CN101037227A - Preparation method of Nano TiO2 composite sol having visible light catalytic activation - Google Patents
Preparation method of Nano TiO2 composite sol having visible light catalytic activation Download PDFInfo
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- CN101037227A CN101037227A CN 200710051565 CN200710051565A CN101037227A CN 101037227 A CN101037227 A CN 101037227A CN 200710051565 CN200710051565 CN 200710051565 CN 200710051565 A CN200710051565 A CN 200710051565A CN 101037227 A CN101037227 A CN 101037227A
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Abstract
The present invention discloses a preparation method of nanometer TiO2 composite sol with visible light photocatalysis activity, which comprises the steps of: forming two steady coating structures of nanometer order particles at room temperature by a Triton x 100/n-hexyl alcohol/cyclohexane microemulsion system; dispersing the mixed solution by alcohol, and then titrating into an amount of water while agitating, and then agitating continuously; obtaining precipitate by centrifugal separation, and scrubbing for many times to neutrality; reacting with an amount of acid for a certain time under the condition of agitating and heating so as to obtain the sol raw liquid which should be diluted properly when used for photocatalytic reaction system. The present invention has a simple technology, a convenient operation and a low cost, and is capable of being used for preparing other nanometer TiO2 composite sol sensitized by narrow gap semiconductors, besides, can avoid the coalescence of nanometer order TiO2 during calcination process with an excellent stability. The nanometer TiO2 composite sol of the present invention can be used for the degradation of environmental pollutant and for the switch of solar energy.
Description
Technical field
The present invention relates to the crossing domain of subjects such as material, nanometer, chemistry, environmental science and biology, more specifically relate to a kind of tool visible light catalytic activity nano TiO
2The low temperature preparation method of complex sol.
Background technology
TiO
2Photocatalyst because of its have inexpensive, nontoxic, catalytic activity is high, oxidation capacity is strong, chemical stability is good, abrasion resistance and can recycle etc. advantage, and become catalyzer ideal in the environmental treatment.TiO
2Three kinds of forms in (promptly amorphous, Detitanium-ore-type and rutile-type), anatase crystal demonstrates higher photocatalytic activity, thereby the emphasis that becomes research and use.In the traditional preparation process process, be the anatase octahedrite phase, need heat-treat, at present the synthetic TiO of sol-gel method that extensively adopts or hydrothermal method at the high temperature about 400 ℃ for making its crystal conversion
2Powder or film all need inevitably through this high-temperature calcination process.Yet, under this high temperature during sintering because grain growth and surperficial dehydroxylation process often cause the remarkable reduction of material specific surface area and degree of hydroxylation, cause the loss of catalytic activity, because research confirms, bigger specific surface area and surface hydroxylation degree, help the right effective separation in light induced electron-hole, the object that helps simultaneously degrading is in the absorption of catalyst surface, thereby improves its photocatalysis performance.In addition, cause particle agglomeration, influence TiO because calcining heats up
2Dispersiveness, thereby limit its application.
TiO
2Photocatalytic activity is subjected to the restriction of two factors: the one, and simple TiO
2Semi-conductor is during as photocatalyst, because quantum yield is low, and it is compound easily taken place by the electronics that generates after the optical excitation and hole, makes that its photocatalytic activity is limited; The 2nd, TiO
2Energy gap be 3.2eV, corresponding excitation wavelength is 387nm, in order to pursue nano level high catalytic activity, significant quantum size effect can occur in addition, causes the further blue shift of optical absorption band, causes the visible light utilising efficiency extremely low.This just need be to nano-TiO
2Carry out suitable doping and modification, and possess the active TiO of special light at some
2In the Composite Preparation, pyroprocessing tends to cause some side reactions, reduces the preparation efficiency of material, or the rising preparation cost.Therefore, low temperature prepares the nano-TiO of tool visible light catalysis activity
2Matrix material has become the important breakthrough point of this area research.
Summary of the invention
The object of the present invention is to provide a kind of tool visible light catalytic activity nano TiO
2The preparation method of complex sol is to realize visible light catalysis activity.Below with the nanocrystalline sensitization nano-TiO of CdS
2The complex sol photocatalyst be example because titanium precursor body viscosity is bigger, localized precipitation and form hard coacervate, and Cd easily
2+And S
2-The generation CdS precipitation that very easily reacts accumulates in TiO
2The surface is so the present invention selects to adopt the micro emulsion method to obtain uniform nano level CdS-TiO
2The clad structure of particle, then with sour peptization to obtain nano-tube/CdS-TiO that particle diameter is about 2nm
2Complex sol.This is easy to implement the method, and raw material is cheap and easy to get, and is easy and simple to handle, and the colloidal sol good dispersity that obtains, and has bigger specific surface area and surface hydroxylation degree.
