CN101376112B - Method for preparing anatase titanic oxide sol - Google Patents
Method for preparing anatase titanic oxide sol Download PDFInfo
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- CN101376112B CN101376112B CN200810200700XA CN200810200700A CN101376112B CN 101376112 B CN101376112 B CN 101376112B CN 200810200700X A CN200810200700X A CN 200810200700XA CN 200810200700 A CN200810200700 A CN 200810200700A CN 101376112 B CN101376112 B CN 101376112B
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Abstract
The invention relates to a preparation method of anatase phase titanium dioxide sol. The invention utilizes inorganic acid which contains titanium as a main material to conduct pyrohydrolysis on a solution of inorganic acid to get anatase phase or titanium dioxide white sediment of anatase and rutile mixed crystal; and adopts mineral acid as a dispergator to conduct dispergation at the temperature of 50 to 100 DEG C and get the sol of anatase phase titanium dioxide nano-crystal. The crystal size and crystallinity of titanium dioxide in the sol can be controlled by altering the production conditions and dispergation technology of the white sediment. The invention can get the anatase phase titanium dioxide transparent sol which does no contain organic stabilizer and has a crystal size of a plurality of nonameters. Furthermore, the sol has the characteristics of high density, high stability, transparency, etc.
Description
Technical field
The invention belongs to the preparation field of TiO 2 sol, particularly relate to a kind of preparation method of anatase titanic oxide sol.
Background technology
In recent years, the photocatalytic activity of nano titanium oxide is subjected to extensive concern, and the application relevant with photocatalysis mainly comprises: degradation of sewage and airborne multiple pollutant, automatically cleaning technology, anti-biotic material, antifogging coating and conversion of solar energy etc.
Nano titanium oxide be meant its crystallite dimension in 100 nanometers with interior titanium dioxide product, replace fine titanium dioxide powder can improve its quantum yield with it, yet in sewage disposal, be a great problem during it is used from separating the sewage of photocatalysis treatment and reclaiming photochemical catalyst always.Titanium dioxide is fixed on the variety carrier, prepares titanium deoxid film and can avoid nano particle to reclaim difficult problem in actual applications.In addition, titania nanoparticles attached on the multiple materials such as plastics, pottery, glass and metal, except can the photochemical catalyst of being fixed, also can be obtained: antifog glass and pottery, anti-biotic material and be used in aspects such as solar cell.
The amorphous titania (hydrated titanium dioxide of being called, metatitanic acid or positive metatitanic acid are also arranged) that obtains with the titanium hydrolysis of alkoxide is the dispergation raw material, can obtain colloidal sol [C.J.Brinker, the F.Arendse of milk shape through dispergation, P.Comte, M.Jirousek, F.Lenzmann, V.Shklover, M.
Nanocrystalline titanium oxide electrodes for photovoltaicapplications, J.Am.Ceram.Soc.80 (1997) 3157], concentration is low, turbidity greatly and titanium dioxide wherein be mainly impalpable structure.Obtain the amorphous titania precipitation with aqueous hydrolysis, obtain TiO 2 sol existing patent application [high Lian, Zhang Qinghong through dispergation again with inorganic titanium salt, Sun Jing, Zheng Shan, Chinese patent application number 00127951.3], the degree of crystallinity of anatase phase titanium dioxide wherein haves much room for improvement.
Japan Patent has been reported the colloidal sol that directly obtains titanium dioxide and a large amount of inorganic ions with the precipitation of inorganic titanium salt without washing with the inorganic acid dispergation, process ion exchange resin is removed main inorganic ions (Japan Patent JP10-158015) wherein again, for the ion in the solution of removing high concentration, ion exchange resin efficient is not high, is difficult to remove fully inorganic ions wherein yet.
The colloidal sol of amorphous titania is subjected to two major limitation in using: (1): the photocatalytic activity of amorphous titania is low, make the titanium dioxide crystallization, must be through high-temperature calcination.Titania is grown fast under the hot conditions, thereby in the titanium dioxide granule film that obtains, the crystallite dimension of titanium dioxide is big; (2) material that is used as carrier is restricted, and can't obtain the titanium dioxide film of crystalline state in the material of non-refractories such as plastics.Also patent report has been arranged and made complexing agent,, obtained the titanium dioxide film [middle river is still controlled for high shore filial piety one, bank this wide time, the adult that comes out, bridge is originally stepped on, Chinese patent application numbers 96112659.0] of crystalline state with materials such as ammonium titanium fluoride solution impregnation mineral wools with boric acid.But can form white precipitate in this technology, need, just can obtain titanium dioxide film uniformly with special technology precipitation separation.Sol-gel processing is the common method of preparation titanium deoxid film, but content of organics height wherein, the film of making will enough approach, so that burn organic matter, therefore will obtain certain thickness film must flood or apply repeatedly.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of anatase titanic oxide sol, this method is a kind of short-cut method for preparing TiO 2 sol, the TiO 2 sol that obtains have do not contain organic stabilizing agent, crystallite dimension is the anatase titanic oxide sol of several nanometers, and concentration height, good stability and characteristics such as transparent.The crystallite dimension of titanium dioxide and degree of crystallinity can be controlled by the preparation condition reconciliation adhesive process that changes white precipitate in the colloidal sol.
