CN103950975B - Method for preparing hollow rutile micron titanium dioxide - Google Patents
Method for preparing hollow rutile micron titanium dioxide Download PDFInfo
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- CN103950975B CN103950975B CN201410153916.0A CN201410153916A CN103950975B CN 103950975 B CN103950975 B CN 103950975B CN 201410153916 A CN201410153916 A CN 201410153916A CN 103950975 B CN103950975 B CN 103950975B
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Abstract
The invention relates to a method for preparing a hollow rutile micron titanium dioxide and belongs to the field of fine chemical engineering. The method comprises the following steps: dropwise adding tetrabutyl titanate to a mixed solution of distilled water and concentrated hydrochloric acid; adding a polyhydroxy organic matter to the mixed solution, carrying out hydrothermal reaction, filtering, washing by the distilled water, drying and calcining to obtain a target product. The wall thickness of the power is 100-150nm. An X-ray powder diffraction (XRD) spectrum shows that the powder is rutile TiO2, a scanning electron microscope (SEM) scanning image shows that powder is of a hollow rutile micron titanium dioxide structure of which the surface is combined by nanorods, and a transverse electric and magnetic field (TEM) transmission image shows that the powder is of a hollow structure. The method is simple in process and safe to operate, generates less environmental pollutants, can produce stable-quality hollow rutile micron titanium dioxide and is applicable to massive production.
Description
Technical field
The present invention relates to a kind of method preparing hollow rutile-type hum silicon dioxide titanium, belong to field of fine chemical.
Background technology
Titanium dioxide is a kind of special white inorganic functional materials.Due to titanium dioxide stable in properties, nontoxic, reacting with other materials hardly under normal temperature, is a kind of intermediate oxide of slant acidity, therefore it as photocatalyst, sterilization material, solar cell raw material and antiultraviolet material etc., can be with a wide range of applications.
At present, prepared the titanic oxide material of various pattern, wherein the titanium dioxide of hollow structure is owing to having the character such as unique low density, photocatalysis performance and photoelectric properties, therefore can be widely used in photonic crystal, catalyzer and sorbent material etc.But on this basis, in order to improve the catalytic performance of titanium dioxide and absorption property etc. further, some researchists get down to the titanium dioxide powder that preparation has special hollow structure.
There is multiple method can prepare the titanium dioxide powder with hollow structure, comprise template, hydro-thermal-solvent-thermal method, ultrasonic method and LBL self-assembly method etc.Have in the method for the target product of hollow structure in these preparations, there is due to hydrothermal method the advantages such as easy and simple to handle, controllability, cost are low and the product pellet purity prepared is high, good dispersity, good crystalline, be therefore hopeful most to realize batch production.
Summary of the invention
The object of this invention is to provide the method for a kind of preparation surface simply by the hollow rutile-type hum silicon dioxide titanium of homogeneous nanometer rod close-packed arrays, the method technique is simple, and operational safety, environmental pollutant are few, steady quality, can be applicable to scale operation.
For solving the problems of the technologies described above, the present invention realizes like this.
A kind of method preparing hollow rutile-type hum silicon dioxide titanium, it is characterized in that, comprise the following steps: tetrabutyl titanate is dropwise joined in the mixing solutions of distilled water and concentrated hydrochloric acid, in above-mentioned mixed solution, add poly-hydroxy organism, hydro-thermal reaction, filter, distilled water wash, drying, calcining, obtains object product.
As a kind of preferred version, poly-hydroxy organism of the present invention is cyclodextrin or polyvinylpyrrolidone.
Further, concentrated hydrochloric acid consumption of the present invention is 2.5 ~ 3.5:1 with the ratio of tetrabutyl titanate volume.
Further, the temperature of hydro-thermal reaction of the present invention can select 100 DEG C ~ 180 DEG C.
Further, the time of hydro-thermal reaction of the present invention is 1 h ~ 4 h.
