CN104275170B - A kind of { 001} face anatase TiO2The normal temperature preparation method of monocrystalline - Google Patents
A kind of { 001} face anatase TiO2The normal temperature preparation method of monocrystalline Download PDFInfo
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- CN104275170B CN104275170B CN201410477852.XA CN201410477852A CN104275170B CN 104275170 B CN104275170 B CN 104275170B CN 201410477852 A CN201410477852 A CN 201410477852A CN 104275170 B CN104275170 B CN 104275170B
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Abstract
The invention discloses one { 001} face anatase TiO2Normal temperature preparation method. The present invention is achieved through the following technical solutions: the mixed liquor of dehydrated alcohol and butyl titanate drops to the mixed liquor of dehydrated alcohol, deionized water and HF, obtains TiO2Colloidal sol, ageing 24h under room temperature, by the TiO of ageing2Gel centrifugal settles, with distilled water, absolute ethanol washing 3 times, dry, grind after can obtain { the anatase TiO that 001} face exposes2Monocrystalline. This preparation method substantially at room temperature carries out, process is simple, reaction temperature and, easily controllable, the catalyst prepared has higher catalysis activity, can be used for photocatalytic degradation volatile organic matter and hardly degraded organic substance.
Description
Technical field
The present invention relates to catalysis material technical field, be specifically related to one { 001} face anatase TiO2The normal temperature preparation method of monocrystalline.
Background technology
TiO2Because of advantages such as oxidability are strong, the active height of catalysis, physico-chemical property are stable and inexpensive, nontoxic, it is widely used in the photocatalysis field such as wastewater treatment, air cleaning and sterilization be self-cleaning.
The application of titanium dioxide has close contacting with its crystal structure and surface nature. Titanium dioxide is a kind of polymorphous compound, has 3 kinds of crystal habits in nature: rutile-type, anatase titanium dioxide and plate titanium-type. Research shows three kinds of crystal formation TiO2Relative photolytic activity order be: anatase (AT) > > rutile (RT) > > brockite (BT) type TiO2. TiO for anatase crystal2Crystal, its different crystal faces have again different activity. Wherein 001} face be considered as most activity crystal face. But { 001} face anatase TiO2Surface can average out to 0.90J m-2, much larger than { the 0.44J m in 101} face-2, because in crystal growing process, plane of crystal can be more low, more easily retains, and therefore in building-up process, { pole, 001} face is not easily formed.
Recent studies indicate that, HF can help to the { exposure in 001} face as morphology control agent. HF can enable the main cause that 001} face remains is, in reaction system, fluorion and TiO2Ti between have very strong active force, can effectively reduce the surface in 001} face can so that it is surface can lower than the surface in 101} face can so that { 001} is retained. But its preparation process generally requires the hydrothermal temperature of more than 100 DEG C or calcination (such as patent 201010231407.7,201310134847.4,201210083319.6 etc.) just can complete, complicated process of preparation, power consumption.
Summary of the invention
It is an object of the invention to provide one { 001} face anatase TiO2The room temperature preparation method of monocrystalline. This preparation method process is simple, reaction temperature and, easily controllable, the catalyst prepared has higher catalysis activity.
The purpose of the present invention is achieved through the following technical solutions:
1. the mixed liquor of preparation dehydrated alcohol and butyl titanate, is designated as solution A;
2. prepare the mixed liquor of dehydrated alcohol, deionized water and HF, be designated as solution B;
3. B solution is added dropwise in solution A, obtains TiO2Colloidal sol, ageing under room temperature;
4. by the TiO of ageing2Gel centrifugal settles, with distilled water, absolute ethanol washing 3 times, dry, grind after obtain TiO2Monocrystalline.
The mol ratio of described butyl titanate, dehydrated alcohol, deionized water and HF is butyl titanate: dehydrated alcohol: deionized water: HF=1: 10: 100: 1.
Described B solution is added drop-wise to the speed control system of dripping of solution A and drips at 2-3 per second, and mixed on low speed stirs 1-2 hour.
Described digestion time is 24h.
Described drying temperature is 80-100 DEG C.
Described anatase TiO2Monocrystalline granularity is at 100-400nm, and the special standby field of Environment Protection that is adapted at, as degraded volatile organic matter and the photocatalyst of energy degradation of organic substances, has broad application prospects.
