CN1865155A - Method for synthesizing soluble titanium dioxide nano crystal in low temperature - Google Patents
Method for synthesizing soluble titanium dioxide nano crystal in low temperature Download PDFInfo
- Publication number
- CN1865155A CN1865155A CN 200610034931 CN200610034931A CN1865155A CN 1865155 A CN1865155 A CN 1865155A CN 200610034931 CN200610034931 CN 200610034931 CN 200610034931 A CN200610034931 A CN 200610034931A CN 1865155 A CN1865155 A CN 1865155A
- Authority
- CN
- China
- Prior art keywords
- titanium dioxide
- titanium
- reaction
- dioxide nano
- hydrochloric acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
This invention provides a chemical method for synthesizing soluble titanium dioxide nanocrystal at low temperature, characterizing in that: using titanium tetrachloride and titanium trichloride mixed hydrochloric acid solution as titanium source, with hydrogen dioxide and alkaline solution as adjuvant material, applying open system reflux reaction apparatus or closed system low-temperature heat reaction apparatus, leave the reaction for 1-12 h between 100 and 180Deg C. The yield of the titanium dioxide nanocrystal synthesized by this method is 30-70g/l. The obtained titanium dioxide nano particle has an anatase phase structure and a high degree of crystallization. The particle size is homogeneous and the particle diameter is distributed between 3 and 20nm, which is easily dispersed. The titanium dioxide nanocrystal has superior photocatalysis, deodorizing, antibacterial and mildew-resistant properties. This method is characterized of combining hydrolysis, crystallization and dispersion in one step, low reaction temperature, strong apparatus universality, easy-obtained and low cost raw material, and high yield.
Description
[technical field]
The invention provides a kind of method of synthesis of titanium dioxide nanocrystal, provide a kind of low temperature the synthetic very easily method of the titanium dioxide nano-crystal of dispersive anatase octahedrite phase structure especially, belong to field of nano material preparation.
[background technology]
In recent years, along with science and technology development, the titanium dioxide crystal that it is found that nanoscale has excellent photocatalysis property, promptly under the irradiation of ultraviolet ray (UV), have very strong oxidation/reducing property, can realize the functions such as the thorough mineralising of room temperature, antibacterial and mouldproof and ultraviolet screener of bio-refractory organic pollutant.Thereby the application of relevant titanium dioxide nano-crystal and synthetic method thereof become key subjects, and the various countries scientific worker launches research from different perspectives.
At present, research great majority to the synthetic method of titanium dioxide nano-crystal concentrate on collosol-gelatum system, co-precipitation hydrolyzation system, microemulsion system direction (needing the elevated temperature heat crystallization), and direction such as the hydro-thermal under the higher temperature conditions, solvent thermal synthetic system.With these method synthetic titanium dioxide nano-crystal particles hard aggregation (needing experience elevated temperature heat crystallization) taking place more greatly and easily, is difficult to disperse and dissolving; Perhaps very high to the requirement of reactor, be difficult for amplifying, be difficult to adapt to suitability for industrialized production.
So the existing scientific and technological person of part begins the composition problem of titanium dioxide nano-crystal under the cold condition is launched research, and has the part achievement to come out.Some synthetic method, comprise co-precipitation hydrolysis method, acidifying dispergation method, alkalization peptisation, the hot method of hydrothermal/solvent etc., in documents such as CN 1295977A (Chinese invention patent publication number, down together), CN 1323743A, CN 1363521A, CN 1583888A, CN 1654335A, CN 1218878C, CN 1631999A, CN 1709987A, CN 1571756A, CN 1706749A, CN 1170775C, CN 1562768A and CN 1686608A, disclose.But in the synthetic method of titanium dioxide nano-crystal, there is following defective under these cold condition:
(1) process is loaded down with trivial details, the reaction system complexity, and the technological process of production is long.Generally the titaniferous inorganic salt with the tetravalence attitude are the titanium source, and by the alkali lye neutralization, the titaniferous inorganic salt are hydrolyzed into the titanium hydroxide/hydration titanic acid of amorphous structure, the titanium hydroxide of gained amorphous structure in washes clean (to detect less than Cl
-Ion, SO
4 2-Ions etc. are foundation) after, be scattered in again in the solution such as mineral acid or alkali, through dispergation/peptization and crystallization process, make needed titanium dioxide nano-crystal.