Further, in retort furnace of the present invention, calcining temperature is 350 DEG C ~ 550 DEG C.
Further, in retort furnace of the present invention, calcination time is 2 h ~ 4 h.
The present invention adopts hydrothermal method, and tetrabutyl titanate, as the precursor preparing target product, prepares the hollow rutile-type hum silicon dioxide titanium material of surface by homogeneous nanometer rod close-packed arrays by changing experiment condition.
Concrete preparation process is as follows.
Tetrabutyl titanate is dropwise joined in the mixing solutions of distilled water and concentrated hydrochloric acid, the poly-hydroxy organism powder little over amount is added in mixed solution, hydro-thermal reaction, filter, distilled water wash repeatedly, drying, calcining, finally obtains the hollow rutile-type hum silicon dioxide titanium of surface by homogeneous nanometer rod close-packed arrays.
Concrete preparation condition is as follows.
1, the ratio of concentrated hydrochloric acid and the volume of tetrabutyl titanate: 2.5 ~ 3.5:1.
2, hydrothermal temperature and the time: the temperature of hydro-thermal reaction is 100 DEG C ~ 180 DEG C, and the time is 1 h ~ 4 h.
3, wash, dry: washing is to reduce the ion of powder surface and weakening the color of powder; Dry object is only the moisture of removing powder surface.
4, calcining temperature and the time: calcining temperature is 350 DEG C ~ 550 DEG C, calcination time is 2 h ~ 4 h.
Best mode for carrying out the invention is.
1 ~ 3 mL tetrabutyl titanate is dropwise joined (V in the mixed solution of 20 mL distilled water and concentrated hydrochloric acid
concentrated hydrochloric acid: V
tetrabutyl titanate=2.5 ~ 3.5:1), be stirred to mixed solution clarification, in above-mentioned mixed solution, add cyclodextrin, continue to stir, be transferred to by mixed solution in reactor, controlling temperature of reaction is 100 DEG C ~ 180 DEG C, and the reaction times is 1 h ~ 4 h, afterwards, filter, washing is for several times, dry, powder is put into retort furnace 350 DEG C ~ 550 DEG C calcining 2 h ~ 4 h, obtain the hollow rutile-type hum silicon dioxide titanium of surface by homogeneous nanometer rod close-packed arrays.
Present invention process is simple, and operational safety, environmental pollutant are few, steady quality, can be applicable to scale operation.Powder wall thickness 100-150 nm of the present invention.XRD figure spectrum display powder is rutile TiO
2.SEM scan image display morphology microstructure is the hollow rutile-type hum silicon dioxide titanium structure that surface is combined by nanometer rod.TEM transmission image display powder inside is hollow structure.
Compared with prior art, the present invention has following features.
1, preparation process involved in the present invention is simple, adopts hydrothermal method.Using tetrabutyl titanate as the precursor preparing target product, tetrabutyl titanate is joined in the mixed solution of distilled water and concentrated hydrochloric acid, stir, afterwards poly-hydroxy organism powder is added wherein, stir, be transferred in reactor, heating for some time, obtain the mixing solutions of intense violet color powder, filter, washing is for several times, dry, be placed in retort furnace to calcine, finally obtain the hollow rutile-type hum silicon dioxide titanium of surface by homogeneous nanometer rod close-packed arrays.
2, the surface adopting the inventive method to prepare has qualitative absolute predominance by the hollow rutile-type hum silicon dioxide titanium of homogeneous nanometer rod close-packed arrays, is greater than 99 % by the content of XRD test result known hollow rutile-type hum silicon dioxide titanium.
3, found by scanning electron microscope (SEM) test, its pattern of rutile titanium dioxide adopting the inventive method to prepare is the hollow structure of surface by homogeneous nanometer rod close-packed arrays, this means that this titanium dioxide has larger specific surface area.
Accompanying drawing explanation
Below in conjunction with the drawings and specific embodiments, the invention will be further described.Protection scope of the present invention is not only confined to the statement of following content.
