CN101348240B - Sol-solvent-thermal method for synthesizing nanocrystalline oxide powder - Google Patents
Sol-solvent-thermal method for synthesizing nanocrystalline oxide powder Download PDFInfo
- Publication number
- CN101348240B CN101348240B CN2007101192009A CN200710119200A CN101348240B CN 101348240 B CN101348240 B CN 101348240B CN 2007101192009 A CN2007101192009 A CN 2007101192009A CN 200710119200 A CN200710119200 A CN 200710119200A CN 101348240 B CN101348240 B CN 101348240B
- Authority
- CN
- China
- Prior art keywords
- inorganic salt
- preparation
- solvent
- sol
- colloidal sol
- 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.)
- Expired - Fee Related
Links
Images
Abstract
The invention provides a sol-solvent thermal method for synthesizing a nanocrystalline oxide powder. The method comprises the following: (1) a step of preparation of inorganic salt mother liquids, during which the inorganic salt taken as a material is dissolved in an organic liquid medium or water to prepare a mother liquid of the inorganic salt with definite concentration; (2) a step of preparation of a precipitation reactant liquid, during which alkali is dissolved in an organic liquid medium or water, proper quantity of surfactants are added to prepare the precipitation reactant liquid with definite concentration; (3) a step of preparation of sols, during which, at a certain temperature, while stirring, the prepared reactant liquid is slowly added in the prepared mother liquid of the inorganic salt, the reactant liquid and the mother liquid of the inorganic salt are kept reacting for a period of time after adding the reactant liquids in the mother liquid of the inorganic salt, and the transparent sols are obtained; and (4) a step of solvent thermal reaction of the sols, during which the prepared sols are put in a reaction kettle and reacted for a period of time under a certain temperature and pressure, the products obtained are subjected to filtering, washing and drying, and the nanocrystalline oxide powder is obtained.
Description
Technical field
The present invention relates to the technology of preparing of ceramic nano-powder, be meant a kind of synthetic technology that is equipped with oxide nanocrystalline with the hot legal system of sol-solvent especially.
Background technology
Nano-oxide is widely used in making catalyzer, fine ceramics, matrix material, magneticsubstance, fluorescent material, wet quick property transmitter and infrared absorbing material etc.The preparation of nano-metal-oxide generally can be divided into vapor phase process, liquid phase method and solid phase method.Compare with vapor phase process, solid phase method, the liquid phase method ratio is easier to be controlled to nuclear-growth, particulate chemical constitution more easy to control, and the material of forming for complexity also can obtain the good powder of chemical uniformity.Liquid phase method is divided into solvent-gel method, the precipitator method, hydrolysis method, hydro-thermal (solvent thermal) method, microemulsion method, supercritical drying etc., yet, because the specific surface energy of nano particle is big, forms easily and reunite, directly influenced material property.The reunion, the realization dispersed nano crystalline flour system that overcome nano particle become nanocrystalline synthetic technical bottleneck fully.
Summary of the invention
The objective of the invention is to prevent that the reunion of nano particle, the low temperature of realization dispersed nano crystalline flour body from synthesizing, for this reason, a kind of novel method of sol-solvent heat is provided, it has overcome the used expensive raw material of traditional sol-gel method (alkoxide), has overcome the hydrothermal method pyrohydrolysis and has easily produced the deficiency of reunion.Method easy handling of the present invention is regulated and control, flow process is simple, be easy to scale preparation.
For achieving the above object, technical solution of the present invention provides a kind of sol-solvent by the use of thermal means of synthesizing nanocrystalline oxide powder, and it comprises the steps:
(1) inorganic salt mother liquor preparation: with inorganic salt is raw material, and it is dissolved in organic medium or the water, is mixed with the inorganic salt mother liquor; The concentration of metal ion is 0～1.0mol/L in the inorganic salt mother liquor;
(2) precipitin reaction agent solution preparation: alkali is dissolved in organic medium or the water, and the tensio-active agent toward wherein adding 0.005～0.05 times of mole of metal ion in the inorganic salt mother liquor is mixed with the precipitin reaction agent solution, and the concentration of its reactant solution is 0～15mol/L;
(3) preparation of colloidal sol: under 60～100 ℃ of temperature, under whipped state, the reactant solution for preparing slowly is added drop-wise in the inorganic salt mother liquor of preparation, dropwises the back and continue reaction 30～60 minutes, obtain transparent organic medium colloidal sol (or water-sol);
(4) solvent thermal reaction of colloidal sol: the colloidal sol of preparation is placed reactor, and after reacting 1～10h under 100～300 ℃ of temperature and pressure 0.1～10MPa, the product of formation after filtration, after the washing, drying, obtain the nano-crystal oxide powder.