(2) mass consumption of resources such as alkali, acid solution and water produces a large amount of waste water simultaneously, is unfavorable for environmental improvement.The titaniferous inorganic salt compound can produce more mineral acid in hydrolytic process, need to neutralize (promptly in the neutral process hydrolysis taking place) with a large amount of alkali lye, needs extra mineral acid to carry out dispergation and crystallization after the titanium hydroxide of gained amorphous structure is waited to have washed again.
(3) the reaction mass kind is many, and product purity is not high.Except that titanium-containing compound, also need some alkali lye, acid solution, organic solvent, tensio-active agent etc.Also make simultaneously the separation purification difficulty of product increase, be difficult to obtain the titanium dioxide nano-crystal of higher degree.
(4) productive rate of unit reaction volume is lower, and productive rate is generally only about 10～25g/l.
[summary of the invention]
At the deficiency of above-mentioned existing method and technology, the invention provides a kind of method of synthesizing soluble titanium dioxide nano crystal in low temperature.The gained titanium dioxide nano-particle has the anatase octahedrite phase structure and degree of crystallinity is higher, uniform particles and size distribution be in 3～20nm, characteristics such as dispersion very easily, has excellent photocatalysis activity, deodorizing, antibiotic and fungicidal properties simultaneously.
For achieving the above object, technical scheme provided by the present invention is: with titaniferous mixing salt acid solution is the titanium source, with hydrogen peroxide, alkali lye is auxiliary material, adopt the back flow reaction device of the system of opening wide or the low-temperature hydrothermal reaction unit of enclosed system, behind 100～180 ℃ of temperature ranges reaction, 1～12h, make titanium dioxide nano-crystal through cooling, centrifugation, removal of impurities.
Concrete operations step or process are as follows:
(1) configuration precursor solution
With titaniferous mixing salt acid solution is the titanium source, and the adding aqueous hydrogen peroxide solution also mixes, and adds appropriate alkaline liquor at last to regulate pH value and salify, stirs, and obtains precursor solution.
Precursor solution is formulated by titaniferous hydrochloric acid soln (titanium source), aqueous hydrogen peroxide solution, alkali lye and water, and the volume parts ratio of each component is: V
The titaniferous hydrochloric acid soln: V
Aqueous hydrogen peroxide solution: V
Alkali lye: V
Water=1.0: (0.1～0.6): (2.8～3.2): (1.5～2.5).
Wherein:
The titaniferous hydrochloric acid soln is the mixing salt acid solution of titanium tetrachloride and titanous chloride; The Ti of tetravalence attitude in the titanium source
4+The Ti of ion and three valence states
3+The ratio of ionic amount of substance
Total amount of substance concentration of contained titanium elements is 1.0～5.0mol/l;
Hydrogen peroxide is commercially available analytical pure or chemical pure aqueous hydrogen peroxide solution, and mass percentage concentration is 10.0～30.0%;
Alkali lye is sodium hydroxide solution, and amount of substance concentration is 1.0～5.0mol/l, preferred 1.5～2.5mol/l;
Water is distilled water or deionized water.
(2) hydrolysis and crystallization
Can adopt back hydrolysis and crystallization under the condition of normal pressure.The precursor solution that has prepared is shifted in the back flow reaction device of the system of opening wide, at 100～180 ℃ of temperature range reaction 1～12h.Wherein temperature of reaction is preferred 110～150 ℃, preferred 3～8h of reaction times.
