CN1239393C - Method for preparing mesoporous rare-earth oxide - Google Patents
Method for preparing mesoporous rare-earth oxide Download PDFInfo
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- CN1239393C CN1239393C CN 02158777 CN02158777A CN1239393C CN 1239393 C CN1239393 C CN 1239393C CN 02158777 CN02158777 CN 02158777 CN 02158777 A CN02158777 A CN 02158777A CN 1239393 C CN1239393 C CN 1239393C
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Abstract
The present invention relates to a preparation method of mesoporous rare earth oxides. The method comprises the steps of gel preparation, solvent displacement and calcination. The method comprises the following specific steps of dissolving strong rare earth acid salts with crystallized water into deionized water to be prepared into a solution, respectively adding water-soluble high molecules or water-soluble organic alcohol and organic amine as mixing templates to form chelate bodies with the solution of the strong rare earth acid salts under a quick agitating condition, evenly depositing the mixtures by using ammonia, urea and urea derivatives as precipitating agents to react and produce the mesoporous intermediate phases of rare earth hydroxide, aging and washing products by crystallized water after reactions, displacing the products by anhydrous alcohol, and drying and calcining the products to obtain mesoporous rare earth oxide powder. The present invention is suitable for preparing the mesoporous oxide powder of all lanthanide rare earth metal elements, and the mesoporous rare earth oxide powder has the advantages of good mesoporous uniformity, low cost and easy industrialization.
Description
Technical field
The present invention relates to the preparation method of mesoporous material, particularly relate to a kind of preparation of mesoporous rare-earth oxide.
Background technology
Mesoporous material has become a new subject forward position of material science as a kind of type material.Mesopore molecular sieve broken through traditional molecular sieve the micropore size scope (＜2nm), and there are higher specific surface and size distribution even, and (2.0～50nm), making it is serving as that the main aspects of forming such as material preparation have wide purposes to macromolecular absorption, catalysis with it to be in mesoporous scope.Show very application prospects in fields such as chemical industry catalysis, environmental protection filtration, optics, photoelectron materials.Along with the development of nanotechnology, owing to be in the good dispersity of the nanoparticle in the mesoporous solid, a little less than the coupling between the particle, interface coupling effect between particle and the mesoporous solid wall or the like makes mesic hole compound often present many new capabilities in recent years.
The conventional preparation method of mesoporous material mainly is the template hydrothermal method, promptly by the lytropic liquid crystals of amphiphile, amphiphilic molecule organized assembles as the supramolecule template, have the meso-hole structure material of crystal phase structure with preparation.Therefore template has considerable influence to the structurally ordered degree and the thermostability of mesoporous material, and the different mesoporous materials of forming of preparation need be selected the template that suits.The preparation method has single template and two kinds of operational paths of mixed templates, it has been generally acknowledged that mixed templates technology can bring into play the advantage of different templates agent, can obtain that structurally ordered degree is high, the mesoporous material of Heat stability is good.As Wang Tongwen etc. (Wang Tongwen, Dai Lerong. Acta PhySico-Chimica Sinica, 2001,17 (1): 10～14) reported the aliphatic amide (C of employing cetyl trimethylammonium bromide (CTAB) with different carbon chain
nNH
2n+3, n=8,10,12,14,16) make mixed templates, at the tetramethyl-oxyammonia is under the condition of alkali source, has synthesized the titanium-containing silicon oxide Ti-MCM-41 molecular screen material with hexagonal mesoporous structure, and this method is exactly the mixed templates of having selected for use at the titanium monox mesoporous material.Rare earth oxide light, magnetic, catalysis, excellent performance such as high temperature resistant are widely used in field of functional materials such as optics, photoelectron material, magneticsubstance, function ceramics, special glass and high mechanical strength potteries.And the rare earth class mesoporous material have report for the oxide mesoporous material in unit, many in its synthetic method based on single template route, having reported with the hexadecyl trimethyl ammonium bromide to be template as " D.Terribile, A.Trovarelli, J.Llorca; et a1.Journal of Catalysis; 1998,178 (1): 299-308 ", is the feedstock production mesoporous ceria with inorganic Cerium II Chloride salt, used template price is more expensive, and preparation cost is higher.Adopt the preparation of mixed templates route not appear in the newspapers at rare earth mesoporous material.