The thinking of the present invention is to adopt simple sol-gel process, changes in the past to being hydrolyzed the preparation thinking suppressed containing titanium precursors, adds the ratio of flood, set up the hydrolysis-polymerization reaction formulation system being primary solvent with water. Its mechanism is add the consumption of flood, promotes butyl titanate complete hydrolysis, it is suppressed that polymerization; Change conventional charging sequence, butyl titanate is added drop-wise in HF aqueous solution, control drop rate, it is ensured that water yield during hydrolysis is superfluous, is beneficial to it and is fully hydrolyzed; It is simultaneously introduced HF as morphology control agent, aligns realizing the spontaneous of hydrolyzate, at room temperature grow { the TiO2 crystal that 001} face exposes.
The present invention has such advantages as relative to prior art and effect:
(1) present invention adopts simple sol-gel process, change in the past to being hydrolyzed the preparation thinking suppressed containing titanium precursors, add the ratio of flood, promote butyl titanate complete hydrolysis, it is suppressed that polymerization, make the charging sequence that change is conventional, butyl titanate is added drop-wise in HF aqueous solution, and controls drop rate, it is ensured that water yield during hydrolysis is superfluous, it is beneficial to it be fully hydrolyzed, at room temperature just can form uniform anatase TiO2。
(2) present invention introduces HF as morphology control agent, align realizing the spontaneous of hydrolyzate, at room temperature grow { the TiO that 001} face exposes2Monocrystalline.
(3) reaction condition of the present invention is gentle, device is simple, less costly.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope diagram of the sample of the embodiment of the present invention 1 preparation
Fig. 2 is the X ray crystallogram of the sample of the embodiment of the present invention 1 preparation
Fig. 3 is the effectiveness comparison of this catalyst and P25 degradation of methylene blue under visible ray. Can be seen that { the 001} face anatase TiO that a process for preparing2Monocrystalline has better catalytic effect than P25 under visible light.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention will be described in detail, but the embodiment of this programme is not limited to this.
The technical scheme is that the simple sol-gel process of employing, change in the past to being hydrolyzed the preparation thinking suppressed containing titanium precursors, add the ratio of flood, promote butyl titanate complete hydrolysis, it is suppressed that polymerization; Change conventional charging sequence, butyl titanate is added drop-wise in HF aqueous solution, control drop rate, it is ensured that water yield during hydrolysis is superfluous, is beneficial to it and is fully hydrolyzed; It is simultaneously introduced HF as morphology control agent, aligns realizing the spontaneous of hydrolyzate, at room temperature grow { the TiO that 001} face exposes2Crystal.
Embodiment 1
1. measure 30.4mL dehydrated alcohol to join in 35.2mL butyl titanate, be designated as solution A;
2. measure 30.4mL dehydrated alcohol to join in 180mL water, be simultaneously introduced 20.2mLHF, be designated as solution B;
3. B solution is added dropwise in solution A, and the speed control system of dripping is dripped at 2-3 per second, and mixed on low speed stirs 2 hours, obtains TiO2Colloidal sol, ageing under room temperature;
4. by the TiO of ageing 2d2Colloidal sol centrifugal sedimentation, with distilled water, ethanol cyclic washing 3 times, dries in 100 DEG C of air dry ovens, obtains TiO after grinding2Powder.
Catalyst photocatalytic activity method of testing: evaluate the photocatalytic activity of catalyst with the methylene blue solution that Photocatalytic Activity for Degradation initial concentration is 20mg/L. Concretely comprising the following steps: weigh 1g catalyst powder and join in 100mL methylene blue solution, dark place stands 30min, the impact of deduction absorption; With 500W xenon lamp for light source, utilize JB420 optical filter elimination ultraviolet light, by the magnetic agitation under visible ray shines of the methylene blue solution after standing in camera bellows, liquid level distance light source 20cm, sample once every 30min; After sample solution centrifugal sedimentation, take supernatant and survey respective absorbance calculating methylene blue concentration, and then calculate degradation rate.
Fig. 1 is the scanning electron microscope diagram of the sample of the embodiment of the present invention 1 preparation; Fig. 2 is the X ray crystallogram of the sample of the embodiment of the present invention 1 preparation; Fig. 3 is the effectiveness comparison of this catalyst and P25 degradation of methylene blue under visible ray. From Fig. 1 and Fig. 2 this it appears that prepare is { the anatase TiO that 001} face exposes2Monocrystalline, { the 001} face anatase TiO that a process for preparing as can be seen from Figure 32Monocrystalline has better catalytic effect than P25 under visible light.
