CN102674451A - Preparation method of {001} face exposed titanium dioxide nanocrystals - Google Patents
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- CN102674451A CN102674451A CN201210159220XA CN201210159220A CN102674451A CN 102674451 A CN102674451 A CN 102674451A CN 201210159220X A CN201210159220X A CN 201210159220XA CN 201210159220 A CN201210159220 A CN 201210159220A CN 102674451 A CN102674451 A CN 102674451A
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Abstract
The invention relates to a preparation method of nanocrystals, particularly a preparation method of {001} face exposed titanium dioxide nanocrystals. The invention solves the technical problems of large particle size and small specific areas in the {001} face exposed titanium dioxide nanocrystals prepared by the existing method. The method comprises the following steps: 1. preparing protonized titanic acid hydrate; 2. washing the protonized titanic acid hydrate with alcohol, transferring into a polytetrafluoroethylene hydrothermal kettle, adding alcohol and a hydrofluoric acid water solution, keeping the temperature, carrying out centrifugal separation to obtain a precipitate, washing with water, washing with alcohol, drying, and grinding to obtain the {001} face exposed titanium dioxide nanocrystals. The titanium dioxide product obtained by the method is a pure anatase phase, the exposure rate of the {001} face is 26-66%, the maximum specific area is 155m<2>g<-1>, and the minimum average particle size of the crystals is 11nm.
Description
Technical field
The present invention relates to a kind of preparation of nano crystal.
Background technology
In recent years, photocatalysis technology causes the extensive concern of countries in the world as administering one of effective means of environmental problem.Titanium dioxide optical catalyst because of its have inexpensive, nontoxic, catalytic activity is high, oxidation capacity is strong, chemicalstability is good, abrasion resistance and can recycle etc. advantage, and become catalyzer ideal in the environmental treatment.TiO
2Photocatalysis performance depend primarily on crystalline phase, expose crystal face, grain-size and specific surface area.Common TiO
2Three kinds of crystal formations are arranged, and are respectively anatase octahedrite, rutile and brookite.Wherein anatase octahedrite is because the redox ability of photoproduction charge carrier is stronger, and the surface is easy to adsorb oxygen and life-span of strengthening the photoproduction charge carrier, so have higher photocatalytic activity.Theoretical all show with experiment, anatase octahedrite the 001} face is the high energy crystal face, and its activity be superior to thermodynamics more stable { (surface energy: { the 001} face is 0.90J m to the 101} face
-2, and { the 101} face is 0.44J m
-2).Therefore, { the 001} face just becomes the research focus in the titanium oxide crystal face engineering to preparation high energy.
2008, Yang Huagui seminar overcame relevant technical difficulty, had synthesized that { 001} face exposure is 47% anatase phase titanium dioxide monocrystalline (H.G.Yang, C.H.Sun through hydrothermal method; S.Z.Qiao, J.Zou, G.Liu, S.C.Smith; H.M.Cheng and G.Q.Lu, Nature, 2008,453; 638.), again ratio is increased to 64% subsequently, but the mean sizes of gained titanium dioxide single crystalline reaching 1.09 μ m, specific surface area only has 1.6m
2g
-1(H.G.Yang, G.Liu, S.Z.Qiao, C.H.Sun, Y.G.Jin, S.C.Smith, J.Zou, H.M.Cheng and G.Q.Lu, J.Am.Chem.Soc., 2009,131,4078).For heterogeneous reaction, less grain-size means bigger specific surface area and more avtive spot, and this helps the abundant contact of reactant with titanium dioxide nano-crystal, and the photocatalytic activity of final strongthener.And { the 001} face exposes among the preparation method of anatase phase titanium dioxide, is precursor with titanium salt, titanium alkoxide or titanium valve directly mostly, and the grain-size of products therefrom is commonly about hundreds of nanometers even micron order at present.Reason is that titanium salt, titanium alkoxide and titanium valve are at aqueous solvent thermal system reactive behavior higher (B.H.Wu, C.Y.Guo, N.F.Zheng; Z.X.Xie and G.D.Stucky, J.Am.Chem.Soc., 2008,130; 17563.), { the 001} face exposes anatase phase titanium dioxide, and then the crystal growing process of product is difficult controls, and gained titanium dioxide granule size is often bigger if directly be used for preparation; Specific surface area is also less, is unfavorable for raising (S.W.Liu, J.G.Yu and M.Jaroniec, the J.Am.Chem.Soc. of material catalytic activity; 2010,132,11914.).Therefore, seeking novel precursor prepares nano level { the 001} face exposes anatase phase titanium dioxide, has become the important breakthrough point of this area research.
