CN109081372A - A kind of anatase-type nanometer titanium dioxide, and its preparation method and application - Google Patents
A kind of anatase-type nanometer titanium dioxide, and its preparation method and application Download PDFInfo
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Abstract
The present invention relates to a kind of anatase-type nanometer titanium dioxide, and its preparation method and application, the nano-titanium dioxide preparation method includes: that Titanium alkoxides are dispersed in nonaqueous solvents by (1), obtains Titanium alkoxides alcoholic solution；(2) strong protonic acid is added in Titanium alkoxides alcoholic solution, forerunner's dispersion liquid is made；(3) forerunner's dispersion liquid is heated up and carries out solvent heat treatment, anatase-type nanometer titanium dioxide is made.Purity >=99.9% of the anatase-type nanometer titanium dioxide, partial size≤10nm, breadth coefficient≤0.5, the nano-titanium dioxide have absorption to ultraviolet light.The pure anatase-type nanometer titanium dioxide product of size tunable is made using a step solvent-thermal method by the present invention, and without calcining, low energy consumption, simple process, can be quickly converted to industrialized production.
Description
Technical field
The invention belongs to catalysis material technical fields, and in particular to a kind of anatase-type nanometer titanium dioxide and its system
Preparation Method and purposes, the anatase-type nanometer titanium dioxide is in photochemical catalyst, catalyst carrier, cosmetics and weaving
The fields such as heat stabilizer of UV resistant agent, silicon rubber.
Background technique
With human society and economic continuous development, energy shortage and problem of environmental pollution also occur therewith, therefore
While development, people also increasingly energy resources and environmental problem have been set up the technologies of many processing pollutions at present.Such as
The technology of common processing pollutant has physical method, chemical method and bioanalysis etc., these methods have their own advantages, but most of presence pair
Contaminant degradation is not thorough, easily causes secondary pollution, cost of investment big and the disadvantages of operating cost is high.
It has been delivered from Fujishima and Honda in 1972 in Nature periodical about in TiO2Photodegradation water on electrode
Since paper, numerous scholars surround photochemical conversion and synthesis, explore a variety of metal oxides with photocatalysis effect
It is nanocrystalline, and extensive work is put to develop its efficient preparation process and improve light-catalysed efficiency.
But nano-titanium dioxide powder is due to property such as particle is tiny, large specific surface area, high, the coordination wretched insufficiencies of surface energy
Matter causes it easily to reunite, so solution nano-titanium dioxide powder dispersion is uneven, dispersion concentration is low, effective utilization
Low, the problems such as application cost is high is all the key problem for needing to face and solve in nano-titanium dioxide powder research and production.
CN103482697A discloses a kind of partial size adjustable titanium dioxide microballoon sphere of preparing under anhydrous solvent heat condition
Method dissolves titanium alkoxide in solvent first, then adds carboxylic acid and obtains clear solution, transfers the solution into solvent thermal
In, solvent thermal reaction is carried out, then be centrifuged, it is dry.The partial size of titanium dioxide microballoon sphere can dissolve the solvent of Titanium alkoxides by changing
Composition adjust.The preparation method of the titanium dioxide microballoon sphere is simple, is not necessarily to template, is at low cost, easily extensive synthesis, but makes
The partial size of the titanium dioxide microballoon sphere obtained is larger, and catalytic activity and catalytic efficiency are lower.
CN103626227B discloses a kind of rutile titanium dioxide micro Nano material and its low temperature preparation method, passes through
Hydro-thermal method prepares the rutile micro Nano material by one-dimensional nano line for primitive structure composition.The 1-dimention nano linear diameter 5
~10nm, 200~300nm of nanowire length, microsphere diameter about 400~600nm.Raw material used in the preparation process is inexpensively easy
, experiment safety is good and high conversion rate, but needs calcination processing during the experiment, energy consumption is larger.
CN103332737B discloses a kind of preparation method of nano TiO 2 powder, comprising the following steps: with titanium alcohol
Salt is presoma, and dehydrated alcohol is solvent, and glacial acetic acid is pH adjusting agent, first prepares TiO 2 sol；It again will be amine-terminated hyperbranced
The ethanol solution of fluidized polymer is added in TiO 2 sol, obtains the precursor solution containing Hyperbranched Polymer with Terminal Amido；It will
Precursor solution is transferred in hydrothermal reaction kettle, is lauched thermal response 1~for 24 hours in 100~300 DEG C of temperature conditions；Obtained solution
It is dried after repeatedly washing, the nano-titanium dioxide powder of pure Hyperbranched Polymer with Terminal Amido modification can be obtained.It is described
Nano-titanium dioxide high stability, but reaction temperature is higher during the preparation process for material, and energy consumption is larger.
