CN102716732A - Method for synthesizing TiO2 microsphere with high voidage and high specific surface area - Google Patents

Method for synthesizing TiO2 microsphere with high voidage and high specific surface area Download PDF

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CN102716732A
CN102716732A CN2012101733994A CN201210173399A CN102716732A CN 102716732 A CN102716732 A CN 102716732A CN 2012101733994 A CN2012101733994 A CN 2012101733994A CN 201210173399 A CN201210173399 A CN 201210173399A CN 102716732 A CN102716732 A CN 102716732A
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tio
tio2
microballoon
surface area
specific surface
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CN102716732B (en
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董如林
刘淑赟
王彩霞
陈智栋
金长春
王文昌
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Nantong Hailite Rubber and Plastic Machinery Co Ltd
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Changzhou University
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Abstract

The invention discloses a method for synthesizing a TiO2 microsphere with high voidage and high specific surface area, belonging to the technical field of photochemical catalysts. Oil-water interface stabilization with or without a surfactant is carried to obtain the spherical or approximately spherical TiO2, the size of the TiO2 can be regulated by the amount of the used surfactant within a certain scope, the prepared TiO2 has a compressible plastic deformation capability and is in an interpenetrating network structure formed by nano crystal grains and gaps, the specific surface area of the structure is 58-68<2>/g, the pore diameter is 8.4-9.1nm, and the gap volume fraction is 47-59%. Ultraviolet light catalytic degradation experiments of spherical grains on methylene blue show that the TiO2 microsphere has excellent photochemical catalyst activity. Compared with the common emulsion system, the process is simple and the cost is low.

