CN104419976A - TiO2 single crystal and preparation method thereof - Google Patents
TiO2 single crystal and preparation method thereof Download PDFInfo
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- CN104419976A CN104419976A CN201310385238.6A CN201310385238A CN104419976A CN 104419976 A CN104419976 A CN 104419976A CN 201310385238 A CN201310385238 A CN 201310385238A CN 104419976 A CN104419976 A CN 104419976A
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- monocrystalline
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Abstract
The invention provides a TiO2 single crystal and a preparation method thereof. The preparation method comprises the steps of mixing titanic peroxide sol with the aqueous solution of hydrofluoric acid together in a reactor of which a lining is polytetrafluoroethylene, and performing a hydrothermal crystallization reaction in an airtight environment. The preparation method is capable of reducing the grain size of the decahedral TiO2 single crystal with a large quantity of exposed {101} and {001} crystal faces and increasing the specific surface area of the TiO2 single crystal. The preparation method is capable of preparing a flat-end two-cone decahedral TiO2 single crystal with crossed double faces.
Description
Technical field
The present invention relates to a kind of TiO
2monocrystalline and preparation method thereof, particularly has the nanometer tack bipyramid decahedron TiO of two-sided cruciate flower
2monocrystalline and preparation method thereof.
Background technology
TiO
2be typical semiconductor material, because its physical and chemical performance is excellent, cheap, nontoxic, anticorrosive etc., advantage is widely used in dye sensitization solar battery, photocatalytic pollutant degradation and photocatalysis hydrogen production field.In recent years, along with developing rapidly of nanotechnology, special appearance TiO
2material is more and more subject to the favor of researcher.Especially TiO is finely controlled
2the surface topography of nano material, exposes the study hotspot that a large amount of high reactivity crystal face becomes above-mentioned field gradually.
Anatase octahedrite, rutile, brookite are three kinds of common TiO
2crystal formation, wherein especially with anatase structured excellent performance, therefore noticeable.According to wulff principle, anatase octahedrite TiO
2monocrystalline has top tack bipyramid decahedron pattern usually, exposes a large amount of { 101} crystal face and few { 001} crystal face.This is because anatase octahedrite { 101} face is thermodynamically stable low energy crystal face, { 001} crystal face then has higher crystal face energy, high energy in single crystal growth process the 001} crystal face speed of growth very fast and rapidly minimizing even disappear, { 101} crystal face then because the speed of growth is slowly exposed to plane of crystal in a large number, thus forms the decahedral typical pattern of tack bipyramid.As everyone knows, TiO
2the reactive behavior of the different crystal face of nano material is completely different, particularly anatase octahedrite TiO
2reduction and oxidation activity site lay respectively at { 101} and { 001} crystal face.Therefore, artificial control TiO
2material microscopic appearance, exposes for different reaction systems the performance that specific crystal face very likely significantly promotes material.Up to now, existing a large amount of research work is devoted to expose anatase octahedrite TiO
2specific active crystal face.In US20110189081, Yang etc. openly use that titanium tetrafluoride is precursor, hydrofluoric acid is morphology control agent, have synthesized that { 001} face exposure is the micron-scale tack bipyramid decahedron anatase octahedrite TiO of 47% under hydrothermal condition
2.But this material crystals enormous size, specific surface area is less, and active being difficult to realizes efficiently.Therefore, design new materials synthesis route, prepare the TiO with special exposure crystal face of nano-scale
2monocrystalline has important scientific research meaning and actual application value.
Summary of the invention
The object of the invention is the deficiency overcoming existing preparation method, innovatively proposes a kind of to expose a large amount of { 101} and { 001} crystal face and the TiO that grain-size is little, specific surface area is large
2monocrystalline and preparation method thereof.
In order to reach foregoing invention object, the invention provides a kind of TiO
2the preparation method of monocrystalline, it is mix in the reactor of tetrafluoroethylene that the method to comprise peroxo titanic acid sol and hydrofluoric acid aqueous solution at liner, and carries out hydrothermal crystallizing reaction in closed environment.