Aforesaid method, its described organic medium is ethylene glycol, glycerol, glycol ether, triglycol, propylene glycol, butyleneglycol, pentanediol, neopentyl glycol (2,2-dimethyl-1, ammediol), various polyvalent alcohols such as sorbyl alcohol, Xylitol, nucite, terpinol (Terpineol 350), menthol, N.F,USP MANNITOL, polyester polyvalent alcohol, polyether glycol maybe can be dissolved in one or more of polyvalent alcohol of low-carbon alcohol or water.
Aforesaid method, its described alkali is mineral alkali or organic basess such as quadrol, trolamine such as ammoniacal liquor, sodium hydroxide, potassium hydroxide.
Aforesaid method, in the solvent thermal reaction of its described colloidal sol, solvent for use is organic medium solvent or water medium solvent.
Aforesaid method, its described inorganic salt are main group, subgroup, rare earth metal inorganic salts, as inorganic salt such as Al, Zn, Fe, Ti, Ce, Zr, Y.
Aforesaid method, its described tensio-active agent are polyvinylpyrrolidone (PVP), hydroxy propyl cellulose (HPC), polyvinyl alcohol etc.
Beneficial effect of the present invention:
The preparation-obtained metallic oxide nanocrystal homogeneous grain diameter of the present invention, narrowly distributing, the reunion degree is little, and crystalline form physically well develops.The advantage of this invention: (1) easily equal and quantitative mix some trace elements, realize the even doping on the molecular level, the preparation multi-component material; (2) raw materials cost is relatively low; (3) synthesis temperature is low; (4) gained nano particle purity height, good dispersity, crystal formation is good, and controlled amount; (5) simple, the easy handling regulation and control of flow process.
The hot method of sol-solvent of the present invention is applicable to the preparation of nano-oxide crystal, prepares as nano-crystal oxides such as cerium oxide, titanium oxide, ferric oxide, aluminum oxide, zinc oxide, zirconium white, yttrium oxide.
Description of drawings:
Fig. 1 is the schema of the hot method of sol-solvent;
Fig. 2 is TiO
2The XRD figure of powder;
Fig. 3 is Fe
2O
3The XRD figure of powder;
Fig. 4 is CeO
2The XRD figure of powder;
Fig. 5 is TiO
2The sem photograph of powder (FESEM);
Fig. 6 is Fe
2O
3The sem photograph of powder (FESEM);
Fig. 7 is CeO
2The sem photograph of powder (FESEM);
Fig. 8 is TiO
2Dynamic light (DLS) the size distribution figure of powder;
Fig. 9 is Fe
2O
3Dynamic light (DLS) the size distribution figure of powder;
Figure 10 is CeO
2Dynamic light (DLS) the size distribution figure of powder.
Embodiment
See Fig. 1, the inventive method comprises the steps:
(1) inorganic salt mother liquor preparation: with inorganic salt is raw material, and it is dissolved in organic medium or the water, is mixed with finite concentration inorganic salt mother liquor;
(2) precipitin reaction agent solution preparation: alkali is dissolved in organic medium or the water,, is mixed with certain density precipitin reaction agent solution toward wherein adding an amount of tensio-active agent;
(3) preparation of colloidal sol (sol): at a certain temperature, under whipped state, the reactant solution for preparing slowly is added drop-wise in the inorganic salt mother liquor of preparation, dropwises the back and continue reaction for some time, obtain transparent colloidal sol;
(4) solvent thermal reaction of colloidal sol: the colloidal sol of preparation is placed reactor, and after the suitable time of reaction under certain temperature and the pressure, the product of formation after filtration, after the washing, drying, obtain the nano-crystal oxide powder.
Take by weighing 3.113g TiCl
4, join carefully in 50mL0 ℃ the ethanol, add 50mL ethylene glycol again, and fully stir, obtain the titanium salt mother liquor of 0.164mol/L.Take by weighing 2.725g strong aqua (wt%=25～28%, down together) and 0.5g polyvinylpyrrolidone (PVP), join successively in the ethanol of 30mL, be made into the precipitin reaction agent solution of 1.4mol/L.Mother liquor is placed 80 ℃ water bath with thermostatic control, and fully stir; Behind the preheating 5min, lentamente splash in mother liquor with the speed of about 1mL/min the precipitin reaction agent solution; After the precipitin reaction agent solution dropwises, continue under this temperature, to react 30min, obtain the colourless colloidal sol of clear at last.Measure 40mL colloidal sol, placing volume is the reactor of pressure certainly of 50mL, 150 ℃ of temperature of reaction, pressure 1MPa, time 3h.After reaction finished, the question response still naturally cooled to room temperature, took out slip, and the speed centrifugation 5min with 8000rpm respectively washs 2～3 times with dehydrated alcohol and acetone then successively.At last with wet-milling at 70 ℃ of following dry 2h, promptly get particle diameter and be the white Detitanium-ore-type TiO about 10nm
2Powder.See also Fig. 2,5,8.