Summary of the invention:
The objective of the invention is to propose that a kind of employing mixed templates prepares the thermostability height, pore size distribution is narrow, the method for cheap mesoporous rare-earth oxide.
Technical scheme of the present invention:
Present method comprises preparing gel, solvent exchange and roasting process: the rare earth inorganic acid salt that at first will have crystal water is dissolved in the deionized water wiring solution-forming, and rare earth ion concentration is 1 * 10
-3-1.0mol/L, in this solution, add high molecular weight water soluble polymer and organic amine, or water-soluble organic pure and mild organic amine is formed mixed templates, wherein the addition of water-soluble polymers or water-soluble organic alcohol is 10-100g/L (by the overall product of reaction soln), addition/the rare earth ion of organic amine (mol ratio) is 0.01: 1-2: 1, slowly be warming up to 60 ℃～120 ℃ under the high-speed stirring condition, template and rare earth ion form the chelating body, drip mass concentration subsequently and be 25%～35% ammoniacal liquor, urea or urea derivative solution are as precipitation agent, ammoniacal liquor wherein, urea and urea derivative/rare earth ion (mol ratio)=2.0: 1.0-10.0: 1.0, generate the mesoporous intermediate phase precipitation of rare-earth hydroxide, after dropwising, continue to stir 0.5-10 hour, and then ageing 12h～24h, precipitated product to medium-sized (pH=7.0), does not have Cl through deionized water wash after testing
-1, SO
4 -2And NO
3 -1Ion, filtration can obtain rare earth mesoporous hydrogel.Mesoporous hydrogel with dehydrated alcohol displacement for several times after, filter and promptly obtain mesoporous alcogel, will place under the air at room temperature after the seasoning, obtain having the powder of meso-hole structure, then at 350 ℃～750 ℃ roasting 2～6h removing impurity wherein,, promptly get the mesoporous rare-earth oxide powder.
Above-mentioned mesoporous alcogel this throw out before carrying out seasoning that obtains washs with deionized water or anhydrous organic solvent, or washs with anhydrous organic solvent then with deionized water wash earlier.
Addition/the rare earth ion of above-mentioned organic amine (mol ratio) preferably 0.1: 1-1: 1.
Above-mentioned ammoniacal liquor, urea or urea derivative, the consumption preferred proportion is relatively: ammoniacal liquor, urea or urea derivative/rare earth ion (mol ratio)=4: 1～8: 1 (mol ratio),
When being precipitation agent with ammoniacal liquor in the aforesaid method, reaction is under 60-120 ℃ of stirring condition, splashes into ammoniacal liquor with fixed speed, after dropwising, continues constant temperature and stirs the ageing again of lowering the temperature then 0.5-2.0 hours;
When being precipitation agent with urea and urea derivative in the aforesaid method, reaction be 60-120 ℃ refluxing and stirring condition under carried out 0.5-10 hours;
Above-mentioned rare earth inorganic acid salt means the inorganic acid salt of lanthanide rare metallic element, and the lanthanide rare metallic element comprises: elements such as La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu.
Aforesaid method middle-weight rare earths inorganic acid salt obtained aqueous solution is that one or more inorganic salt of rare earth in lanthanide rare muriate, rare earth sulfate, the rare earth nitrate are dissolved in the deionized water, to obtain the mesoporous rare-earth oxide powder of compound system.
Above-mentioned anhydrous organic solvent is methyl alcohol, ethanol, propyl alcohol, acetone, dme and ether.
Above-mentioned organic amine comprises: diethylamine, triethylamine, Tri N-Propyl Amine, tripropyl amine, 1,3-propylene diamine, n-Butyl Amine 99, isobutylamine, TERTIARY BUTYL AMINE, 1,4-butanediamine, hexanediamine, n-octyl amine, octodrine, positive nonyl amine, n-Decylamine, amino dodecane, cetylamine, stearylamine.
Above-mentioned water-soluble polymers is polyoxyethylene glycol (PEG) or the polypropylene glycol (PPG) of weight-average molecular weight between 200-19000, carboxymethyl cellulose, Natvosol (HEC) and the hydroxypropylcellulose (HPC) of weight-average molecular weight between 200-25000, and the polyvinylpyrrolidone (PVP) of weight-average molecular weight between 1000-1000000, fatty alcohol-polyoxyethylene ether (AEO), Soxylat A 25-7-polyethenoxy ether-Soxylat A 25-7 triblock copolymer (EPE).
Above-mentioned water-soluble organic alcohol is to be selected from C
1-C
8Fatty alcohol, C
1-C
8Aliphatic diol, C
1-C
8Aliphatic tribasic alcohol, C
2-C
8Aliphatic series tetravalent alcohol, C
3-C
8Aliphatics alcohols in the aliphatic series pentavalent alcohol or their mixture.
Above-mentioned fatty alcohol is ethylene glycol, glycerol, neopentyl glycol, TriMethylolPropane(TMP), tetramethylolmethane, ring pentanediol, Xylitol, sorbyl alcohol, glycol ether, dipropylene glycol or their mixture.
Temperature of reaction has considerable influence to rare earth ion and template formation chelating body in the aforesaid method, if temperature is too high, the stability of chelating body is affected, to reacting unfavorable; And temperature is low excessively, can influence the crystallization process of rare earth mesoporous phase again, so need strict control reaction temperature.The temperature of reaction optimum control is in 80 ℃～100 ℃ scopes.
The displacement solvent load is not strict with in the aforesaid method, generally determines according to the building-up reactions economy, the replacement solvent consumption can be controlled in 20%～80% the scope of whole displacement mixture weight, and optimum control is 30%～50%.
Effect of the present invention: the present invention utilizes the characteristic of organic amine molecule, construct template and rare earth ion formation inner complex jointly with water-soluble polymer or water-soluble organic alcohol, generate the mesoporous intermediate phase of rare-earth hydroxide with ammoniacal liquor, urea or urea derivative reaction, the product meso-hole structure is easy to control; Even and the narrow distribution range in aperture, mean pore size is between 3-20nm; Specific surface area＞200m
2/ g; Thermostability height (600 ℃ of meso-hole structures that still can remain intact); Preparation process is simple, and is with low cost; This method scope of application is wide, can also prepare compound rare-earth mesopore oxide powder.
(1) preparation of mesoporous rare-earth oxide gel:
The rare earth inorganic acid salt that will have crystal water is dissolved in deionized water and is made into material solution, and wherein rare earth ion concentration is 1 * 10
-3-1.0mol/L joins material solution in the reaction vessel, and constantly stirs; The high molecular weight water soluble polymer or the water-soluble organic alcohol that in material solution, add 10-100g/L (by the overall product of reaction soln), form mixed template with organic amine, addition/the rare earth ion of organic amine (mol ratio) is 0.01: 1-2: 1, under the high-speed stirring condition, slowly be warming up to 80 ℃～100 ℃ after forming mixing solutions, drip stoichiometric ammoniacal liquor with certain speed, promptly generate the mesoporous intermediate phase hydration of rare-earth hydroxide colloidal sol precipitation, continue to stir 0.5～2.0 hour, and then ageing 12h～24h; The aqueous solution that can also in mixing solutions, add stoichiometric urea or urea derivative, join simultaneously in the reactor that has condensation reflux unit and whipping appts, mixed solution in the high-speed stirring reactor, to be mixed evenly after, heat-up rate with 2-10 ℃/min begins heating, treat temperature be raised to require temperature after, remain on and reacted under this temperature 4～8 hours, intensification makes urea or urea derivative hydrolysis, promptly generate the mesoporous intermediate phase hydration of rare-earth hydroxide colloidal sol precipitation, pH value in the prosecution reaction process is treated that the pH value remains unchanged, and is no longer emitted CO
2Back 0.5-1.0 hours stops heating, continues to be stirred to temperature and drops to about 30 ℃, and this moment, reaction was finished.The temperature of reaction of this step is 60-120 ℃, ammoniacal liquor, urea or urea derivative/rare earth ion=and 2.0: 1.0-10.0: 1.0 (mol ratios).In this implementation step, the rare earth inorganic acid salt means the inorganic acid salt of lanthanide rare metallic element, and the lanthanide rare metallic element comprises: elements such as La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu.Rare earth inorganic acid salt obtained aqueous solution is that one or more inorganic salt of rare earth in lanthanide rare muriate, rare earth sulfate, the rare earth nitrate are dissolved in the deionized water, to obtain the mesoporous rare-earth oxide powder of compound system.Organic amine comprises: diethylamine, triethylamine, Tri N-Propyl Amine, tripropyl amine, 1,3-propylene diamine, n-Butyl Amine 99, isobutylamine, TERTIARY BUTYL AMINE, 1,4-butanediamine, hexanediamine, n-octyl amine, octodrine, positive nonyl amine, n-Decylamine, amino dodecane, cetylamine, stearylamine.Water-soluble polymers is polyoxyethylene glycol (PEG) or the polypropylene glycol (PPG) of weight-average molecular weight between 200-19000, carboxymethyl cellulose, Natvosol (HEC) and the hydroxypropylcellulose (HPC) of weight-average molecular weight between 200-25000, and the polyvinylpyrrolidone (PVP) of weight-average molecular weight between 1000-1000000, fatty alcohol-polyoxyethylene ether (AEO), Soxylat A 25-7-polyethenoxy ether-Soxylat A 25-7 triblock copolymer (EPE).Water-soluble organic alcohol is to be selected from C
1-C
8Fatty alcohol, C
1-C
8Aliphatic diol, C
1-C
8Aliphatic tribasic alcohol, C
2-C
8Aliphatic series tetravalent alcohol, C
3-C
8Aliphatics alcohols in the aliphatic series pentavalent alcohol or their mixture, as: ethylene glycol, glycerol, neopentyl glycol, TriMethylolPropane(TMP), tetramethylolmethane, ring pentanediol, Xylitol, sorbyl alcohol, glycol ether, dipropylene glycol or their mixture.
(2) washing and solvent exchange: will the be above-mentioned synthetic rare earth metal hydration colloidal sol that makes, use deionized water, through multiple times of filtration, washing to neutrality (about pH=7.0), also do not have Cl after testing
-1, SO
4 -2And NO
3 -1Behind the ion, the gel 0.5-24h that wears out, with an amount of dehydrated alcohol carry out solvent exchange for several times after, filter alcogel.
(3) drying and roasting:, before carrying out seasoning, wash, or wash with anhydrous organic solvent then with deionized water wash earlier with deionized water or anhydrous organic solvent with the above-mentioned alcogel that obtains.Move in the Stainless Steel Disc and spread out, under the condition of room temperature, air flowing, seasoning promptly gets the rare earth mesoporous oxide compound xerogel with mesoporous feature.Xerogel is moved into muffle furnace, and roasting 2-6h in 200 ℃ of-750 ℃ of scopes can obtain the mesoporous rare-earth oxide powder.Used anhydrous organic solvent is methyl alcohol, ethanol, propyl alcohol, acetone, dme and ether.
In the drying and roasting process of above-mentioned steps 3 alcogel: also can adopt drying meanss such as hig h-speed centrifugal spray drying, vacuum-drying, expansion drying.
