CN101597083A - A kind of preparation method of monodisperse nano-titanium dioxide - Google Patents
A kind of preparation method of monodisperse nano-titanium dioxide Download PDFInfo
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- CN101597083A CN101597083A CNA2009100437845A CN200910043784A CN101597083A CN 101597083 A CN101597083 A CN 101597083A CN A2009100437845 A CNA2009100437845 A CN A2009100437845A CN 200910043784 A CN200910043784 A CN 200910043784A CN 101597083 A CN101597083 A CN 101597083A
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Abstract
The invention discloses a kind of preparation method of monodisperse nano-titanium dioxide, being of the feature of this method utilizes bicarbonate of ammonia to decompose the water of generation fast, makes the rapid hydrolysis of titanate precursor generate hydration complex ion [Ti (H
2O)
6]
4+(being growth unit) causes in the system growth unit concentration to reach satiety rapidly and closes state, brings out TiO
2Nanoparticle nucleation centre explosive type forms (explosion type nucleation), makes TiO
2Two stages of the nucleation of nanoparticle and growth are separately disperseed TiO thereby prepare list
2Nanoparticle.Adopt the TiO of present method preparation
2Nanoparticle has the purity height, and particle is little, and specific surface area is big; Narrow diameter distribution, its size be characteristics such as adjustable in 1.5～40nm scope.Simultaneously, present method have that simple to operate, speed of response is fast, production cost is lower, be easy to apply, advantages of environment protection.
Description
Technical field
The present invention relates to a kind of preparation method of monodisperse nano-titanium dioxide, the metal nanometer material preparing technical field.
Background technology
Nano-TiO
2Because the reactive behavior height, ultraviolet radiation absorption is strong and visible light permeability good, have a wide range of applications at aspects such as environmental protection, coating, printing ink, packaging material for food, makeup, solar cell, gas sensor and function ceramics.In many application, particulate size and shape determine the important factor of performance often.Mono-dispersed nano TiO
2Particle removes has common nano-TiO
2Characteristic outside, because the size of its homogeneous, the method that is considered to " from bottom to top " is constructed the most promising in the nano-device " construction module ", at aspects such as the self-assembly of photonic crystal, chromatograph packing material, granulometry thing, flat-panel monitors very big potential using value is arranged.Therefore, the preparation nano-TiO that monodispersity is good, particle diameter is controlled
2Has crucial meaning.
At present, nano-TiO
2Chemical preparation process vapor phase process and liquid phase method two big classes are generally arranged.In the vapor phase process, as titanium tetrachloride oxyhydrogen flame hydrolysis method, titanium tetrachloride vapour phase oxidation process, titanic acid ester gas phase hydrolysis method etc., though but the higher nano-powder of preparation quality, gas-phase reaction will make the material gasification, and energy consumption is higher; In addition, at high temperature moment is finished the gas phase process of reaction, DESIGN OF REACTOR, material, input and output material mode etc. is all required very high, has a series of technical problems.In the liquid phase method, be the hydrolysis method of starting raw material and the powder of sol-gel method (Sol-gel) preparation with titanium tetrachloride, titanic acid ester, normal temperature is amorphous substance down, needs just can make lattice perfection through high-temperature roasting.And roasting process often brings particulate hard aggregation problem, and particle diameter, distribution and the shape of nanoparticle can not be well controlled.In actual production process, the size-grade distribution of nano-powder often need produce a large amount of wastings of resources through complicated sieve classification process control, causes the increase of production cost.
From the formation mechanism of nanoparticle, its growth is a dynamic process, can be divided into " nucleation " and " growth " two stages.Wherein, nucleation process plays an important role to the size distribution of final product, is the key of preparation monodisperse nanoparticle.Therefore, the nanoparticle of a large amount of preparation size homogeneous, must make two stages of nucleation and growth separately with the mode nucleation (explosion type nucleation) of outburst in the short as far as possible time, unified process of growth could generate the roughly consistent nanoparticle of size.Recently, the Li Yadong professor seminar of Qinghua university is mixed bicarbonate of ammonia with oleic acid, triethylamine, tetrabutyl titanate and normal hexane, by solvent-thermal method, utilize bicarbonate of ammonia to be heated to decompose fast the water that generates to make tetrabutyl titanate hydrolysis and nucleation, prepared nearly monodispersed TiO
2Nanoparticle (Chem.Eur.J.2006,12:2383-2391).Need to prove, in their experiment, used exhibiting high surface promoting agent-oleic acid, itself and TiO
2The ratio of presoma-tetrabutyl titanate is up to 25: 1 (V/V), and used toxic reagent (triethylamine) and solvent (normal hexane), and environment is existed pollute, the preparation cost height, and do not meet the social needs of the present age " Green Chemistry ".