Embodiment 2
Take by weighing 2.0g FeCl
36H
2O joins in the 50mL ethanol, adds the 50mL glycerol again, and fully stirs, and obtains the mother liquid of iron salt of 0.074mol/L.Take by weighing 0.970g strong aqua and 0.2g polyvinylpyrrolidone (PVP), join successively in the ethanol of 30mL, be made into the precipitant solution of 0.5mol/L.Mother liquor is placed 80 ℃ water bath with thermostatic control, and fully stir; Behind the preheating 5min, lentamente splash in mother liquor with the speed of about 1mL/min the precipitin reaction agent solution; After the precipitin reaction agent solution dropwises, continue under this temperature, to react 30min, obtain the pale brown look colloidal sol of clear at last.Measure 40mL colloidal sol, placing volume is the reactor of pressure certainly of 50mL, 150 ℃ of temperature of reaction, pressure 1MPa, time 3h.After reaction finished, the question response still naturally cooled to room temperature, took out slip, and the speed centrifugation 5min with 8000rpm respectively washs 2～3 times with dehydrated alcohol and acetone then successively.At last with wet-milling at 70 ℃ of following dry 2h, promptly get particle diameter and be the red-brown α-Fe about 30nm
2O
3Powder.See also Fig. 3,6,9.
Embodiment 3
Take by weighing 3.0g (NH
4)
2Ce (NO
3)
66H
2O joins in the 50mL ethanol, adds in the mixed solution of 50mL ethylene glycol/glycerin (volume ratio 1:1) again, and fully stirs, and obtains the cerium salt mother liquor of 0.046mol/L.Take by weighing 2.725g strong aqua and 0.5g polyvinylpyrrolidone (PVP), join successively in the ethanol of 30mL, be made into the precipitin reaction agent solution of 1.4mol/L.Mother liquor is placed 80 ℃ water bath with thermostatic control, and fully stir; Behind the preheating 5min, lentamente splash in mother liquor with the speed of about 1mL/min the precipitin reaction agent solution; After the precipitin reaction agent solution dropwises, continue under this temperature, to react 30min, obtain the orange-yellow colloidal sol of clear at last.Measure 80mL colloidal sol, placing volume is the reactor of pressure certainly of 100mL, at 250 ℃, 4MPa, time 3h.After reaction finished, the question response still naturally cooled to room temperature, took out slip, and the speed centrifugation 5min with 8000rpm respectively washs 2～3 times with dehydrated alcohol and acetone then successively.At last with wet-milling at 80 ℃ of following dry 2h, promptly get particle diameter and be the light yellow CeO about 20～50nm
2Powder.See also Fig. 4,7,10.
Claims (7)
1. the sol-solvent by the use of thermal means of a synthesizing nanocrystalline oxide powder is characterized in that, comprise the steps: the preparation of (1) inorganic salt mother liquor: with inorganic salt is raw material, and it is dissolved in organic medium or the water, is mixed with the inorganic salt mother liquor; In the inorganic salt mother liquor concentration of metal ion greater than 0 less than 1.0mol/L; (2) precipitin reaction agent solution preparation: alkali is dissolved in organic medium or the water, toward the tensio-active agent that wherein adds 0.005～0.05 times of mole of metal ion in the inorganic salt mother liquor, be mixed with the precipitin reaction agent solution, the concentration of its reactant solution greater than 0 less than 15mol/L; (3) preparation of colloidal sol: under 60～100 ℃ of temperature, under whipped state, the reactant solution for preparing slowly is added drop-wise in the inorganic salt mother liquor of preparation, dropwises the back and continue reaction 30～60 minutes, obtain transparent the organic medium colloidal sol or the water-sol; (4) solvent thermal reaction of colloidal sol: the colloidal sol of preparation is placed reactor, and after reacting 1～10h under 100～300 ℃ of temperature and pressure 0.1～10MPa, the product of formation after filtration, after the washing, drying, obtain the nano-crystal oxide powder.
