CN1331760C - Process for preparing nano-TiO2 precursor - Google Patents
Process for preparing nano-TiO2 precursor Download PDFInfo
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- CN1331760C CN1331760C CNB2005100514453A CN200510051445A CN1331760C CN 1331760 C CN1331760 C CN 1331760C CN B2005100514453 A CNB2005100514453 A CN B2005100514453A CN 200510051445 A CN200510051445 A CN 200510051445A CN 1331760 C CN1331760 C CN 1331760C
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Abstract
The present invention belongs to the preparation field of nanometer materials, particularly to a preparation method of a precursor of nanometer titanium dioxide. The method comprises the following steps that titanium sulfate is added into water to be stirred until complete dissolution, and a solution A with the titanium sulfate concentration more than 1 mol/ L is formed; then, acetylacetone is added into the solution A to be stirred for 0.5 to 24 hours at the temperature of 15 to 75 DEG C to form a dark brown solution B; a mole ratio of the quantity of the added acetylacetone to the titanium sulfate of the solution A is 2 to 5; finally, the solution B is added to an acetone solution as the acetone solution is stirred; the volume ratio of the solution B to the acetone solution is less than 0.5; the mixed solution is stirred continuously to obtain light yellow granules which are then naturally aired or baked to obtain the precursor of the nanometer titanium dioxide of the present invention. The method of the present invention has the advantages of easy acquirement, low cost and easy storage and transportation of raw materials, moderate hydrolytic speed of the prepared precursor of the nanometer titanium dioxide, and easy control of the reaction condition for preparing the titanium dioxide; the precursor of the nanometer titanium dioxide can dissolve in organic solvent, such as ethanol, etc., and the method is suitable for preparing composite materials of titanium dioxide/ organic matrix.
Description
Technical field
The present invention relates to belong to the preparation field of nano material, specifically relate to a kind of preparation method of nano-TiO 2 precursor.
Background technology
Nano titanium oxide is as a kind of important inorganic functional material, because of it has high photocatalytic activity, good weathering resistance, erosion resistance, intensive ultraviolet screening ability and can produce many particular performances such as peculiar colour effect, and enjoy people's attention at numerous areas such as wastewater treatment, sun-proof skin care, coating and automotive industry, transmitter, function ceramics, photocatalysts.In addition, titanium dioxide/organic matrix nano composite material can with many feature set of inorganic, organic, nanoparticle have many specific performances, is just becoming one of research focus of people.
Nano titanium oxide still is that the preparation of titanium dioxide/organic matrix nano composite material all will be selected suitable TiO 2 precursor earlier.Nano-TiO 2 precursor commonly used mainly includes organic titanate, titanium tetrachloride and titanium sulfate.But organic titanate and titanium tetrachloride are liquid phase, and and easy deliquescence, make that the storage of raw material and transportation are very inconvenient; Organic titanate is on the high side simultaneously, causes the cost of product higher, is unfavorable for the popularization of suitability for industrialized production; In addition, the hydrolysis rate of organic titanate and titanium tetrachloride is too fast, is unfavorable for the control of experiment condition.Advantages such as and though titanium sulfate has unsuitable deliquescence, and are cheap, it can only be dissolved in the water, and can not directly be dissolved in the organic solvent, and this has just limited its application aspect preparation titanium dioxide/organic matrix matrix material.
Summary of the invention
The objective of the invention is to overcome in the existing nano-TiO 2 precursor the easy deliquescence of organic titanate and titanium tetrachloride and be unfavorable for that accumulating, price height cause the cost height, hydrolysis rate is too fast and be unfavorable for the control of experiment condition; Titanium sulfate can not directly be dissolved in the organic solvent and limit the defective of its application, thus provide a kind of raw material should get, with low cost, be easy to accumulating, and the preparation method of the moderate nano-TiO 2 precursor of hydrolysis rate.