Also can adopt hydro-thermal hydrolysis and crystallization under the cold condition.The precursor solution that has prepared is shifted in the hydro-thermal reaction device of enclosed system, at 100～180 ℃ of temperature range reaction 1～12h.Wherein temperature of reaction is preferred 110～150 ℃, preferred 3～8h of reaction times.
(3) Separation ﹠ Purification: mainly refer to cooling, centrifugation, removal of impurities, be common routine operation process.
Centrifugation gained titanium dioxide nano-crystal promptly obtains a kind of colloidal dispersion that contains the titanium dioxide nano-crystal of adjustable concentration through dialysis purification or nanofiltration purification; Perhaps handle and to obtain a kind of soluble titanium dioxide nano-powder through low-temperature vacuum drying.
Centrifugation gained clear liquid mainly contains sodium-chlor, hydrochloric acid and the very little titanium dioxide nano-crystal of a spot of particle, and it underpressure distillation can be obtained certain density hydrochloric acid soln, can be used for disposing precursor solution, can be used for also that other is industrial.Residue then can extract sodium-chlor and titanium dioxide.
Among the present invention, the titanium source can add mixed in hydrochloric acid by titanium tetrachloride and titanous chloride and make, and also can be made by titanium sponge and excessive titanium tetrachloride, hydrochloric acid reaction.Because the titanous chloride hydrochloric acid soln is normally made by the reaction of titanium sponge, titanium tetrachloride and hydrochloric acid, so the mixing salt acid solution of titanium tetrachloride and titanous chloride also can be made by titanium sponge and excessive titanium tetrachloride, the reaction of hydrochloric acid.Because wherein excessive titanium tetrachloride provides the Ti of tetravalence attitude
4+Ion, the titanium sponge that reacts then changes the Ti of three valence states into
3+Ion.Reduced the link of titanous chloride being carried out purifying, and the hydrochloric acid soln of titanium tetrachloride and titanous chloride mix link, so, dispose the titanium source with titanium sponge and excessive titanium tetrachloride, hydrochloric acid reaction, production cost is lower.
The method of synthesizing soluble titanium dioxide nano crystal in low temperature provided by the invention has following advantage:
(1) because the titaniferous inorganic salt of three valence states exist with the form of hydrochloric acid soln or sulphuric acid soln usually, have good water-soluble and non-volatility, be suitable for liquid-phase hydrolysis, it is synthetic just to be fit to low temperature.So the present invention selects the mixing salt acid solution of titanium tetrachloride and titanous chloride as the titanium source, help the synthetic of titanium dioxide nano-crystal under the low-temperature condition greatly.Outside the demineralizing acid, only contain the Ti of tetravalence attitude in the titanium source
4+The Ti of ion and three valence states
3+Ion, whole composition is very simple.
(2) the titaniferous amount height of titanium tetrachloride, but the titanium dioxide of the amount of the titanium tetrachloride output same substance of unit amount of substance, be that productive rate can be improved in the titanium source, and raw material is cheap and easy to get.
(3) in building-up process, the interpolation of hydrogen peroxide plays a part very crucial to the formation of titanium dioxide nano-crystal, hydrogen peroxide can slowly-releasing the formation of control titanium dioxide nano-crystal, delay growing up fast of crystal grain, from following specific embodiment as can be seen, add a spot of hydrogen peroxide in reactant, what synthesize is anatase octahedrite phase structure (solubility is good) titanium dioxide nano-crystal.On the contrary, if there is not hydrogen peroxide to participate in reaction, in similar reaction system, can only make the titanium dioxide nano-crystal (referring to CN1172993C, CN1086364C) of rutile phase structure (solubility is poor).Simultaneously, since hydrogen peroxide molecule can with the Ti of three valence states
3+The ion coordination complexing also forms peroxidation titanous acid coordination ion, simultaneously can with the Ti of tetravalence attitude
4+Ion forms peroxidation metatitanic acid coordination ion, and these two kinds of peroxidation coordination ions can effectively form the titanium dioxide nano-crystal crystal seed.