The preparation method of anatase titanic oxide sol of the present invention comprises step:
(1) preparation of titanium dioxide precipitation
The titaniferous inorganic matter is made into the aqueous solution of 0.1mol/L～3mol/L, rising temperature to 40～100 ℃, add the inorganic alkali solution of 1mol/L～3mol/L as precipitating reagent, insulation hydrolysis 2～24 hours, in and pH to alkalescent (pH7～8), anatase mutually or the hydrated titanium dioxide white precipitate that mixes mutually of anatase and rutile, wherein, the mol ratio of hydroxide ion is 1:4 to 1:4.5 in titanium in the titaniferous inorganic matter and the inorganic base;
(2) dispergation of titanium dioxide precipitation
The sediment of water-washing step (1) preparation to remove inorganic ions, gets gelatinous hydrated titanium dioxide;
Gelatinous hydrated titanium dioxide is poured in 0.05mol/L～2mol/L inorganic acid solution, stirring, ultrasonic dispersion, obtain the suspension of milk shape, stir and be warming up to 50～100 ℃, be incubated 1～24 hour, carry out dispergation, obtain transparent TiO 2 sol, colloidal sol showed light blue when concentration was higher, wherein, hydrated titanium dioxide precipitation (wherein containing titanium dioxide is 10 to 16wt%, and all the other are water) is 60g～120g:50～100ml with the amount ratio of inorganic acid.
Titaniferous inorganic matter in the described step (1) is a kind of in titanium tetrachloride, titanium sulfate, titanyl sulfate, the ammonium titanium fluoride or their mixture.
Inorganic base in the described step (1) is a kind of in NaOH, potassium hydroxide, ammoniacal liquor, urea, six methines, four ammoniums or their mixture.
Inorganic acid in the described step (2) is a kind of in hydrochloric acid, nitric acid or the phosphoric acid or their mixture.
The titanium dioxide maximum concentration is that mass percent is 10% in the TiO 2 sol in the described step (2), the particle size of titanium dioxide aggregate is even, narrow diameter distribution, and control technological parameter diplomatic corps aggressiveness particle diameter is about 10 nanometer to 120 nanometers (dynamic laser scattering method).
In the titanium dioxide precipitation preparation of the present invention, reaction equation:
Ti
4++2H
2O＝TiO
2+4H
+ (1)
TiO
2++H
2O＝TiO
2+4H
+ (2)
In top (1) and (2) formula, TiO
2Form with hydrate exists, and hydrolysis is the endothermic reaction, and the rising temperature helps improving hydrolysis rate.It can also be seen that from formula (1) and formula (2) hydrolysis produces a large amount of hydrogen quantum, these hydrogen ions can suppress proceeding of hydrolysis.
The hydrogen ion that generates with the alkali neutralization reaction can make the hydrolysis acceleration.Solution is neutralized to neutrality or alkalescent, the titanium in the solution all is precipitated out, improve the yield of reaction.
The white precipitate titanium dioxide that is used for dispergation among the present invention is anatase phase or anatase and rutile phase mixture, obtain containing the colloidal sol of a certain amount of precipitation behind anatase and the rutile phase mixture dispergation, after leaving standstill, the upper strata is an anatase titanic oxide sol, the bottom is the red schorl phase titanium dioxide precipitation, thereby, separablely go out anatase titanic oxide sol.
Inorganic ions concentration is unfavorable for the dispergation of titanium dioxide too greatly, also can influence the practical application of colloid, and the precipitate component washing that hydrolysis obtains to titanium salt is a very important step.By improving the temperature of titanium salt solution, obtain degree of crystallinity titanium dioxide preferably, also can make the detersive efficiency of precipitation higher.
In addition, inorganic acid can not be sulfuric acid or hydrofluoric acid, makes the precipitation dissolving because they can form complex compound with titanium, thereby can not obtain colloidal sol, controls crystallization and dispergation process by the concentration and the temperature of regulating inorganic acid.