2. method according to claim 1, it is characterized in that, organic medium is ethylene glycol, glycerol, glycol ether, triglycol, propylene glycol, butyleneglycol, pentanediol, neopentyl glycol (2 in described (1) step, 2-dimethyl-1, ammediol), the various polyvalent alcohols of sorbyl alcohol, Xylitol, nucite, terpinol, menthol, N.F,USP MANNITOL, polyester polyol, polyether glycol.
3. method according to claim 1 is characterized in that, alkali is the organic bases of the mineral alkali of ammoniacal liquor, sodium hydroxide, potassium hydroxide or quadrol, trolamine in described (2) step.
4. method according to claim 1 is characterized in that, in the solvent thermal reaction of described (4) step colloidal sol, solvent for use is the organic medium solvent or the water medium solvent of colloidal sol.
5. method according to claim 1 is characterized in that, inorganic salt are main group, subgroup, rare earth metal inorganic salt in described (3) step.
6. method according to claim 5 is characterized in that, main group, subgroup, rare earth metal inorganic salt are the inorganic salt of Al, Zn, Fe, Ti, Ce, Zr, Y in described (3) step.
7. method according to claim 1 is characterized in that, in described (2) step tensio-active agent be polyvinylpyrrolidone (PVP), hydroxy propyl cellulose (HPC), polyvinyl alcohol one of them.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101192009A CN101348240B (en) | 2007-07-18 | 2007-07-18 | Sol-solvent-thermal method for synthesizing nanocrystalline oxide powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101192009A CN101348240B (en) | 2007-07-18 | 2007-07-18 | Sol-solvent-thermal method for synthesizing nanocrystalline oxide powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101348240A CN101348240A (en) | 2009-01-21 |
| CN101348240B true CN101348240B (en) | 2011-09-21 |
Family
ID=40267241
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007101192009A Expired - Fee Related CN101348240B (en) | 2007-07-18 | 2007-07-18 | Sol-solvent-thermal method for synthesizing nanocrystalline oxide powder |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101348240B (en) |
Families Citing this family (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101456567B (en) * | 2008-12-25 | 2011-07-20 | 中国计量学院 | Method for synthesizing high temperature stabilizing type alpha-Al2O3 nano powder |
| CN101481140B (en) * | 2009-02-27 | 2011-05-25 | 上海师范大学 | Preparation of multi-level flower-like structure titanium dioxide |
| US8492304B2 (en) * | 2009-12-30 | 2013-07-23 | National Cheng Kung University | Iron complex, manufacturing method thereof and supported iron oxide catalyst constructed thereby |
| KR101894056B1 (en) * | 2010-04-23 | 2018-10-04 | 픽셀리전트 테크놀로지스 엘엘씨 | Synthesis, Capping and Dispersion of Nanocrystals |
| CN102452684B (en) * | 2010-10-18 | 2014-01-29 | 清华大学 | Method for one-step synthesis of mono-dispersed barium titanate nanocrystalline by self-regulating solvent thermal |
| EP3190083B1 (en) | 2010-10-27 | 2020-08-26 | Pixelligent Technologies, LLC | Synthesis, capping and dispersion of nanocrystals |
| CN102180515B (en) * | 2011-03-21 | 2013-03-20 | 杭州万景新材料有限公司 | Preparation method for nano titanium dioxide with high visible light catalytic activity and water dispersion thereof |
| CN102206486A (en) * | 2011-04-11 | 2011-10-05 | 北京理工大学 | Preparation method for Zno quantum dot |
| CN102796493A (en) * | 2012-08-24 | 2012-11-28 | 内蒙古大学 | Spherical monodisperse high-cerium polishing powder and preparation method thereof |
| CN103523826A (en) * | 2013-10-16 | 2014-01-22 | 黑龙江大学 | Preparation method of tin-doped titanium dioxide |
| CN103773373B (en) * | 2014-01-10 | 2015-04-15 | 天津师范大学 | Preparation method of folic acid self-assembled water-soluble rare-earth doped up-converted nanometer material |
| CN104192901A (en) * | 2014-08-26 | 2014-12-10 | 卜艳茹 | Preparation method of titanium oxide film and titanium oxide film |
| CN104310488A (en) * | 2014-09-24 | 2015-01-28 | 西北大学 | Nanometer iron oxide preparation method |
| CN106277049B (en) * | 2015-06-08 | 2017-08-15 | 北京化工大学 | A kind of transparent nano zirconium oxide liquid dispersion and preparation method and application |
| CN105731384B (en) * | 2016-01-13 | 2018-06-19 | 南京林业大学 | A kind of preparation method of inorganic oxide nano-powder |
| CN105585043B (en) * | 2016-03-11 | 2017-04-12 | 九江学院 | Preparation method of flowerlike cerium oxide nano-material |