This field needs to develop a kind of titanium dioxide nano material, and make preparation titanium dioxide nano material have compared with
High activity and photocatalysis performance, can satisfy the demand of numerous areas.
Summary of the invention
In view of the deficiencies of the prior art, one of the objects of the present invention is to provide a kind of anatase-type nanometer titanium dioxides
Preparation method, the preparation method include the following steps:
(1) Titanium alkoxides are dispersed in nonaqueous solvents, obtain Titanium alkoxides alcoholic solution；
(2) non-dehydration property strong protonic acid is added in Titanium alkoxides alcoholic solution, forerunner's dispersion liquid is made；
(3) forerunner's dispersion liquid is heated up and carries out solvent heat treatment, anatase-type nanometer titanium dioxide is made.
The present invention uses Titanium alkoxides as titanium source, and alcoholic solvent is added in Titanium alkoxides, on the one hand Titanium alkoxides can be made molten in alcohol
It is evenly dispersed in liquid；On the other hand pure and mild few non-dehydration property strong protonic acid environment of water can inhibit the growth of titanium nucleus, and then obtain
Obtain the lesser nanometer anatase titania of partial size.
Non- dehydration property strong protonic acid is added in the present invention in Titanium alkoxides alcoholic solution, during the preparation process water or water-less environment less
Under strong acid system can inhibit the growth of nucleus, so the addition of non-dehydration property strong protonic acid can further suppress titanium nucleus
Growth, and then obtain the lesser nanometer anatase titania of partial size.
Non- dehydration property strong protonic acid of the present invention, which refers to, will not generate dehydration to system after strong protonic acid is added
Strong protonic acid.
The pure anatase-type nanometer titanium dioxide product of size tunable is made using a step solvent-thermal method by the present invention, without forging
It burns, low energy consumption, simple process, can be quickly converted to industrialized production, and the amount of every batch of processing Titanium alkoxides can reach feather weight.
Preferably, step (1) the of the present invention nonaqueous solvents is any a kind or at least two kinds of of combination in alkylol.
Preferably, the molecular formula of the alkylol is CxH2x+1OH, the integer that wherein x is 2~12；Alternatively, the alkylol
Structural formula beThe wherein integer that n is 1~6.
Preferably, the integer that the x is 2~12, such as 3,5,7,9,11 etc..
Preferably, the integer that the n is 1~6, such as 2,3,4,5 etc..
Preferably, the preparation method of the Titanium alkoxides alcoholic solution is that Titanium alkoxides are dispersed in nonaqueous solvents in a cold water bath
In.
Preferably, the molar ratio of the Titanium alkoxides and nonaqueous solvents be 1:3~1:50, such as 1:5,1:6,1:7,1:10,
1:13,1:15,1:20,1:23,1:25,1:30,1:35,1:40,1:45,1:48 etc..
When the molar ratio of Titanium alkoxides and nonaqueous solvents is greater than 1:3, Titanium alkoxides concentration is excessive, during the reaction titanium dioxide
Coagulation easily occurs, and then the partial size formed is excessive；When the molar ratio of Titanium alkoxides and nonaqueous solvents is less than 1:50, Titanium alkoxides concentration mistake
It is small, and then production efficiency is low, increased costs.
Preferably, the alkylol includes ethyl alcohol, propyl alcohol, isopropanol, butanol, isobutanol, amylalcohol, hexanol, benzyl alcohol, benzene
Any one or at least two combination, such as ethyl alcohol, propyl alcohol, isopropanol, phenylpropanol etc. in ethyl alcohol or phenylpropanol.
Preferably, the temperature of the cold bath is 0 DEG C~15 DEG C, such as 1 DEG C, 5 DEG C, 10 DEG C, 12 DEG C etc..
Preferably, step (2) the of the present invention non-dehydration property strong protonic acid is inorganic acid.