The objective of the invention is to realize by the following technical solutions:
The invention provides a kind of preparation method of nano-TiO 2 precursor, comprise the steps:
1) titanium sulfate is added to the water, is stirred to dissolving fully, form the solution A of titanium sulfate concentration greater than 1mol/L;
Described water can be more purified water such as distilled water, redistilled water and deionized water;
The saturated solution of described solution A preferably sulfuric acid titanium;
2) in solution A, add methyl ethyl diketone, stir 0.5～24h down, form brown solution B at 15～75 ℃; The add-on of methyl ethyl diketone and the mol ratio of the titanium sulfate in the solution A are 2～5;
3) under condition of stirring solution B is joined acetone soln, the volume ratio of solution B and acetone then has yellow particle to generate less than 0.5 at once, continues to stir 1～12h, with above-mentioned solution filtration or centrifugal, obtains light yellow particle;
The weight content of water is 0.1～1% in the described acetone soln;
4) the light yellow particle that step 3) is obtained, natural air drying, or under 40～80 ℃, dry 1～10h, obtain nano-TiO 2 precursor of the present invention.
Compared with prior art, the nano-TiO 2 precursor of method preparation provided by the invention has following advantage:
1. this nano-TiO 2 precursor is from titanium sulfate, and raw material should get, and is with low cost.
2. this nano-TiO 2 precursor preparation technology flow process is simple, is suitable for suitability for industrialized production.
3. this nano-TiO 2 precursor is solid, is unsuitable for deliquescence, is easy to store and transportation.
4. this nano-TiO 2 precursor hydrolysis rate is moderate, and reaction conditions is easy to control when preparation titanium dioxide.
5. this nano-TiO 2 precursor directly can obtain the titania nanoparticles of particle diameter at 100～500nm through high-temperature calcination.
6. this nano-TiO 2 precursor directly is dissolved in the water, and need not any processing can obtain particle diameter is about 10nm, the Ti of no agglomeration (OH)
4Particle.
7. this nano-TiO 2 precursor can be dissolved among the organic solvents such as ethanol, is suitable for the preparation of titanium dioxide/organic matrix matrix material.
Description of drawings
Fig. 1 is the TEM photo of the nano-TiO 2 precursor of the embodiment of the invention 1 preparation;
Fig. 2 is the thermal analysis curve of the nano-TiO 2 precursor of the embodiment of the invention 1 preparation;
Fig. 3 is the XRD curve of nano-TiO 2 precursor after 600 ℃ of calcinings of the embodiment of the invention 1 preparation;
Fig. 4 is the direct Ti that obtains soluble in water (OH) of nano-TiO 2 precursor of the embodiment of the invention 1 preparation for using
4Nano particle.
Embodiment
Embodiment 1.
The titanium sulfate (0.078mol) of 10g is joined in the 15ml distilled water, be stirred to dissolving fully, form solution A.The methyl ethyl diketone that adds 20ml (0.2mol) in solution A stirs 24h at 15 ℃, forms brown solution B.Under condition of stirring, solution B 5ml slowly joined the 1L water content and be 1% acetone soln, then have yellow particle to generate at once, continue to stir 12h.Above-mentioned solution is filtered, and the light yellow particle natural air drying with obtaining obtains nano-TiO 2 precursor of the present invention.
With transmission electron microscope (TEM) test, as shown in Figure 1, this nano-TiO 2 precursor is a spheroidal particle, and its powder granularity is in 100～500nm scope.
This nano-TiO 2 precursor is carried out heat analyzes, its TG-DTA curve as shown in Figure 2, when temperature reached 500 ℃, this nano-TiO 2 precursor decomposed fully.
With this nano-TiO 2 precursor 600 ℃ of calcining 2h in retort furnace, can obtain spherical dispersive titania nanoparticles, the particle diameter of this titania nanoparticles is in the scope of 100～500nm, its XRD curve as shown in Figure 3, as seen this titania nanoparticles is a Detitanium-ore-type.
