CN102786087A

CN102786087A - Method for preparing titanium dioxide sol

Info

Publication number: CN102786087A
Application number: CN2012103021015A
Authority: CN
Inventors: 周忠华; 阳欢; 沈开波; 黄悦
Original assignee: Xiamen University
Current assignee: Xiamen University
Priority date: 2012-08-22
Filing date: 2012-08-22
Publication date: 2012-11-21

Abstract

The invention provides a method for preparing titanium dioxide sol, relating to sol. The prepared titanium dioxide sol is high in concentration, good in stability and transparent; the cost is relatively low; the operation temperature is low; the device is simple without pollution, and industrial production is easy to expand. The method comprises the steps of adding inorganic titanium salt into hydrochloric acid; then adding deionized water to obtain mixing solution; adding ammonia water to the mixing solution to generate white sediment; filtering and washing the white sediment by the deionized water until the pH value is neutral (pH is about 7); adding hydrogen peroxide and distilled water into washed sediment, agitating and peptizing to obtain the transparent buffer titanium dioxide sol. Not only is the method simple, but also the stability and transparency can be kept for a long time without adding any reagent.

Description

A kind of preparation method of TiO 2 sol

Technical field

The present invention relates to a kind of colloidal sol, especially relate to a kind of preparation method of TiO 2 sol.

Background technology

Nano titanium oxide has the character of many uniquenesses, thereby is widely used in various technical fields.Under the situation of illumination, nano titanium oxide produces strong oxidation capacity and super hydrophilicity, can be used for fields such as the utilization of processing, the sun power of purification, the sewage of air, antibiotic, virus killing and automatically cleaning.Be prepared into film to titanium oxide, the characteristics such as quantum size effect, surface and interface effect that have nano material owing to its size refinement have improved the activity of nano titanium oxide, thereby have good actual application and be worth.At present, synthesis of nano TiO ₂Method mainly be traditional methods such as sol-gel method (sol-gel), magnetron sputtering method, chemical Vapor deposition process (CVD) and static self-assembly.Utilizing the hydrolysis of metal alkoxide and the sol-gel method of polycondensation is a kind of effective ways that prepare nano material, has synthesized the TiO of size-grade distribution homogeneous ₂Colloidal sol and nano-TiO ₂Powder, but metal alkoxide costs an arm and a leg, toxicity is big, and facile hydrolysis is inflammable, is unfavorable for scale operation.And picture magnetron sputtering method, chemical Vapor deposition process (CVD) and static self-assembly rule require height at aspects such as technology and equipments, complex process, and investment is big.Therefore, develop a kind of with low costly, simple to operate, be easy to the TiO of scale operation ₂The preparation method of colloidal sol is very necessary, and it more helps further developing nano-TiO ₂Material, and TiO ₂The application of film aspect.

At publication number is that CN 1323743A and publication number are all to mention inorganic salt with titanium in the Chinese patent of CN 1295977A (like TiCl ₄) be the TiO 2 sol of feedstock production, in the preparation process of colloidal sol, all used HNO like HCl ₃As dispergator, publication number is that the temperature of dispergation is controlled at 0 ~ 90 ℃ in the Chinese patent of CN 1323743A Deng mineral acid, and the time of dispergation is 12 ~ 60h; Publication number is that the temperature of the Chinese patent dispergation of CN 1295977A is controlled at 30 ~ 100 ℃, and the time of dispergation is 0 ~ 24h.The improvements of this patent just are that used dispergator is a ydrogen peroxide 50; The temperature of dispergation is also just controlled at normal temperatures; Required time is also very short; Only need one to two hours, the improvement on dispergation temperature and the dispergation required time all helps the reduction of industrial production cost and the raising of production efficiency greatly.

, publication number mentioned a kind of method of preparation of stable and transparent TiO 2 sol in being the Chinese patent of CN 101827650A; But relate in the presence of specific alpha hydroxy acid in its described method, could form transparent and stable TiO 2 sol.In publication number is the Chinese patent of CN 101898789A, mention a kind of neutral titanium oxide of high storage stability and the preparation method of colloidal sol thereof, related preparation raw material adopts inorganic salt, precipitation agent and oxygenant etc.