Preferably, the non-dehydration property strong protonic acid includes any one in concentrated hydrochloric acid, hydrofluoric acid, hypochlorous acid or perchloric acid
Kind or at least two combination, preferred concentrated hydrochloric acid.
Preferably, water content≤12mol/L in step (2) the of the present invention presoma, such as 0.5mol/L, 2mol/L,
4mol/L, 8mol/L, 10mol/L, 11mol/L etc..
Preferably, acidity value >=1mol/L in the presoma, for example, 2mol/L, 3mol/L, 4mol/L, 5mol/L,
6mol/L, 7mol/L, 8mol/L, 9mol/L, 10mol/L etc..
Preferably, the rate of step (3) the of the present invention heating is 3 DEG C/min~10 DEG C/min, such as 4 DEG C/min, 5
DEG C/min, 6 DEG C/min, 7 DEG C/min, 8 DEG C/min, 9 DEG C/min etc..
Preferably, the temperature of the solvent heat treatment is 70 DEG C~200 DEG C, preferably 120 DEG C~170 DEG C, such as 80 DEG C, 90
DEG C, 100 DEG C, 110 DEG C, 120 DEG C, 150 DEG C, 170 DEG C, 180 DEG C etc..
When the temperature of heat treatment is less than 70 DEG C, heat treatment time is longer and product not easily generated；The temperature of heat treatment is greater than
At 200 DEG C, it is wider and uncontrollable that particle size distribution range is made.
Preferably, the time of the solvent heat treatment be 10min~5 day, preferably 1~6h, for example, 20min, 40min, 1h,
2h, 4h, 6h, 8h, 12h, 15h, 20h, 1 day, 2 days, 3 days, 4 days etc..
Preferably, the Titanium alkoxides in step (2) the Titanium alkoxides alcoholic solution of the present invention include tetraethyl titanate, metatitanic acid isopropyl
Any one or at least two combination, such as tetraethyl titanate, isopropyl titanate etc. in ester or butyl titanate.
Preferably, the molar ratio of Titanium alkoxides and non-dehydration property strong protonic acid is 1:3~1:10 in the Titanium alkoxides alcoholic solution,
Such as 1:4,1:5,1:6,1:7,1:8,1:9 etc..
When the molar ratio of Titanium alkoxides and non-dehydration property strong protonic acid is greater than 1:3 in Titanium alkoxides alcoholic solution, the non-strong matter of dehydration property
Sub- acid inhibits the growth result of titanium nucleus unobvious；The molar ratio of Titanium alkoxides and non-dehydration property strong protonic acid in Titanium alkoxides alcoholic solution
When less than 1:10, the water content contained in non-dehydration property strong protonic acid be will increase, and then accelerated particle growth becomes particle diameter distribution
It is wide.
Preferably, water content≤62wt% in the non-dehydration property strong protonic acid, for example, 0.01wt%, 1wt%, 5wt%,
10wt%, 20wt%, 30wt%, 40wt%, 50wt%, 60wt% etc..
Preferably, amount >=10g of the preparation method every batch of processing Titanium alkoxides of the titanium dioxide nano material, such as
20g, 50g, 80g, 1kg, 2kg, 5kg, 10kg etc..
Preferably, ethanol washing, centrifuge separation and drying process are carried out after solvent heat treatment of the present invention.
Preferably, the revolving speed of the centrifuge separation is 2000r/min~12000r/min, such as 3000r/min, 4000r/
Min, 5000r/min, 6000r/min, 7000r/min, 8000r/min, 10000r/min etc..
Preferably, the time of the centrifuge separation is 5min~15min, such as 6min, 7min, 10min, 12min etc..
Preferably, the temperature of the drying is 50 DEG C~80 DEG C, such as 55 DEG C, 60 DEG C, 65 DEG C, 70 DEG C, 75 DEG C etc..
Preferably, the time of the drying is 2h~4h, such as 2h, 2.5h, 3h etc..