To achieve these goals, the present invention adopts following technical measures:
Its step is as follows:
(a) microemulsion system of elder generation's preparation 10-50ml, the mol ratio of regulating oil phase, tensio-active agent, cosurfactant, water is 32: 1: 2: 2, oil phase can be hexanaphthene, hexahydroaniline, tensio-active agent is Triton X-100, AOT or Brij35, and cosurfactant is propyl carbinol or n-hexyl alcohol.(b) under 200-2000 rev/min magnetic agitation condition, in above-mentioned microemulsion system, slowly drip the presoma of 0.5～1mmol titanium, presoma is titanium tetrachloride or titanium sulfate, titanyl sulfate, butyl (tetra) titanate, isopropyl titanate, drip off the back and continue to stir 30～60min, make it hydrolysis in nano level " pond ", and nucleation, growth, form nanoparticle at last.(c) then add the precursor solution of cadmium (Cd) of 25～55 μ l 0.3mol/L and the (NH of 50～105 μ l17wt%
4)
2S solution, the presoma of Cd can be Cd (NO
3)
2, CdCl
2, continue down to stir 1～3 day in room temperature (20-25 ℃) subsequently to obtain uniform and stable nano level CdS-TiO
2The clad structure of particle.(d) the yellow pulpous state liquid with above-mentioned gained dilutes with 10～50ml alcohol, can use ethanol or Virahol during dilution, dropwise add in 15～40ml water under agitation condition, warming-in-water to 60 after dropwising～80 ℃ continues to stir 30～60 minutes under this temperature; (e) centrifugation goes out light-yellow precipitate, and washes with water 3-5 time, removes the organic solvent and the Cd of precipitation surface absorption
2+, S
2-Plasma; (f) add 0.04～0.1mol/L acid solution at last, seal bottleneck, continue down to stir 4～8 hours, promptly get the nano-TiO of the nano-tube/CdS sensitization of tool visible light catalysis activity in 60～80 ℃
2Colloidal sol, acid are hydrochloric acid, acetic acid, nitric acid or both mixing acid of 1: 1 arbitrarily.The rotating speed of magnetic agitation is 200～2000 rev/mins in the entire reaction course.Nano-tube/CdS-TiO that the present invention obtains
2The complex sol particle diameter is about 2nm, and it is very stable to have bigger specific surface area and a photocatalysis property, can be used for the degradation treatment of a large amount of organic pollutants for a long time.
The present invention is directed to powder TiO in the prior art
2Or TiO
2Major defects such as film disperses inhomogeneous, and particle diameter is bigger than normal, and the visible light utilization ratio is extremely low, the composite hydrolysis product that dissolves each presoma with diluted acid makes nano-tube/CdS-TiO
2Complex sol.Adopt the present invention, materials safety is easy to get, and is cheap, easy and simple to handle, do not need harsh experiment condition, makes laboratory mass preparation and even suitability for industrialized production become possibility.Transmission electron microscope results proves that the product particle diameter is very little, is about 2nm, transparent homogeneous and good dispersiveness is arranged, stability, the CdS-TiO that uv-visible absorption spectra explanation the present invention makes
2Complex sol has certain absorption at visible region 400-500nm, can extensively utilize sunlight to remove toxic organic compound in the environment, administer waste water, purify air and aspect such as bacteria growing inhibiting, and the photodegradation of non-visible light sensitizing dye (methylene blue) experimental results show that its photocatalytic activity obviously is better than pure TiO
2Or CdS sample.