Summary of the invention
{ the 001} face exposes the technical problem that the titanium dioxide nanocrystalline particle size is big, specific surface area is little, and a kind of { preparation method of 001} face exposure titanium dioxide nanocrystalline is provided in order to solve existing method preparation in the present invention.
A kind of the 001} face exposes the preparation method of titanium dioxide nanocrystalline, and concrete steps are following:
One, titanium salt is joined in ethanol or the Virahol, being mixed with 50mL～100mL concentration is the alcoholic solution of 0.1mol/L～0.5mol/L;
Two, the alcoholic solution that under agitation condition, step 1 is prepared splashes in 60mL～120mL deionized water; Under bath temperature is 60 ℃～90 ℃ condition, stirred 30 minutes～100 minutes then, add alkaline solution 50mL～300mL of 0.5mol/L～5.0mol/L with 300～1000 rev/mins stirring velocitys; Sealing; Continue to stir 4 hours～12 hours at 60 ℃～90 ℃ then, spinning goes out white precipitate, and with deionized water wash white precipitate 3～5 times; To supernatant pH value is neutral, obtains protonated hydration metatitanic acid;
Three, protonated hydration metatitanic acid is washed 3～5 times with alcohol, transfer to then in the tetrafluoroethylene water heating kettle, pure and mild 0.5mL～the 5mL mass concentration was 20%～40% hydrofluoric acid aqueous solution to add 2mL～6mL, 150 ℃～220 ℃ insulations 12 hours～48 hours;
Four, the reaction solution that step 3 is obtained is that spinning goes out deposition under 3000 rev/mins～8000 rev/mins the condition at rotating speed; Then at 60 ℃～100 ℃ following dry 24h～48h; Warp washing, alcohol are washed, dry, grinding, promptly get { 001} face exposure titanium dioxide nanocrystalline.
Titanium salt described in the step 1 is titanium tetrachloride, titanium sulfate, titanyl sulfate, butyl(tetra)titanate or isopropyl titanate.
Alkaline solution described in the step 2 is sodium hydroxide solution, potassium hydroxide solution or sodium carbonate solution.
Alcohol described in the step 3 is ethanol or Virahol.
To wash used alcohol be ethanol or Virahol to alcohol in the step 4.
The present invention is directed to that existing precursor makes { it is bigger than normal that the 001} face exposes the anatase phase titanium dioxide particle diameter; Specific surface area is low excessively; The not high major defect of photocatalytic activity adopts protonated hydration metatitanic acid to be novel presoma, and { the 001} face exposes titanium dioxide nanocrystalline in the preparation of solvent thermal system.The titanium dioxide product that adopts present method to obtain is pure anatase octahedrite phase, and { 001} face exposure is 26%～66%, and specific surface area is up to 155m
2g
-1, crystal median size minimum is 11nm, its photocatalysis efficiency significantly is superior to large size { the 001} face exposure titanium oxide of traditional method preparation.And the starting material that use are cheap and easy to get, easy and simple to handle, and equipment and technology is simple, can be widely used as photocatalyst material and photovaltaic material, can be used in and administer waste water, purify air, aspect such as opto-electronic conversion.