Colloidal sol is carried out transmission electron microscope observing find, under optimized conditions, the crystallite dimension of titanium dioxide with colloidal sol vacuum drying at room temperature, is carried out X-ray powder diffraction (XRD) analysis for being about 5 nanometers, and titanium dioxide is the anatase phase.Beneficial effect:
(1) content of titanium dioxide height in Zhi Bei the TiO 2 sol, do not contain organic matter in the colloidal sol, can obtain the nano-particular film of anatase phase titanium dioxide in actual applications by infusion process, because titanium dioxide itself wherein is crystalline state, needn't can obtain the anatase phase titanium dioxide film through calcining with in calcining (calcining can strengthen the combination of titanium dioxide and matrix) below 400 ℃, colloidal sol can comprise film forming on the multiple matrix of plastics, and can obtain the titanium dioxide film of different-thickness by the concentration that changes TiO 2 sol;
(2) stability of the TiO 2 sol of this high concentration, high stability shows and can not assemble when long storage time can not precipitate and dilute and form flocculent deposit, room temperature preservation can not form precipitation in 1 year, did not also form precipitation and big aggregate with distilled water 1:100 dilution proportion;
(3) transparency of TiO 2 sol shows that the TiO 2 sol of 0.01mol/L does not have scattering and absorption at visible region, and the colloidal sol of 1.0mol/L is the transparent body azury;
(4) titanium dioxide in the colloidal sol is the anatase phase, and the crystal grain that phase transformation causes when having avoided high-temperature calcination crystallization in the amorphous titania colloidal sol is grown up rapidly, can obtain superfine nano-crystalline titanium dioxide granule film;
(5) colloidal sol of high stability is the medium preparation with water, can easily realize mixing, (organic polymer, pottery, glass or metal) prepares transition metal oxide/titanium dioxide or noble metal/titanium dioxide composite nanocrystalline membrana granulosa on multiple matrix.
Description of drawings
Fig. 1 is the TiO 2 sol abosrption spectrogram of variable concentrations, and wherein, the concentration of TiO 2 sol is respectively: (a) 0.163mol/L, (b) 0.082mol/L, (c) 0.054mol/L, (d) 0.041mol/L, (e) 0.027mol/L.
Fig. 2 is a TiO 2 sol through the figure of the X-ray diffraction (XRD) after the vacuum drying under the room temperature, and all diffraction maximums all can belong to and are anatase phase titanium dioxide among the figure, the XRD figure of the amorphous titania that (a) prepares under the room temperature after through drying at room temperature behind the dispergation; (b) be that the anatase phase titanium dioxide that 60 ℃ of hydrolysis prepare precipitates through the XRD figure after the drying at room temperature behind the dispergation.
Fig. 3 is the high-resolution-ration transmission electric-lens photo with the TiO 2 sol of method preparation provided by the invention.
Fig. 4 is the XRD figure of rutile precipitation that can not dispergation behind the titanium dioxide precipitation of mixing crystal formation (anatase and rutile) of preparation and the dispergation.Abscissa is the 2 θ angles of diffraction among the figure, and unit is degree; Ordinate is a relative intensity.
Fig. 5 is the high-resolution-ration transmission electric-lens photo of the TiO 2 sol of embodiment 3 preparations.
The specific embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
After 1mol/L titanium sulfate solution 100mL is warming up to 60 ℃, in 60 ℃ of insulations, drip the sodium hydroxide solution 400mL of 1mol/L, be neutralized to the pH value and approximate 7,60 ℃ are incubated 4 hours, obtain white precipitate, use the distilled water cyclic washing, obtain gelatinous solid, getting moist precipitate 80 grams (amounting to into titanium dioxide is 12 grams) is dispersed in it in hydrochloric acid of 100 milliliters of 1mol/L, in 60 ℃ of dispergation 2 hours, obtain light blue vitreosol, the concentration of titanium dioxide is 0.92mol/L.
Hydrionic concentration finds that hydrogen ion is not consumed before and after measuring dispergation, shows that dispergation is irrelevant with the dissolving of positive metatitanic acid.Behind deionized water dilution different multiples, its ultraviolet-visible absorption spectra does not absorb at visible region as shown in Figure 1.Use light path to make reference with deionized water during test, can find that the colloidal sol of method preparation provided by the invention has the better transparency than document (Japan Patent JP10-158015) as the quartz colorimetric utensil of 10mm.
Titanium dioxide concentration in the colloidal sol behind the deionized water dilution different multiples is measured with inductance linking atom absorption spectrum.Get the powder that vacuum drying obtains and carry out X-ray diffraction analysis, the result shows that titanium dioxide wherein is the anatase phase, shown in Fig. 2 (b).