(4) in building-up process, after the adding appropriate alkaline liquor, can regulate the pH value of reaction system, the control hydrolysis speed of response helps the formation of the titanium dioxide nano-crystal of certain crystallographic structure, rather than the titanium dioxide nano-crystal of amorphous structure; And salify (sodium-chlor) also can play the ligand complex effect to the formation of titanium dioxide nano-crystal.
(5) in building-up process, after the adding appropriate alkaline liquor, the titanium dioxide nano-crystal that the reaction back is generated is saltoutd from reaction mother liquor easily and is separated.
In sum, utilize method provided by the invention can realize successfully that the low temperature of titanium dioxide nano-crystal is synthetic, catchment simultaneously and separate, crystallization, be scattered in the single step reaction and finish, the productive rate of unit reaction compartment is higher, the reaction times is also shorter, corresponding technical process is also short, and energy consumption is also low.And, the reaction unit highly versatile, raw material is easy to get inexpensive, is fit to very much industrialized production.
[embodiment]
Below will be from the volume ratio of each component, the Ti of tetravalence attitude
4+The Ti of ion and three valence states
3+The ratio n of ionic amount of substance
Ti4+: n
Ti3+, temperature of reaction and reaction times 4 angles set forth specific embodiments of the invention.
Embodiment 1
The volume ratio of each component is V
The titaniferous hydrochloric acid soln: V
Aqueous hydrogen peroxide solution: V
Alkali lye: V
Water=1.0: 0.3: 3.0: 1.7 o'clock, wherein the titaniferous hydrochloric acid soln was the mixing salt acid solution (Ti of tetravalence attitude of titanium tetrachloride and titanous chloride
4+The Ti of ion and three valence states
3+The ratio of ionic amount of substance
The total amount of substance concentration that contains titanium elements is 3.8mol/l); Hydrogen peroxide is the chemical pure aqueous hydrogen peroxide solution, and mass percentage concentration is 30.0%; Alkali lye is the sodium hydroxide solution of 2.0mol/l; Water is deionized water.At first be according to
Ratio preparation titanium source mixes titanium tetrachloride and titanous chloride hydrochloric acid soln and gets final product.In the titaniferous hydrochloric acid soln, add aqueous hydrogen peroxide solution, water and the alkali lye of respective volume then according to each component volume ratio successively, and stir, obtain a kind of wine-colored clear solution, i.e. precursor solution.With it transfer in the reflux that opens wide system, hydrolysis and crystallization 6.0h under 135 ℃ of temperature, cooling, centrifugation, clear liquid reclaims, precipitation is disperseed and dissolving and nanofiltration purification with distilled water.XRD spectra shows that the gained titanium dioxide nano-crystal is the anatase octahedrite phase structure, and it is 3～20nm that TEM records its granularity, and productive rate is 50g/l.
Embodiment 2
The volume ratio of each component is V
The titaniferous hydrochloric acid soln: V
Aqueous hydrogen peroxide solution: V
Alkali lye: V
Water=1.0: 0.1: 2.8: 2.1 o'clock, wherein the titaniferous hydrochloric acid soln be titanium tetrachloride and titanous chloride the mixing salt acid solution (
The total amount of substance concentration that contains titanium elements is 2.5mol/l); Hydrogen peroxide is the chemical pure aqueous hydrogen peroxide solution, and mass percentage concentration is 30.0%; Alkali lye is the sodium hydroxide solution of 2.2mol/l; Water is deionized water.The formulation operations of presoma is identical with embodiment 1.In the reflux of unlimited system, hydrolysis and crystallization 4.5h under 155 ℃ of temperature cool off with it transfer, centrifugation, and the clear liquid recovery, precipitation disperses with distilled water and dissolves also nanofiltration to purify.XRD spectra shows that the gained titanium dioxide nano-crystal is the anatase octahedrite phase structure, and it is 3～20nm that TEM records its granularity, and productive rate is 33g/l.