Description

A kind of high voidage, high-specific surface area TiO 2The synthetic method of microballoon
Technical field
The present invention relates to a kind of high-specific surface area TiO 2Microsphere photocatalyst and preparation method thereof belongs to the technical field of photochemical catalyst.
Background technology
TiO 2Semiconductor obtains extensive studies as photochemical catalyst because of its excellent physics, chemical stability and high catalytic activity.TiO 2Photocatalytic activity receive the influence of factors such as crystal habit, particle diameter and crystallinity.At TiO 2Anatase, brockite and three kinds of crystalline state of rutile-type in, with Detitanium-ore-type TiO 2Catalytic activity the highest, therefore,, concentrate on the TiO of this crystal habit mostly as the application study of photochemical catalyst 2On the other hand, TiO 2The particle diameter of powder also influences its photocatalytic activity, nano-TiO to a great extent 2Powder has showed high catalytic activity because of its nanometer size effect and high specific area, but nano-TiO 2Powder is little because of particle size, thereby has Separation of Solid and Liquid difficulty, TiO in the separation process 2Difficult problems such as photochemical catalyst loss.To this problem, some researchers have proposed some solutions, as with nano-TiO 2Powder carries out granulation (CN101879441A), utilizes sol-gel process to prepare nano-TiO 2Powder is modulated TiO with glass cement then 2Colloid obtains TiO through mist projection granulating and heat treatment again 2Microballoon.In addition, can be with nano-TiO 2Particle carries out load or processes TiO on appropriate carriers 2The form of film is used, but also exists TiO in recycling process 2Coming off or problem that the actual light catalytic efficiency is lower of photochemical catalyst.
Summary of the invention
To this problem that exists in the practical application, the present invention proposes a kind of directly synthetic porous TiO with single die wall of dispersion that utilizes 2The method of microballoon.Compare with the emulsion system of routine; Because of the organic solvent that do not use other as oil phase with can not use surfactant; Avoided some influences that processing brought of follow-up Recovery of Organic Solvent problem and surfactant, so this technology is simple, with low cost, and environmental protection.The TiO that is synthesized 2Microballoon is a kind of low-density and has the random network structure in a large amount of nano-scales cavity, and whole structures is made up of nanocrystal and nanometer space; In this dispersion, use or do not use surfactant to carry out that oil-water interface is stable can to obtain sphere and type spherical TiO respectively 2Microballoon; The average-size of microballoon (several micron) within the specific limits can be regulated through changing amount of surfactant; Prepared TiO 2Microballoon has compressible plastic deformation ability, and its specific area is 58～68 m 2/ g, hole diameter are 8.4～9.1 nm, and void volume fraction is 47～59 %.Spherolite shows that to the ultraviolet catalytic degradation experiment of methylene blue it has good photocatalytic activity.
The present invention realizes above-mentioned TiO 2The technical scheme of microballoon is: utilize the emulsifying technology principle, will directly form the emulsion oil-in-water dispersion as oil phase and water by the stable tetrabutyl titanate (TBOT) of acetylacetone,2,4-pentanedione (ACAC).Place hydrothermal treatment consists 24 h under 100～200 ℃ the condition then, obtain TiO 2Microballoon.Spherolite promptly can be used as photocatalyst applications behind 550 ℃ of heat treatment 0.5 h in air.Because titanium hydrolysis of alkoxide speed is very high, so it is stable to adopt the acetylacetone,2,4-pentanedione complexing agent that it is carried out complexing; Tetrabutyl titanate system and the water stable by acetylacetone,2,4-pentanedione have certain compatibility; And the butanols that produces after its hydrolysis can play certain stabilization on the interface of two phases; So the tetrabutyl titanate system as reactant can be dispersed into small drop in aqueous phase voluntarily under condition of stirring; Extra organic solvent need not be added as oil phase, and the surfactant of interface stability effect can be do not used.
A kind of high voidage and high specific area TiO 2The preparation method of microballoon, carry out according to following step:
(1) tetrabutyl titanate (TBOT) and acetylacetone,2,4-pentanedione (ACAC) are pressed the amount of substance ratio n(ACAC)/ n(TBOT)=1～5 mix, stirring reaction 0.5 h prepares oil phase liquid;
(2) get a certain amount of this oil phase liquid and under condition of stirring, join in the aqueous solution of water or DBSA, form milky dispersion; The oil phase that adds and the volume ratio of water do V o/ V w=0.05～0.5;
(3) above-mentioned dispersion is transferred in the agitated reactor that has cup in the polytetrafluoroethylene (PTFE) reaction 24 h under 100～200 ℃ temperature;
(4) reacted product is after processes such as centrifugation, water washing and washing with alcohol, dry 2 h under 100 ℃ temperature;
(5) at last with sample 550 ℃ of heat treatment 0.5 h in Muffle furnace, can obtain TiO 2Microspherical catalyst.
Wherein the concentration of the aqueous solution of the described DBSA of step (1) is 72-800mg/L.
Advantage of the present invention:
1. the TiO that synthesizes of the present invention 2Microballoon sedimentation in aqueous media is easy, has solved nano-TiO 2Not segregative technical problem during powder uses has improved TiO 2The repeat usage of photochemical catalyst.
2. the present invention's employing prepares TiO to the one step of the hydrothermal treatment consists of emulsification dispersion 2Microsphere photocatalyst, synthesis technique is simple.
3. the emulsification system of the present invention's employing is compared with the emulsion system of routine; Because of the organic solvent that do not use other as oil phase with can not use surfactant; Some influences that processing brought of follow-up Recovery of Organic Solvent problem and surfactant have been avoided, so not only technology is simple but also with low cost for this synthetic method.
4. the TiO that the present invention synthesized 2Spherolite 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 is made up of nanocrystal and nanometer space; Therefore photocatalytic activity is high, can be applicable to industrial dyeing waste water, contains the processing of greasy dirt waste water etc.
5. the prepared TiO of the present invention 2The average-size of microballoon (several micron) within the specific limits can be regulated through changing amount of surfactant
6. the prepared TiO of the present invention 2Microballoon has overcome the frangible characteristics of general inorganic material fragility, has compressible plastic deformation ability, thereby in use is difficult for breaking, and repeat usage is high.
Description of drawings:
The TiO that Fig. 1: embodiment 1 is prepared 2The electron micrograph of particulate (not using surfactant), its right-of-center in political views figure is the photo of the bigger multiplication factor of respective left figure sample.
The TiO that Fig. 2: embodiment 2 is prepared 2The electron micrograph of particulate (concentration of DBSA, 72 mg/L), its right-of-center in political views figure is the photo of the bigger multiplication factor of respective left figure sample.
The TiO that Fig. 3: embodiment 2 is prepared 2The electron micrograph of particulate (concentration of DBSA, 800 mg/L), its right-of-center in political views figure is the photo of the bigger multiplication factor of respective left figure sample.
Fig. 4: the TiO that the present invention is prepared 2Particulate is to the ultraviolet catalytic degradation effect figure of methylene blue.
Concrete embodiment
With concrete embodiment the present invention is further specified below.
Embodiment 1:
(1) 5 mL tetrabutyl titanates is mixed stirring reaction 0.5 h with 2 mL acetylacetone,2,4-pentanediones.This reaction is exothermic reaction.When reverting to room temperature, the temperature of treating system just can carry out next step operation.
(2) under condition of stirring, aforesaid liquid is joined in the 50 mL redistilled waters, form milky dispersion.Continue to stir 1 h.
(3) above-mentioned dispersion is transferred in the agitated reactor that has cup in the polytetrafluoroethylene (PTFE) reaction 24 h under 150 ℃ temperature.
(4) reacted product is after processes such as centrifugation, water washing and washing with alcohol, dry 2 h under 100 ℃ temperature.
(5) at last sample 550 ℃ of heat treatment 0.5 h in Muffle furnace are obtained TiO 2Microspherical catalyst.Its electron micrograph such as Fig. 1.It is dispersed preferably to see that particle has, and its outward appearance is similar to sphere.The surface of spherolite shows comparatively coarse on microcosmic simultaneously.
(6) prepared TiO 2The photocatalysis performance test process of microballoon is following:
(a) with 40 mg TiO 2The microballoon 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 the solution.
(b) the suspension system with above-mentioned steps (a) configuration places the uviol lamp of 30 W to shine down, and fluorescent tube is apart from liquid level 14 cm.Adopt the regularly concentration of methylene blue in the mensuration system of spectrophotometer.Before measuring methylene blue concentration, must adopt centrifugal separation method that system is carried out Separation of Solid and Liquid earlier, the clear solution of getting the upper strata then carries out the mensuration of absorbance.
(c) by the degradation rate of the change calculations methylene blue of methylene blue concentration in the system.The degradation rate of methylene blue and UV-irradiation time relation are as shown in Figure 4.When shining 4 h, the degradation rate of methylene blue is 96.3%.
Embodiment 2:
(1) 5 mL tetrabutyl titanates is mixed stirring reaction 0.5 h with 2 mL acetylacetone,2,4-pentanediones.This reaction is exothermic reaction.When reverting to room temperature, the temperature of treating system just can carry out next step operation.
(2) under condition of stirring, aforesaid liquid is joined 50 mL, concentration is in the aqueous solution of 72 mg/L DBSAs, forms milky dispersion.Continue to stir 1 h.
(3) above-mentioned dispersion is transferred in the agitated reactor that has cup in the polytetrafluoroethylene (PTFE) reaction 24 h under 150 ℃ temperature.
(4) reacted product is after processes such as centrifugation, water washing and washing with alcohol, dry 2 h under 100 ℃ temperature.
(5) at last sample 550 ℃ of heat treatment 0.5 h in Muffle furnace are obtained TiO 2Microspherical catalyst.Its electron micrograph such as Fig. 2.It is dispersed preferably to see that particle has, and its outward appearance is perfectly spherical.With respect to the sample of embodiment 1 preparation, the surface of spherolite is comparatively smooth on microcosmic.
(6) prepared TiO 2The photocatalysis performance test process of microballoon is following:
(a) with 40 mg TiO 2The microballoon 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 the solution.
(b) the suspension system with above-mentioned steps (a) configuration places the uviol lamp of 30 W to shine down, and light is apart from liquid level 14 cm.Adopt the regularly concentration of methylene blue in the mensuration system of spectrophotometer.Before measuring methylene blue concentration, must adopt centrifugal separation method that system is carried out Separation of Solid and Liquid earlier, the clear solution of getting the upper strata then carries out the mensuration of absorbance.
(c) by the degradation rate of the change calculations methylene blue of methylene blue concentration in the system.The degradation rate of methylene blue and UV-irradiation time relation are as shown in Figure 4.When shining 4 h, the degradation rate of methylene blue is 93.8%.
 