Protonated hydration metatitanic acid (H
2Ti
5O
113H
2O) have with anatase octahedrite like crystalline network, for example share on the limit and zigzag structure.In the solvent thermal reaction process; Lamellated protonated hydration metatitanic acid can keep the zig-zag crystalline network constant and direct cracking generates the anatase octahedrite ultra-fine grain; Grow up gradually through crystal growing process subsequently; So can realize the controlled preparation of product pattern and size through adjustment and control system composition and reaction conditions, the more important thing is, compare with titanium valve with titanium salt, titanium alkoxide; This lamellated protonated metatitanic acid with the process of hydrofluoric acid reaction in performance gentle more, thereby more help the crystalline growth control.Therefore; { the 001} face exposes titanium dioxide nanocrystalline for novel presoma preparation to adopt protonated hydration metatitanic acid; Reaction process is gentle, and { 001} face exposure and grain-size are controlled, and specific surface area is big for products therefrom; Catalytic activity is high, has potential using value and vast market prospect at aspects such as environmental improvement and photovaltaic materials.
Description of drawings
Fig. 1 is the experiment one preparation { transmission electron microscope photo of 001} face exposure titanium dioxide nanocrystalline;
Fig. 2 is experiment one preparation { the high-resolution-ration transmission electric-lens photo of 001} face exposure titanium dioxide nanocrystalline;
Fig. 3 is that { the 001} face exposes the XRD figure spectrum of titanium dioxide nanocrystalline in experiment one preparation;
Fig. 4 is the experiment two preparations { transmission electron microscope photos of 001} face exposure titanium dioxide nanocrystalline;
Fig. 5 is the experiment three preparations { transmission electron microscope photos of 001} face exposure titanium dioxide nanocrystalline;
Fig. 6 is the experiment three preparations { transmission electron microscope photos of 001} face exposure titanium dioxide nanocrystalline;
Fig. 7 is that { the 001} face exposes the XRD figure spectrum of titanium dioxide nanocrystalline in experiment three preparations;
Fig. 8 is the experiment two preparations { N of 001} face exposure titanium dioxide nanocrystalline
2Aspiration attaches/desorption isotherm, among the figure-●-represent desorption isotherm ,-◆-represent adsorption isothermal line;
Fig. 9 is the experiment three preparations { N of 001} face exposure titanium dioxide nanocrystalline
2Aspiration attaches/desorption isotherm, among the figure-●-represent desorption isotherm ,-■-represent adsorption isothermal line;
Figure 10 is { 001} face exposure titanium dioxide nanocrystalline and { the 001} face exposure titanium dioxide nanocrystalline ultraviolet catalytic degradating organic dye 2 of testing three preparations that experiment two prepares; The 4-NSC 2879; Time dependent ultraviolet-visible light spectrogram, a representes to test { the 001} face exposure titanium dioxide nanocrystalline ultraviolet catalytic degradating organic dye 2,4 dichloro phenol of three preparations among the figure; Time dependent ultraviolet-visible light spectrogram; B representes to test { 001} face exposure titanium dioxide nanocrystalline ultraviolet catalytic degradating organic dye 2,4 dichloro phenol, the time dependent ultraviolet-visible light spectrogram of two preparations.
Embodiment
Technical scheme of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: this embodiment a kind of the 001} face exposes the preparation method of titanium dioxide nanocrystalline, and concrete steps are following:
One, titanium salt is joined in ethanol or the Virahol, being mixed with 50mL～100mL concentration is the alcoholic solution of 0.1mol/L～0.5mol/L;
Two, the alcoholic solution that under agitation condition, step 1 is prepared splashes in 60mL～120mL deionized water; Under bath temperature is 60 ℃～90 ℃ condition, stirred 30 minutes～100 minutes then, add alkaline solution 50mL～300mL of 0.5mol/L～5.0mol/L with 300～1000 rev/mins stirring velocitys; Sealing; Continue to stir 4 hours～12 hours at 60 ℃～90 ℃ then, spinning goes out white precipitate, and with deionized water wash white precipitate 3～5 times; To supernatant pH value is neutral, obtains protonated hydration metatitanic acid;
Three, protonated hydration metatitanic acid is washed 3～5 times with alcohol, transfer to then in the tetrafluoroethylene water heating kettle, pure and mild 0.5mL～the 5mL mass concentration was 20%～40% hydrofluoric acid aqueous solution to add 2mL～6mL, 150 ℃～220 ℃ insulations 12 hours～48 hours;
Four, the reaction solution that step 3 is obtained is that spinning goes out deposition under 3000 rev/mins～8000 rev/mins the condition at rotating speed; Then at 60 ℃～100 ℃ following dry 24h～48h; Warp washing, alcohol are washed, dry, grinding, promptly get { 001} face exposure titanium dioxide nanocrystalline.