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of monodisperse nano-titanium dioxide.
Thinking of the present invention is such: adopt nontoxic hydrophilic solvent ethanol, help bicarbonate of ammonia and be heated and decompose fast the water and the titanate precursor that produce and mix, and impel its rapid hydrolysis generation hydration complex ion [Ti (H
2O)
6]
4+(being growth unit) causes in the system growth unit concentration to reach satiety rapidly and closes state, brings out TiO
2The nucleation centre explosive type forms (explosion type nucleation), makes TiO
2The nucleation of nanoparticle and two stages of growth are separated, thereby reach the single TiO of dispersion of preparation
2The purpose of nanoparticle.Its preparation process may further comprise the steps:
A, under-10～10 ℃, dehydrated alcohol, bicarbonate of ammonia, titanic acid ester, tensio-active agent are fully stirred, be made into suspension;
B, suspension is warming up to boiling rapidly, reacted 10～30 minutes, obtain light blue transparent colloidal solution;
C, above-mentioned colloidal solution is put into hydrothermal reaction kettle, 80～250 ℃ of insulations 1～20 hour down;
D, after centrifugation, washing, drying, promptly get monodisperse nano-titanium dioxide then.
Being 100 parts with the weight fraction of dehydrated alcohol is benchmark, and the parts by weight of all the other components are as follows:
0.01 part～50 parts of titanic acid ester
0.01 part～60 parts in bicarbonate of ammonia
0.01 part～5 parts of surfactants;
Described titanic acid ester is one or more a mixture of butyl (tetra) titanate, titanium propanolate, titanium ethanolate.
Described tensio-active agent comprises ionogenic surfactant, nonionic surface active agent.
Described ionogenic surfactant is sodium laurylsulfonate, cetyl trimethylammonium bromide or both mixtures.
Described nonionic surface active agent is a polyethenoxy ether class.
Press amount of substance and calculate, the bicarbonate of ammonia in reaction system: titanic acid ester is more than or equal to 2.
The present invention has following beneficial effect, and 1, adopt the nano-titania particle particle of the present invention's preparation little, narrow diameter distribution, its size is adjustable in 1.5～40nm scope.It is big that prepared nano titanium oxide has specific surface area, the reactive behavior advantages of higher; 2, compare with existing monodisperse nano-titanium dioxide preparation method, present method has mild condition, and speed of response is fast, and energy consumption is low, does not need expensive complicated advantages such as sieve classification equipment; 3, the solvent of whole process of preparation use is nontoxic, and recyclable reusing, and is a kind of eco-friendly technology of preparing; 4, to have a production cost low for this method, and technology is simple and convenient, is fit to advantages such as suitability for industrialized production.
Embodiment
Under normal pressure, adopt nontoxic hydrophilic solvent ethanol, the water and the titanate precursor of decomposing generation fast of effectively bicarbonate of ammonia being heated mixes, and makes system keep homogeneous phase, and impels the rapid hydrolysis of presoma to generate hydration complex ion [Ti (H
2O)
6]
4+(being growth unit) causes in the system growth unit concentration to reach satiety rapidly and closes state, brings out TiO
2The nucleation centre explosive type forms, and makes TiO
2The nucleation of nanoparticle and two stages of growth are separated, thereby reach the single TiO of dispersion of preparation
2The purpose of nanoparticle.