The present invention also provides the TiO prepared according to above-mentioned preparation method
2monocrystalline.
Present invention also offers a kind of TiO
2monocrystalline, wherein, described TiO
2the microscopic appearance of monocrystalline is the two-sided tack bipyramid decahedron with cruciate flower.
Preparation method provided by the invention can reduce to expose a large amount of { 101} and { the decahedron TiO of 001} crystal face effectively
2the grain-size of monocrystalline also improves its specific surface area.Adopt preparation method provided by the invention, a kind of novel two-sided tack bipyramid decahedron TiO with cruciate flower can be prepared
2monocrystalline.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and forms a part for specification sheets, is used from explanation the present invention, but is not construed as limiting the invention with embodiment one below.In the accompanying drawings:
Fig. 1 is TiO prepared by the embodiment of the present invention 1
2the pattern schematic diagram of monocrystalline;
Fig. 2 is the two-sided TiO with cruciate flower described in the embodiment of the present invention 1
2x-ray diffraction (XRD) collection of illustrative plates of tack bipyramid decahedron monocrystalline;
Fig. 3 is the two-sided TiO with cruciate flower prepared by embodiment of the present invention 1-3
2scanning electron microscope (SEM) figure of tack bipyramid decahedron monocrystalline, wherein, the corresponding embodiment 3 of corresponding embodiment 2, Fig. 3 c of corresponding embodiment 1, Fig. 3 b of Fig. 3 a;
Fig. 4 is the two-sided TiO with cruciate flower described in the embodiment of the present invention 1
2transmission electron microscope (TEM) figure of tack bipyramid decahedron monocrystalline.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
TiO provided by the invention
2the preparation method of monocrystalline comprises: be mix peroxo titanic acid sol and hydrofluoric acid aqueous solution in the reactor of tetrafluoroethylene at liner, and carries out hydrothermal crystallizing reaction in closed environment.
In the present invention, in order to make the TiO prepared
2monocrystalline performance is better, and under preferable case, the concentration of described peroxo titanic acid sol is 0.05-0.15mol/L, more preferably 0.08-0.12mol/L; Described hydrofluoric acid aqueous solution concentration is 4-5mol/L, more preferably 4.4-4.6mol/L; The volume ratio of peroxo titanic acid sol and hydrofluoric acid aqueous solution is 8-20:1, more preferably 8-12:1.
In the present invention, closed environment can provide by adopting conventional closed reactor such as autoclave, and under preferable case, the stainless steel cauldron that closed environment is tetrafluoroethylene by liner provides.
In the present invention, hydrothermal crystallization method refers in closed reactor (as autoclave), adopts the aqueous solution as reaction medium, by heating reactor, create high temperature, a reaction under high pressure environment, the method for the nanocrystal of the dispersion that cannot be formed under obtaining normal condition.
In the present invention, in order to make the TiO prepared
2monocrystalline performance is better, and under preferable case, the condition of hydrothermal crystallizing reaction comprises: temperature is 150-200 DEG C, and the time is 2-12h, and further preferable temperature is 160-180 DEG C, and the time is 4-8h.
In the present invention, described peroxo titanic acid sol can be the conventional peroxo titanic acid sol of this area, also there is no particular limitation for the preparation method of described peroxo titanic acid sol, one is proposed preferred embodiment at this, the preparation method of described peroxo titanic acid sol comprises: under agitation, by titanium source hydrolysis reaction gained TiO
2powder mixes with hydrogen peroxide, more preferably, to titanium source hydrolysis gained TiO
2add hydrogen peroxide in powder and stir.Wherein, the kind in described titanium source is conventionally known to one of skill in the art, preferably, described titanium source be selected from titanium tetraisopropylate, tetrabutyl titanate, titanyl sulfate and titanium tetrachloride one or more.Wherein, the volumetric concentration of hydrogen peroxide is not particularly limited, and the volumetric concentration of described hydrogen peroxide is generally 20-60%, and under preferable case, the volumetric concentration of described hydrogen peroxide is 30-40%.