Embodiment 2
1. measure 30.4mL dehydrated alcohol to join in 35.2mL butyl titanate, be designated as solution A;
2. measure 30.4mL dehydrated alcohol to join in 180mL water, be simultaneously introduced 20.2mLHF, be designated as solution B;
3. B solution is added dropwise in solution A, and the speed control system of dripping is dripped at 2-3 per second, and mixed on low speed stirs 1.5 hours, obtains TiO2Colloidal sol, ageing under room temperature;
4. by the TiO of ageing 2d2Colloidal sol centrifugal sedimentation, with distilled water, ethanol cyclic washing 3 times, dries in 80 DEG C of air dry ovens, obtains TiO after grinding2Powder.
Catalyst photocatalytic activity method of testing is with embodiment 1.
Above-described embodiment is the present invention preferably embodiment; but embodiments of the present invention are also not restricted to the described embodiments; the change made under other any spirit without departing from the present invention and principle, modification, combination, simplification; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (6)
1. 001 anatase TiO2The normal temperature preparation method of monocrystalline, it is characterised in that realized by following steps:
1. the mixed liquor of preparation dehydrated alcohol and butyl titanate, is designated as solution A;
2. prepare the mixed liquor of dehydrated alcohol, deionized water and HF, be designated as solution B;
3. B solution is added dropwise in solution A, and the mol ratio of described butyl titanate, dehydrated alcohol, deionized water and HF is butyl titanate: dehydrated alcohol: deionized water: HF=1:10:100:1, obtains TiO2Colloidal sol, ageing under room temperature;
4. by the TiO of ageing2Gel centrifugal settles, with distilled water, absolute ethanol washing 3 times, dry, grind after obtain TiO2Monocrystalline.
2. 001 anatase TiO according to right 12The normal temperature preparation method of monocrystalline, it is characterised in that described TiO2Colloidal sol all the other preparation process except drying course all at room temperature carry out.
3. 001 anatase TiO according to right 12The normal temperature preparation method of monocrystalline, it is characterised in that described B solution is added drop-wise to the speed control system of dripping of solution A and drips at 2-3 per second, and mixed on low speed stirs 1-2 hour.
4. 001 anatase TiO according to right 12The normal temperature preparation method of monocrystalline, it is characterised in that described digestion time is 24h.
5. 001 anatase TiO according to right 12The normal temperature preparation method of monocrystalline, it is characterised in that described drying temperature is 80-100 DEG C.
6. 001 anatase TiO according to right 12The normal temperature preparation method of monocrystalline, it is characterised in that described anatase TiO2Monocrystalline granularity is at 100-400nm.
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| CN104689855B (en) * | 2015-02-05 | 2017-01-18 | 西安科技大学 | Preparation method of supported visible-light response WO3/{001}TiO2 compound photocatalyst |
| CN105126713B (en) * | 2015-07-24 | 2017-06-13 | 北京理工大学 | A kind of titanium dioxide parcel nanocrystalline material and preparation method thereof |
| CN105148953B (en) * | 2015-08-28 | 2018-01-16 | 西安科技大学 | A kind of bundle-shaped TiOF2Low temperature preparation method |
| CN107519852A (en) * | 2016-06-22 | 2017-12-29 | 东北林业大学 | A kind of method that normal temperature prepares efficient nano titanium dioxide optical catalyst |
| 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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| KR100807171B1 (en) * | 2007-07-04 | 2008-02-27 | (재)대구경북과학기술연구원 | Titanium Dioxide Photo-Catalyst |
| CN101791545A (en) * | 2010-03-02 | 2010-08-04 | 上海师范大学 | Method for preparing (001) surface-exposed micrometer laminar titanium dioxide photocatalyst |
| CN101949054B (en) * | 2010-08-17 | 2012-12-12 | 浙江大学 | Method for preparing single-crystal anatase titanium dioxide film |
| CN102626613B (en) * | 2012-03-27 | 2014-04-30 | 中国科学院广州地球化学研究所 | {001} surface TiO2 submicron monocrystalline photocatalyst, and preparation method and application thereof |
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| CN102659178A (en) * | 2012-05-11 | 2012-09-12 | 上海师范大学 | Synthesis technology for visible light titanium dioxide nanosheet with exposed {001} face and oxygen defects |
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| CN102976403B (en) * | 2012-12-06 | 2015-08-26 | 南京大学 | A kind of controlled difference exposes the TiO of crystal face 2nanocrystalline preparation method |
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