Summary of the invention

The object of the present invention is to provide a kind of preparation method of TiO 2 sol, prepared TiO 2 sol concentration is higher, and stability is better and transparent, and cost is lower, and service temperature is low, and equipment is simple, and is pollution-free, is easy to enlarge suitability for industrialized production.

The present invention includes following steps:

1) inorganic titanium salt is added in the hydrochloric acid, adds deionized water then, get mixing solutions;

2) in the prepared mixing solutions of step 1), add ammoniacal liquor, generate white precipitate;

3) with step 2) white precipitate of gained is with deionized water suction filtration, washing, is neutral (pH ≈ 7) until the pH value;

4) add ydrogen peroxide 50 and zero(ppm) water in the deposition after the step 3) washing, stir dispergation, promptly obtain transparent light yellow TiO 2 sol.

In step 1), the volume ratio of said inorganic titanium salt, hydrochloric acid and deionized water can be (3～5): (6～10): (100～200); It is 37% hydrochloric acid that said hydrochloric acid can adopt mass concentration.

In step 2) in, the add-on of said ammoniacal liquor and the volume ratio of inorganic titanium salt can be (10～30): (3～5); The mass concentration of said ammoniacal liquor can be 25%～28%.

In step 4), the add-on of said ydrogen peroxide 50 and zero(ppm) water and the volume ratio of inorganic titanium salt can be (5～30): (50～200): (3～5); The time of said stirring dispergation can be 1～2h.

The invention provides and a kind ofly prepare the method for TiO 2 sol, with TiCl by titanium tetrachloride ₄Be raw material, generate deposition with the alkaline solution effect, this deposition is neutral to pH after washing, add deionized water and H ₂O ₂Solution stirs the yellow TiO that obtains stable transparent behind the dispergation ₂Colloidal sol.

The alkaline solution that in preparation method of the present invention, adopts is selected ammoniacal liquor.Ammoniacal liquor is a kind of weak base, is and TiCl ₄When effect generates deposition, can reduce generating sedimentary speed, make the deposition granularity of generation little and even, be more conducive to next step dispergation, ammoniacal liquor can decompose fully at a certain temperature in addition, can residual other ions and influence the TiO after the colloidal sol moulding thus ₂The character of material.That last dispergation adopts is H ₂O ₂Solution, the TR of preparation are room temperature.The TiO of this method preparation ₂Colloidal sol is transparent, stable, can keep the several months can not precipitate, can gelation.Because the titanium oxide prepared of the present invention is amorphous, its when calcining, TiO ₂In Ti-O-H can be more perfect with the Si-O-H bonded of glass surface, make TiO ₂The bonded of film and substrate is more firm, and have good wear resistance can, improved its actual application value greatly, can grow the anatase octahedrite nano titanium oxide crystal grain of homogeneous grain diameter after the photo thermal treatment of Electronic Speculum.

The present invention not only method is simple, and any reagent that need not add other just can keep secular and stablizes and transparent.

Description of drawings

Fig. 1 is 615 ℃ of TiO after the thermal treatment ₂The SEM photo of film.In Fig. 1, scale is 100nm.

Fig. 2 is the crystallization situation of the titanium oxide of heat treatments at different.In Fig. 2, X-coordinate is diffraction angle 2Theta (Degree), and ordinate zou is diffraction intensity Intensity (a.u); Curve a is 60 ℃, and curve b is 250 ℃, and curve c is 450 ℃, and curve d is 615 ℃.

Embodiment

Embodiment 1

TiCl with 3ml ₄Be added drop-wise in the 6ml concentrated hydrochloric acid, add the deionized water of 100ml then, the strong aqua that drips 10ml again generates white precipitate, in the dropping process, is accompanied by magnetic agitation always.With repeatedly suction filtration, washing of deionized water, be neutral (pH ≈ 7) then until the pH value.In this deposition, add the ydrogen peroxide 50 of 5ml afterwards, and add the zero(ppm) water of 50ml, normal temperature stirs dispergation 1h down, promptly obtains yellow transparent TiO ₂Colloidal sol.