Description of drawings
Fig. 1 is nano-tube/CdS-TiO of the present invention
2The uv-visible absorption spectra of photocatalyst solution is found CdS-TiO
2Complex sol has certain absorption at visible region 400-500nm, so can effectively utilize sunlight;
Fig. 2 is nano-tube/CdS-TiO of the present invention
2The XPS collection of illustrative plates of photocatalyst solution proves CdS and TiO thus
2Coexistence, and CdS and TiO
2Mol ratio be 0.009: 1;
Fig. 3 is nano-tube/CdS-TiO of the present invention
2The XRD figure spectrum behind the powder is made in the photocatalyst solution cryodrying, and CdS is sexangle crystalline phase (according to card JCPDS 80-19) as can be seen, TiO
2Be anatase crystal (reading) according to card JCPDS 21-1272;
Fig. 4 is nano-tube/CdS-TiO of the present invention
2TEM of photocatalyst solution (a) and HRTEM (b) collection of illustrative plates are learnt that grain diameter only is 2nm, and are uniformly dispersed;
Fig. 5 is nano-tube/CdS-TiO of the present invention
2Photocatalyst solution is respectively at the time curve of Photocatalytic Degradation of Methylene Blue by Compound under visible light and the solar light irradiation, and as seen from the figure, its photocatalytic activity obviously is better than pure TiO
2Or CdS sample.
Embodiment
Embodiment 1:
A kind of preparation photocatalytic activity nano-TiO
2The method of colloidal sol the steps include:
1. the preparation microemulsion system adds the 90mmol hexahydroaniline as oil phase, and 2.8mmol Triton X-100 is as tensio-active agent, and the 5.6mmol n-hexyl alcohol is as cosurfactant, and the deionized water that adds 100 μ l is as water;
2. under agitation condition, in above-mentioned microemulsion system, slowly drip the presoma of 0.88mmol titanium, drip off the back and continue to stir 30min;
3. under agitation condition, add the precursor solution of Cd of 45 μ l 0.3mol/L and the (NH of 90 μ l 17wt%
4)
2S solution continues down to stir 2 days in room temperature (20-25 ℃) subsequently;
4. with the yellow pulpous state liquid 25ml alcohol dilution of above-mentioned gained, under agitation condition, dropwise add in the 30ml water, dropwise back warming-in-water to 70 ℃, under this temperature, continue to stir 45 minutes;
5. centrifugation goes out light-yellow precipitate, and washes with water 3 or 4 or 5 times, removes the organic solvent and the Cd of precipitation surface absorption
2+, S
2-Plasma;
6. add the 0.04mol/L salpeter solution, seal bottleneck, continue to stir 4 hours down, promptly get the nano-tube/CdS-TiO of tool visible light catalysis activity in 70 ℃
2Complex sol.
Embodiment 2:
A kind of preparation photocatalytic activity nano-TiO
2The method of colloidal sol the steps include:
1. preparation microemulsion system, adding the 90mmol cyclohexane give is oil phase, and 2.8mmol Triton X-100 is as tensio-active agent, and the 5.6mmol n-hexyl alcohol is as cosurfactant, and the deionized water that adds 100 μ l is as water;
2. under agitation condition, in above-mentioned microemulsion system, slowly drip the presoma of 0.88mmol titanium, drip off the back and continue to stir 30min;
3. under agitation condition, add the precursor solution of Cd of 45 μ l 0.3mol/L and the (NH of 90 μ l 17wt%
4)
2S solution continues down to stir 2 days in room temperature (20-25 ℃) subsequently;
4. with the yellow pulpous state liquid 25ml alcohol dilution of above-mentioned gained, under agitation condition, dropwise add in the 30ml water, dropwise back warming-in-water to 70 ℃, under this temperature, continue to stir 45 minutes;
5. centrifugation goes out light-yellow precipitate, and washes with water 3 or 4 or 5 times, removes the organic solvent and the Cd of precipitation surface absorption
2+, S
2-Plasma;
6. add 0.04mol/L nitric acid, hydrochloric acid mixed solution, seal bottleneck, continue to stir 4 hours down, promptly get the nano-tube/CdS-TiO of tool visible light catalysis activity in 70 ℃
2Complex sol.
