CN102718255B

CN102718255B - Preparation method of titanium dioxide hollow nano structure

Info

Publication number: CN102718255B
Application number: CN201210202353.0A
Authority: CN
Inventors: 唐华; 李文静; 李长生
Original assignee: Jiangsu University
Current assignee: Jiangsu University
Priority date: 2012-06-19
Filing date: 2012-06-19
Publication date: 2014-07-30
Anticipated expiration: 2032-06-19
Also published as: CN102718255A

Abstract

The invention relates to nano titanium dioxide, particularly a preparation method of titanium dioxide hollow nano structures. According to the invention, ammonium fluotitanate ((NH4)2TiF6) is used as a precursor, silicon dioxide (SiO2) microspheres are used as a template, and the concentration of the ammonium fluotitanate ((NH4)2TiF6), the hydrothermal time and the silicon dioxide (SiO2) size are regulated to control the size of the hollow microspheres and the thickness of the shell. Thus, under relatively low temperature conditions, the titanium dioxide SiO2 hollow nano microsphere structures of which the sizes and the structures have high isotonicity can be massively synthesized, thereby solving the problem of overwide size distribution range in the past silicon dioxide synthesis process. The method provided by the invention is simple and easy to control, has the advantage of low cost, is suitable for industrial production, and can control the size of the reaction product through reaction conditions.

Description

The preparation method that a kind of titanium dioxide is hollow nanostructured

Technical field

The present invention relates to nano titanium oxide, particularly, is the hollow nanostructured preparation method of a kind of titanium dioxide.

Background technology

Because the nano material of nucleocapsid structure is boundless in the application prospect in the fields such as catalysis, chromatography, bioactive agents protection, wastewater treatment, macromole slow-releasing system, make controlledly to prepare core-shell structured nanomaterials and become the focus of research; Titanium dioxide (TiO ₂) be a kind of more Multifunctional fine inorganic materials of studying, also be important pottery, semi-conductor and catalytic material, again because its performance with uniquenesses such as good weather resisteant, chemical resistance, chemical stability compared with high, nontoxicity, photosensitivity is widely used in the fields such as coating, dielectric materials, ink, papermaking; In recent years, due to titanium dioxide (TiO ₂) multiphase photocatalysis interaction energy effectively by degradable the organic pollutant in large G&W be carbonic acid gas, water and mineral acid, both there is no secondary pollution, can utilize again sun power, be that one meets Sustainable development needs, and have sewage and the air handling new technology of broad prospect of application; Titanium dioxide is due to its nontoxic, high chemical stability, low cost, thereby is widely used the section's material as core-shell particles and hollow structure; Permitted eurypalynous titanium dioxide hollow sphere material although there is diverse ways to prepare, have technical process complexity, be difficult for expanded reproduction, the problem such as quality product has much room for improvement; Current existing synthetic method is mainly by template, comprises hard template (for example, inorganic metal and polymeric colloid particle) and soft template (for example, the molecular template of tensio-active agent and polymkeric substance), and without template; Hard template method forms nucleocapsid structure and tiny balloon on template particles surface by self-assembly method or sol-gel method layer by layer conventionally, and the former complex process need relate to and repeatedly use the polyelectrolyte with xenogenesis electric charge; And sol-gel method is difficult to control the generating rate of Titanium dioxide nanoparticle, can cause a large amount of gatherings of offspring, affect the dispersiveness of microballoon; Synthesizing without template is to make nucleocapsid structure or tiny balloon by hydro-thermal or solvent-thermal method one step, although the method technique is simple, quick, is difficult to overcome product distribution of sizes wide, the shortcoming that impurity is more; Therefore, contriver seeks low cost always, simple effective method is prepared titanium dioxide hollow Nano micro-sphere structure.

Summary of the invention

The object of the present invention is to provide a kind of titanium dioxide hollow nanostructured and preparation method thereof, the method can solve the problem of the hollow nanostructured pattern of titanium dioxide and distribution of sizes, the hollow nanostructured size ratio of titanium dioxide preparing is more even, and particle size distribution range is between 100 ~ 400nm.

Above-mentioned purpose is achieved by the following technical solution: with ammonium titanium fluoride ((NH ₄) ₂tiF ₆) be precursor, with silicon-dioxide (SiO ₂) microballoon is template, by regulating ammonium titanium fluoride ((NH ₄) ₂tiF ₆) concentration, hydro-thermal time and silicon-dioxide (SiO ₂) size control the size of tiny balloon and the thickness of shell, thereby under relatively low temperature condition, synthetic size and structure all have high hollow nanostructured with tropism's titanium dioxide in a large number.

Particularly, comprise the steps:

(1) silica dioxide granule that is 85 ~ 95nm by even particle size distribution, median size adds ammonium titanium fluoride ((NH ₄) ₂tiF ₆) in the aqueous solution; Silicon-dioxide is 1:2-1:4 with the ratio of the amount of substance of ammonium titanium fluoride;

(2) by even above-mentioned solution stirring, 60-80 DEG C of insulation 6 ~ 24h;

(3) product stirring being completed cleans suction filtration with distilled water or ethanol and collects;

(4) product of collecting is dry;

(5) product is calcined to 2h at 450 ~ 550 DEG C, obtain titanium dioxide hollow Nano micro-sphere structure.

Described ammonium titanium fluoride ((NH ₄) ₂tiF ₆) concentration of the aqueous solution is 0.02 ~ 0.08mol/L.

The inventive method technique is simple, with low cost, control the pattern of product by the restriction of spherical template, thereby under relatively low temperature condition, having synthesized in a large number size and structure all has high hollow nanostructured with tropism's titanium dioxide, the distribution of sizes scope in synthesis of titanium dioxide microballoon process in the past of having solved is excessive, the problem of complex process, the hollow nanostructured epigranular of titanium dioxide for preparing, and average particle size range is 100 ~ 400nm.

Brief description of the drawings

The scanning electron microscope picture that Fig. 1 is the silica template ball that uses in the present invention;

Fig. 2 is the scanning electron microscope picture of the spherical tio2 nano hollow structure of embodiment 1;

Fig. 3 is the x ray diffraction picture of the spherical tio2 nano hollow structure of embodiment 1;

Fig. 4 is the scanning electron microscope picture of the spherical tio2 nano hollow structure of embodiment 2;

Fig. 5 is the scanning electron microscope picture of the spherical tio2 nano hollow structure of embodiment 3;

Fig. 6 is the transmission electron microscope picture of the spherical tio2 nano hollow structure of embodiment 4.

Embodiment

Further describe the present invention by embodiment below, as known by the technical knowledge, the present invention also can describe by other the scheme that does not depart from the technology of the present invention feature, and therefore changes within the scope of the present invention all or that be equal in the scope of the invention are all included in the invention.

embodiment 1:

By even particle size distribution, silicon-dioxide (as Fig. 1) particle that median size is 85 ~ 95nm adds 40ml ammonium titanium fluoride ((NH ₄) ₂tiF ₆) in the aqueous solution, silicon-dioxide is 1:2 with the ratio of the amount of substance of ammonium titanium fluoride; Insulation 24h by above-mentioned solution at 60 DEG C, cleans suction filtration by distilled water for product or ethanol and collects, and by product dry 8h at the temperature of 60 DEG C, and then at 450 DEG C, calcines 2h and obtains titanium dioxide hollow Nano micro-sphere structure.

The present embodiment product (titanium dioxide hollow Nano micro-sphere structure) is carried out to electron-microscope scanning to observe its microscopic appearance, and result as shown in Figure 2 products therefrom particle diameter is about 100nm left and right; The present embodiment product is entered to XRD test, and result is corresponding with standard P DF card, and particulate component is pure titanium dioxide, as shown in Figure 3.

embodiment 2:

By even particle size distribution, silicon-dioxide (as Fig. 1) particle that median size is 85 ~ 95nm adds 40ml ammonium titanium fluoride ((NH ₄) ₂tiF ₆) in the aqueous solution, silicon-dioxide is 1:3 with the ratio of the amount of substance of ammonium titanium fluoride; Above-mentioned solution is incubated to 6h under the condition of 80 DEG C, distilled water for product or ethanol is cleaned to suction filtration and collect, by product dry 8h at the temperature of 60 DEG C, and then at 500 DEG C, calcine 2h and obtain titanium dioxide hollow Nano micro-sphere structure.

The present embodiment product (titanium dioxide hollow Nano micro-sphere structure) is carried out to electron-microscope scanning to observe its microscopic appearance, and result as shown in Figure 4 products therefrom particle diameter is about 105nm left and right.

embodiment 3:

By even particle size distribution, silicon-dioxide (as Fig. 1) particle that median size is 85 ~ 95nm adds 40ml ammonium titanium fluoride ((NH ₄) ₂tiF ₆) in the aqueous solution, silicon-dioxide is 1:4 with the ratio of the amount of substance of ammonium titanium fluoride; By above-mentioned solution lower insulation 12h under the condition of 70 DEG C, distilled water for product or ethanol are cleaned to suction filtration and collect, by product dry 8h at the temperature of 60 DEG C, and then at 550 DEG C, calcine 2h and obtain titanium dioxide hollow Nano micro-sphere structure.

The present embodiment product (titanium dioxide hollow Nano micro-sphere structure) is carried out to sem test to observe its microscopic appearance, and as shown in Figure 5, products therefrom particle diameter is about the ball shape structure of 300nm left and right to result.

embodiment 4:

By even particle size distribution, silicon-dioxide (as Fig. 1) particle that median size is 85 ~ 95nm adds 40ml ammonium titanium fluoride ((NH ₄) ₂tiF ₆) in the aqueous solution, silicon-dioxide is 1:2 with the ratio of the amount of substance of ammonium titanium fluoride; Above-mentioned solution is incubated to 12h under the condition of 70 DEG C, distilled water for product or ethanol is cleaned to suction filtration and collect, by product dry 8h at the temperature of 60 DEG C, and then at 500 DEG C, calcine 2h and obtain titanium dioxide hollow Nano micro-sphere structure.

The present embodiment product (titanium dioxide hollow Nano micro-sphere structure) is carried out to transmission electron microscope scanning to observe its microscopic appearance, and as shown in Figure 6, products therefrom particle diameter is about the hollow ball shape structure of 350nm left and right to result, and shell thickness is about 100nm.

Claims

1. the hollow nanostructured preparation method of titanium dioxide, is characterized in that comprising the steps:

(4) product of collecting is dry;

(5) product is calcined to 2h at 450 ~ 550 DEG C, obtain titanium dioxide hollow Nano micro-sphere structure;

2. the hollow nanostructured preparation method of a kind of titanium dioxide as claimed in claim 1, is characterized in that: the particle size distribution range of described titanium dioxide hollow Nano microballoon is between 100 ~ 400nm.