Embodiment 2

TiCl with 5ml ₄Be added drop-wise in the 10ml concentrated hydrochloric acid, add the deionized water of 200ml then, the strong aqua that drips 30ml again generates white precipitate, in the dropping process, is accompanied by magnetic agitation always.With repeatedly suction filtration, washing of deionized water, be neutral (pH ≈ 7) then until the pH value.In this deposition, add the ydrogen peroxide 50 of 30ml afterwards, and add the zero(ppm) water of 200ml, normal temperature stirs dispergation 2h down, promptly obtains transparent light yellow TiO ₂Colloidal sol.

Embodiment 3

TiCl with 3ml ₄Be added drop-wise in the 8ml concentrated hydrochloric acid, add the deionized water of 150ml then, the strong aqua that drips 20ml again generates white precipitate, in the dropping process, is accompanied by magnetic agitation always.With repeatedly suction filtration, washing of deionized water, be neutral (pH ≈ 7) then until the pH value.In this deposition, add the ydrogen peroxide 50 of 15ml afterwards, and add the zero(ppm) water of 100ml, normal temperature stirs dispergation 1h down, promptly obtains yellow transparent TiO ₂Colloidal sol.

Embodiment 4

Get the TiO of preparation among the embodiment 3 ₂Colloidal sol is coated on the clean common Sodelimesilica Glass of some pre-treatment, respectively at 60 ℃ of oven dry 1h down, in 250 ℃ of oven dry 1h down, in 450 ℃ of calcining 1h down, in 615 ℃ of calcining 1h down.Observed the surface topography of sample then with SEM, and characterized its crystallization situation with XRD.Fig. 1 provides 615 ℃ of TiO after the thermal treatment ₂The SEM photo of film.

Performance test:

1. acid-and base-resisting property: get the above-mentioned print of filming that formed, put into the hydrochloric acid of 1mol/L and the NaOH solution of 1mol/L respectively, soaking at room temperature 72h.The rete no change, and film do not come off, and shows that this film has good chemicalstability.

2. crystal formation: the crystallization situation of measuring the titanium oxide under differing temps (60 ℃, 250 ℃, 450 ℃, the 615 ℃) heat-treat condition with X-ray diffraction analysis.As can be seen from Figure 2, when temperature was low, titanium oxide was non-crystalline state, and along with the rising of temperature, percent crystallinity is good more, and the crystal formation of titanium oxide is an anatase octahedrite.

Claims

1. the preparation method of a TiO 2 sol is characterized in that may further comprise the steps:

3) with step 2) white precipitate of gained is with deionized water suction filtration, washing, is neutral until the pH value;

2. the preparation method of a kind of TiO 2 sol as claimed in claim 1 is characterized in that in step 1), and the volume ratio of said inorganic titanium salt, hydrochloric acid and deionized water is (3～5): (6～10): (100～200).

3. the preparation method of a kind of TiO 2 sol as claimed in claim 1 is characterized in that in step 1), and said hydrochloric acid employing mass concentration is 37% hydrochloric acid.

4. the preparation method of a kind of TiO 2 sol as claimed in claim 1 is characterized in that in step 2) in, the add-on of said ammoniacal liquor and the volume ratio of inorganic titanium salt are (10～30): (3～5).

5. the preparation method of a kind of TiO 2 sol as claimed in claim 1 is characterized in that in step 2) in, the mass concentration of said ammoniacal liquor is 25%～28%.

6. the preparation method of a kind of TiO 2 sol as claimed in claim 1 is characterized in that in step 4), and the add-on of said ydrogen peroxide 50 and zero(ppm) water and the volume ratio of inorganic titanium salt are (5～30): (50～200): (3～5).

7. the preparation method of a kind of TiO 2 sol as claimed in claim 1 is characterized in that in step 4), and the time of said stirring dispergation is 1～2h.