The reaction that takes place is as follows:
Ti(OR)
4+2H
2O→TiO
2+4ROH
The present invention will be further described below in conjunction with embodiment
Embodiment 1:
In the 250ml there-necked flask, add 100g dehydrated alcohol, 0.1g tetrabutyl titanate, 0.1g polyethenoxy ether class Triton X 100, after being cooled to 0 ℃, adding 0.5g bicarbonate of ammonia also stirs, heating up rapidly, (about 100 ℃ of temperature rise rate/Min) to ethanol seethes with excitement, and keep 10Min, obtain light blue transparent colloidal solution.Then colloidal solution is changed in the hydrothermal reaction kettle, be incubated 5 hours down, after centrifugation, washing, drying, promptly get monodisperse nano-titanium dioxide again at 150 ℃.The atomic force microscope test result shows that monodisperse nano-titanium dioxide size of particles is even, the about 1.5nm of its particle diameter,
Embodiment 2:
In the 250ml there-necked flask, add 100g dehydrated alcohol, 0.5g tetrabutyl titanate, 0.1g polyethenoxy ether class Triton X 100, after being cooled to 0 ℃, adding 1.5g bicarbonate of ammonia also stirs, heating up rapidly, (about 100 ℃ of temperature rise rate/Min) to ethanol seethes with excitement, and keep 10Min, obtain light blue transparent colloidal solution.Then colloidal solution is changed in the hydrothermal reaction kettle, be incubated 5 hours down, after centrifugation, washing, drying, promptly get monodisperse nano-titanium dioxide again at 150 ℃.The atomic force microscope test result shows that as shown in Figure 2: monodisperse nano-titanium dioxide size of particles is even, the about 5nm of its particle diameter; X-ray diffraction presentation of results, its crystal formation are anatase octahedrite; N
2The adsorption-desorption experimental result shows that calculating its specific surface area by the BET method is 398.5m
2/ g.
Embodiment 3:
In the 250ml there-necked flask, add 100g dehydrated alcohol, 1.0g tetrabutyl titanate, 0.2g polyethenoxy ether class Triton X 100, after being cooled to 0 ℃, adding 3.0g bicarbonate of ammonia also stirs, heating up rapidly, (about 100 ℃ of temperature rise rate/Min) to ethanol seethes with excitement, and keep 10Min, obtain light blue transparent colloidal solution.Then colloidal solution is changed in the hydrothermal reaction kettle, be incubated 5 hours down, after centrifugation, washing, drying, promptly get monodisperse nano-titanium dioxide again at 150 ℃.The atomic force microscope test result shows that monodisperse nano-titanium dioxide size of particles is even, the about 10nm of its particle diameter.
Embodiment 4:
In the 250ml there-necked flask, add 100g dehydrated alcohol, 2.0g tetrabutyl titanate, 0.5g polyethenoxy ether class Triton X 100, after being cooled to 0 ℃, adding 6.0g bicarbonate of ammonia also stirs, heating up rapidly, (about 100 ℃ of temperature rise rate/Min) to ethanol seethes with excitement, and keep 10Min, obtain light blue transparent colloidal solution.Then colloidal solution is changed in the hydrothermal reaction kettle, be incubated 5 hours down, after centrifugation, washing, drying, promptly get monodisperse nano-titanium dioxide again at 150 ℃.The atomic force microscope test result shows that monodisperse nano-titanium dioxide size of particles is even, the about 20nm of its particle diameter.
Embodiment 5:
In the 250ml there-necked flask, add 100g dehydrated alcohol, 10.0g tetrabutyl titanate, 1.0g polyethenoxy ether class Triton X 100, after being cooled to 0 ℃, adding 12.0g bicarbonate of ammonia also stirs, heating up rapidly, (about 100 ℃ of temperature rise rate/Min) to ethanol seethes with excitement, and keep 10Min, obtain light blue transparent colloidal solution.Then colloidal solution is changed in the hydrothermal reaction kettle, be incubated 5 hours down, after centrifugation, washing, drying, promptly get monodisperse nano-titanium dioxide again at 150 ℃.The atomic force microscope test result shows that monodisperse nano-titanium dioxide size of particles is even, the about 40nm of its particle diameter.
Embodiment 6:
In the 250ml there-necked flask, add 100g dehydrated alcohol, 1.0g tetrabutyl titanate, 0.5g sodium laurylsulfonate (SDS), after being cooled to 0 ℃, adding 3.0g bicarbonate of ammonia also stirs, heating up rapidly, (about 100 ℃ of temperature rise rate/Min) to ethanol seethes with excitement, and keep 10Min, obtain light blue transparent colloidal solution.Then colloidal solution is changed in the hydrothermal reaction kettle, be incubated 5 hours down, after centrifugation, washing, drying, promptly get monodisperse nano-titanium dioxide again at 150 ℃.The atomic force microscope test result shows that monodisperse nano-titanium dioxide size of particles is even, the about 10nm of its particle diameter.