The relative consumption of preferred each component is in the present embodiment: ammoniacal liquor or urea/rare earth ion (mol ratio) preferred proportion is 4.0: 1.0-8.0: 1.0, more preferably 5.0: 1.0-6.0: 1.0, the addition of water-soluble polymers or water-soluble organic alcohol is 20-80g/L preferably, especially preferably 40-50g/L.Addition/the rare earth ion of organic amine (mol ratio) preferably 0.2: 1-1.5: 1, especially preferably 0.5: 1-1: 1.
Description of drawings:
Fig. 1 is the mesoporous cerium oxide (CeO that the present invention prepares
2) electromicroscopic photograph of powder.
Fig. 2 is the mesoporous cerium oxide (CeO that the present invention prepares
2) liquid nitrogen physical adsorption (BET) the pore size distribution test curve of powder.
Embodiment
Embodiment 1:
Take by weighing 20.21g four cerium sulfate hydrates (Ce (SO
4)
24H
2O) be made into the solution that volumetric molar concentration is 250ml0.2mol/L, add respectively then 4gPEG-6000 and 10.1g triethylamine (cerous sulfate: triethylamine (mol ratio)=1: 2), mixing and stirring.Slowly be heated to 80 ℃ then, dropwise drip the 31ml mass concentration again and be 25% ammonia soln, generate the mesoporous phase of rare earth element hydroxide, after reacting completely, 80 ℃ of temperature maintenances are constant, continue to stir one hour, thereafter stop heating, be cooled to the chamber. temperature, ageing 12h, product repeatedly washs to PH=7.0 through deionized water, and removes Cl
-1And SO
4 2-Ion with absolute ethanol washing displacement three times, gets mesoporous alcogel again.400 ℃ of roastings are 3 hours in muffle furnace, meso-pore Ce O
2Powder is 98.5% by theoretical calculated yield, and it is 5.5nm that BET records the aperture.The high resolution electron microscopy photo shows that its pass is six squares, and the aperture is about about 5nm (sees accompanying drawing 1), its pore size distribution curve (seeing accompanying drawing 2).
Embodiment 2:
Adopt the step identical, cerous sulfate with embodiment 1: triethylamine (mol ratio)=1: 1, PEG molecular weight and consumption are constant, and ammonia volume is constant, after dropping ammonia reacts completely, washing with alcohol three times, air-dry in the air, obtain meso-pore Ce O
2Powder is 97.5% by theoretical calculated yield, and it is 4.7nm that BET records the aperture.The high resolution electron microscopy photo shows that its pass is six squares, and the aperture is about about 5nm
Embodiment 3:
Adopt the step identical, cerous sulfate with embodiment 1: triethylamine (mol ratio)=1: 0.5, PEG molecular weight and consumption are constant, and ammonia volume is constant, the post-processing step that employing and embodiment one are identical, 600 ℃ of roastings are 3 hours in muffle furnace, obtain meso-pore Ce O
2Powder is 97.8% by theoretical calculated yield, and it is 9.4nm that BET records the aperture.
Embodiment 4:
Adopt the step identical, cerous sulfate with embodiment 1: triethylamine (mol ratio)=1: 0.1, PEG molecular weight and consumption are constant, and ammonia volume is constant, the post-processing step that employing and embodiment one are identical, 600 ℃ of roastings are 3 hours in muffle furnace, obtain meso-pore Ce O
2Powder is 95.8% by theoretical calculated yield, and it is 9.9nm that BET records the aperture.
Embodiment 5:
Adopt the step identical with embodiment 1, the consumption of triethylamine is constant, and adopting molecular weight is 19000 PEG, and consumption remains unchanged, and ammonia volume is constant, the post-processing step that employing and embodiment one are identical, and 600 ℃ of roastings are 3 hours in muffle furnace, obtain meso-pore Ce O
2Powder is 98.8% by theoretical calculated yield, and it is 3.5nm that BET records the aperture.
