CN101117233A - Method for preparing high specific surface area meso-porous cerium dioxide micro-balloon - Google Patents
Method for preparing high specific surface area meso-porous cerium dioxide micro-balloon Download PDFInfo
- Publication number
- CN101117233A CN101117233A CNA2007101194019A CN200710119401A CN101117233A CN 101117233 A CN101117233 A CN 101117233A CN A2007101194019 A CNA2007101194019 A CN A2007101194019A CN 200710119401 A CN200710119401 A CN 200710119401A CN 101117233 A CN101117233 A CN 101117233A
- Authority
- CN
- China
- Prior art keywords
- specific surface
- surface area
- meso
- minutes
- high specific
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention relates to a preparation method for meso-porous cerium dioxide microsphere with the high specific surface area, which belongs to rare earth oxide material field. The invention is characterized in that: by using the hydrothermal method, the meso-porous cerium oxide powder with spherical or semi spherical shape which is provided with the high specific surface area and homogeneous appearance is prepared; (NH4)2Ce(NO3)4 used as the cerium source is dissolved into anhydrous alcohol and completely mixed by stirring about 30 minutes to 60 minutes, N-dimethylformamide is added to mixed about 5 minutes to 30 minutes after acid is added, the solution is added into the hydrothermal reaction kettle and reacts in 100 DEG C to 160 DEG C about 40 hours to 140 hours, the Ce(COOH)3 precursor is obtained, and then the obtained Ce(COOH)3 precursor is sintered in 350DEG C to 450 DEG C about 2 hours to 8 hours, and after cooling, the spherical semi spherical meso-porous cerium dioxide with high specific surface area is obtained. The invention has the advantages of easy preparation method, simple equipment, low synthesis temperature, low raw material cost, excellent repeatability and expensive surfactant as the template agent without required. The meso-porous cerium dioxide formed by the invention is provided with high sphericity, homogeneous size, narrow pore-size range and large specific surface area.
Description
Technical field:
The invention belongs to genus rare earth oxide material field, relate to a kind of mesoporous ceria preparation methods, particularly adopt micron, submicron order sphere, the semisphere of non-template agent preparation, specific surface area 150-280m
2/ g, the method for the meso-porous titanium dioxide cerium material of aperture 3-10nm.
Background technology:
CeO
2Be a kind of important compound in the rare earth family,, loaded metal dispersed high multinomial good characteristic good and getting most of the attention with its storage oxygen performance.Meso-pore Ce O
2Owing to its structural stability has CeO
2All character, comprise good chemical stability, store up oxygen oxygen release function, and the quick oxygen of high temperature room diffusibility by force.While meso-pore Ce O
2Have nano level duct structure, high-specific surface area again, can greatly widen CeO
2Application Areas.At present, meso-pore Ce O
2Preparation mainly contain surfactant templates method, sol-gel process, and hard template method etc.These methods mainly in shortcomings such as template or precursor material price height, complicated process of preparation, are unfavorable for large-scale production and application.Therefore the developing low-cost preparation has the long-pending CeO of meso-porous structural high specific surface
2Method significant.In addition, the external pattern of material also can produce the impact that can not be ignored to its performance and application, and the microspheroidal material has the significant application value of going out because having the advantages such as lower coefficient of friction, good flowability, close heap and dispersiveness in various fields.
Summary of the invention
The purpose of this invention is to provide a kind of with simple and easy process cheaply obtain height ratio than area, exterior appearance homogeneous, can handling strong micron, spherical, the hemispherical mesoporous ceria preparation methods of submicron order.
A kind of preparation method of high specific surface area meso-porous cerium dioxide micro-balloon utilizes that Hydrothermal Preparation is spherical, hemispherical to have high specific surface area and than the mesoporous cerium oxide powder of homogeneous exterior appearance.Presoma is Ce (COOH)
3With (NH
4)
2Ce (NO
3)
4Be dissolved in stirring in the absolute ethyl alcohol as the cerium source and it fully mixed in 30～60 minutes, add again N after adding a certain amount of acid, dinethylformamide (DMF) stirs after 5～30 minutes and puts into hydrothermal reaction kettle, 100～160 ℃ of temperature range internal reactions 40～140 hours, gained sample Ce (COOH)
3Sintering is after 2～8 hours in 350～450 ℃ of temperature ranges for presoma, presoma, and cooled sample namely obtains spherical, the hemispherical mesoporous cerium oxide of high-specific surface area.