In the present invention, prepare in the preferred implementation of peroxo titanic acid sol above-mentioned, the method for described titanium source hydrolysis comprises: with continuous stirring, dropwise joined in deionized water in titanium source.The temperature of described hydrolysis is not particularly limited, and usually can at room temperature carry out, as 20-40 DEG C.
Prepare in the preferred implementation of peroxo titanic acid sol above-mentioned, TiO
2there is no particular limitation with the consumption of hydrogen peroxide, under preferable case, and TiO
2the concentration of pertitanic acid in the peroxo titanic acid sol obtained is made to be 0.05-0.15mol/L, more preferably 0.08-0.12mol/L with the consumption of hydrogen peroxide.
The present invention also provides the TiO prepared according to above-mentioned preparation method
2monocrystalline.This TiO
2monocrystalline is Detitanium-ore-type, and its microscopic appearance is the two-sided tack bipyramid decahedron with cruciate flower.In addition, the TiO prepared by ordinary method
2decahedron monocrystalline size is micron order, and specific surface area is all less than 10m
2/ g, and TiO of the present invention
2monocrystalline size (size of this monocrystalline refers to median size, is approximately spherical gained by monocrystalline) is 40-80nm, and specific surface area is 20-40m
2/ g.Contriver finds TiO provided by the invention
2monocrystalline has special microtexture (decahedral end face and bottom surface gully all cruciferous) and nano level grain-size due to it, light induced electron and hole can be separated efficiently, thus all have a good application prospect in dye sensitization solar battery, photocatalytic pollutant degradation and photocatalysis hydrogen production field.
TiO provided by the invention
2the preparation method of monocrystalline is simple to operate, and reaction conditions is gentle, and preparation cost is cheap, is applicable to heavy industrialization preparation.
Below will be described the present invention by specific embodiment.
TiO
2the grain-size of monocrystalline is obtained by SEM figure and TEM figure observation.
TiO
2the measuring method of the specific surface area of monocrystalline is N
2adsorption desorption is tested.
Embodiment 1
The present embodiment is for illustration of TiO provided by the invention
2the preparation method of monocrystalline.
Under magnetic stirring, 1mmol titanium tetraisopropylate be dropwise added in 100mL deionized water, titanium tetraisopropylate is fully hydrolyzed, filter, wash and after eliminating residual organic matter, obtain white TiO
2powder; By 10mL volumetric concentration be again 30% hydrogen peroxide solution mix with above-mentioned white powder, continuously stirring obtains safran peroxo titanic acid sol; Being 0.1mol/L by gained 10mL(concentration subsequently) to be transferred to liner be in the stainless steel hydrothermal reaction kettle of tetrafluoroethylene to peroxo titanic acid sol, and add the hydrofluoric acid aqueous solution that 1mL concentration is 4.52mol/L, put into 180 DEG C of baking ovens after sealing and react 8 hours.Room temperature to be naturally cooled to (25 DEG C), repeatedly washs gained white precipitate with ethanol and deionized water, and in 80 DEG C of baking ovens dry 24 hours.Final acquisition sample is the two-sided TiO with cruciate flower
2nanometer tack bipyramid decahedron monocrystalline, N
2the specific surface area that adsorption desorption records is about 30m
2/ g.
Fig. 1 is TiO prepared by the embodiment of the present invention 1
2the schematic diagram of monocrystalline, in Fig. 1, upper bottom surface is that { 001} crystal face, 8 sides are { 101} crystal face.In addition, it can also be seen that from Fig. 1, the decahedral end face that the present invention prepares and bottom surface gully all cruciferous.
Fig. 2 (X-ray diffraction spectrogram) shows that gained sample has Detitanium-ore-type TiO
2characteristic diffraction peak, and peak shape is sharp-pointed, and degree of crystallinity is higher.
The TiO of preparation can be found out by Fig. 3 a and Fig. 4
2the grain-size of monocrystalline is about 50-80nm.
Embodiment 2
The present embodiment is for illustration of TiO provided by the invention
2the preparation method of monocrystalline.
Sample preparation steps is identical with embodiment 1, unlike, the hydro-thermal reaction time is 4 hours, and obtaining sample is the two-sided TiO with cruciate flower
2nanometer tack bipyramid decahedron monocrystalline.
The TiO of preparation can be found out by Fig. 3 b
2the grain-size of monocrystalline is about 50-80nm, N
2the specific surface area that adsorption desorption records is about 28m
2/ g.
Embodiment 3
The present embodiment is for illustration of TiO provided by the invention
2the preparation method of monocrystalline.
Sample preparation steps is identical with embodiment 1, unlike, the hydro-thermal reaction time is 6 hours, and obtaining sample is the two-sided TiO with cruciate flower
2nanometer tack bipyramid decahedron monocrystalline.
The TiO of preparation can be found out by Fig. 3 c
2the grain-size of monocrystalline is about 50-80nm, N
2the specific surface area that adsorption desorption records is about 29m
2/ g.
Embodiment 4-6
The present embodiment is for illustration of TiO provided by the invention
2the preparation method of monocrystalline.
Sample preparation steps is identical with embodiment 1, unlike, titanium source changes into titanyl sulfate, tetrabutyl titanate and titanium tetrachloride successively, and result can obtain the two-sided TiO with cruciate flower equally
2nanometer tack bipyramid decahedron monocrystalline.
The TiO prepared
2the grain-size of monocrystalline is all about 50-80nm, N
2the specific surface area that adsorption desorption records is respectively 29m
2/ g, 30m
2/ g, 30m
2/ g.
Embodiment 7
The present embodiment is for illustration of TiO provided by the invention
2the preparation method of monocrystalline.
Under magnetic stirring, 1mmol titanium tetraisopropylate be dropwise added to 100mL deionized water, titanium tetraisopropylate is fully hydrolyzed, filter, wash and after eliminating residual organic matter, obtain white TiO
2powder; By 12mL volumetric concentration be again 50% hydrogen peroxide solution mix with above-mentioned white powder, continuously stirring obtains safran peroxo titanic acid sol; Being 0.05mol/L by gained 12mL(concentration subsequently) to be transferred to liner be in the stainless steel hydrothermal reaction kettle of tetrafluoroethylene to peroxo titanic acid sol, and add the hydrofluoric acid aqueous solution that 1mL concentration is 4.2mol/L, put into 150 DEG C of baking ovens after sealing and react 4 hours.Room temperature to be naturally cooled to (25 DEG C), repeatedly washs gained white precipitate with ethanol and deionized water, and in 80 DEG C of baking ovens dry 24 hours.Final acquisition sample is the two-sided TiO with cruciate flower
2nanometer tack bipyramid decahedron monocrystalline, its grain-size is 40-60nm, N
2the specific surface area that adsorption desorption records is about 35m
2/ g.
From the result of above embodiment, TiO prepared by the present invention
2monocrystalline exposes a large amount of { 101} and { 001} crystal face, and grain-size is about 40-80nm, specific surface area is 20-40m
2/ g, and the TiO prepared by ordinary method adopting prior art
2monocrystalline size is micron order, and specific surface area is all less than 10m
2/ g.In addition, contriver finds TiO provided by the invention
2monocrystalline has the two-sided decahedral structure of tack bipyramid containing cruciate flower and nano level grain-size due to it, light induced electron and hole can be separated efficiently, thus all have a good application prospect in dye sensitization solar battery, photocatalytic pollutant degradation and photocatalysis hydrogen production field.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode, in order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (10)
1. a TiO
2the preparation method of monocrystalline, is characterized in that, it is mix in the reactor of tetrafluoroethylene that the method to comprise peroxo titanic acid sol and hydrofluoric acid aqueous solution at liner, and carries out hydrothermal crystallizing reaction in closed environment.
