CN101830501A - Method for preparing soluble anatase titanium dioxide - Google Patents
Method for preparing soluble anatase titanium dioxide Download PDFInfo
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- CN101830501A CN101830501A CN200910047610A CN200910047610A CN101830501A CN 101830501 A CN101830501 A CN 101830501A CN 200910047610 A CN200910047610 A CN 200910047610A CN 200910047610 A CN200910047610 A CN 200910047610A CN 101830501 A CN101830501 A CN 101830501A
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Abstract
The invention belongs to the fields of chemistry and chemical industry and materials, and relates to a method for preparing soluble titanium dioxide with photo-catalytic activity by a controlled non-hydrosol-gel method. The method comprises the following steps of: dissolving titanium halide and/or titanium alkoxide serving as a precursor into anhydrous organic alcohol solution at a certain temperature; and obtaining a white powdery product by the controlled non-hydrosol-gel drying process at the temperature of between 40 and 150 DEG C, wherein the dimension of the grains is 5 to 100nm. The prepared titanium dioxide powder has excellent dispersibility or dissolubility in water and organic solvents under the condition of not adding any surface modifier. The method for preparing the soluble titanium dioxide is simple and applied to large-scale industrialized production. The prepared titanium dioxide can be widely applied to the field of catalysis, and other related fields of environment self-cleaning materials, biological materials, organic and inorganic composite materials, coatings, ceramics, film materials, and the like.
Description
Technical field
The invention belongs to chemical and material field, relate to a kind of preparation method with soluble titanium dioxide of photocatalytic activity,
Background technology
Prior art discloses nano titanium oxide owing to have excellent properties such as nontoxic, highlight catalytic active and uv-absorbing function and good biocompatibility, has become a kind of inorganic materials of Multifunction.
At present, the preparation method of nano titanium oxide mainly is divided into vapor phase process and liquid phase method.The vapor phase process comparative maturity be the main method of present mass preparation titanium dioxide, but there is complex process equipment in vapor phase process, needs problems such as high-temperature calcination.The low temperature liquid phase sol-gel method is the focus of present experimental study as the important method of preparation nano titanium oxide.The liquid phase sol-gel method can be divided into hydrolytic sol gel (comprising hydrothermal method) and non-aqueous sol-gel (comprising solvent-thermal method) again.Preparing the relevant patent of titanium dioxide with the low temperature hydrolysis collosol and gel has: CN1295977A, CN1562768A, CN1583888A, CN1785503A, CN1654335A etc., but because no matter be that titanium tetrachloride or titanic acid ester are as TiO 2 precursor, its hydrolysis reaction all is very violent, and hydrolysis, the reaction of reuniting between condensation and particle is almost carried out simultaneously, is difficult to control respectively.Generally speaking, slight changes such as various reaction conditionss such as temperature, concentration, pH value all may have influence on the crystallization of the finished product, size of particles etc.Circulation ratio that we can say the hydrolytic sol gel reaction is generally relatively poor.
Non-aqueous sol-gel is reflected in the organic solvent and carries out, and does not have the existence of water, therefore can be to carrying out better controlled in hydrolysising condition various reactions more rambunctious.Organic solvent in the non-aqueous sol-gel not only as the Sauerstoffatom donor of metal oxide, and affects surface chemistry performance, the crystallographic dimension of oxide compound even crystalline structure strongly.Utilize the non-aqueous sol-gel reaction, multiple nano-metal-oxide (Niederberger, Nonaqueous Sol-Gel Routes to Metal Oxide Nanoparticles, Acc.Chem.Res.2007,40,793-800) successfully prepared, wherein also comprise titanium dioxide.Prior art CN101053829 is with titanium tetrachloride, ethanol and polyoxyethylene glycol are presoma, utilize the non-aqueous sol-gel method to prepare titanium deoxid film, but, used the high-temperature calcination process in this method in order to obtain crystalline titania with photocatalytic activity.Cheng Wang (Synthesis of nanocrystalline TiO2 in alcohols, Powder Technology 125 (2002) 39-44) etc. reported with solvent-thermal method and prepared nano titanium oxide, similar to hydrothermal method, this method has also been utilized high-tension apparatus, and the preparation titanium dioxide surface do not have the organic active group, so do not have solubility yet.In order to obtain titanium dioxide with crystallization solubleness, Niederberger (Tailoring the Surface and Solubility Properties of Nanocrystalline Titania by a Nonaqueous In Situ Functionalization Process, Chem.Mater.2004,16,1202-1208) with titanium tetrachloride, phenylcarbinol and surface-modifying agent Dopamine HCL etc. are reaction raw materials, utilize non-aqueous sol-gel to prepare the soluble titanium dioxide of crystallization, the amount of surface-modifying agent has very large influence to crystallinity and solubility, but a large amount of properties-correcting agent of surface coverage also have disadvantageous effect to the catalytic performance of titanium dioxide.