Fig. 1-1 is micron hollow TiO prepared by the inventive method
2special spheroid calcining cross-reference schematic diagram (before A section burning).
Fig. 1-2 is micron hollow TiO prepared by the inventive method
2special spheroid calcining cross-reference schematic diagram (B section is burnt rear).
Fig. 2 is micron hollow TiO prepared by the inventive method
2the XRD figure picture of special spheroid.
Fig. 3-1 is micron hollow TiO prepared by the inventive method
2the SEM image of special spheroid.
Fig. 3-2 is micron hollow TiO prepared by the inventive method
2the SEM image of special spheroid.
Fig. 4-1 is micron hollow TiO prepared by the inventive method
2the TEM image of special spheroid.
Fig. 4-2 is micron hollow TiO prepared by the inventive method
2the TEM image of special spheroid.
Embodiment
Be described further technical scheme of the present invention below in conjunction with embodiment, following examples do not form limitation of the invention.
Embodiment 1.
1 mL tetrabutyl titanate is dropwise joined (concentrated hydrochloric acid 3 mL) in the mixed solution of 20 mL distilled water and concentrated hydrochloric acid, be stirred to mixed solution clarification, 0.04 g cyclodextrin powder is added in above-mentioned mixed solution, continue to stir, mixed solution is transferred in reactor, controlling temperature of reaction is 140 DEG C, reaction times is 2 h, afterwards, filter, washing is for several times, dry, powder is put into retort furnace 450 DEG C calcining 2 h, obtain the hollow rutile-type hum silicon dioxide titanium of surface by homogeneous nanometer rod close-packed arrays.
Embodiment 2.
2 mL tetrabutyl titanates are dropwise joined (concentrated hydrochloric acid 5 mL) in the mixed solution of 20 mL distilled water and concentrated hydrochloric acid, be stirred to mixed solution clarification, 7.7 g cyclodextrin powder are added in above-mentioned mixed solution, continue to stir, mixed solution is transferred in reactor, controlling temperature of reaction is 160 DEG C, reaction times is 2 h, afterwards, filter, washing is for several times, dry, powder is put into retort furnace 450 DEG C calcining 2 h, obtain the hollow rutile-type hum silicon dioxide titanium of surface by non-homogeneous nanometer rod close-packed arrays.
Embodiment 3.
3 mL tetrabutyl titanates are dropwise joined (concentrated hydrochloric acid 10 mL) in the mixed solution of 20 mL distilled water and concentrated hydrochloric acid, be stirred to mixed solution clarification, 11.6 g cyclodextrin powder are added in above-mentioned mixed solution, continue to stir, mixed solution is transferred in reactor, controlling temperature of reaction is 180 DEG C, reaction times is 2 h, afterwards, filter, washing for several times, dry, powder is put into retort furnace 450 DEG C calcining 2 h, obtain single bar-shaped rutile titanium dioxide (part) and surface by the hollow rutile-type hum silicon dioxide titanium of non-homogeneous nanometer rod close-packed arrays.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (3)
1. prepare the method for hollow rutile-type hum silicon dioxide titanium for one kind, it is characterized in that, comprise the following steps: 1 mL tetrabutyl titanate is dropwise joined in the mixed solution of 20 mL distilled water and concentrated hydrochloric acid, concentrated hydrochloric acid 3 mL, be stirred to mixed solution clarification, 0.04 g cyclodextrin powder is added in above-mentioned mixed solution, continue to stir, mixed solution is transferred in reactor, controlling temperature of reaction is 140 DEG C, reaction times is 2 h, afterwards, filter, washing for several times, dry, powder is put into retort furnace 450 DEG C calcining 2 h, obtain the hollow rutile-type hum silicon dioxide titanium of surface by homogeneous nanometer rod close-packed arrays, the content of hollow rutile-type hum silicon dioxide titanium is greater than 99 %.