This nano-TiO 2 precursor 10g is dissolved in the 1L deionized water, stirs 0.5～2h, need not be any other processing, can obtain the Ti (OH) of white
4Particle.Its SEM photo as shown in Figure 4, the Ti that obtains (OH)
4The particle diameter of nano particle is about 10nm, and no agglomeration has good dispersiveness.This particle is calcined under differing temps, also can be obtained titania nanoparticles.
Embodiment 2.
The titanium sulfate (0.1mol) of 12.8g is joined in the 10ml redistilled water, be stirred to dissolving fully, form solution A.The methyl ethyl diketone that adds 0.2mol in solution A stirs 0.5h at 75 ℃, forms brown solution B.Under condition of stirring, solution B 50ml slowly joined the 1L water content and be 0.1% acetone soln, then have yellow particle to generate at once, continue to stir 1h.With above-mentioned solution centrifugal, the light yellow particle that obtains is dried 10h at 40 ℃, obtain nano-TiO 2 precursor of the present invention.
Embodiment 3.
The titanium sulfate (0.1mol) of 12.8g is joined in the 100ml deionized water, be stirred to dissolving fully, form solution A.The methyl ethyl diketone that adds 0.5mol in solution A stirs 12h at 50 ℃, forms brown solution B.Under condition of stirring, solution B 200ml slowly joined the 1L water content and be 0.5% acetone soln, then have yellow particle to generate at once, continue to stir 5h.With above-mentioned solution centrifugal, the light yellow particle that obtains is dried 1h at 80 ℃, obtain nano-TiO 2 precursor of the present invention.
Claims (5)
1, a kind of preparation method of nano-TiO 2 precursor comprises the steps:
1) titanium sulfate is added to the water, is stirred to dissolving fully, form the solution A of titanium sulfate concentration greater than 1mol/L;
2) in solution A, add methyl ethyl diketone, stir 0.5～24h down, form brown solution B at 15～75 ℃; The add-on of methyl ethyl diketone and the mol ratio of the titanium sulfate in the solution A are 2～5;
3) under condition of stirring solution B is joined acetone soln, the volume ratio of solution B and acetone then has yellow particle to generate less than 0.5 at once, continues to stir 1～12h, with above-mentioned solution filtration or centrifugal, obtains light yellow particle;
4) the light yellow particle that step 3) is obtained, natural air drying or oven dry obtain nano-TiO 2 precursor.
2, the preparation method of nano-TiO 2 precursor as claimed in claim 1 is characterized in that: described water is distilled water, redistilled water or deionized water.
3, the preparation method of nano-TiO 2 precursor as claimed in claim 1 is characterized in that: described solution A is the saturated solution of titanium sulfate.
4, the preparation method of nano-TiO 2 precursor as claimed in claim 1 is characterized in that: the weight content of water is 0.1～1% in the described acetone soln.
5, the preparation method of nano-TiO 2 precursor as claimed in claim 1 is characterized in that: the oven dry described in the step 4) is to carry out 1～10h under 40～80 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100514453A CN1331760C (en) | 2005-03-04 | 2005-03-04 | Process for preparing nano-TiO2 precursor |
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| CNB2005100514453A CN1331760C (en) | 2005-03-04 | 2005-03-04 | Process for preparing nano-TiO2 precursor |
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| CN1827529A CN1827529A (en) | 2006-09-06 |
| CN1331760C true CN1331760C (en) | 2007-08-15 |
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| CNB2005100514453A Expired - Fee Related CN1331760C (en) | 2005-03-04 | 2005-03-04 | Process for preparing nano-TiO2 precursor |
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| CN106280251A (en) * | 2016-08-10 | 2017-01-04 | 袁春华 | A kind of preparation method of LED encapsulation nano composite material |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1295977A (en) * | 2000-12-19 | 2001-05-23 | 中国科学院上海硅酸盐研究所 | Simple method for preparing titanium dioxide collosol |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1295977A (en) * | 2000-12-19 | 2001-05-23 | 中国科学院上海硅酸盐研究所 | Simple method for preparing titanium dioxide collosol |
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