Embodiment 3
The volume ratio of each component is V
The titaniferous hydrochloric acid soln: V
Aqueous hydrogen peroxide solution: V
Alkali lye: V
Water=1.0: 0.2: 3.2: 1.5 o'clock, wherein the titaniferous hydrochloric acid soln be titanium tetrachloride and titanous chloride the mixing salt acid solution (
The total amount of substance concentration that contains titanium elements is 3.0mol/l); Hydrogen peroxide is the chemical pure aqueous hydrogen peroxide solution, and mass percentage concentration is 30.0%; Alkali lye is the sodium hydroxide solution of 1.8mol/l; Water is deionized water.The formulation operations of precursor solution is identical with embodiment 1.With it transfer in the reflux that opens wide system, hydrolysis and crystallization 7.0h under 145 ℃ of temperature, cooling, centrifugation, clear liquid reclaims, precipitation is disperseed and dissolving and nanofiltration purification with distilled water.XRD spectra shows that the gained titanium dioxide nano-crystal is the anatase octahedrite phase structure, and it is 3～20nm that TEM records its granularity, and productive rate is 40g/l.
Embodiment 4
The volume ratio of each component is V
The titaniferous hydrochloric acid soln: V
Aqueous hydrogen peroxide solution: V
Alkali lye: V
Water=1.0: 0.4: 3.0: 1.6 o'clock, wherein the titaniferous hydrochloric acid soln be titanium tetrachloride and titanous chloride the mixing salt acid solution (
The total amount of substance concentration that contains titanium elements is 4.1mol/l); Hydrogen peroxide is the chemical pure aqueous hydrogen peroxide solution, and mass percentage concentration is 30.0%; Alkali lye is the sodium hydroxide solution of 2.0mol/l; Water is deionized water.The formulation operations of precursor solution is identical with embodiment 1.With it transfer in the reflux that opens wide system, hydrolysis and crystallization 5.0h under 130 ℃ of temperature, cooling, centrifugation, clear liquid reclaims, precipitation is disperseed and dissolving and nanofiltration purification with distilled water.XRD spectra shows that the gained titanium dioxide nano-crystal is the anatase octahedrite phase structure, and it is 3～20nm that TEM records its granularity, and productive rate is 55g/l.
Embodiment 5
The volume ratio of each component is V
The titaniferous hydrochloric acid soln: V
Aqueous hydrogen peroxide solution: V
Alkali lye: V
Water=1.0: 0.6: 3.0: 1.6 o'clock, wherein the titaniferous hydrochloric acid soln be titanium tetrachloride and titanous chloride the mixing salt acid solution (
The total amount of substance concentration that contains titanium elements is 4.7mol/l); Hydrogen peroxide is the chemical pure aqueous hydrogen peroxide solution, and mass percentage concentration is 30.0%; Alkali lye is the sodium hydroxide solution of 2.2mol/l; Water is deionized water.The formulation operations of presoma is identical with embodiment 1.In the low-temperature hydrothermal device of enclosed system, hydrolysis and crystallization 5.0h under 125 ℃ of temperature cool off with it transfer, centrifugation, and the clear liquid recovery, precipitation disperses with distilled water and dissolves also nanofiltration to purify.XRD spectra shows that the gained titanium dioxide nano-crystal is the anatase octahedrite phase structure, and it is 8～20nm that TEM records its granularity, and productive rate is 63g/l.
Embodiment 6
Investigate the influence of differential responses time to product on embodiment 1 basis, concrete operations are identical with embodiment 1.Reaction times is selected 3.0h, 5.0h, 7.0h, 9.0h.Operation is to pipette total reaction mother liquor 1/4 volume solution after for some time in hydrolysis and crystallization from reaction system, and with it cooling, centrifugation, clear liquid reclaims, and precipitation disperses to purify with dissolving and nanofiltration with distilled water.Product detects crystalline structure, TEM detection particle size size with XRD respectively.Experimental result shows that the product under the differential responses time is the anatase octahedrite phase structure, and size-grade distribution is close, and (3～20nm), productive rate is 50g/l.