Summary of the invention
The objective of the invention is shortcoming, a kind of preparation method of soluble anatase titanium dioxide is provided, relate in particular to the titanium dioxide powder that the controlled non-aqueous sol-gel method preparation of a kind of low temperature has the crystallization solubleness at above prior art existence.
Particularly, the present invention is a raw material with the titanium tetrachloride that is easy to get or the alkyl oxide and the absolute alcohol of titanium, than under the low reaction temperatures, utilizes controlled very simply and easily non-aqueous sol-gel method preparation to have the titanium dioxide of special nucleus shell structure.The titanium dioxide that utilizes the present invention to prepare can obtain having the transparent titanium dioxide water-sol and the organosol of different concns at an easy rate, and these characteristics have very big benefit to the application of titanium dioxide, can expand its Application Areas greatly.Utilize TiO 2 sol can directly be mixed with coating, preparation has the photocatalytic activity titanium deoxid film, also can directly mix polymkeric substance titanium dioxide organic inorganic hybridization film or other matrix materials that the coating preparation is transparent with macromolecular solution.
In the titanium dioxide process disclosed by the invention, its process is, under the whipped state, the presoma of titanium dioxide slowly is added drop-wise in the alcoholic solvent, obtains transparent titanium alcoholic solution.With this solution ageing 1-100 hour at a certain temperature, obtain the titanium alcosol then.Colloidal sol is placed under 40-150 ℃, and the controlled non-aqueous sol-gel process through 3-180 hour obtains titanium dioxide powder powder solid.Comprise the steps:
1) halogenide of titanium, the alkoxide or their mixture of titanium are added drop-wise to the uniform titanium alcoholic solution of formation in the absolute alcohol at a certain temperature as presoma;
2) with above-mentioned solution certain temperature ageing 1-100 hour;
3) solution after the ageing is carried out controlled non-aqueous sol-gel under 40-150 ℃ of condition and handle, obtain white powder titanium dioxide, this is the soluble titanium dioxide product of crystallization.
Among the present invention, controlled non-aqueous sol-gel treating processes is, with titanium alcoholic solution ageing 1-100 hour in advance, then with solution under 40-150 ℃, through 3-180 hour processing, the titanium dioxide that obtains having crystalline texture.
Among the present invention, the halogenide of titanium is generally titanium tetrachloride, and the alkoxide of titanium refers to contain the saturated carbon hydrogen group and links to each other with titanium by Sauerstoffatom, and as tetrabutyl titanate, tetraethyl titanate, isopropyl titanate comprise but do not limit.
Among the present invention, the grain-size of the Powdered titanium dioxide of final white is the 5-100 nanometer.
Among the present invention, the presoma of titanium is added drop-wise to the temperature that forms homogeneous solution in the absolute alcohol and is controlled at 5-80 ℃.
Among the present invention, the alcohols of dissolving TiO 2 precursor is one or more alcohols mixtures wherein such as methyl alcohol, ethanol, Virahol, propyl carbinol, phenylcarbinol, phenylethyl alcohol.
Among the present invention, the presoma of titanium and alcohols mass ratio are 2: 1-1: 100.
Among the present invention, the ageing temperature of titanium alcoholic solution is 0-100 ℃.
The titania powder of the present invention's preparation has typical anatase octahedrite feature crystal formation through the XRD test shows.X-ray photoelectron power spectrum (XPS), thermogravimetic analysis (TGA) (TGA) and Infrared spectroscopy (IR) show have a large amount of organic groups to be present in titanium dioxide surface.The titanium dioxide that makes by this invention of above analysis revealed has special nucleocapsid structure, is the good titanium dioxide of crystalline texture in inside, and the surface then has hydroxyl, alkoxyl group and small part titanium chlorine structure.This gives good water-soluble of titanium dioxide and organic solvent dissolution performance.