The concrete technology condition is: (NH
4)
2Ce (NO
3)
4Solution concentration in reaction solution is 0.0685mol/L, (NH
4)
2Ce (NO
3)
4With the mol ratio of absolute ethyl alcohol 3: 103～1: 103, adding acid was solubility strong acid, its H
+Concentration in reaction liquid is between 0.04～0.1mol/L, (NH4)
2Ce (NO
3)
4With the mol ratio of DMF (DMF) 8: 303～1: 114.
Material preparation method of the present invention is simple and easy, and equipment is simple, and synthesis temperature is low; Cost of material is cheap, need not expensive tensio-active agent and makes template; Good reproducibility.Advantages such as the mesoporous ceria that obtains has sphericity height, yardstick homogeneous, and pore diameter range is narrow, and specific surface area is big.Specific surface area reaches 150-280m
2/ g, aperture 2-10nm., the cerium dioxide that the present invention obtains is micron, submicron order, makes this ball be easy to be controlled, and can effectively evade nano-scale particle is difficult for recovery in application shortcoming.
Description of drawings
Fig. 1 is the XRD figure spectrum of final product, illustrates that obtaining sample is CeO
2Single phase.
Fig. 2 is the absorption/desorption isotherm of this sample, and the reference area that from then on can find out this sample among the figure is 185.1m
2/ g has bigger specific area.
Fig. 3, Fig. 4 are the stereoscan photograph of sample, and sample has kept spherical preferably and hemispherical pattern.
Embodiment
Embodiment one
With 1g (NH
4)
2Ce (NO
3)
6Be dissolved in 9ml ethanol, drip the hydrochloric acid of 1ml 2mol/L, stirred 30 minutes, add 10ml DMF and stir after 10 minutes, put into reactor.100 degree reactions 140 hours, obtain black sphere and hemispherical material.With the sample that obtains in air with 3 degree/minute speed be fired to behind 350 degree insulation 3 hours.Cooled sample promptly obtains spherical, the hemispherical mesoporous cerium oxide of high-specific surface area.
Embodiment two
With 1g (NH
4)
2Ce (NO
3)
6Be dissolved in 5ml ethanol, drip the hydrochloric acid of 1ml 2mol/L, stirred 40 minutes, add 10ml DMF and stir after 10 minutes, put into reactor.100 ℃ of reactions 160 hours, obtain black sphere and semisphere material.With the sample that obtains in air with 1 degree/minute speed be fired to 380 ℃ after insulation 2 hours.Cooled sample promptly obtains spherical, the hemispherical mesoporous cerium oxide of high-specific surface area, and the specific surface area of this sample is 196.2m
2/ g
Embodiment three
With 1g (NH
4)
2Ce (NO
3)
6Be dissolved in 5ml ethanol, drip the hydrochloric acid of 1.5ml 2mol/L, stirred 35 minutes, add 10ml DMF and stir after 10 minutes, put into reactor.After 60 hours, be cooled to the room temperature ageing 20 hours 140 ℃ of reactions, obtain black sphere and semisphere material in reaction under 140 ℃ of temperature after 25 hours again.With the sample that obtains in air with 1 degree/minute speed be fired to 400 ℃ after insulation 3 hours.Cooled sample promptly obtains spherical, the hemispherical mesoporous cerium oxide of high-specific surface area, and the specific surface area of this sample is 201.1m
2/ g.
Claims (5)
1. the preparation method of a high specific surface area meso-porous cerium dioxide micro-balloon is characterized in that utilizing hydro-thermal method to prepare spherical, hemispherical mesoporous cerium oxide powder with high-specific surface area and homogeneous exterior appearance; Presoma is Ce (COOH)
3With (NH
4)
2Ce (NO
3)
4Be dissolved in stirring in the absolute ethyl alcohol as the cerium source and it fully mixed in 30～60 minutes, add again N after adding acid, dinethylformamide stirs after 5～30 minutes and puts into hydrothermal reaction kettle, 100～160 ℃ of temperature range internal reactions 40～140 hours, and gained sample Ce (COOH)
3Sintering is after 2～8 hours in 350～450 ℃ of temperature ranges for presoma, presoma, and cooled sample namely obtains spherical, the hemispherical mesoporous cerium oxide of high-specific surface area;
The concrete technology condition is: (NH
4)
2Ce (NO
3)
4Solution concentration in reaction solution is 0.0685mol/L, (NH
4)
2Ce (NO
3)
4With the mol ratio of absolute ethyl alcohol 3: 103～1: 103, adding acid was solubility strong acid, its H
+Concentration in reaction liquid between 0.04～0.12mol/L, (NH
4)
2Ce (NO
3)
4With the mol ratio of DMF 8: 303～1: 114.