Nano-tube/CdS-TiO
2The visible light catalysis activity example of complex sol:
1. get nano-tube/CdS-TiO
2Photocatalyst solution 2.5ml is diluted with water to 5ml, adds the methylene blue aqueous solution of 8 μ mol, is statically placed in the halogen tungsten lamp irradiation down of 500W, and with the following light of spectral filter elimination 420nm, observes its degraded situation and (see Fig. 5 a).The visible light catalysis activity of finding this matrix material obviously is better than simple nano-tube/CdS and TiO
2
2. get nano-tube/CdS-TiO
2Photocatalyst solution 2.5ml is diluted with water to 5ml, adds the methylene blue aqueous solution of 8 μ mol, is statically placed in the sunlight irradiation (AM 1.5) down at high noon, observes its degraded situation (seeing Fig. 5 b).The photocatalytic activity of finding this matrix material obviously is better than simple nano-tube/CdS and TiO
2
Claims (4)
1. tool visible light catalytic activity nano TiO
2The preparation method of complex sol, it comprises the following steps:
(a) preparation microemulsion system, the mol ratio of regulating oil phase, tensio-active agent, cosurfactant, water is 32: 1: 2: 2;
(b) under agitation condition, in above-mentioned microemulsion system, drip the presoma of 0.5～1mmol titanium, drip off the back and continue to stir 30～60min;
(c) under agitation condition, add the precursor solution of dysprosium of 25～55 μ l 0.3mol/L and the (NH of 50～105 μ l 17wt%
4)
2S solution at room temperature stirred 1～3 day subsequently;
(d) the yellow pulpous state liquid with above-mentioned gained dilutes with 10～50ml alcohol, dropwise adds in 15～40ml water under agitation condition, and warming-in-water to 60 after dropwising～80 ℃ continues to stir 30～60 minutes under this temperature;
(e) centrifugation goes out light-yellow precipitate, and washes with water 3-5 time, removes the organic solvent and the Cd of precipitation surface absorption
2+, S
2-Plasma;
(f) add 0.04～0.1mol/L acid solution, seal bottleneck, continue to stir 4～8 hours down, promptly get the nano-TiO of tool visible light catalysis activity in 60～80 ℃
2Complex sol, acid are hydrochloric acid, acetic acid, nitric acid or 1: 1 mixture of above-mentioned any two kinds of acid, and the magnetic agitation rotating speed is 200-2000 rev/min in the whole process;
Described oil phase is hexanaphthene or hexahydroaniline;
Described tensio-active agent is Triton X-100, AOT or Brij35;
Described cosurfactant is propyl carbinol or n-hexyl alcohol.
2. a kind of tool visible light catalytic activity nano TiO according to claim 1
2The preparation method of complex sol is characterized in that: the presoma of titanium is titanium tetrachloride or titanium sulfate, titanyl sulfate, butyl (tetra) titanate, isopropyl titanate.
3. a kind of tool visible light catalytic activity nano TiO according to claim 1
2The preparation method of complex sol is characterized in that: the presoma of cadmium is Cd (NO
3)
2Or CdCl
2
4. a kind of tool visible light catalytic activity nano TiO according to claim 1
2The preparation method of complex sol is characterized in that: use ethanol or Virahol during the dilution microemulsion.
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Cited By (2)
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|---|---|---|---|---|
| CN106475116A (en) * | 2016-08-27 | 2017-03-08 | 浙江和谐光催化科技有限公司 | TiO2/Sb2S3Composite photocatalyst colloid preparation method |
| CN107253736A (en) * | 2017-08-16 | 2017-10-17 | 四川理工学院 | A kind of preparation method of anatase titanium dioxide monocrystalline |
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| CN100475335C (en) * | 2003-09-22 | 2009-04-08 | 中国科学院化学研究所 | Photocatalyst responding to visible light, and preparation method and application thereof |
| CN1593749A (en) * | 2004-07-05 | 2005-03-16 | 华东理工大学 | Process for preparing nanometer titanium dioxide membrane photocatalyst |
| CN1327953C (en) * | 2004-08-30 | 2007-07-25 | 中国科学院上海硅酸盐研究所 | Photocatalyst of nano titanium oxide modifed by cadmium selenide and preparation method |
| CN100348318C (en) * | 2005-11-28 | 2007-11-14 | 浙江大学 | Nanometer, composite semiconductor photocatalyst, and its prepn. method |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106475116A (en) * | 2016-08-27 | 2017-03-08 | 浙江和谐光催化科技有限公司 | TiO2/Sb2S3Composite photocatalyst colloid preparation method |
| CN107253736A (en) * | 2017-08-16 | 2017-10-17 | 四川理工学院 | A kind of preparation method of anatase titanium dioxide monocrystalline |
| CN107253736B (en) * | 2017-08-16 | 2019-03-12 | 四川理工学院 | A kind of preparation method of anatase titanium dioxide monocrystalline |
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