=9.5) fully, regulate pH value=115 of precipitated liquid with NaOH, to increase the combination degree of Ce+Zr and surfactant, obtain showing slightly the precipitation of purple.
(3) then sediment was changed in 70～80 ℃ the oil bath over to ageing 5.5～6 days (132～144h), behind the aged substance suction filtration, distilled water with 60～70 ℃ of heat washs earlier, wash with cold distilled water the back, embathe several times with acetone again, remove solution, put into 100～120 ℃ baking oven freeze-day with constant temperature 36h, change 600～650 ℃ of roasting 2h of Muffle furnace over to, make the high-specific surface area cerium zirconium sosoloid.
Embodiment 2:
(1) cerium zirconium sosoloid of high-specific surface area, its chemical molecular formula are Ce
xZr
1-xO
2(wherein x=0.1～1.0).In the ratio of Ce: Zr, with Ce=0.5, the mol ratio of Zr=0.5 is calculated and is taken by weighing 9.6867g cerous nitrate (Ce (NO
3)
36H
2O), 9.7626g zirconium nitrate (Zr (NO
3)
45H
2O), 13.6446～15.5938g surfactant (C
16Alkyl trimethyl ammonium bromide), add an amount of water-soluble separating.
(2) in the 600ml beaker, add 125ml ammoniacal liquor (25%) and 125ml distilled water, mix (pH=9.5).Under stirring fast the speed of raw materials mixed liquid with 60 droplets/minute slowly is added drop-wise in the ammoniacal liquor, the control rate of addition makes its precipitation (pH 〉=9.5) fully, regulates pH value=11.5 of precipitated liquid with NaOH, obtains showing slightly the precipitation of purple.
(3) then sediment was changed in 70～80 ℃ the oil bath over to ageing 5.5～6 days (132～144h), behind the aged substance suction filtration, aquae destillata with 60～70 ℃ of heat washs earlier, wash with cold aquae destillata the back, embathe several times with acetone again, remove solution, put into 100～120 ℃ baking oven freeze-day with constant temperature 36h, change 600～650 ℃ of roasting 2h of Muffle furnace over to, make the high-specific surface area cerium zirconium sosoloid.
Claims (3)
1, a kind of preparation method of cerium zirconium sosoloid of high-specific surface area, the chemical molecular formula of cerium zirconium sosoloid is Ce
xZr
1-xO
2, described component cerium, zirconium mol ratio are Ce=x, Zr=1-x, and x=0.1～＜1.0 is characterized in that described its preparation method: be with cerous nitrate Ce (NO
3)
36H
2O and zirconium nitrate Zr (NO
3)
45H
2The O presoma is a raw material, by above-mentioned cerium, zirconium mol ratio preparation cerium, the zirconium mixed aqueous solution, add a certain proportion of cationic surfactant, back and above-mentioned cerium are dissolved in water, aqueous zirconium mixes, under agitation the speed of mixed liquor with 60 droplets/minute is added drop-wise in the ammoniacal liquor, make its precipitation fully, regulate pH value=11.5 of precipitated liquid then with NaOH, sediment is changed over to ageing 132～144h in 70～80 ℃ the oil bath, behind the suction filtration, distilled water with 60～70 ℃ of heat washs earlier, embathe with acetone with cold distilled water washing the back again, removes solution, put into 100～120 ℃ baking oven inner drying 36h, change 600～650 ℃ of roasting 2h of Muffle furnace over to.
2, the preparation method of high-specific surface area cerium zirconium sosoloid according to claim 1 is characterized in that described cationic surfactant is a softex kw, and consumption is 70～80% of a cerium zirconium precursor body weight.
3, the preparation method of high-specific surface area cerium zirconium sosoloid according to claim 1, the described sediment of its feature is placed on ageing 132h in 70～80 ℃ the oil bath.
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| CN1242844C true CN1242844C (en) | 2006-02-22 |
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| CN101074490B (en) * | 2007-06-15 | 2011-05-04 | 北京工业大学 | Method for producing spherical, tie-shaped and octahedral polycrystalline Ce0.6Zr0.3Y0.1O2 particles of um sizes |
| CN101829557A (en) * | 2010-04-20 | 2010-09-15 | 上海大学 | Magnesium modified cerium-zirconium solid solution and preparation method thereof |
| CN103316658B (en) * | 2013-05-31 | 2016-04-06 | 南京劲鸿茂科技有限公司 | A kind of nanometer composite cerium zirconium solid solution and preparation method thereof |
| CN106058241B (en) * | 2016-07-21 | 2018-06-19 | 天津巴莫科技股份有限公司 | Ce1-xZrxO2Nano Solid Solution homogeneous modification anode material for lithium-ion batteries and preparation method thereof |
| CN109806881A (en) * | 2017-11-20 | 2019-05-28 | 中国科学院大连化学物理研究所 | A kind of iron-molybdic catalyst and preparation method thereof for prepn. of formaldehyde by oxidation of methanol |
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Assignee: Hangzhou Daming Fluorescence Material Co., Ltd. Assignor: Zhejiang University Contract fulfillment period: 2007.8.15 to 2013.8.15 contract change Contract record no.: 2008330000774 Denomination of invention: Highly specific surface area possessed cerium-zirconium solid solution and its preparing method Granted publication date: 20060222 License type: Exclusive license Record date: 2008.9.28 |
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Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2007.8.15 TO 2013.8.15; CHANGE OF CONTRACT Name of requester: HANGZHOU DAMING FLUORESCENCE MATERIALS CO., LTD. Effective date: 20080928 |