2. method according to claim 1, wherein, the concentration of described peroxo titanic acid sol is 0.05-0.15mol/L, more preferably 0.08-0.12mol/L, the concentration of described hydrofluoric acid aqueous solution is 4-5mol/L, more preferably 4.4-4.6mol/L, the volume ratio of peroxo titanic acid sol and hydrofluoric acid aqueous solution is 8-20:1, more preferably 8-12:1.
3. preparation method according to claim 1, wherein, the condition of hydrothermal crystallizing reaction comprises: temperature is 150-200 DEG C, and the time is 2-12h, and further preferable temperature is 160-180 DEG C, and the time is 4-8h.
4. according to preparation method described arbitrarily in claim 1-3, wherein, the preparation method of described peroxo titanic acid sol comprises: under agitation, by titanium source hydrolysis gained TiO
2powder mixes with hydrogen peroxide.
5. preparation method according to claim 4, wherein, the volumetric concentration of described hydrogen peroxide is 20-60%, and preferably, the volumetric concentration of described hydrogen peroxide is 30-40%.
6. preparation method according to claim 4, wherein, the described method by the hydrolysis of titanium source comprises: under agitation, dropwise joined in deionized water in titanium source.
7. the preparation method according to claim 4 or 6, wherein, described titanium source be selected from titanium tetraisopropylate, tetrabutyl titanate, titanyl sulfate and titanium tetrachloride one or more.
8. according to TiO prepared by the preparation method in claim 1-7 described in any one
2monocrystalline.
9. a TiO
2monocrystalline, is characterized in that, described TiO
2the microscopic appearance of monocrystalline is the two-sided tack bipyramid decahedron with cruciate flower.
10. TiO according to claim 9
2monocrystalline, wherein, described TiO
2the crystal formation of monocrystalline is Detitanium-ore-type, and monocrystalline is of a size of 40-80nm, and specific surface area is 20-40m
2/ g.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104722289A (en) * | 2015-03-19 | 2015-06-24 | 中国科学院电工研究所 | Method for preparing ultrafine powder in nano titanium dioxide structure |
| CN105347394A (en) * | 2015-11-26 | 2016-02-24 | 黑龙江大学 | Method for synthesizing hierarchical-structure TiO2 microspheres by one-step hydrothermal method |
| CN107268014A (en) * | 2017-06-05 | 2017-10-20 | 同济大学 | A kind of preparation method and application of titanium dioxide/carbon aerogels photocathode |
| CN112028119A (en) * | 2020-09-09 | 2020-12-04 | 晋中学院 | Anatase TiO with co-exposed {101}, {100} and {111} -crystal faces2Nanocrystal |
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| CN101949053A (en) * | 2010-07-14 | 2011-01-19 | 中国科学院电工研究所 | Method for preparing anatase TiO2 single crystal |
| CN103243387A (en) * | 2012-02-01 | 2013-08-14 | 国家纳米科学中心 | Preparation method of anatase TiO2 monocrystal having high-activity (110) face |
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| CN101660203A (en) * | 2009-09-09 | 2010-03-03 | 中国科学院电工研究所 | Preparation method of anatase single crystal TiO2 with large active surface |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104722289A (en) * | 2015-03-19 | 2015-06-24 | 中国科学院电工研究所 | Method for preparing ultrafine powder in nano titanium dioxide structure |
| CN105347394A (en) * | 2015-11-26 | 2016-02-24 | 黑龙江大学 | Method for synthesizing hierarchical-structure TiO2 microspheres by one-step hydrothermal method |
| CN107268014A (en) * | 2017-06-05 | 2017-10-20 | 同济大学 | A kind of preparation method and application of titanium dioxide/carbon aerogels photocathode |
| CN112028119A (en) * | 2020-09-09 | 2020-12-04 | 晋中学院 | Anatase TiO with co-exposed {101}, {100} and {111} -crystal faces2Nanocrystal |
| CN112028119B (en) * | 2020-09-09 | 2022-10-11 | 晋中学院 | Anatase TiO with co-exposed {101}, {100} and {111} -crystal faces 2 Nanocrystal |
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