2. the preparation method of a kind of high specific surface area meso-porous cerium dioxide micro-balloon according to claim 1 is characterized in that: (NH
4)
2Ce (NO
3)
4And between the mol ratio of absolute ethyl alcohol 3: 103～3: 206, mixing time is between 30～40 minutes.
3. the preparation method of a kind of high specific surface area meso-porous cerium dioxide micro-balloon according to claim 1, it is characterized in that: the acid of adding is solubility strong acid, its H
+The concentration in reaction solution 0.06～0.10 between.
4. the preparation method of a kind of high specific surface area meso-porous cerium dioxide micro-balloon according to claim 1 is characterized in that: (NH
4)
2Ce (NO
3)
4And between the mol ratio of DMF 17: 404～13: 206, mixing time is between 10～20 minutes.
5. the preparation method of a kind of high specific surface area meso-porous cerium dioxide micro-balloon according to claim 1, it is characterized in that: the sintering temperature of presoma is between 350～400 ℃, and sintering time is between 2～4 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007101194019A CN100567160C (en) | 2007-07-23 | 2007-07-23 | A kind of preparation method of high specific surface area meso-porous cerium dioxide micro-balloon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007101194019A CN100567160C (en) | 2007-07-23 | 2007-07-23 | A kind of preparation method of high specific surface area meso-porous cerium dioxide micro-balloon |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101117233A true CN101117233A (en) | 2008-02-06 |
| CN100567160C CN100567160C (en) | 2009-12-09 |
Family
ID=39053523
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2007101194019A Expired - Fee Related CN100567160C (en) | 2007-07-23 | 2007-07-23 | A kind of preparation method of high specific surface area meso-porous cerium dioxide micro-balloon |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100567160C (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100586862C (en) * | 2008-03-13 | 2010-02-03 | 同济大学 | Method for manufacturing high purity nano-cerium dioxide |
| CN101804318A (en) * | 2010-04-16 | 2010-08-18 | 北京科技大学 | Preparation of lanthanum doping cerium dioxide porous microspheres and application thereof to Cr<6+> removal |
| CN101857260A (en) * | 2010-06-29 | 2010-10-13 | 上海大学 | Method for preparing spherical cerium dioxide nano material with square-sheet surface structure by hydrothermal method |
| CN101584981B (en) * | 2009-06-12 | 2010-12-01 | 华中师范大学 | Low-temperature preparation method of ceria nano-crystalline microsphere of graduation structure |
| CN101825551B (en) * | 2009-07-23 | 2011-07-27 | 中国科学院过程工程研究所 | Cerium dioxide microsphere used as dimension standard material |
| CN102757079A (en) * | 2012-05-16 | 2012-10-31 | 成都理工大学 | Hydrothermal synthesis process for preparing mesoporous CeO2 |
| CN102951940A (en) * | 2012-11-05 | 2013-03-06 | 昆明理工大学 | Mesoporous cerium dioxide material preparation method |
| CN103253695A (en) * | 2013-05-24 | 2013-08-21 | 成都理工大学 | Normal pressure heat treatment process for synthesizing mesoporous CeO2 from CeO2 hydrosol |
| CN103965036A (en) * | 2014-05-12 | 2014-08-06 | 青岛科技大学 | Method for preparing tapered cerium formate |
| CN105585043A (en) * | 2016-03-11 | 2016-05-18 | 九江学院 | Preparation method of flowerlike cerium oxide nano-material |
| CN109133144A (en) * | 2018-10-22 | 2019-01-04 | 九江学院 | A kind of preparation method of monodisperse ultra-small grain size ceria nano-crystalline |
| CN109467117A (en) * | 2018-11-08 | 2019-03-15 | 乐山师范学院 | A kind of no template preparation CeO2The method and CeO of mesoporous material2Mesoporous material |
-
2007
- 2007-07-23 CN CNB2007101194019A patent/CN100567160C/en not_active Expired - Fee Related
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100586862C (en) * | 2008-03-13 | 2010-02-03 | 同济大学 | Method for manufacturing high purity nano-cerium dioxide |
| CN101584981B (en) * | 2009-06-12 | 2010-12-01 | 华中师范大学 | Low-temperature preparation method of ceria nano-crystalline microsphere of graduation structure |
| CN101825551B (en) * | 2009-07-23 | 2011-07-27 | 中国科学院过程工程研究所 | Cerium dioxide microsphere used as dimension standard material |
| CN101804318A (en) * | 2010-04-16 | 2010-08-18 | 北京科技大学 | Preparation of lanthanum doping cerium dioxide porous microspheres and application thereof to Cr<6+> removal |