From the foregoing description as can be seen, according to method of the present invention institute synthetic titanium dioxide nano-crystal have the anatase octahedrite phase structure and crystallization better, particle scale little and even (3～20nm), very easily be scattered in the water equal solvent.Experiment shows that this titanium dioxide nano-crystal has excellent photocatalysis activity, and PARA FORMALDEHYDE PRILLS(91,95), benzene, toluene all have good photocatalytic degradation effect; Have deodorizing antibiotic and fungicidal properties preferably simultaneously.This soluble titanium dioxide nano-crystal can be directly used in suspension system with the form of colloidal dispersion, or is used for the immobilization system of form of film, thereby in fields such as plastics, pottery, glass, inside/outside walls wide market application prospect is arranged.
Soluble titanium dioxide nano-crystal synthetic method provided by the invention will replace traditional synthetic method, becomes market mainstream technology, and leads the New Wave of technological revolution.
More than be preferred forms of the present invention, according to content disclosed by the invention, some identical, replacement schemes that those of ordinary skill in the art can expect apparently all should fall into protection scope of the present invention.
Claims (5)
1. the method for a synthesizing soluble titanium dioxide nano crystal in low temperature, step comprises configuration precursor solution-hydrolysis and crystallization-Separation ﹠ Purification, it is characterized in that, concrete steps are as follows:
(1) configuration precursor solution: with titaniferous mixing salt acid solution is the titanium source, and the adding aqueous hydrogen peroxide solution also mixes, and adds appropriate alkaline liquor at last to regulate pH value and salify, stirs, and obtains precursor solution;
(2) hydrolysis and crystallization;
(3) Separation ﹠ Purification: mainly refer to cooling, centrifugation, removal of impurities.
2. according to the method for the described synthesizing soluble titanium dioxide nano crystal in low temperature of claim 1, it is characterized in that, in the described step (1), described precursor solution is formulated by titaniferous hydrochloric acid soln, aqueous hydrogen peroxide solution, alkali lye and water, and the volume parts ratio of each component is: V
The titaniferous hydrochloric acid soln: V
Aqueous hydrogen peroxide solution: V
Alkali lye: V
Water=1.0: (0.1～0.6): (2.8～3.2): (1.5～2.5);
Wherein:
The titaniferous hydrochloric acid soln is the mixing salt acid solution of titanium tetrachloride and titanous chloride; The Ti of tetravalence attitude in the titanium source
4+The Ti of ion and three valence states
3+The ratio n of ionic amount of substance
Ti4+: n
Ti3+=0～7.0, total amount of substance concentration of contained titanium elements is 1.0～5.0mol/l;
Hydrogen peroxide is commercially available analytical pure or chemical pure aqueous hydrogen peroxide solution, and mass percentage concentration is 10.0～30.0%;
Alkali lye is sodium hydroxide solution, and amount of substance concentration is 1.0～5.0mol/l, preferred 1.5～2.5mol/l;
Water is distilled water or deionized water.
3. according to the method for the described synthesizing soluble titanium dioxide nano crystal in low temperature of claim 2, it is characterized in that, described titaniferous hydrochloric acid soln (titanium source) is mixed by titanium tetrachloride and titanous chloride hydrochloric acid soln, also can be made by titanium sponge and excessive titanium tetrachloride, hydrochloric acid reaction.
4. according to the method for the described synthesizing soluble titanium dioxide nano crystal in low temperature of claim 3, it is characterized in that, in the described step (2), the precursor solution that has prepared is shifted in the back flow reaction device of the system of opening wide, at 100～180 ℃ of temperature range reaction 1～12h, wherein temperature of reaction is preferred 110～150 ℃, preferred 3～8h of reaction times.