The titanium dioxide that aforesaid method is obtained is distributed to and obtains the titanium dioxide vitreosol in water or the organic solvent.Its process is as follows, the 10g titania powder is joined in the deionized water of 1g-10000g, can see titania powder " dissolving " rapidly, be scattered in the water, form transparent titania hydrosol, the water-sol titanium dioxide mass concentration that this method obtains can be up to 90%, and highly stable, and room temperature state is stored 2 months down, and also gel-free or precipitation take place.
Utilize the titanium dioxide of method for preparing to be dissolved into organic solvent such as dimethyl formamide (DMF), N,N-DIMETHYLACETAMIDE (DMAC), methyl-2-pyrrolidone (NMPN) can conveniently obtain corresponding titanium dioxide organosol in ethanol (EtOH) and the dimethyl sulfoxide (DMSO) (DMSO) etc.
The present invention utilizes simple controlled non-aqueous sol-gel method, successfully prepared the crystalline titania powder under the lesser temps, and this titanium dioxide has good water dispersible and organic solvent dispersiveness simultaneously, can form the TiO 2 sol of transparent and stable, significantly expand the Application Areas of titanium dioxide.
The inventive method is simple, is fit to large-scale industrial production.The product titanium dioxide that makes can be applied in catalytic field widely, environment self-cleaning material, biomaterial, organic/inorganic composite material, coating, other association areas such as pottery and thin-film material.
For the ease of understanding, below will describe in detail of the present invention by concrete drawings and Examples.It needs to be noted, specific examples and accompanying drawing only are in order to illustrate, obviously those of ordinary skill in the art can illustrate according to this paper, within the scope of the invention the present invention is made various corrections and change, and these corrections and change are also included in the scope of the present invention.
Description of drawings
Fig. 1 is the titanium dioxide XRD spectra.
Fig. 2 is the 10wt% titania hydrosol.
Fig. 3 is a 5wt% titanium dioxide organic solvent colloidal sol,
Wherein, (a) dimethyl formamide colloidal sol, (b) ethanol colloidal sol.
Embodiment
Embodiment 1
Stir down fast, the 10g titanium tetrachloride slowly is added drop-wise in the three-necked flask that 10g dehydrated alcohol (5 ℃) are housed, obtain transparent solution, 80 ℃ of following ageings 1 hour.Then colloidal sol is carried out controlled non-aqueous sol-gel reaction at 150 ℃, obtain white powder.XRD test shows, titanium dioxide are the crystallization anatase octahedrite, grain-size 5 nanometers.See Fig. 1.
Embodiment 2
Stir down fast, the 10g titanium tetrachloride slowly is added drop-wise in the three-necked flask that 1000g Virahol (80 ℃) are housed, obtain clear solution, 0 ℃ of following ageing 100 hours.Then colloidal sol is carried out controlled non-aqueous sol-gel reaction at 40 ℃, obtain white powder.XRD test shows, product are typical anatase titanium dioxide, grain-size 15 nanometers.Be dissolved in the water and obtain vitreosol.See Fig. 2.
Embodiment 3
Stir down fast, 50 ℃ of control reaction temperature slowly are added drop-wise to titanium tetrachloride 10g in the three-necked flask that 80g propyl carbinol and Virahol (mass ratio 1: 1) mixed solvent are housed, and obtain clear solution, 100 ℃ of following ageings 72 hours.Then colloidal sol is carried out controlled non-aqueous sol-gel reaction at 100 ℃, obtain white solid.White solid is dissolved in DMF can be got transparent organosol (Fig. 3 a).
Embodiment 4
Stir down fast, the 5g titanium tetrachloride is mixed with the 5g tetrabutyl titanate, 70 ℃ of control reaction temperature slowly are added drop-wise in the three-necked flask that the 80g alcohol solvent is housed then, obtain clear solution, 40 ℃ of following ageings 72 hours.Then colloidal sol is carried out controlled non-aqueous sol-gel reaction at 80 ℃, obtain white solid, grain-size 10 nanometers.The transparent water colloidal sol that gets soluble in water is dissolved in DMSO and can gets transparent organosol.
Embodiment 5
Stir down fast, the 5g titanium tetrachloride is mixed with the 5g isopropyl titanate, 80 ℃ of control reaction temperature slowly are added drop-wise in the three-necked flask that 200g propyl carbinol solvent is housed then, obtain clear solution, 60 ℃ of following ageings 20 hours.Then colloidal sol is carried out controlled non-aqueous sol-gel reaction at 100 ℃, obtain white solid, grain-size 12 nanometers.The transparent water colloidal sol that gets soluble in water is dissolved in ethanol (EtOH) and can gets transparent organosol (Fig. 3 b).
