CN102701276B - Hollow TiO2 microsphere synthesizing method - Google Patents

Hollow TiO2 microsphere synthesizing method Download PDF

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CN102701276B
CN102701276B CN201210172919.XA CN201210172919A CN102701276B CN 102701276 B CN102701276 B CN 102701276B CN 201210172919 A CN201210172919 A CN 201210172919A CN 102701276 B CN102701276 B CN 102701276B
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hollow
spherical particle
tio2
tio
microballoon
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CN102701276A (en
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董如林
王彩霞
刘淑赟
陈智栋
金长春
王文昌
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Liyang Chang Technology Transfer Center Co., Ltd.
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Changzhou University
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Abstract

The invention discloses a hollow TiO2 microsphere synthesizing method, and belongs to the field of solar energy utilizing photovoltaic technology and photocatalysts. In the hollow TiO2 microsphere synthesizing method, through hydrothermal treatment, tetrabutyl titanate is directly taken as an oil phase and forms an emulsion dispersion system with water to obtain a TiO2 hollow spherical particle; a hollow characteristic is obtained through simple change in the mixing sequence of raw materials; the substantial part of the TiO2 hollow spherical particle has a three-dimensional interpenetrating network structure formed by a nano TiO2 crystal grain and a nano-sized space; the average diameter of the spherical particle is 0.5-1.5 microns and can be adjusted by changing the adding amount of a surfactant; the specific surface area of the spherical particle is 32-97 m2/g; the apparent density of the spherical particle is 1.91 g/cm3. When the hollow spherical particle is used as an electrode material of a dye-sensitized TiO2 solar cell, the optical path can be elongated and the utilization efficiency of light energy can be improved; and when the hollow spherical particle is used as a photocatalyst, the photocatalytic activity is high and the hollow spherical particle is easily separated from a liquid medium.

Description

A kind of hollow TiO 2the synthetic method of microballoon
Technical field
The present invention relates to a kind of hollow TiO 2the preparation method of microballoon, belongs to photovoltaic technology and photocatalyst field that sun power utilizes.
Background technology
The major objective of solar cell research is to be devoted to improve light-photoelectric transformation efficiency.For dye sensitization TiO 2solar cell, its photoelectric transformation efficiency and TiO 2the microstructure of electrode has close relationship.When forming the TiO of electrode 2size of particles increases to when suitable with visible wavelength, because its enhancing to visible ray scattering process has extended light path, thereby is conducive to improve the capture rate of dye molecule to light.But TiO 2when being beneficial to scattering of light, the increase of size of particles also reduced TiO 2specific surface area.And the TiO of little nano-scale 2particle has large specific surface area, but is unfavorable for the scattering effect of visible ray.Therefore, self-assembling formation utilize nanoparticle and macrobead TiO 2the thinking of electrode is prepared in combination.Research shows, for macrobead TiO 2microballoon, is hollow microsphere if within forms cavity, and the scattering that utilizes its spherical shell and cavity can further extend light path and increase the assimilated efficiency of light, thereby is conducive to improve the light-photoelectric transformation efficiency of solar cell.On the other hand, at TiO 2as the application aspect of photocatalyst, nano-TiO 2powder has showed relatively high catalytic activity because of its nanometer size effect and high specific surface area, but nano-TiO 2powder in use with the separation difficulty of medium liquid.Therefore, also need still can not obviously reduce its specific surface area by increasing the size of particle.Synthesizing porous property TiO 2microballoon can address this problem equally.
Summary of the invention
For above-mentioned this requirement, the present invention proposes a kind of stable dispersion system of tensio-active agent that utilizes and synthesizes hollow TiO 2the method of microballoon.Adopt the method (being about to water adds in oil phase) that changes reinforced order to obtain the stable double-deck interface dispersion system of tensio-active agent, thereby realize the synthetic of hollow sphere; The method is compared with conventional emulsion system, because the organic solvent that do not use other is as oil phase, has avoided the recovery problem of follow-up organic solvent, so technique is simple, with low cost, and environmental protection; The TiO of synthesized 2the spherical shell of microballoon is a kind of low density and the random network structure with a large amount of nano-scales cavity, and whole structures consists of nanocrystal and nano-space; The size of spherolite can be regulated by changing the consumption of tensio-active agent; Prepared hollow TiO 2microballoon specific surface area is 97 m 2/ g, apparent density is 1.91 g/cm 3.
The present invention realizes above-mentioned TiO 2the technical scheme of hollow microsphere is: it is stable that tetrabutyl titanate (TBOT) first uses methyl ethyl diketone (ACAC) to carry out complexing before using, and using it as oil phase.Then, in the above-mentioned oil phase aqueous solution of tensio-active agent slowly being added under the condition stirring, form milky dispersion system.At the aqueous solution, enter on a small quantity after oil phase, under the effect of tensio-active agent, first formed the emulsion of w/o type.Along with the further increase of aqueous solution add-on, emulsion system is converted into O/W type from w/o type.Original globule in oil phase forming has formed the kernel water in dispersed oil droplets.In fact formed W/O/W type emulsion.Then this emulsion system is placed in to Water Under thermal treatment 24 h of 100～200 ℃, the TBOT particle generation hydrolysis-condensation reaction of dispersion forms anatase titanium dioxide TiO 2, the kernel water comprising volatilizees and the cavity of formation spherolite in dry and heat treatment process subsequently.In this reaction, because titanium hydrolysis of alkoxide speed is very high, so it is stable to adopt ACAC complexing agent in advance it to be carried out to complexing.
A kind of hollow TiO 2the preparation method of microballoon, carries out according to following step:
(1) tetrabutyl titanate (TBOT) and methyl ethyl diketone (ACAC) are pressed to amount of substance ratio n(ACAC)/ n(TBOT)=1～5 are mixed into oil phase liquid, stirring reaction 0.5 h.
(2) aqueous solution of getting the Witco 1298 Soft Acid of certain volume slowly joins in above-mentioned oil phase liquid in the situation that stirring, and forms milky dispersion system; Wherein said oil phase with the water volume ratio adding is v o/ v w=0.05～0.6;
(3) above-mentioned dispersion system is transferred in the reactor with cup in tetrafluoroethylene, at the temperature of 100～200 ℃, reacts 24 h;
(4) reacted product, after the processes such as centrifugation, water washing and washing with alcohol, is dried 2 h at the temperature of 100 ℃.
(5) finally by sample 550 ℃ of thermal treatment 0.5 h in retort furnace, can obtain hollow TiO 2microballoon.
Wherein the concentration of the aqueous solution of the Witco 1298 Soft Acid described in step (1) is 72～800 mg/L.
advantage of the present invention:
1. the synthetic TiO of the present invention 2hollow sphere can utilize the surfaces externally and internally of its spherical shell incident scattering of light to be improved to the efficiency of light absorption of dye sensitization solar battery.The synthetic TiO of the present invention simultaneously 2hollow sphere sedimentation in aqueous media is easy, as photocatalyst, uses, and can improve TiO 2the repeat usage of photocatalyst.
2. the one step that the present invention's employing is carried out hydrothermal treatment consists to emulsion dispersion system is prepared TiO 2hollow sphere, synthesis technique is simple.
3. the emulsification system that the present invention adopts is compared with conventional emulsion system, because the organic solvent that do not use other is as oil phase, has avoided the recovery problem of follow-up organic solvent, so not only technique is simply but also with low cost for this synthetic method.
4. the TiO of synthesized of the present invention 2hollow sphere size has certain Tile Width, can mate the monochromatic ray of various wavelength in sunlight, thereby can further increase incident scattering of light degree, improves the efficiency of light absorption of dye sensitization solar battery.
5. the TiO of synthesized of the present invention 2the spherical shell of microballoon presents a kind of low density and has the random network structure in a large amount of nano-scales cavity on microcosmic, and whole structures consists of nanocrystal and nano-space, therefore photocatalytic activity is high, also can be applicable to dyeing wastewater, containing the processing of oil-polluted water etc.
6. the prepared TiO of the present invention 2the mean sizes of microballoon can be regulated by changing the consumption of tensio-active agent within the specific limits.
accompanying drawing explanation:
The TiO that Fig. 1: embodiment 1 is prepared 2the electron micrograph of hollow sphere, wherein right figure is the photo of the larger magnification of corresponding left figure sample.