As optimal technical scheme, the preparation method of anatase-type nanometer titanium dioxide of the present invention, including walk as follows
It is rapid:
(1) in 0 DEG C~15 DEG C cold baths, it is 1:3~1:50 by the molar ratio of Titanium alkoxides and ethyl alcohol, Titanium alkoxides is dispersed
Titanium alkoxides alcoholic solution is obtained in ethanol；
(2) ratio for being 1:3~1:10 in the molar ratio of Titanium alkoxides and hydrochloric acid in Titanium alkoxides alcoholic solution, it is molten in Titanium alkoxides alcohol
Concentrated hydrochloric acid is added in liquid, presoma is made, water content≤12mol/L in presoma, acidity value >=1mol/L in presoma；
(3) presoma is risen to 120 DEG C~170 DEG C with 3 DEG C/min~10 DEG C/min heating rate, carried out at solvent heat
1h~6h is managed, the material system containing titanium dioxide is made；
(4) by containing titanium dioxide material system carry out ethanol washing, 2000r/min~12000r/min revolving speed from
The heart separates 5min~15min and 50 DEG C~80 DEG C dry 2h~4h, and anatase-type nanometer titanium dioxide is made.
The second object of the present invention is to provide a kind of anatase-type nanometer titanium dioxide, the nano-titanium dioxide passes through mesh
One of described in method be prepared.
Preferably, purity >=99.9% of the nano-titanium dioxide, for example, 99.91%, 99.93%, 99.95%,
99.99% etc..
Preferably, partial size≤10nm of the nano-titanium dioxide, such as 3nm, 5nm, 7nm, 9nm etc..
Preferably, breadth coefficient≤0.5 of the nano-titanium dioxide, such as 0.1,0..2,0.3,0.4 etc..
Preferably, the nano-titanium dioxide has absorption to ultraviolet light.
The nanometer anatase titania purity that the present invention is prepared is greater than 99.9%, product cut size is controllable, distribution compared with
Narrow, dispersion stability is splendid.
The three of the object of the invention are to provide a kind of purposes of anatase-type nanometer titanium dioxide as described in the second purpose, institute
Nano-titanium dioxide is stated as catalyst carrier, ultraviolet shielded material, the active component of light-catalyzed reaction, silicon rubber thermostabilization
Agent, ultraviolet absorbing agent, battery material, functional coating and water purification material.
Compared with prior art, the invention has the following beneficial effects:
(1) on the one hand the present invention can make Titanium alkoxides evenly dispersed in alcoholic solution using alcohol as solvent；Another aspect alcohol
It can inhibit the growth of titanium nucleus, and then obtain purity and be greater than 99.9%, the lesser nanometer anatase titania of partial size.
(2) non-dehydration property strong protonic acid, the addition of non-dehydration property strong protonic acid is added in the present invention in Titanium alkoxides alcoholic solution
The growth of titanium nucleus can be further suppressed, and then obtains the nanometer anatase titania that partial size is less than 10nm.
(3) the pure anatase-type nanometer titanium dioxide product of size tunable, nothing are made using a step solvent-thermal method by the present invention
It needs to calcine, low energy consumption, and simple process can be mass.
Detailed description of the invention
Fig. 1 is the sample XRD diagram that the specific embodiment of the invention 1 obtains.
Fig. 2 is one of the sample TEM figure that the specific embodiment of the invention 1 obtains.
Fig. 3 is the two of the sample TEM figure that the specific embodiment of the invention 1 obtains.
Specific embodiment
Of the invention for ease of understanding, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that the implementation
Example is only to aid in the understanding present invention, should not be regarded as a specific limitation of the invention.
Embodiment 1
A kind of preparation method of anatase-type nanometer titanium dioxide includes the following steps:
(1) in 1 DEG C of cold bath, it is 1:10 by the molar ratio of isopropyl titanate and ethyl alcohol, isopropyl titanate is dispersed in
Isopropyl titanate alcoholic solution is obtained in ethyl alcohol；
(2) ratio for being 1:5 in the molar ratio of isopropyl titanate and hydrochloric acid in isopropyl titanate alcoholic solution, in metatitanic acid isopropyl
Concentrated hydrochloric acid is added in ester alcohol solution, presoma is made；
(3) presoma is risen to 150 DEG C with the heating rate of 5 DEG C/min, carries out solvent heat treatment 2h, be made and contain dioxy
Change the material system of titanium；
(4) material system containing titanium dioxide is subjected to ethanol washing, the revolving speed of 10000r/min is centrifugated 10min
With 60 DEG C of dry 3h, anatase-type nanometer titanium dioxide is made, Fig. 1 is the XRD characterization of the anatase-type nanometer titanium dioxide
Map, the characteristic peak of titanium dioxide is sharp and without miscellaneous peak as can be seen from Figure, shows that crystallization is purer anatase type nano
Titanium dioxide.Fig. 2 and Fig. 3 is that the TEM of the anatase-type nanometer titanium dioxide characterizes map, as can be seen from Figure anatase
Type nano-titanium dioxide can be seen that anatase titanium dioxide particle has elliposoidal pattern, and partial size≤10nm is dispersed good
It is good.
Embodiment 2
The difference from embodiment 1 is that the molar ratio of isopropyl titanate and ethyl alcohol is 1:3 in step (1), anatase is made
Type nano-titanium dioxide.
Embodiment 3
The difference from embodiment 1 is that the molar ratio of isopropyl titanate and ethyl alcohol is 1:50 in step (1), rutile titania is made
Mine type nano-titanium dioxide.
Embodiment 4
The difference from embodiment 1 is that the molar ratio of isopropyl titanate and ethyl alcohol is 1:2 in step (1), anatase is made
Type nano-titanium dioxide.
Embodiment 5
The difference from embodiment 1 is that the molar ratio of isopropyl titanate and ethyl alcohol is 1:53 in step (1), rutile titania is made
Mine type nano-titanium dioxide.
Embodiment 6
The difference from embodiment 1 is that the molar ratio of isopropyl titanate and hydrochloric acid is 1:3 in step (2), anatase is made
Type nano-titanium dioxide.
Embodiment 7
The difference from embodiment 1 is that the molar ratio of isopropyl titanate and hydrochloric acid is 1:10 in step (2), rutile titania is made
Mine type nano-titanium dioxide.
Embodiment 8
The difference from embodiment 1 is that the molar ratio of isopropyl titanate and hydrochloric acid is 1:2 in step (2), anatase is made
Type nano-titanium dioxide.
Embodiment 9
The difference from embodiment 1 is that the molar ratio of isopropyl titanate and hydrochloric acid is 1:12 in step (2), rutile titania is made
Mine type nano-titanium dioxide.
Embodiment 10
A kind of preparation method of anatase-type nanometer titanium dioxide includes the following steps:
(1) in 0 DEG C of cold bath, it is 1:10 by the molar ratio of butyl titanate and propyl alcohol, butyl titanate is dispersed in
Butyl titanate alcoholic solution is obtained in propyl alcohol；
(2) ratio for being 1:5 in the molar ratio of butyl titanate and hydrofluoric acid in butyl titanate alcoholic solution, in metatitanic acid four
Hydrofluoric acid is added in butyl ester alcoholic solution, presoma is made；
(3) presoma is risen to 150 DEG C with the heating rate of 5 DEG C/min, carries out solvent heat treatment 2h, be made and contain dioxy
Change the material system of titanium；
(4) material system containing titanium dioxide is subjected to ethanol washing, the revolving speed of 2000r/min is centrifugated 15min
With 50 DEG C of dry 2h, anatase-type nanometer titanium dioxide is made.
Embodiment 11
A kind of preparation method of anatase-type nanometer titanium dioxide includes the following steps:
(1) in 15 DEG C of cold baths, it is 1:10 by the molar ratio of tetraethyl titanate and benzyl alcohol, tetraethyl titanate is dispersed
Tetraethyl titanate alcoholic solution is obtained in benzyl alcohol；
(2) ratio for being 1:5 in the molar ratio of tetraethyl titanate and perchloric acid in tetraethyl titanate alcoholic solution, in metatitanic acid four
Perchloric acid is added in ethyl ester alcoholic solution, presoma is made；
(3) presoma is risen to 150 DEG C with the heating rate of 5 DEG C/min, carries out solvent heat treatment 2h, be made and contain dioxy
Change the material system of titanium；
(4) material system containing titanium dioxide is subjected to ethanol washing, the revolving speed of 12000r/min is centrifugated 5min
With 80 DEG C of dry 4h, anatase-type nanometer titanium dioxide is made.
Comparative example 1
The difference from embodiment 1 is that ethyl alcohol is replaced with equimolar water.
Comparative example 2
The difference from embodiment 1 is that concentrated hydrochloric acid is replaced with equimolar citric acid.
Comparative example 3
The difference from embodiment 1 is that concentrated hydrochloric acid is replaced with the equimolar concentrated sulfuric acid.
Performance test:
The anatase-type nanometer titanium dioxide being prepared is performed the following performance tests:
(1) number average bead diameter is measured by laser particle size analyzer.
(2) particle diameter distribution is measured by laser particle size analyzer.
Table 1
| Number average bead diameter (nm) | Particle diameter distribution coefficient | |
| Embodiment 1 | 2.4 | 0.158 |
| Embodiment 2 | 9.5 | 0.448 |
| Embodiment 3 | 6.6 | 0.354 |
| Embodiment 4 | 10.0 | 0.500 |
| Embodiment 5 | 2.5 | 0.198 |
| Embodiment 6 | 7.5 | 0.355 |
| Embodiment 7 | 4.4 | 0.224 |
| Embodiment 8 | 8.8 | 0.341 |
| Embodiment 9 | 3.4 | 0.252 |
| Embodiment 10 | 4.2 | 0.289 |
| Embodiment 11 | 3.9 | 0.248 |
| Comparative example 1 | 102.5 | 0.756 |
| Comparative example 2 | 78.5 | 0.689 |
| Comparative example 3 | 13.2 | 0.531 |
It can be seen from Table 1 that embodiment 1-11 is during preparing nano-titanium dioxide, for the strong acid under few water environment
Environment can inhibit the growth of nucleus, and then nano-titanium dioxide obtained partial size≤10nm.
It can be seen from Table 1 that the partial size of nano-titanium dioxide is larger in embodiment 4, it may be possible to due to isopropyl titanate
Content is excessive, and coagulation easily occurs for the titanium dioxide generated during the reaction, so the partial size that titanium dioxide is made is larger.
It can be seen from Table 1 that the partial size of nano-titanium dioxide is larger in embodiment 8, it may be possible to due to content of hydrochloric acid mistake
It is low, it is poor to the growth inhibition of titanium nucleus, so the partial size that titanium dioxide is made is larger.
It can be seen from Table 1 that comparative example 1 is larger relative to 1 partial size of embodiment, it may be possible to since comparative example is molten with water
Agent, water cannot inhibit titanium to crystallize during the preparation process, so the partial size that titanium dioxide is made is larger.
It can be seen from Table 1 that comparative example 2 is larger relative to 1 partial size of embodiment, it may be possible to due in the citric acid of addition
Water content is excessively high, and then poor to the growth inhibition of titanium crystallization, so the partial size that titanium dioxide is made is larger.
The concentrated sulfuric acid is added in comparative example 3, is dehydration property strong protonic acid, product titanium dioxide obtained does not have anatase
Type.
The Applicant declares that the present invention is explained by the above embodiments detailed process equipment and process flow of the invention,
But the present invention is not limited to the above detailed process equipment and process flow, that is, it is above-mentioned detailed not mean that the present invention must rely on
Process equipment and process flow could be implemented.It should be clear to those skilled in the art, any improvement in the present invention,
Addition, selection of concrete mode of equivalence replacement and auxiliary element to each raw material of product of the present invention etc., all fall within of the invention
Within protection scope and the open scope.
Claims (10)
1. a kind of preparation method of anatase-type nanometer titanium dioxide, which is characterized in that the preparation method includes the following steps:
(1) Titanium alkoxides are dispersed in nonaqueous solvents, obtain Titanium alkoxides alcoholic solution；
(2) non-dehydration property strong protonic acid is added in Titanium alkoxides alcoholic solution, forerunner's dispersion liquid is made；
(3) forerunner's dispersion liquid is heated up and carries out solvent heat treatment, anatase-type nanometer titanium dioxide is made.
2. preparation method as described in claim 1, which is characterized in that step (1) nonaqueous solvents is appointing in alkylol
The combination of a kind or at least two kinds of of meaning；
Preferably, the molecular formula of the alkylol is CxH2x+1OH, the integer that wherein x is 2~12；Alternatively, the knot of the alkylol
Structure formula isThe wherein integer that n is 1~6；
Preferably, the preparation method of the Titanium alkoxides alcoholic solution is that Titanium alkoxides are dispersed in nonaqueous solvents in a cold water bath；
Preferably, the molar ratio of the Titanium alkoxides and nonaqueous solvents is 1:3~1:50；
Preferably, the alkylol includes ethyl alcohol, propyl alcohol, isopropanol, butanol, isobutanol, amylalcohol, hexanol, benzyl alcohol, benzyl carbinol
In phenylpropanol any one or at least two combination；
Preferably, the temperature of the cold bath is 0 DEG C~15 DEG C.