Claims (9)
1. the preparation method of a soluble anatase titanium dioxide is characterized in that comprising the steps:
1) halogenide of titanium, the alkoxide or their mixture of titanium are added drop-wise to the uniform titanium alcoholic solution of formation in the absolute alcohol at a certain temperature as presoma;
2) with above-mentioned solution certain temperature ageing 1-100 hour;
3) solution after the ageing is carried out controlled non-aqueous sol-gel under 40-150 ℃ of condition and handle, obtain white powder titanium dioxide.
2. preparation method according to claim 1, the controlled non-aqueous sol-gel treating processes that it is characterized in that described step 3) was: with titanium alcoholic solution ageing 1-100 hour in advance, then with solution under 40-150 ℃, through 3-180 hour processing, the titanium dioxide that obtains having crystalline texture.
3. preparation method according to claim 1, the halogenide that it is characterized in that described titanium is titanium tetrachloride.
4. preparation method according to claim 3, the alkoxide that it is characterized in that described titanium is including but not limited to tetrabutyl titanate, tetraethyl titanate or isopropyl titanate.
5. preparation method according to claim 1, the grain-size that it is characterized in that described white powder titanium dioxide is the 5-100 nanometer.
6. preparation method according to claim 1, the presoma that it is characterized in that described titanium is added drop-wise to the temperature that forms homogeneous solution in the absolute alcohol and is controlled at 5-80 ℃.
7. preparation method according to claim 1, the alcohols that it is characterized in that described dissolving TiO 2 precursor is one or more the mixture in methyl alcohol, ethanol, Virahol, propyl carbinol, phenylcarbinol or the ethanol.
8. preparation method according to claim 1 is characterized in that the presoma of described titanium and alcohols mass ratio are 2: 1-1: 100.
9. preparation method according to claim 1, the ageing temperature that it is characterized in that described titanium alcoholic solution is 0-100 ℃.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102180515A (en) * | 2011-03-21 | 2011-09-14 | 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 |
| CN105664808A (en) * | 2016-01-13 | 2016-06-15 | 云南大学 | Method for preparing stable nano anatase titanium dioxide alcohol phase sol at low temperature |
| CN106517323A (en) * | 2017-01-13 | 2017-03-22 | 中国科学院重庆绿色智能技术研究院 | Preparation method of TiO2 quantum dot nano-material and relevant products |
| CN107572583A (en) * | 2017-08-01 | 2018-01-12 | 成都博美实润科技有限公司 | A kind of preparation method of dichloride in anatase type titanium colloidal sol |
| CN108585036A (en) * | 2018-07-12 | 2018-09-28 | 昆明理工大学 | A kind of nano-TiO2Preparation method |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1078565C (en) * | 1999-01-22 | 2002-01-30 | 清华大学 | Method for preparing nano sized titanium dioxide powder by alcoholysis from titanic chloride |
| CN100566819C (en) * | 2006-08-17 | 2009-12-09 | 复旦大学 | Preparation method with nano titanic oxide catalyst of photocatalytic activity |
| CN100591620C (en) * | 2008-04-23 | 2010-02-24 | 华中师范大学 | Preparation of high photocatalysis activity titanium dioxide nano-stick by non-hydrosol-gel method and surface functionalization |
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- 2009-03-13 CN CN200910047610A patent/CN101830501B/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102180515A (en) * | 2011-03-21 | 2011-09-14 | 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 |
| CN105664808A (en) * | 2016-01-13 | 2016-06-15 | 云南大学 | Method for preparing stable nano anatase titanium dioxide alcohol phase sol at low temperature |
| CN106517323A (en) * | 2017-01-13 | 2017-03-22 | 中国科学院重庆绿色智能技术研究院 | Preparation method of TiO2 quantum dot nano-material and relevant products |
| CN107572583A (en) * | 2017-08-01 | 2018-01-12 | 成都博美实润科技有限公司 | A kind of preparation method of dichloride in anatase type titanium colloidal sol |
| CN108585036A (en) * | 2018-07-12 | 2018-09-28 | 昆明理工大学 | A kind of nano-TiO2Preparation method |
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