Embodiment 7:
In the 250ml there-necked flask, add 100g dehydrated alcohol, 1.0g tetrabutyl titanate, 0.5g cetyl trimethylammonium bromide (CTAB), after being cooled to 0 ℃, adding 3.0g bicarbonate of ammonia also stirs, heating up rapidly, (about 100 ℃ of temperature rise rate/Min) to ethanol seethes with excitement, and keep 10Min, obtain light blue transparent colloidal solution.Then colloidal solution is changed in the hydrothermal reaction kettle, be incubated 5 hours down, after centrifugation, washing, drying, promptly get monodisperse nano-titanium dioxide again at 150 ℃.The atomic force microscope test result shows: monodisperse nano-titanium dioxide size of particles is even, the about 8nm of its particle diameter.
Claims (7)
1, a kind of preparation method of monodisperse nano-titanium dioxide, its preparation process is:
A. under-10～10 ℃, dehydrated alcohol, bicarbonate of ammonia, titanic acid ester, tensio-active agent are fully stirred, be made into suspension;
B. suspension is warming up to boiling rapidly, reacted 10～30 minutes, obtain light blue transparent colloidal solution;
C. above-mentioned colloidal solution is put into hydrothermal reaction kettle, be incubated 1～20 hour down at 80～250 ℃;
D. after centrifugation, washing, drying, promptly get monodisperse nano-titanium dioxide then.
2, the preparation method of a kind of monodisperse nano-titanium dioxide according to claim 1 is characterized in that: being 100 parts with the weight fraction of dehydrated alcohol is benchmark, and the parts by weight of all the other components are as follows:
0.01 part～50 parts of titanic acid ester
0.01 part～60 parts in bicarbonate of ammonia
0.01 part～5 parts of surfactants;
3, the preparation method of a kind of monodisperse nano-titanium dioxide according to claim 1 is characterized in that: described titanic acid ester is one or more a mixture of butyl (tetra) titanate, titanium propanolate, titanium ethanolate.
4, the preparation method of a kind of monodisperse nano-titanium dioxide according to claim 1 is characterized in that: described tensio-active agent comprises ionogenic surfactant, nonionic surface active agent.
5, the preparation method of a kind of monodisperse nano-titanium dioxide according to claim 4 is characterized in that: described ionogenic surfactant is sodium laurylsulfonate, cetyl trimethylammonium bromide or both mixtures.
6, the preparation method of a kind of monodisperse nano-titanium dioxide according to claim 4 is characterized in that: described nonionic surface active agent is a polyethenoxy ether class.
7, the preparation method of a kind of monodisperse nano-titanium dioxide according to claim 1 is characterized in that: press amount of substance and calculate, the bicarbonate of ammonia in reaction system: titanic acid ester is more than or equal to 2.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102583526A (en) * | 2012-01-31 | 2012-07-18 | 桂林理工大学 | Preparation method of titanium dioxide classification balls containing three crystalline phases |
| CN114538508A (en) * | 2022-02-28 | 2022-05-27 | 深圳陶陶科技有限公司 | Zirconium dioxide powder and preparation method thereof |
-
2009
- 2009-06-29 CN CN2009100437845A patent/CN101597083B/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102583526A (en) * | 2012-01-31 | 2012-07-18 | 桂林理工大学 | Preparation method of titanium dioxide classification balls containing three crystalline phases |
| CN102583526B (en) * | 2012-01-31 | 2014-01-08 | 桂林理工大学 | Preparation method of titanium dioxide classification balls containing three crystalline phases |
| CN114538508A (en) * | 2022-02-28 | 2022-05-27 | 深圳陶陶科技有限公司 | Zirconium dioxide powder and preparation method thereof |
| CN114538508B (en) * | 2022-02-28 | 2023-12-26 | 深圳陶陶科技有限公司 | Zirconium dioxide powder and preparation method thereof |
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