The TiO that Fig. 2: embodiment 2 is prepared 2the electron micrograph of hollow sphere, wherein right figure is the photo of the larger magnification of corresponding left figure sample.
Fig. 3: the TiO that the present invention is prepared 2the photocatalytic degradation effect of hollow sphere to methylene blue.
Fig. 4: the TiO that the present invention is prepared 2the digital camera photo of hollow sphere water system suspension liquid before standing and after standing 1.5 h.Experiment shows that spherolite has good settling character in water.
Fig. 5: TiO 2the relation of the transmittance of hollow microsphere electrode film and the number of plies of filming.
concrete embodiment
With specific embodiment, the present invention is further described below.
Embodiment 1:
(1) 5 mL tetrabutyl titanates are mixed to stirring reaction 0.5 h with 2 mL methyl ethyl diketones.This reaction is thermopositive reaction.When reverting to room temperature, the temperature of system just can carry out next step operation.
(2) get 50 mL, the aqueous solution of 72 mg/L Witco 1298 Soft Acids slowly joins in aforesaid liquid in the situation that stirring, and forms milky dispersion system.Continue to stir 1 h.
(3) above-mentioned dispersion system is transferred in the reactor with cup in tetrafluoroethylene, at the temperature of 150 ℃, reacts 24 h.
(4) reacted product, after the processes such as centrifugation, water washing and washing with alcohol, is dried 2 h at the temperature of 100 ℃.
(5) finally sample 550 ℃ of thermal treatment 0.5 h in retort furnace are obtained to TiO 2microspherical catalyst.Its electron micrograph is as Fig. 1.Can see that particle appearance is spherical, surface shows comparatively coarse on microcosmic; There is good dispersiveness; The size of particle has certain Tile Width, and the mean diameter of being added up by microscopic is 1.5 microns; Can observe spherolite and be hollow morphology, the similar Pericarppium arachidis hypogaeae structure of ball wall simultaneously.By N 2the surface-area that adsorption experiment records is 97 m 2/ g.
(6) prepared TiO 2the photocatalysis performance test process of microballoon is as follows:
(a) by 40 mg hollow TiO 2microballoon powder is scattered in 50 mL, and concentration is in the aqueous solution of methylene blue of 5 mg/L, adopts magnetic agitation that powder granule is dispersed in solution.
(b) the suspension system of above-mentioned steps (a) configuration is placed under the ultraviolet lamp of 30 W and irradiates, fluorescent tube is apart from liquid level 14 cm.Adopt spectrophotometer regularly to measure the concentration of system Methylene Blue solution.Measure before methylene blue concentration, must first adopt centrifugal separation method to carry out solid-liquid separation to system, the clear solution of then getting upper strata carries out the mensuration of absorbancy.
(c) by the photocatalytic activity of the change calculations methylene blue of system Methylene Blue concentration.The relation of the degradation rate of methylene blue and UV-irradiation time as shown in Figure 3.While irradiating 4 h, the degradation rate of methylene blue is 92%.
(7) prepared TiO 2the separation performance evaluation procedure of hollow microsphere and water is as follows:
(a) TiO that configuration solid content is 20 g/L 2hollow microsphere aqueous suspension, is placed in the test tube that fills 8 these suspension liquids of mL on test-tube stand.In standing process, because of particles settling, it is Clear & Transparent that the top of test tube becomes gradually, bottom solid content increases, observation suspension liquid is tapered to and is occurred that obvious transparent layer and needed time of white solid layering, Fig. 3 have represented the digital camera photo of the standing 1.5 h front and back of suspension liquid by homogeneous turbid system.The photo of Fig. 3 shows: in 1.5 h, the spherolite in suspension liquid almost all deposits, and has good natural sediment characteristic.
(b) system after layering is carried out to separation, the wet solid after separation is dry 2 h at 100 ℃, weigh after cooling.By operation before and after microballoon Mass Calculation TiO 2the rate of recovery after hollow microsphere is used is 99%.
(8) TiO 2the preparation of hollow microsphere electrode and the test process of transmittance thereof are as follows:
(a) 0.5 g hollow sphere is disperseed in the mixed solvent of 4.5 mL water and 4.5 mL dehydrated alcohols composition, stir suspension liquid and make solvent evaporates to system there is suitable viscosity, adopt frictioning method to form coating at glass basic surface.
(b) coating is carried out repetition coating operation after being dried.
(c) adopt UV-spectrophotometry to measure the absorbancy of different thickness film, and calculate thus the transmittance of film.Fig. 4 has represented the relation of transmittance and its thickness of film.Filming 1～2 layer time, film has higher transmittance, but the number of plies is increased to 3 layers when above, and the transmittance of film is down to approximately 1%.Therefore as membrane electrode, use, film 3 layers time and can meet service requirements.
Embodiment 2:
(1) 5 mL tetrabutyl titanates are mixed to stirring reaction 0.5 h with 2 mL methyl ethyl diketones.This reaction is thermopositive reaction.When reverting to room temperature, the temperature of system just can carry out next step operation.
(2) get 50 mL, the aqueous solution of 800 mg/L Witco 1298 Soft Acids slowly joins in aforesaid liquid in the situation that stirring, and forms milky dispersion system.Continue to stir 1 h.
(3) above-mentioned dispersion system is transferred in the reactor with cup in tetrafluoroethylene, at the temperature of 150 ℃, reacts 24 h.
(4) reacted product, after the processes such as centrifugation, water washing and washing with alcohol, is dried 2 h at the temperature of 100 ℃.
(5) finally sample 550 ℃ of thermal treatment 0.5 h in retort furnace are obtained to TiO 2microspherical catalyst.Its electron micrograph is as Fig. 2.Particle profile is similar to the product that embodiment 1 obtains, and except spheroidal particle, has also generated the powder of some nano-scales in system.The spheroidal particle mean diameter of being added up by microscopic is 0.5 micron.By N 2the surface-area that adsorption experiment records is 32 m 2/ g.
(6) prepared TiO 2the photocatalysis performance test process of microballoon is as follows:
(a) by 40 mg TiO 2microballoon powder is scattered in 50 mL, and concentration is in the aqueous solution of methylene blue of 5 mg/L, adopts magnetic agitation that powder granule is dispersed in solution.
(b) the suspension system of above-mentioned steps (a) configuration is placed under the ultraviolet lamp of 30 W and irradiates, fluorescent tube is apart from liquid level 14 cm.Adopt spectrophotometer regularly to measure the concentration of system Methylene Blue.Measure before methylene blue concentration, must first adopt centrifugal separation method to carry out solid-liquid separation to system, the clear solution of then getting upper strata carries out the mensuration of absorbancy.
(c) by the degradation rate of the change calculations methylene blue of system Methylene Blue concentration.Fig. 3 has shown the prepared hollow TiO of embodiment 2 2the photocatalytic degradation effect of microballoon to methylene blue.After UV-irradiation 4 h, the degradation rate of methylene blue reaches 99 %.