Embodiment 6:
Adopt step and the proportioning identical with embodiment 1, in the neodymium chloride solution of the 0.2mol/L of the 250ml for preparing, (Neodymium trichloride: triethylamine (mol ratio)=1: 2), dropping 20ml ammoniacal liquor obtains Nd (OH) to add the triethylamine of 4gPEG-6000 and 10.1g respectively
3Mesoporous mutually after, adopt the post-processing step identical with embodiment 1,600 ℃ of roastings are 3 hours in muffle furnace, must mesoporous Nd
2O
3Powder is 98.8% by theoretical calculated yield, and it is 3nm that BET records the aperture.
Embodiment 7:
Adopt step and the proportioning identical with embodiment 1, in the samarium trichloride solution of the 0.2mol/L of the 250ml for preparing, (samarium trichloride: triethylamine (mol ratio)=1: 2), dropping 20ml ammoniacal liquor obtains Sm (OH) to add the triethylamine of 4gPEG-6000 and 10.1g respectively
3Mesoporous mutually after, adopt the post-processing step identical with embodiment 1,600 ℃ of roastings are 3 hours in muffle furnace, must mesoporous Sm
2O
3Powder is 99.2% by theoretical calculated yield, and it is 5.7nm that BET records the aperture.
Embodiment 8:
Take by weighing 20.21g four cerium sulfate hydrates (Ce (SO
4)
24H
2O) be made into the solution that volumetric molar concentration is 0.2mol/L, add 4gPEG-6000 and 4.625g amino dodecane (cerous sulfate: amino dodecane (mol ratio)=1: 0.5) then respectively, adopt the step identical with embodiment 1, in the dropping process, after dropping 30ml ammoniacal liquor finishes, adopt the post-processing step identical with embodiment 1,600 ℃ of roastings are 3 hours in muffle furnace, must meso-pore Ce O
2Powder is 97.8% by theoretical calculated yield, and it is 5.5nm that BET records the aperture.
Embodiment 9:
Take by weighing 20.21g four cerium sulfate hydrates (Ce (SO
4)
24H
2O) be made into the solution that volumetric molar concentration is 0.2mol/L, add 4gPEG-6000 and 7.725g stearylamine (cerous sulfate: stearylamine (mol ratio)=1: 0.5) then respectively, adopt the step identical with embodiment 1, in the dropping process, after dropping 30ml ammoniacal liquor finishes, adopt the post-processing step identical with embodiment 1,600 ℃ of roastings are 3 hours in muffle furnace, must meso-pore Ce O
2Powder is 98.4% by theoretical calculated yield, and it is 6.5nm that BET records the aperture.
Claims (8)
1, a kind of preparation method of mesoporous rare-earth oxide, comprise preparing gel, solvent exchange and roasting process, it is characterized in that: the rare earth inorganic acid salt that muriate, vitriol and/or the nitrate that will be selected from lanthanide series metal has crystal water is dissolved in the deionized water wiring solution-forming, and rare earth ion concentration is 1 * 10
-3-1.0mol/L, in this solution, add high molecular weight water soluble polymer and organic amine composition mixed templates, wherein the addition of high molecular weight water soluble polymer is by the overall product of reaction soln, for: 10-100g/L, the mol ratio of the addition/rare earth ion of organic amine is 0.01: 1-2: 1, slowly be warming up to 60 ℃～120 ℃ under the high-speed stirring condition, template and rare earth ion form the chelating body, drip mass concentration subsequently and be 25%～35% ammoniacal liquor or urea soln as precipitation agent, wherein the mol ratio of precipitation agent/rare earth ion is 2.0: 1.0-10.0: 1.0, generate the mesoporous intermediate phase precipitation of rare-earth hydroxide, after dropwising, continue to stir 0.5-10 hour, and then ageing 12h～24h, precipitated product to neutral pH=7.0, does not have Cl through deionized water wash after testing
-1, SO
4 -2And NO
3 -1Ion, filtration can obtain rare earth mesoporous hydrogel, after mesoporous hydrogel is replaced for several times with dehydrated alcohol, filter and promptly obtain mesoporous alcogel, mesoporous alcogel is placed under the air at room temperature after the seasoning, obtain having the powder of meso-hole structure, obtain the mesoporous rare-earth oxide powder at 350 ℃～750 ℃ roasting 2～6h then, described high molecular weight water soluble polymer is polyoxyethylene glycol or the polypropylene glycol of weight-average molecular weight between 200-19000, the carboxymethyl cellulose of weight-average molecular weight between 200-25000, Natvosol and hydroxypropylcellulose, and the polyvinylpyrrolidone of weight-average molecular weight between 1000-1000000, fatty alcohol-polyoxyethylene ether, Soxylat A 25-7-polyethenoxy ether-Soxylat A 25-7 triblock copolymer, described organic amine is: diethylamine, triethylamine, Tri N-Propyl Amine, tripropyl amine, 1, the 3-propylene diamine, n-Butyl Amine 99, isobutylamine, TERTIARY BUTYL AMINE, 1, the 4-butanediamine, hexanediamine, n-octyl amine, octodrine, positive nonyl amine, n-Decylamine, amino dodecane, cetylamine or stearylamine.