The titanium dioxide product that adopts this embodiment method to obtain is pure anatase octahedrite phase, and { 001} face exposure is 26%～66%, and specific surface area is up to 155m
2g
-1, crystal median size minimum is 11nm,
Embodiment two: what this embodiment and embodiment one were different is that the titanium salt described in the step 1 is titanium tetrachloride, titanium sulfate, titanyl sulfate, butyl(tetra)titanate or isopropyl titanate.Other is identical with embodiment one.
Embodiment three: what this embodiment and embodiment one were different is that the alkaline solution described in the step 2 is sodium hydroxide solution, potassium hydroxide solution or sodium carbonate solution.Other is identical with embodiment one.
Embodiment four: what this embodiment and embodiment one were different is that the alcohol described in the step 3 is ethanol or Virahol.Other is identical with embodiment one.
Embodiment five: this embodiment and embodiment one are different be in the step 4 alcohol to wash used alcohol be ethanol or Virahol.Other is identical with embodiment one.
Embodiment six: this embodiment is different with one of embodiment one to five is that the concentration of alcoholic solution described in the step 1 is 0.2mol/L～0.4mol/L.Other is identical with one of embodiment one to five.
Embodiment seven: this embodiment is different with one of embodiment one to five is that the concentration of alcoholic solution described in the step 1 is 0.3mol/L.Other is identical with one of embodiment one to five.
Embodiment eight: this embodiment is different with one of embodiment one to five is that the concentration of alkaline solution described in the step 2 is 1mol/L～4mol/L.Other is identical with one of embodiment one to five.
Embodiment nine: this embodiment is different with one of embodiment one to five is that the concentration of alkaline solution described in the step 2 is 1mol/L.Other is identical with one of embodiment one to five.
Embodiment ten: this embodiment is different with one of embodiment one to five is that the mass concentration of hydrofluoric acid aqueous solution described in the step 3 is 40%.Other is identical with one of embodiment one to five.
Adopt following experimental verification effect of the present invention:
Experiment one:
A kind of the preparation method that the 001} face exposes titanium dioxide nanocrystalline is following:
One, butyl(tetra)titanate is joined in the ethanol, be mixed with the alcoholic solution that 75mL concentration is 0.35mol/L;
Two, under agitation condition, the alcoholic solution of step 1 preparation is splashed in the 90mL deionized water, under bath temperature is 70 ℃ condition, continue to stir 50 minutes then with 500 rev/mins stirring velocitys; The sodium hydroxide solution 300mL that adds 1mol/L, sealing continues to stir 12 hours at 70 ℃ then; Spinning goes out white precipitate; And with deionized water wash white precipitate 4 times, be neutral to supernatant pH value, obtain protonated hydration metatitanic acid;
Three, with protonated hydration metatitanic acid with washed with isopropyl alcohol 3 times, transfer to then in the tetrafluoroethylene water heating kettle (volume is 40mL), add 6mL Virahol and 0.5mL mass concentration and be 40% hydrofluoric acid aqueous solution, be incubated 12 hours at 180 ℃;
Four, the reaction solution that step 3 is obtained is that spinning goes out deposition under 4000 rev/mins the condition at rotating speed, at 60 ℃ of dry 24h down,, promptly get { 001} face exposure titanium dioxide nanocrystalline through washing, washing with alcohol, drying, grinding then.
Find out that by Fig. 1 (scale is 100 nanometers among the figure) product is homodisperse nanocrystalline, even size distribution is approximately 11nm, and { 001} face proportion is about 26%.
Can know that by Fig. 2 two groups of intersection crystal faces are respectively { the 101} face and { 011} face of anatase octahedrite.
Can know TiO by Fig. 3
2Be pure anatase octahedrite phase, and crystal property is good.
But by Fig. 8 knowledge capital Experiment Preparation { specific surface area that the 001} face exposes titanium dioxide nanocrystalline is 155m
2g
-1
Experiment two:
A kind of the preparation method that the 001} face exposes titanium dioxide nanocrystalline is following:
One, butyl(tetra)titanate is joined in the ethanol, be mixed with the alcoholic solution that 75mL concentration is 0.35mol/L;
Two, under agitation condition, the alcoholic solution of step 1 preparation is splashed in the 90mL deionized water, under bath temperature is 70 ℃ condition, stirred 50 minutes then with 500 rev/mins stirring velocitys; The sodium hydroxide solution 300mL that adds 1.0mol/L, sealing continues to stir 12 hours at 70 ℃ then; Spinning goes out white precipitate; And with deionized water wash white precipitate 4 times, be neutral to supernatant pH value, obtain protonated hydration metatitanic acid;
Three, protonated hydration metatitanic acid is washed 3 times with alcohol, transfer to then in the tetrafluoroethylene water heating kettle, adding 6mL Virahol and 1mL mass concentration were 40% hydrofluoric acid aqueous solution, 180 ℃ of insulations 12 hours;
Four, the reaction solution that step 3 is obtained is that spinning goes out deposition under 4000 rev/mins the condition at rotating speed, at 60 ℃ of dry 24h down,, promptly get { 001} face exposure titanium dioxide nanocrystalline through washing, washing with alcohol, drying, grinding then.
Find out that by Fig. 4 (scale is 100 nanometers among the figure) product is homodisperse nanocrystalline, even size distribution is approximately 24nm, and { 001} face proportion is about 66%.。
Experiment three:
A kind of the preparation method that the 001} face exposes titanium dioxide nanocrystalline is following:
One, the 3.8mL butyl(tetra)titanate is joined in the tetrafluoroethylene water heating kettle, adding 6mL Virahol and 0.5mL mass concentration were 40% hydrofluoric acid aqueous solution, 180 ℃ of insulations 12 hours;
Two, the reaction solution that step 1 is obtained is that spinning goes out deposition under 4000 rev/mins the condition at rotating speed, at 60 ℃ of dry 24h down,, promptly get { 001} face exposure titanium dioxide nanocrystalline through washing, washing with alcohol, drying, grinding then
Find out that by Fig. 5 (scale is 100 nanometers among the figure) product is homodisperse nanocrystalline, even size distribution, the length of side is approximately 76nm, and { 001} face proportion is about 88%.
Can know that by Fig. 6 spacing is that the crystal face of 0.235nm is { 001} a crystal face.
Can know TiO by Fig. 7
2Be pure anatase octahedrite phase, and crystal property is good.
But by Fig. 9 knowledge capital Experiment Preparation { specific surface area that the 001} face exposes titanium dioxide nanocrystalline is 58m
2g
-1
Confirmatory experiment one obtain the 001} face expose that titanium dioxide nanocrystalline and experiment three obtain the 001} face exposes the photocatalytic activity of titanium dioxide nanocrystalline:
1. get respectively that experiment one obtains the 001} face expose that titanium dioxide nanocrystalline and experiment three obtain { the 001} face exposes titanium dioxide nanocrystalline 10mg and is positioned in 2 50mL beakers, and then adds the Hydrogen chloride (pH is about 2.3) of 10mL 0.005mol/L respectively;
2. add 40 μ L mass concentrations respectively and be 0.2% the 2,4 dichloro phenol aqueous solution in above-mentioned two kinds of reaction systems, be statically placed in the high voltage mercury lamp irradiation down of 100W, calculate 2,4 dichloro phenol concentration over time through the uv-visible absorption spectra test.
Can find out by Figure 10, experiment one preparation { the 001} face exposes titanium dioxide nanocrystalline and has higher photocatalytic activity.