Claims (2)

1. a hollow TiO 2the preparation method of microballoon, is characterized in that carrying out according to following step:
(1) by tetrabutyl titanate and methyl ethyl diketone, by amount of substance ratio, be 1～5 to be mixed into oil phase liquid, stirring reaction 0.5 h;
(2) aqueous solution of getting the Witco 1298 Soft Acid of certain volume slowly joins in above-mentioned oil phase liquid in the situation that stirring, and forms milky dispersion system; Wherein said oil phase is 0.05～0.6 with the water volume ratio adding;
(3) above-mentioned dispersion system is transferred in the reactor with cup in tetrafluoroethylene, at the temperature of 100～200 ℃, reacts 24 h;
(4) reacted product, after centrifugation, water washing and washing with alcohol process, is dried 2 h at the temperature of 100 ℃;
(5) finally by sample 550 ℃ of thermal treatment 0.5 h in retort furnace, can obtain hollow TiO 2microballoon.
2. a kind of hollow TiO according to claim 1 2the preparation method of microballoon, is characterized in that the concentration of the aqueous solution of the Witco 1298 Soft Acid that step (2) is wherein described is 72～800 mg/L.
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CN103894163B (en) * 2012-12-24 2016-02-24 北京有色金属研究总院 A kind of high-performance nano TiO 2photocatalyst material and preparation method thereof
CN103950975B (en) * 2014-04-17 2015-05-06 渤海大学 Method for preparing hollow rutile micron titanium dioxide
CN104192895B (en) * 2014-08-12 2018-07-10 渤海大学 A kind of nano-TiO2The preparation method of microballoon
CN104310466B (en) * 2014-10-10 2016-03-09 常州大学 A kind of hollow titanium dioxide microballoon based on gel ball presoma and preparation method thereof
CN104817106B (en) * 2015-05-07 2017-03-15 中国科学院合肥物质科学研究院 TiO2The solvent process for thermosynthesizing of hollow-core construction sub-micron ball
CN105348795A (en) * 2015-12-01 2016-02-24 仇颖超 Preparation method of modified titanium dioxide/polyimide resin composite
CN107021522B (en) * 2017-05-05 2018-12-28 常州大学 A kind of monodisperse TiO based on microemulsion2The synthetic method of microballoon
CN107253735A (en) * 2017-07-21 2017-10-17 陕西科技大学 Hollow nano TiO 2 microballoon and preparation method thereof
CN113772722A (en) * 2021-10-28 2021-12-10 中国科学院合肥物质科学研究院 TiO with special hollow structure2Preparation method of micro-spheres

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1765511A (en) * 2005-10-13 2006-05-03 武汉理工大学 PH adjusting hydrothermal preparation method of active nano crystal mesoporous titanium dioxide photocatalytic material
CN101381099A (en) * 2008-10-13 2009-03-11 彩虹集团公司 Nano TiO2 preparation method
US20110189081A1 (en) * 2008-03-25 2011-08-04 Gao Qing Lu Crystalline inorganic species having optimised reactivity

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1765511A (en) * 2005-10-13 2006-05-03 武汉理工大学 PH adjusting hydrothermal preparation method of active nano crystal mesoporous titanium dioxide photocatalytic material
US20110189081A1 (en) * 2008-03-25 2011-08-04 Gao Qing Lu Crystalline inorganic species having optimised reactivity
CN101381099A (en) * 2008-10-13 2009-03-11 彩虹集团公司 Nano TiO2 preparation method

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