5. according to the method for the described synthesizing soluble titanium dioxide nano crystal in low temperature of claim 3, it is characterized in that, in the described step (2), the precursor solution that has prepared is shifted in the low-temperature hydrothermal reaction unit of enclosed system, at 100～180 ℃ of temperature range reaction 1～12h.Wherein temperature of reaction is preferred 110～150 ℃, preferred 3～8h of reaction times.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100349319A CN100488621C (en) | 2006-04-06 | 2006-04-06 | Method for synthesizing soluble titanium dioxide nano crystal in low temperature |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100349319A CN100488621C (en) | 2006-04-06 | 2006-04-06 | Method for synthesizing soluble titanium dioxide nano crystal in low temperature |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1865155A true CN1865155A (en) | 2006-11-22 |
| CN100488621C CN100488621C (en) | 2009-05-20 |
Family
ID=37424328
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006100349319A Expired - Fee Related CN100488621C (en) | 2006-04-06 | 2006-04-06 | Method for synthesizing soluble titanium dioxide nano crystal in low temperature |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100488621C (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101844806A (en) * | 2010-06-09 | 2010-09-29 | 华南师范大学 | Method for ethylene diamine tetraacetic acid (EDTA)-assisted hydrothermal synthesis of nanometer porous titanium dioxide(TiO2) |
| CN102503166A (en) * | 2011-10-21 | 2012-06-20 | 厦门大学 | Preparation method of one-dimensional rutile TiO2 nanorod array film |
| CN103553124A (en) * | 2013-11-08 | 2014-02-05 | 中国科学技术大学 | Method for preparing blue titanium dioxide |
| CN105478151A (en) * | 2014-09-15 | 2016-04-13 | 中国科学院大连化学物理研究所 | Crystal phase controllable nitrogen-doped titanium dioxide preparation method |
| CN107799654A (en) * | 2017-09-15 | 2018-03-13 | 华南师范大学 | A kind of high efficiency plane perovskite solar cell and preparation method thereof |
| CN108128803A (en) * | 2018-03-09 | 2018-06-08 | 陕西科技大学 | A kind of method that water-soluble titanium dioxide nano-particle is prepared using titanium valve as presoma |
| CN113699523A (en) * | 2021-08-23 | 2021-11-26 | 浙江工业大学 | Method for in-situ growth of titanium dioxide quantum dots on surface of implant |
| CN114162860A (en) * | 2021-03-23 | 2022-03-11 | 耐酷时(北京)科技有限公司 | Preparation method of titanium dioxide porous ball |
-
2006
- 2006-04-06 CN CNB2006100349319A patent/CN100488621C/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101844806A (en) * | 2010-06-09 | 2010-09-29 | 华南师范大学 | Method for ethylene diamine tetraacetic acid (EDTA)-assisted hydrothermal synthesis of nanometer porous titanium dioxide(TiO2) |
| CN102503166A (en) * | 2011-10-21 | 2012-06-20 | 厦门大学 | Preparation method of one-dimensional rutile TiO2 nanorod array film |
| CN103553124A (en) * | 2013-11-08 | 2014-02-05 | 中国科学技术大学 | Method for preparing blue titanium dioxide |
| CN103553124B (en) * | 2013-11-08 | 2015-03-11 | 中国科学技术大学 | Method for preparing blue titanium dioxide |
| CN105478151A (en) * | 2014-09-15 | 2016-04-13 | 中国科学院大连化学物理研究所 | Crystal phase controllable nitrogen-doped titanium dioxide preparation method |
| CN105478151B (en) * | 2014-09-15 | 2018-12-07 | 中国科学院大连化学物理研究所 | A kind of preparation method for the nitrogen-doped titanium dioxide that crystal phase is controllable |
| CN107799654A (en) * | 2017-09-15 | 2018-03-13 | 华南师范大学 | A kind of high efficiency plane perovskite solar cell and preparation method thereof |
| CN108128803A (en) * | 2018-03-09 | 2018-06-08 | 陕西科技大学 | A kind of method that water-soluble titanium dioxide nano-particle is prepared using titanium valve as presoma |