2, according to the preparation method of claim 1, it is characterized in that: the mol ratio of the addition/rare earth ion of organic amine is 0.1: 1-1: 1.
3, the method that requires according to right 1 is characterized in that the mol ratio of precipitation agent/rare earth ion is 4: 1～8: 1.
4, according to the preparation method of right 1, it is characterized in that: when being precipitation agent with ammoniacal liquor, reaction is under 60-120 ℃ of stirring condition, splashes into ammoniacal liquor with fixed speed, after dropwising, continues constant temperature and stirs the ageing again of lowering the temperature then 0.5-2.0 hour.
5, according to the preparation method of right 1, it is characterized in that: when being precipitation agent with urea, reaction is to carry out 0.5-10 hour under 60-120 ℃ of backflow and stirring condition.
6, according to the preparation method of right 1, it is characterized in that: described lanthanide series metal is selected from La, Ce, Pr, Nd, Pm, Sm, Eu or Gd.
7, according to the preparation method of right 1, it is characterized in that: mesoporous alcogel washed with deionized water or anhydrous organic solvent before carrying out seasoning, or wash with anhydrous organic solvent then with deionized water wash earlier, described anhydrous organic solvent is methyl alcohol, ethanol, propyl alcohol, acetone, dme or ether.
8, the method that requires according to right 1, it is characterized in that: temperature of reaction is controlled in 80 ℃～100 ℃ scopes.
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| CN100372759C (en) * | 2006-08-25 | 2008-03-05 | 南京大学 | Preparation method of mesopore metal oxide |
| CN101024166B (en) * | 2007-02-15 | 2011-10-05 | 中国科学院上海硅酸盐研究所 | Crystallized mesoporous metal oxide with uniform shape and appearance and preparing method |
| CN101386419B (en) * | 2007-09-12 | 2010-09-29 | 北京有色金属研究总院 | Composite nano cerium dioxide sol preparation method |
| KR101720205B1 (en) * | 2014-10-08 | 2017-04-03 | 알이엠텍 주식회사 | Method for producing metal oxide powder |
| CN105236462B (en) * | 2015-08-17 | 2018-06-22 | 包头稀土研究院 | The method for preparing large specific surface area spherical cerium oxide |
| CN105585043B (en) * | 2016-03-11 | 2017-04-12 | 九江学院 | Preparation method of flowerlike cerium oxide nano-material |
| CN109731579A (en) * | 2018-12-25 | 2019-05-10 | 天津大学 | A kind of mesoporous lanthanum oxide catalyst of nickel load and preparation method thereof |
| CN111620362B (en) * | 2020-04-24 | 2023-05-05 | 广西科学院 | Microwave preparation method of mesoporous holmium oxide powder |
| CN116102049A (en) * | 2022-12-28 | 2023-05-12 | 常州市卓群纳米新材料有限公司 | Preparation method of high-purity nano neodymium oxide |
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