Claims (10)
1. one kind the 001} face exposes the preparation method of titanium dioxide nanocrystalline, it is characterized in that a kind of the 001} face exposes the preparation method of titanium dioxide nanocrystalline, and concrete steps are following:
One, titanium salt is joined in ethanol or the Virahol, being mixed with 50mL～100mL concentration is the alcoholic solution of 0.1mol/L～0.5mol/L;
Two, the alcoholic solution that under agitation condition, step 1 is prepared splashes in 60mL～120mL deionized water; Under bath temperature is 60 ℃～90 ℃ condition, stirred 30 minutes～100 minutes then, add alkaline solution 50mL～300mL of 0.5mol/L～5.0mol/L with 300～1000 rev/mins stirring velocitys; Sealing; Continue to stir 4 hours～12 hours at 60 ℃～90 ℃ then, spinning goes out white precipitate, and with deionized water wash white precipitate 3～5 times; To supernatant pH value is neutral, obtains protonated hydration metatitanic acid;
Three, protonated hydration metatitanic acid is washed 3～5 times with alcohol, transfer to then in the tetrafluoroethylene water heating kettle, pure and mild 0.5mL～the 5mL mass concentration was 20%～40% hydrofluoric acid aqueous solution to add 2mL～6mL, 150 ℃～220 ℃ insulations 12 hours～48 hours;
Four, the reaction solution that step 3 is obtained is that spinning goes out deposition under 3000 rev/mins～8000 rev/mins the condition at rotating speed; Then at 60 ℃～100 ℃ following dry 24h～48h; Warp washing, alcohol are washed, dry, grinding, promptly get { 001} face exposure titanium dioxide nanocrystalline.
2. said a kind of { the 001} face exposes the preparation method of titanium dioxide nanocrystalline, it is characterized in that the titanium salt described in the step 1 is titanium tetrachloride, titanium sulfate, titanyl sulfate, butyl(tetra)titanate or isopropyl titanate according to claim 1.
3. said a kind of { the 001} face exposes the preparation method of titanium dioxide nanocrystalline, it is characterized in that the alkaline solution described in the step 2 is sodium hydroxide solution, potassium hydroxide solution or sodium carbonate solution according to claim 1.
4. said a kind of { the 001} face exposes the preparation method of titanium dioxide nanocrystalline, it is characterized in that the alcohol described in the step 3 is ethanol or Virahol according to claim 1.
5. said a kind of { the 001} face exposes the preparation method of titanium dioxide nanocrystalline, it is characterized in that in the step 4 that it is ethanol or Virahol that alcohol is washed used alcohol according to claim 1.
According to claim 1,2,3,4 or 5 said a kind of { the 001} face exposes the preparation method of titanium dioxide nanocrystalline, and the concentration that it is characterized in that alcoholic solution described in the step 1 is 0.2mol/L～0.4mol/L.
According to claim 1,2,3,4 or 5 said a kind of { the 001} face exposes the preparation method of titanium dioxide nanocrystalline, and the concentration that it is characterized in that alcoholic solution described in the step 1 is 0.3mol/L.
According to claim 1,2,3,4 or 5 said a kind of { the 001} face exposes the preparation method of titanium dioxide nanocrystalline, and the concentration that it is characterized in that alkaline solution described in the step 2 is 1mol/L～4mol/L.
According to claim 1,2,3,4 or 5 said a kind of { the 001} face exposes the preparation method of titanium dioxide nanocrystalline, and the concentration that it is characterized in that alkaline solution described in the step 2 is 1mol/L.
According to claim 1,2,3,4 or 5 said a kind of { the 001} face exposes the preparation method of titanium dioxide nanocrystalline, and the mass concentration that it is characterized in that hydrofluoric acid aqueous solution described in the step 3 is 40%.
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| CN103861576A (en) * | 2014-03-06 | 2014-06-18 | 天津大学 | Heterojunction nano-tube array film photocatalysis material for exposing high-energy surface of anatase titanium dioxide, and preparation method and application of photocatalysis material |
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| CN105063719A (en) * | 2015-08-18 | 2015-11-18 | 合肥工业大学 | Homogeneous nanocrystal modified TiO2 nanotube array and preparation method thereof |
| CN107500350A (en) * | 2017-09-25 | 2017-12-22 | 首都师范大学 | A kind of anatase TiO of the crystal face of exposure 0012And preparation method thereof |
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| CN109967062A (en) * | 2019-03-11 | 2019-07-05 | 浙江万里学院 | A kind of high energy crystal face exposure TiO2The preparation method of photochemical catalyst |
| 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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