| CN114162860A (en) * | 2021-03-23 | 2022-03-11 | 耐酷时(北京)科技有限公司 | Preparation method of titanium dioxide porous ball |
| CN114162860B (en) * | 2021-03-23 | 2023-11-03 | 耐酷时(北京)科技有限公司 | Preparation method of micron-sized titanium dioxide porous sphere with surface rich in nano holes |
| CN113699523A (en) * | 2021-08-23 | 2021-11-26 | 浙江工业大学 | Method for in-situ growth of titanium dioxide quantum dots on surface of implant |
| CN113699523B (en) * | 2021-08-23 | 2023-12-12 | 浙江工业大学 | Method for in-situ growth of titanium dioxide quantum dots on implant surface |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100488621C (en) | 2009-05-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100488621C (en) | Method for synthesizing soluble titanium dioxide nano crystal in low temperature | |
| CN101559979B (en) | Method for preparing extrafine anatase titanium dioxide nano rods | |
| Zhou et al. | Controllable synthesis of three-dimensional well-defined BiVO4 mesocrystals via a facile additive-free aqueous strategy | |
| CN104098132B (en) | One kind prepares { 100 } crystal face Anatase TiO2The method of nano particle | |
| Li et al. | Surface effect of natural zeolite (clinoptilolite) on the photocatalytic activity of TiO2 | |
| Song et al. | Synthesis and characterization of magnesium hydroxide by batch reaction crystallization | |
| CN100500281C (en) | Preparation method of soluble titanium dioxide nano-crystal | |
| Dong et al. | Ultrafast formation of ZnO mesocrystals with excellent photocatalytic activities by a facile Tris-assisted antisolvent process | |
| CN100445209C (en) | Preparation method of new type nano-titanium dioxide powder | |
| CN101955222A (en) | Method for preparing anatase-phase titanium dioxide sol | |
| CN1344682A (en) | Prepn of nano-cobaltosic oxide powder | |
| CN102219255B (en) | Preparation method for mixed crystal form nanometer titanium dioxide turbid liquor with high stability | |
| CN1686823A (en) | Method for preparing anatase type nano-titanium dioxide in high phase-transition temperature and high specific area | |
| CN1765511A (en) | PH adjusting hydrothermal preparation method of active nano crystal mesoporous titanium dioxide photocatalytic material | |
| CN105399138A (en) | Perovskite SrTiO3 tetragonal nanoparticle preparation method and product | |
| CN105883910A (en) | Preparation method and product for perovskite SrTiO3 porous nano particles | |
| CN1248550A (en) | Process for preparing titanic schorl phase titanium dioxide nanometer crystal under room temp. | |
| CN1277749C (en) | Process for preparing rutile phase titanium dioxide nano-powder | |
| CN1283555C (en) | Method for preparing rutile nano titanium dioxide | |
| CN1214978C (en) | Ordered mesoporous molecnlar sieve material with wltrahigh hydrothermal stability and synthesis method thereof | |
| CN106111104A (en) | Lamellar zinc silicon layer dihydroxy complex hydroxide photocatalyst preparation method and application | |
| CN1948167A (en) | Synthesis method of cobaltosic oxide nano-tube | |
| CN1556034A (en) | Synthesis method of magnesium hydroxide nano pipe | |
| CN108325513A (en) | A kind of nano titanium dioxide photocatalyst and its pyrolytic preparation method of doping cerium | |
| CN108423713B (en) | Preparation method and application of manganese titanate nanosheet material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: Shenzhen Eubo New Material Technology Co., Ltd. Assignor: Shenzhen Institute of Stinghua University Contract record no.: 2011440020258 Denomination of invention: Method for synthesizing soluble titanium dioxide nano crystal in low temperature Granted publication date: 20090520 License type: Exclusive License Open date: 20061122 Record date: 20110622 |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090520 Termination date: 20180406 |