| CN108585058B (en) * | 2018-05-15 | 2020-06-16 | 合肥学院 | α -Fe for cosmetics2O3Preparation method of nano wafer and nano ring |
| CN109529802B (en) * | 2018-11-12 | 2021-12-28 | 山东国瓷功能材料股份有限公司 | Cerium-zirconium composite oxide and preparation method and application thereof |
| CN110668481A (en) * | 2019-09-09 | 2020-01-10 | 西安理工大学 | Nano aluminum oxide and preparation method and application thereof |
| CN112978772B (en) * | 2019-12-02 | 2023-01-10 | 中国石油化工股份有限公司 | Polycrystalline gamma-alumina octahedral particle and preparation method thereof |
| CN112808258A (en) * | 2020-12-25 | 2021-05-18 | 沈阳化工大学 | Preparation method of crystal form adjustable graphene composite material |
| CN115228396B (en) * | 2022-07-26 | 2024-02-02 | 宣城市晶和环保新材料科技有限公司 | Preparation method of nano cerium sol |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1342517A (en) * | 2001-08-31 | 2002-04-03 | 清华大学 | Process for preparing mesoporous TiOw powder and film photocatalyst by sol-gel method |
| CN1709987A (en) * | 2005-07-08 | 2005-12-21 | 清华大学 | Preparation of titanium dioxide nano water-based coating by alkali peptication process |
-
2007
- 2007-07-18 CN CN2007101192009A patent/CN101348240B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1342517A (en) * | 2001-08-31 | 2002-04-03 | 清华大学 | Process for preparing mesoporous TiOw powder and film photocatalyst by sol-gel method |
| CN1709987A (en) * | 2005-07-08 | 2005-12-21 | 清华大学 | Preparation of titanium dioxide nano water-based coating by alkali peptication process |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101348240A (en) | 2009-01-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101348240B (en) | Sol-solvent-thermal method for synthesizing nanocrystalline oxide powder | |
| Djuričić et al. | Nanostructured cerium oxide: preparation and properties of weakly-agglomerated powders | |
| CN101214928B (en) | Method for synthesizing high specific surface area ordered mesoporous metal oxide by using hard template agent | |
| CN101306828B (en) | Device and process for preparing rare-earth compound uniform micro powder | |
| CN102757081B (en) | Synthesis method of cerium oxide hydrosol dispersed by PVA (Polyvinyl Alcohol) | |
| CN101786902B (en) | Preparation method for zirconium silicate wrapped cadmium sulfide selenide scarlet pigment | |
| CN104607178A (en) | Preparation method of bismuth tungstate-titanium dioxide heterojunction composite photocatalysis material | |
| CN104591275B (en) | Aqueous medium disperses the synthetic method of cerium Zirconium oxide nano material | |
| Wang et al. | Chemical co-precipitation synthesis and properties of pure-phase BiFeO3 | |
| CN101717116A (en) | Surface active agent assisting alcohol-hydrothermal method for preparing anthoid BiVO4 | |
| CN102161498B (en) | Preparation method of uniformly dispersed nano lanthanum oxide | |
| Khaledi et al. | Improving ZnAl2O4 structure by using chelating agents | |
| CN104108737B (en) | The synthetic method of copper-rare earth nano petal-shaped metal-oxide | |
| CN103449503B (en) | Method for preparing nanometer gahnite | |
| CN104528799A (en) | Preparation method of ultrafine magnesium-based rare earth hexaaluminate powder | |
| CN103288136A (en) | Hydrothermal synthesis method of shape-controllable molybdenum dioxide submicrocrystals | |
| CN103395835B (en) | Preparation method of oil soluble monoclinic crystal type nano zirconium dioxide particle | |
| CN107827153B (en) | A kind of preparation method of nanometer of silver vanadate | |
| CN101891236B (en) | Method for synthesizing monodisperse samarium-doped rare earth cerium oxide nanocrystal | |
| CN103101963A (en) | Method of preparing and purifying transparent nano-zinc oxide sol | |
| CN106315690A (en) | Porous cobalt tetroxide nanosheet and preparation method thereof | |
| CN103708548B (en) | A kind of method utilizing kind of crystallization to synthesize monoclinic form zirconium dioxide nanoparticles between water-oil interface | |
| CN106082298A (en) | A kind of preparation method of cerium bismuth composite oxide nano-bar material | |
| CN1321942C (en) | Method for preparing Nano crystal of metal oxide of anti agglomeration | |
| CN109879305B (en) | Preparation of micron-sized monodisperse LaAlO3:xMm+Method for producing spherical particles |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110921 Termination date: 20210718 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |