CN100488621C - 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
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- CN100488621C CN100488621C CNB2006100349319A CN200610034931A CN100488621C CN 100488621 C CN100488621 C CN 100488621C CN B2006100349319 A CNB2006100349319 A CN B2006100349319A CN 200610034931 A CN200610034931 A CN 200610034931A CN 100488621 C CN100488621 C CN 100488621C
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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, the method for the titanium dioxide nano-crystal of the synthetic anatase phase structure of very easily disperseing of a kind of low temperature is provided 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 pollution.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 synthesis system.With the synthetic titanium dioxide nano-crystal particle of these methods 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 cryogenic conditions is launched research, and has the part achievement to come out.Some synthetic method, comprise co-precipitation Hydrolyze 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 cryogenic conditions:
(1) process is loaded down with trivial details, the reaction system complexity, and the technological process of production is long.Generally the titaniferous inorganic salts with the tetravalence attitude are the titanium source, and by the alkali lye neutralization, the titaniferous inorganic salts are hydrolyzed into the titanium hydroxide/hydration titanic acid of impalpable structure, the titanium hydroxide of gained impalpable 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 inorganic acid or alkali, through dispergation/peptization and crystallization process, make needed titanium dioxide nano-crystal.
(2) a large amount of consumption of resources such as alkali, acid solution and water produce a large amount of waste water simultaneously, are unfavorable for environmental improvement.The titaniferous inorganic salt compound can produce more inorganic acid in hydrolytic process, need to neutralize (promptly in the process of neutralization hydrolysis taking place) with a large amount of alkali lye, needs extra inorganic acid to carry out dispergation and crystallization after the titanium hydroxide of gained impalpable 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, surfactant 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 phase structure and degree of crystallinity is higher, uniform particles and particle diameter are distributed 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 salt-mixture 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 salt-mixture 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 solution (titanium source), aqueous hydrogen peroxide solution, alkali lye and water, and the volume parts ratio of each component is: V
The titaniferous hydrochloric acid solution: 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 solution is the salt-mixture acid solution of titanium tetrachloride and titanium trichloride; The Ti of tetravalence attitude in the titanium source
4+The Ti of ion and three valence states
3+The ratio of the amount of substance of ion
Total amount of substance concentration of contained titanium elements is 1.0～5.0mol/l;
Hydrogen peroxide is the pure or chemical pure aqueous hydrogen peroxide solution of commercially available analysis, 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 reaction temperature is preferred 110～150 ℃, preferred 3～8h of reaction time.
Also can adopt hydro-thermal hydrolysis and crystallization under the cryogenic conditions.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 reaction temperature is preferred 110～150 ℃, preferred 3～8h of reaction time.
(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 chloride, hydrochloric acid and the very little titanium dioxide nano-crystal of a spot of particle, and it decompression distillation can be obtained certain density hydrochloric acid solution, can be used for disposing precursor solution, can be used for also that other is industrial.Residue then can extract sodium chloride and titanium dioxide.
Among the present invention, the titanium source can add mixed in hydrochloric acid by titanium tetrachloride and titanium trichloride and make, and also can be made by titanium sponge and excessive titanium tetrachloride, hydrochloric acid reaction.Because the titanium trichloride hydrochloric acid solution is normally made by the reaction of titanium sponge, titanium tetrachloride and hydrochloric acid, so the salt-mixture acid solution of titanium tetrachloride and titanium trichloride 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 titanium trichloride being carried out purifying, and the hydrochloric acid solution of titanium tetrachloride and titanium trichloride 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 salts of three valence states exist with the form of hydrochloric acid solution or sulfuric acid solution usually, have good water-soluble and fixedness, be suitable for liquid-phase hydrolysis, it is synthetic just to be fit to low temperature.So the present invention selects the salt-mixture acid solution of titanium tetrachloride and titanium trichloride 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 Ti3 of ion and three valence states
+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 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 peroxidating titanous acid complex ion, simultaneously can with the Ti of tetravalence attitude
4+Ion forms peroxidating metatitanic acid complex ion, and these two kinds of peroxidating complex 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, control hydrolysis speed helps the formation of the titanium dioxide nano-crystal of certain crystallographic structure, rather than the titanium dioxide nano-crystal of impalpable structure; And salify (sodium chloride) 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 time is also shorter, corresponding technological 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.
[specific 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 of the amount of substance of ion
, reaction temperature and reaction time 4 angles set forth specific embodiments of the invention.
Embodiment 1
The volume ratio of each component is V
The titaniferous hydrochloric acid solution: V
Aqueous hydrogen peroxide solution: V
Alkali lye: V
WaterDuring=1.0:0.3:3.0:1.7, wherein the titaniferous hydrochloric acid solution is the salt-mixture acid solution (Ti of tetravalence attitude of titanium tetrachloride and titanium trichloride
4+The Ti of ion and three valence states
3+The ratio of the amount of substance of ion
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 titanium trichloride hydrochloric acid solution and gets final product.In the titaniferous hydrochloric acid solution, 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 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 solution: V
Aqueous hydrogen peroxide solution: V
Alkali lye: V
WaterDuring=1.0:0.1:2.8:2.1, wherein the titaniferous hydrochloric acid solution be titanium tetrachloride and titanium trichloride the salt-mixture 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 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 solution: V
Aqueous hydrogen peroxide solution: V
Alkali lye: V
WaterDuring=1.0:0.2:3.2:1.5, wherein the titaniferous hydrochloric acid solution be titanium tetrachloride and titanium trichloride the salt-mixture 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 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 solution: V
Aqueous hydrogen peroxide solution: V
Alkali lye: V
WaterDuring=1.0:0.4:3.0:1.6, wherein the titaniferous hydrochloric acid solution be titanium tetrachloride and titanium trichloride the salt-mixture 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 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 solution: V
Aqueous hydrogen peroxide solution: V
Alkali lye: V
WaterDuring=1.0:0.6:3.0:1.6, wherein the titaniferous hydrochloric acid solution be titanium tetrachloride and titanium trichloride the salt-mixture 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 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 time is selected 3.0h, 5.0h, 7.0h, 9.0h.Operation is to pipette overall reaction mother liquor 1/4 volume solution after a period of 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 crystal structure, TEM detection particle size size with XRD respectively.Experimental result shows that the product under the differential responses time is the anatase phase structure, and size distribution is close, and (3～20nm), productive rate is 50g/l.
From the foregoing description as can be seen, the titanium dioxide nano-crystal that synthesizes according to method of the present invention have the anatase 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 salt-mixture acid solution is the titanium source, the adding aqueous hydrogen peroxide solution also mixes, add appropriate alkaline liquor at last to regulate pH value and salify, stir, obtain precursor solution, described titaniferous salt-mixture acid solution is the salt-mixture acid solution of titanium tetrachloride and titanium trichloride;
(2) hydrolysis and crystallization: adopt the back flow reaction device of the system of opening wide or the low-temperature hydrothermal reaction unit of enclosed system, at 100～180 ℃ of temperature range reaction 1～12h;
(3) Separation ﹠ Purification: specifically comprise 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 salt-mixture acid solution, aqueous hydrogen peroxide solution, alkali lye and water, and the volume parts ratio of each component is: V
Titaniferous salt-mixture acid solution: 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 Ti of tetravalence attitude in the titaniferous salt-mixture acid solution
4+The Ti of ion and three valence states
3+The ratio of the amount of substance of ion is 0＜
Total amount of substance concentration of contained titanium elements is 1.0～5.0mol/l;
Hydrogen peroxide is the pure or chemical pure aqueous hydrogen peroxide solution of commercially available analysis, 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;
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 the amount of substance concentration of described alkali lye is 1.5～2.5mol/l.
4. according to the method for claim 1 or 2 described synthesizing soluble titanium dioxide nano crystal in low temperature, it is characterized in that, described titaniferous salt-mixture acid solution is mixed by titanium tetrachloride and titanium trichloride hydrochloric acid solution, is perhaps made by titanium sponge and excessive titanium tetrachloride, hydrochloric acid reaction.
5. according to the method for the described synthesizing soluble titanium dioxide nano crystal in low temperature of claim 1, it is characterized in that reaction temperature is 110～150 ℃, the reaction time is 3～8h.
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| CN101844806B (en) * | 2010-06-09 | 2012-02-01 | 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 |
| CN103553124B (en) * | 2013-11-08 | 2015-03-11 | 中国科学技术大学 | Method for preparing blue titanium dioxide |
| 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 |
| CN107799654B (en) * | 2017-09-15 | 2020-10-09 | 华南师范大学 | High-efficiency planar 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 |
| 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 |
| 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 |
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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 |
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