70 ℃ of following ammoniacal liquor 145mL of dropping 3mol/L in the 1mol/L titanium tetrachloride solution 100mL, 70 ℃ are incubated hydrolysis 12 hours, be neutralized to alkalescent pH value and approximate 8, obtain white precipitate, use the distilled water cyclic washing, obtain gelatinous solid, (amounting to into titanium dioxide is 6 grams to get moist precipitate 40 grams, XRD analysis shows that what obtain under such condition is the mixing crystal formation of anatase and rutile) it is dispersed in the nitric acid of 100 milliliters of 1mol/L, in 80 ℃ of dispergation 8 hours, obtain light blue transparent TiO 2 sol.Contain the white precipitate that part can't dispergation in the colloidal sol, after leaving standstill, by centrifugal precipitate and separate with the bottom, what XRD analysis showed the bottom is precipitated as red schorl phase titanium dioxide, and the colloid on upper strata after super-dry, occurred similar with Fig. 2 (b), can belong to XRD diffraction maximum for anatase.This embodiment illustrates that mixing the crystal formation titanium dioxide precipitation can carry out the selectivity dispergation, and promptly anatase can be by dispergation, and rutile can not be by dispergation.
Fig. 3 is the high-resolution-ration transmission electric-lens photo of anatase titania particle in the colloidal sol of present embodiment preparation, can clearly see the lattice fringe of anatase phase titanium dioxide.
Be precipitated as mixed crystal before the dispergation, can not dispergation be precipitated as rutile, XRD result is as shown in Figure 4.
Embodiment 3
After 0.5mol/L titanium sulfate solution 100mL is warming up to 40 ℃, drip the ammonia spirit 138mL of 1.5mol/L toward solution, 40 ℃ are incubated hydrolysis 20 hours, be neutralized to the pH value and approximate 7, obtain white precipitate, use the distilled water cyclic washing, obtain gelatinous solid, getting moist precipitate 40 gram (amounting to into titanium dioxide is 6.2 grams) is dispersed in it in nitric acid mixed solution of the hydrochloric acid of 25 milliliters of 1mol/L and 25 milliliters of 1mol/L, in 65 ℃ of dispergation 5 hours, obtain light blue vitreosol, the concentration of titanium dioxide is 0.94mol/L.Behind deionized water dilution different multiples, its ultraviolet-visible absorption spectra is similar to Fig. 1, does not absorb at visible region.Get the powder that vacuum drying obtains and carry out X-ray diffraction analysis, the result shows that titanium dioxide wherein is the anatase phase, is similar to shown in Fig. 2 (b).
Fig. 5 is the high-resolution-ration transmission electric-lens photo of titanium dioxide granule in the colloidal sol of present embodiment preparation, can clearly see the lattice fringe of anatase phase titanium dioxide, but degree of crystallinity is a bit weaker than Fig. 3.
Claims (5)
1. the preparation method of an anatase titanic oxide sol comprises step:
(1) the titaniferous inorganic matter is made into the aqueous solution of 0.1mol/L～3mol/L, rising temperature to 40～100 ℃, add the inorganic alkali solution of 1mol/L～3mol/L as precipitating reagent, insulation hydrolysis 2～24 hours, in and pH to pH7～8, get the hydrated titanium dioxide white precipitate, wherein, the mol ratio of hydroxide ion is 1: 4 to 1: 4.5 in titanium in the titaniferous inorganic matter and the inorganic base;
(2) sediment of water-washing step (1) preparation gets gelatinous hydrated titanium dioxide; Gelatinous hydrated titanium dioxide is poured in 0.05mol/L～2mol/L inorganic acid solution, stirring, ultrasonic dispersion, be warming up to 50～100 ℃, be incubated 1～24 hour, carry out dispergation, obtain TiO 2 sol, wherein, the hydrated titanium dioxide precipitation is 60g～120g with the amount ratio of inorganic acid: 50～100ml.
2. the preparation method of anatase titanic oxide sol according to claim 1 is characterized in that: the titaniferous inorganic matter in the described step (1) is a kind of in titanium tetrachloride, titanium sulfate, titanyl sulfate, the ammonium titanium fluoride or their mixture.
3. the preparation method of anatase titanic oxide sol according to claim 1 is characterized in that: the inorganic base in the described step (1) is a kind of in NaOH, potassium hydroxide, the ammoniacal liquor or their mixture.
4. the preparation method of anatase titanic oxide sol according to claim 1 is characterized in that: the inorganic acid in the described step (2) is a kind of in hydrochloric acid, nitric acid or the phosphoric acid or their mixture.
5. the preparation method of anatase titanic oxide sol according to claim 1, it is characterized in that: the titanium dioxide maximum concentration is that mass percent is 10% in the TiO 2 sol in the described step (2), and the particle size of titanium dioxide aggregate is even, aggregation size is 10 nanometer to 120 nanometers.
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