| CN101857260A (en) * | 2010-06-29 | 2010-10-13 | 上海大学 | Method for preparing spherical cerium dioxide nano material with square-sheet surface structure by hydrothermal method |
| CN102757079B (en) * | 2012-05-16 | 2014-06-04 | 成都理工大学 | Hydrothermal synthesis process for preparing mesoporous CeO2 |
| CN102757079A (en) * | 2012-05-16 | 2012-10-31 | 成都理工大学 | Hydrothermal synthesis process for preparing mesoporous CeO2 |
| CN102951940A (en) * | 2012-11-05 | 2013-03-06 | 昆明理工大学 | Mesoporous cerium dioxide material preparation method |
| CN103253695A (en) * | 2013-05-24 | 2013-08-21 | 成都理工大学 | Normal pressure heat treatment process for synthesizing mesoporous CeO2 from CeO2 hydrosol |
| CN103253695B (en) * | 2013-05-24 | 2014-11-12 | 成都理工大学 | Normal pressure heat treatment process for synthesizing mesoporous CeO2 from CeO2 hydrosol |
| CN103965036A (en) * | 2014-05-12 | 2014-08-06 | 青岛科技大学 | Method for preparing tapered cerium formate |
| CN103965036B (en) * | 2014-05-12 | 2015-09-16 | 青岛科技大学 | A kind of preparation method of taper cesium formate |
| CN105585043A (en) * | 2016-03-11 | 2016-05-18 | 九江学院 | Preparation method of flowerlike cerium oxide nano-material |
| CN109133144A (en) * | 2018-10-22 | 2019-01-04 | 九江学院 | A kind of preparation method of monodisperse ultra-small grain size ceria nano-crystalline |
| CN109133144B (en) * | 2018-10-22 | 2021-04-02 | 九江学院 | Preparation method of monodisperse ultra-small particle size cerium dioxide nanocrystal |
| CN109467117A (en) * | 2018-11-08 | 2019-03-15 | 乐山师范学院 | A kind of no template preparation CeO2The method and CeO of mesoporous material2Mesoporous material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100567160C (en) | 2009-12-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100567160C (en) | A kind of preparation method of high specific surface area meso-porous cerium dioxide micro-balloon | |
| CN101792171B (en) | Preparation method of cerium oxide nanoballs | |
| CN103466702B (en) | Method for preparing porous bismuth oxide nano-material without template | |
| CN103691421B (en) | A kind of CeVO 4micron ball photochemical catalyst and preparation method thereof | |
| CN106745111B (en) | A kind of preparation method of high-specific area nano crystalline substance magnesium fluoride | |
| CN101708829B (en) | Method for preparing yttria-stabilized zirconia powder | |
| CN101565204B (en) | Preparation method of porous bismuth oxide powder with high specific surface area | |
| CN105948098B (en) | A kind of spherical lanthana | |
| CN101507917A (en) | Solid base catalyst for synthesizing alkanolamide type compound and preparation method thereof | |
| CN104291382A (en) | Preparation method of lanthanum ferrite porous micro-spheres | |
| CN107452512A (en) | A kind of preparation method of hollow cobalt acid nickel for electrode material for super capacitor | |
| Zahir et al. | Preparation of a Sustainable Shape-Stabilized Phase Change Material for Thermal Energy Storage Based on Mg2+-Doped CaCO3/PEG Composites | |
| CN103204534A (en) | Method for preparing ceric oxide hollow spheres with adjustable shell thickness | |
| CN101260299A (en) | Method for preparing yttrium gadolinium oxide and europium nano luminescent powder by micro-emulsion method | |
| CN100368296C (en) | Method for preparing Nano alpht-A12O3 through catalyzing calcinations in low tempeature | |
| CN103272630A (en) | Nickel-based catalyst taking yttrium-doped SBA-15 as carrier, and preparation method and application thereof | |
| CN110255598A (en) | A kind of preparation method of flower-like microsphere cerous carbonate and ceria | |
| CN106082300A (en) | A kind of asymmetric complicated hollow-core construction CeO2preparation method | |
| CN102070196A (en) | Method for preparing manganese dioxide nano rod at low temperature | |
| CN101234898A (en) | Method for preparing multi-component zirconium oxide based heat barrier oxide nano powder material | |
| CN106430289A (en) | Method for low temperature preparation of high specific surface area nanometer gallate spinel | |
| CN100487172C (en) | Method for preparing dielectric crystal of calcium tungstate rapidly | |
| CN104326500B (en) | A kind of preparation method of fluffy state nano yttrium oxide powder | |
| CN104128173B (en) | Low-cost and high-performance carried catalyst and preparation method thereof | |
| CN104326501A (en) | Method for synthesizing yttrium aluminum garnet nano powder |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20091209 Termination date: 20120723 |