3. preparation method as claimed in claim 1 or 2, which is characterized in that step (2) the non-dehydration property strong protonic acid is nothing
Machine acid；
Preferably, the non-dehydration property strong protonic acid include in concentrated hydrochloric acid, hydrofluoric acid, hypochlorous acid or perchloric acid any one or
At least two combination, preferably concentrated hydrochloric acid.
4. the preparation method as described in one of claim 1-3, which is characterized in that water content in step (2) described presoma≤
12mol/L；
Preferably, acidity value >=1mol/L in the presoma.
5. the preparation method as described in one of claim 1-4, which is characterized in that the rate of step (3) described heating be 3 DEG C/
Min~10 DEG C/min；
Preferably, the temperature of the solvent heat treatment is 70 DEG C~200 DEG C, preferably 120 DEG C~170 DEG C；
Preferably, the time of the solvent heat treatment is 10min~5 day, preferably 1~6h.
6. the preparation method as described in one of claim 1-5, which is characterized in that in step (2) the Titanium alkoxides alcoholic solution
Titanium alkoxides include the combination of any one or at least two in tetraethyl titanate, isopropyl titanate or butyl titanate；
Preferably, the molar ratio of Titanium alkoxides and non-dehydration property strong protonic acid is 1:3~1:10 in the Titanium alkoxides alcoholic solution；
Preferably, water content≤62wt% in the non-dehydration property strong protonic acid；
Preferably, amount >=10g of the preparation method every batch of processing Titanium alkoxides of the titanium dioxide nano material.
7. the preparation method as described in one of claim 1-6, which is characterized in that after solvent heat treatment carry out ethanol washing, from
Heart separation and drying process；
Preferably, the revolving speed of the centrifuge separation is 2000r/min~12000r/min；
Preferably, the time of the centrifuge separation is 5min~15min；
Preferably, the temperature of the drying is 50 DEG C~80 DEG C；
Preferably, the time of the drying is 2h~4h.
8. the preparation method of anatase-type nanometer titanium dioxide as described in one of claim 1-7, which is characterized in that the preparation
Method includes the following steps:
(1) in 0 DEG C~15 DEG C cold baths, it is 1:3~1:50 by the molar ratio of Titanium alkoxides and ethyl alcohol, Titanium alkoxides is dispersed in second
Titanium alkoxides alcoholic solution is obtained in alcohol；
(2) ratio for being 1:3~1:10 in the molar ratio of Titanium alkoxides in Titanium alkoxides alcoholic solution and non-dehydration property strong protonic acid, in titanium
Non- dehydration property strong protonic acid is added in alkoxide alcoholic solution, presoma is made, water content≤12mol/L in presoma, acid in presoma
Angle value >=1mol/L；
(3) presoma is risen to 120 DEG C~170 DEG C with 3 DEG C/min~10 DEG C/min heating rate, carries out solvent heat treatment 1h
The material system containing titanium dioxide is made in~6h；
(4) material system containing titanium dioxide is carried out to the revolving speed centrifugation point of ethanol washing, 2000r/min~12000r/min
Anatase-type nanometer titanium dioxide is made in from 5min~15min and 50 DEG C~80 DEG C dry 2h~4h.
9. a kind of nano-silica that the preparation method of anatase-type nanometer titanium dioxide as described in one of claim 1-8 obtains
Change titanium, which is characterized in that purity >=99.9% of the nano-titanium dioxide；
Preferably, partial size≤10nm of the nano-titanium dioxide；
Preferably, breadth coefficient≤0.5 of the nano-titanium dioxide；
Preferably, the nano-titanium dioxide has absorption to ultraviolet light.
10. a kind of purposes of anatase-type nanometer titanium dioxide as claimed in claim 9, which is characterized in that the nano-silica
Change titanium and is used as catalyst carrier, ultraviolet shielded material, the active component of light-catalyzed reaction, silicon rubber heat stabilizer, ultraviolet light
Absorbent, battery material, functional coating and water purification material.
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