2. prepare the method for hollow rutile-type hum silicon dioxide titanium for one kind, it is characterized in that, comprise the following steps: 2 mL tetrabutyl titanates are dropwise joined in the mixed solution of 20 mL distilled water and concentrated hydrochloric acid, concentrated hydrochloric acid 5 mL, be stirred to mixed solution clarification, 7.7 g cyclodextrin powder are added in above-mentioned mixed solution, continue to stir, mixed solution is transferred in reactor, controlling temperature of reaction is 160 DEG C, reaction times is 2 h, afterwards, filter, washing for several times, dry, powder is put into retort furnace 450 DEG C calcining 2 h, obtain the hollow rutile-type hum silicon dioxide titanium of surface by non-homogeneous nanometer rod close-packed arrays, the content of hollow rutile-type hum silicon dioxide titanium is greater than 99 %.
3. prepare the method for hollow rutile-type hum silicon dioxide titanium for one kind, it is characterized in that, comprise the following steps: 3 mL tetrabutyl titanates are dropwise joined in the mixed solution of 20 mL distilled water and concentrated hydrochloric acid, concentrated hydrochloric acid 10 mL, be stirred to mixed solution clarification, 11.6 g cyclodextrin powder are added in above-mentioned mixed solution, continue to stir, mixed solution is transferred in reactor, controlling temperature of reaction is 180 DEG C, reaction times is 2 h, afterwards, filter, washing for several times, dry, powder is put into retort furnace 450 DEG C calcining 2 h, obtain the single bar-shaped rutile titanium dioxide of part and the hollow rutile-type hum silicon dioxide titanium of surface by non-homogeneous nanometer rod close-packed arrays, the content of hollow rutile-type hum silicon dioxide titanium is greater than 99 %.
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| CN104817106B (en) * | 2015-05-07 | 2017-03-15 | 中国科学院合肥物质科学研究院 | TiO2The solvent process for thermosynthesizing of hollow-core construction sub-micron ball |
| CN104961157A (en) * | 2015-07-03 | 2015-10-07 | 燕山大学 | Synthetic method of rutile TiO2 |
| CN115806313B (en) * | 2022-12-26 | 2024-07-16 | 常州纳欧新材料科技有限公司 | Preparation method of micron-sized rutile titanium dioxide nanocrystalline aggregate |
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| CN101830511A (en) * | 2010-05-18 | 2010-09-15 | 中国科学院上海硅酸盐研究所 | Preparation method of rutile phase vanadium dioxide hollow sphere and application |
| CN102701276A (en) * | 2012-05-29 | 2012-10-03 | 常州大学 | Hollow TiO2 microsphere synthesizing method |
| CN102863020A (en) * | 2012-10-15 | 2013-01-09 | 浙江大学 | Preparation method of hollow titanium dioxide material |
| CN103553127A (en) * | 2013-10-22 | 2014-02-05 | 渤海大学 | Method for preparing anatase type titanium dioxide nano tube |
| CN103626227A (en) * | 2013-11-25 | 2014-03-12 | 国家纳米科学中心 | Rutile type titanium dioxide micro-nano material and preparation method and application thereof |
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Patent Citations (5)
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| CN101830511A (en) * | 2010-05-18 | 2010-09-15 | 中国科学院上海硅酸盐研究所 | Preparation method of rutile phase vanadium dioxide hollow sphere and application |
| CN102701276A (en) * | 2012-05-29 | 2012-10-03 | 常州大学 | Hollow TiO2 microsphere synthesizing method |
| CN102863020A (en) * | 2012-10-15 | 2013-01-09 | 浙江大学 | Preparation method of hollow titanium dioxide material |
| CN103553127A (en) * | 2013-10-22 | 2014-02-05 | 渤海大学 | Method for preparing anatase type titanium dioxide nano tube |
| CN103626227A (en) * | 2013-11-25 | 2014-03-12 | 国家纳米科学中心 | Rutile type titanium dioxide micro-nano material and preparation method and application thereof |
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