CN104649319A - Method for preparing TiO2(B) nano-sponge - Google Patents
Method for preparing TiO2(B) nano-sponge Download PDFInfo
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- CN104649319A CN104649319A CN201510092187.7A CN201510092187A CN104649319A CN 104649319 A CN104649319 A CN 104649319A CN 201510092187 A CN201510092187 A CN 201510092187A CN 104649319 A CN104649319 A CN 104649319A
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- tio
- nanosponges
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- tetrabutyl titanate
- sponge
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Abstract
The invention relates to a method for preparing TiO2(B) nano-sponge and solves the technical problems of the traditional preparation method that relies on high-temperature calcination, has complex preparation and weak crystallization of the product. The method comprises the following steps: taking water as solvent, adding glycolic acid and tetrabutyl titanate, after mixing and stirring, putting in a high pressure reaction kettle to heat up to 120-180 DEG C, reacting for 6-18 hours, washing the obtained white sediment after cooling, centrifuging and drying in an oven to obtain the TiO2(B) nano-sponge. By adopting the method, the use of TiCl4 raw material that is strongly hydrolyzed and fumed when encountering water and the high-concentration strong base with high corrosivity can be avoided, the operation safety can be increased and the high-temperature calcination is not needed, so that the method is simple in operation and is suitable for scale production. The TiO2(B) sponge has superhigh specific surface area and porosity and is suitable for popularizing in the fields of photocatalysis, solar cell and lithium ion battery.
Description
Technical field
The present invention relates to a kind of preparation method of nano material, particularly a kind of TiO
2(B) preparation method of nanosponges.
Background technology
At present, nano-TiO
2wide application prospect is shown in environmental purification and green energy resource.TiO
2common crystalline phase has three kinds, is respectively anatase octahedrite, rutile and brookite.Nearest research finds TiO
2another kind of crystalline phase form can also there is TiO
2(B).This crystalline phase belongs to oblique system, is a kind of than anatase octahedrite and little, the loosely organized metasable state titanium oxide homogeneity variant of rutile density.In order to develop TiO to the full extent
2application prospect, to emerging crystalline phase TiO
2(B) research is risen.TiO
2(B) synthesis traces back to 1980 the earliest, and the people such as Marchand have synthesized TiO by high temperature solid-phase sintering method
2(B) [Materials ResearchBulletin, 1980,15 (8): 1129-1133], but granular size is micron order, and need high-temperature calcination in preparation process.2004, the people such as Bruce obtained TiO in conjunction with highly basic hydrothermal method and ion exchange method
2(B) nano wire [Angewandte Chemie International Edition, 2004,43:2286-2288], but preparation process need use the highly basic of a large amount of severe corrosive, and preparation process is complicated, need realize through multisteps such as highly basic hydro-thermal-ion-exchange-high-temperature calcinations.2010, king to instruct etc. people by simpler ethylene glycol solvent hot one-step synthesis method TiO
2(B) nanometer sheet [Chemical Communications, 2010,46:6801-6803], but the TiCl in experiment
4raw material in atmosphere intense hydrolysis is smoldered, and has strong pungency, runs counter to the principle of Green Chemistry.How to find a kind of simple, green preparation TiO
2(B) method of nanostructure becomes research TiO
2(B) important prerequisite.Further, from TiO
2current most widely used environmental purification and green energy resource field, to nanostructure TiO
2(B) technology of preparing proposes the higher requirement such as high purity, high-crystallinity, high-specific surface area.But, for the TiO with above advantage
2(B) nanosponges there is not yet pertinent literature report.
Summary of the invention
The present invention is for solving conventional Ti O
2(B) rely on high-temperature calcination in preparation method, prepare the technical problem of the shortcoming of complexity and the weak crystallization of product, provide a kind of green to prepare the TiO of high purity, high-crystallinity, high porosity simply, fast
2(B) preparation method of nanosponges.
In order to solve the problems of the technologies described above, technical scheme of the present invention is specific as follows:
A kind of TiO
2(B) preparation method of nanosponges, comprises the following steps:
With 10g water for solvent, add oxyacetic acid and add tetrabutyl titanate until completely dissolved, mix and blend 30s, be placed in autoclave be heated to temperature of reaction be 120-180 DEG C reaction 6-18 hour; The consumption of described tetrabutyl titanate, oxyacetic acid, water is tetrabutyl titanate by weight: oxyacetic acid: water=10 ~ 30:10 ~ 45:100, the white depositions washing will obtained after question response cooling, centrifugal, dry, as for 70 DEG C of dry 6h in baking oven, namely obtain TiO
2(B) nanosponges.
In technique scheme, described temperature of reaction is 140-160 DEG C.
In technique scheme, the described reaction times is 8-12 hour.
In technique scheme, the consumption of described tetrabutyl titanate, oxyacetic acid, water is tetrabutyl titanate by weight: oxyacetic acid: water=10 ~ 15:35 ~ 45:100.
The invention has the beneficial effects as follows:
TiO provided by the invention
2(B) preparation method of nanosponges compared with prior art tool have the following advantages:
1, the TiCl using and meet water intense hydrolysis and smolder is avoided
4raw material and have corrosive high density highly basic, adds the security of operation.
2, in building-up process without the need to can TiO be realized by high-temperature calcination
2(B) height crystallization, and simple to operate, suitable for mass production.
3, obtained TiO
2(B) be the cavernous body that ultra-fine and uniform nanoparticle (particle diameter 5 ~ 10nm) forms, there is the specific surface area and porosity of superelevation, be suitable for very much promoting in fields such as photochemical catalysis, solar cell and lithium ion batteries.
Accompanying drawing explanation
Below in conjunction with the drawings and specific embodiments, the present invention is described in further detail.
The TiO of Fig. 1 prepared by embodiment 1
2(B) the X-ray diffraction spectrogram of nanosponges.
The TiO of Fig. 2 prepared by embodiment 1
2(B) the transmission electron microscope photo of nanosponges.
The TiO of Fig. 3 prepared by embodiment 1
2(B) the high resolution transmission electron microscopy photo of nanosponges.
The TiO of Fig. 4 prepared by embodiment 2
2(B) the X-ray diffraction spectrogram of nanosponges.
The TiO of Fig. 5 prepared by embodiment 2
2(B) the transmission electron microscope photo of nanosponges.
The TiO of Fig. 6 prepared by embodiment 2
2(B) the high resolution transmission electron microscopy photo of nanosponges.
The TiO of Fig. 7 prepared by embodiment 3
2(B) the X-ray diffraction spectrogram of nanosponges.
The TiO of Fig. 8 prepared by embodiment 3
2(B) the transmission electron microscope photo of nanosponges.
The TiO of Fig. 9 prepared by embodiment 3
2(B) the high resolution transmission electron microscopy photo of nanosponges.
The TiO of Figure 10 prepared by embodiment 4
2(B) the X-ray diffraction spectrogram of nanosponges.
The TiO of Figure 11 prepared by embodiment 4
2(B) the transmission electron microscope photo of nanosponges.
The TiO of Figure 12 prepared by embodiment 4
2(B) the high resolution transmission electron microscopy photo of nanosponges.
The TiO of Figure 13 prepared by embodiment 5
2(B) the X-ray diffraction spectrogram of nanosponges.
The TiO of Figure 14 prepared by embodiment 5
2(B) the transmission electron microscope photo of nanosponges.
The TiO of Figure 15 prepared by embodiment 5
2(B) the high resolution transmission electron microscopy photo of nanosponges.
Embodiment
Embodiment 1
In the beaker of 50ml, add 10g water, add 0.45g oxyacetic acid to dissolving completely, continue to add 0.1g tetrabutyl titanate, stir 30s, be placed in 15ml autoclave and be warming up to 160 DEG C of reaction 12h, product naturally cooling is treated in reaction stopping, products therefrom water, ethanol wash respectively, centrifugal, finally as 70 DEG C of dry 6h in baking oven, namely obtain TiO
2(B) nanosponges.
The present embodiment is most preferred embodiment.Fig. 1 ~ 3 are respectively the TiO prepared
2(B) nanocrystalline X-ray diffracting spectrum, transmission electron microscope photo, high resolution transmission electron microscopy photo, products therefrom is TiO
2(B) cavernous body of nanoparticle assembling, wherein nano particle diameter is 5 ~ 10nm.
Embodiment 2
In the beaker of 50ml, add 10g water, add 0.2g oxyacetic acid to dissolving completely, continue to add 0.1g tetrabutyl titanate, stir 30s, be placed in 15ml autoclave and be warming up to 160 DEG C of reaction 12h, product naturally cooling is treated in reaction stopping, products therefrom water, ethanol wash respectively, centrifugal, finally as 70 DEG C of dry 6h in baking oven, namely obtain TiO
2(B) nanosponges.
Compared with embodiment 1, the present embodiment is by tetrabutyl titanate: the weight ratio of oxyacetic acid changes 10:20 into, and products therefrom is TiO
2(B) nanosponges structure.Fig. 4 is the present embodiment TiO
2(B) X-ray diffracting spectrum of nanosponges, Fig. 5 is its transmission electron microscope photo, and Fig. 6 is its high resolution transmission electron microscopy photo.As seen from the figure, pattern is unchanged, but degree of crystallinity slightly reduces.
Embodiment 3
In the beaker of 50ml, add 10g water, add 0.45g oxyacetic acid to dissolving completely, continue to add 0.1g tetrabutyl titanate, stir 30s, be placed in 15ml autoclave and be warming up to 140 DEG C of reaction 12h, product naturally cooling is treated in reaction stopping, products therefrom water, ethanol wash respectively, centrifugal, finally as 70 DEG C of dry 6h in baking oven, namely obtain TiO
2(B) nanosponges.
Compared with embodiment 1, the present embodiment changes temperature of reaction into 140 DEG C, and products therefrom is TiO
2(B) nanosponges structure.Fig. 7 is the present embodiment TiO
2(B) X-ray diffracting spectrum of nanosponges, Fig. 8 is its transmission electron microscope photo, and Fig. 9 is its high resolution transmission electron microscopy photo.As seen from the figure, pattern is unchanged.
Embodiment 4
In the beaker of 50ml, add 10g water, add 0.45g oxyacetic acid to dissolving completely, continue to add 0.1g tetrabutyl titanate, stir 30s, be placed in 15ml autoclave and be warming up to 160 DEG C of reaction 6h, product naturally cooling is treated in reaction stopping, products therefrom water, ethanol wash respectively, centrifugal, finally as 70 DEG C of dry 6h in baking oven, namely obtain TiO
2(B) nanosponges.
Compared with embodiment 1, the present embodiment will change 6h in the reaction times, and products therefrom is TiO
2(B) nanosponges structure.Figure 10 is the present embodiment TiO
2(B) X-ray diffracting spectrum of nanosponges, Figure 11 is its transmission electron microscope photo, and Figure 12 is its high resolution transmission electron microscopy photo.As seen from the figure, pattern is unchanged, and degree of crystallinity slightly reduces.
Embodiment 5
In the beaker of 50ml, add 10g water, add 0.45g oxyacetic acid to dissolving completely, continue to add 0.3g tetrabutyl titanate, stir 30s, be placed in 15ml autoclave and be warming up to 160 DEG C of reaction 12h, product naturally cooling is treated in reaction stopping, products therefrom water, ethanol wash respectively, centrifugal, finally as 70 DEG C of dry 6h in baking oven, namely obtain TiO
2(B) nanosponges.
Compared with embodiment 1, the present embodiment is by tetrabutyl titanate: the weight ratio of oxyacetic acid changes 30:45 into, and products therefrom is TiO
2(B) nanosponges structure.Figure 13 is the present embodiment TiO
2(B) X-ray diffracting spectrum of nanosponges, Figure 14 is its transmission electron microscope photo, and Figure 15 is its high resolution transmission electron microscopy photo.As seen from the figure, pattern is unchanged.
Embodiment 6
In the beaker of 50ml, add 10g water, add 0.1g oxyacetic acid to dissolving completely, continue to add 0.1g tetrabutyl titanate, stir 30s, be placed in 15ml autoclave and be warming up to 180 DEG C of reaction 8h, product naturally cooling is treated in reaction stopping, products therefrom water, ethanol wash respectively, centrifugal, finally as 70 DEG C of dry 6h in baking oven, namely obtain TiO
2(B) nanosponges.
Embodiment 7
In the beaker of 50ml, add 10g water, add 0.35g oxyacetic acid to dissolving completely, continue to add 0.15g tetrabutyl titanate, stir 30s, be placed in 15ml autoclave and be warming up to 120 DEG C of reaction 18h, product naturally cooling is treated in reaction stopping, products therefrom water, ethanol wash respectively, centrifugal, finally as 70 DEG C of dry 6h in baking oven, namely obtain TiO
2(B) nanosponges.
Obviously, above-described embodiment is only for clearly example being described, and the restriction not to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without the need to also giving all embodiments.And thus the apparent change of extending out or variation be still among the protection domain of the invention.
Claims (4)
1. a TiO
2(B) preparation method of nanosponges, is characterized in that, comprises the following steps:
With 10g water for solvent, add oxyacetic acid and add tetrabutyl titanate until completely dissolved, mix and blend 30s, be placed in autoclave be heated to temperature of reaction be 120-180 DEG C reaction 6-18 hour; The consumption of described tetrabutyl titanate, oxyacetic acid, water is tetrabutyl titanate by weight: oxyacetic acid: water=10 ~ 30:10 ~ 45:100, the white depositions washing will obtained after question response cooling, centrifugal, dry, as for 70 DEG C of dry 6h in baking oven, namely obtain TiO
2(B) nanosponges.
2. preparation method according to claim 1, is characterized in that, described temperature of reaction is 140-160 DEG C.
3. preparation method according to claim 1, is characterized in that, the described reaction times is 8-12 hour.
4. the preparation method according to claim 1-3 any one, is characterized in that, the consumption of described tetrabutyl titanate, oxyacetic acid, water is tetrabutyl titanate by weight: oxyacetic acid: water=10 ~ 15:35 ~ 45:100.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105180312A (en) * | 2015-06-26 | 2015-12-23 | 山东红太阳环保产品有限公司 | Application of nanometer sponge in air purification field and method and equipment for performing purifying and processing tiny particles through cooperation of nanometer sponge and air negative air ions |
| CN107792878A (en) * | 2017-10-26 | 2018-03-13 | 福州大学 | A kind of graded structure titanium dioxide（B）Preparation method and its application in lithium ion battery |
| CN109052464A (en) * | 2018-08-09 | 2018-12-21 | 陕西师范大学 | A kind of high-temperature-phase TiO2(B) preparation method of material |
| CN112018374A (en) * | 2020-09-02 | 2020-12-01 | 福州大学 | Nano-structure TiO2(B) And preparation method and application thereof |
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| US6517804B1 (en) * | 2000-02-29 | 2003-02-11 | Korea Atomic Energy Institute | TiO2 ultrafine powder, and process for preparing thereof |
| JP2006182616A (en) * | 2004-12-28 | 2006-07-13 | Tohoku Univ | Method of manufacturing water-soluble titanium compound and manufacturing method of titanium oxide powder using it |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105180312A (en) * | 2015-06-26 | 2015-12-23 | 山东红太阳环保产品有限公司 | Application of nanometer sponge in air purification field and method and equipment for performing purifying and processing tiny particles through cooperation of nanometer sponge and air negative air ions |
| CN105180312B (en) * | 2015-06-26 | 2017-12-19 | 山东红太阳环保产品有限公司 | Application of the nanosponges in air purification field and the method and apparatus with negative aeroion combined purifying processing finely ground particles |
| CN107792878A (en) * | 2017-10-26 | 2018-03-13 | 福州大学 | A kind of graded structure titanium dioxide（B）Preparation method and its application in lithium ion battery |
| CN107792878B (en) * | 2017-10-26 | 2019-09-13 | 福州大学 | A kind of preparation method of graded structure titanium dioxide (B) and its application in lithium ion battery |
| CN109052464A (en) * | 2018-08-09 | 2018-12-21 | 陕西师范大学 | A kind of high-temperature-phase TiO2(B) preparation method of material |
| CN109052464B (en) * | 2018-08-09 | 2020-10-16 | 陕西师范大学 | High-temperature phase TiO2(B) Method for producing a material |
| CN112018374A (en) * | 2020-09-02 | 2020-12-01 | 福州大学 | Nano-structure TiO2(B) And preparation method and application thereof |
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