Embodiment 3:
(1) 5 mL tetrabutyl titanates is mixed stirring reaction 0.5 h with 2 mL acetylacetone,2,4-pentanediones.This reaction is exothermic reaction.When reverting to room temperature, the temperature of treating system just can carry out next step operation.
(2) under condition of stirring, aforesaid liquid is joined 50 mL, concentration is in the aqueous solution of 800 mg/L DBSAs, forms milky dispersion.Continue to stir 1 h.
(3) above-mentioned dispersion is transferred in the agitated reactor that has cup in the polytetrafluoroethylene (PTFE) reaction 24 h under 150 ℃ temperature.
(4) reacted product is after processes such as centrifugation, water washing and washing with alcohol, dry 2 h under 100 ℃ temperature.
(5) at last sample 550 ℃ of heat treatment 0.5 h in Muffle furnace are obtained TiO 2Microspherical catalyst.Its electron micrograph such as Fig. 2.It is dispersed preferably to see that particle also has.Its outward appearance also is spherical with the product of embodiment 2, and the surface is comparatively smooth.Can see that simultaneously pellet surface is owing to the depression that the external force effect stays, show that spherolite inside contains the pore of a large amount of nano-scales, have the ability of plastic deformation, can incompressiblely break.For embodiment 1,2 and 3 samples, by N 2The specific area that absorption method records is respectively 58,65,68 m 2/ g, average pore diameter is respectively 9.1,8.7,8.4 nm.
(6) prepared TiO 2The photocatalysis performance test process of microballoon is following:
(a) with 40 mg TiO 2The microballoon 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 the solution.
(b) the suspension system with above-mentioned steps (a) configuration places the uviol lamp of 30 W to shine down, and light is apart from liquid level 14 cm.Adopt the regularly concentration of methylene blue in the mensuration system of spectrophotometer.Before measuring methylene blue concentration, must adopt centrifugal separation method that system is carried out Separation of Solid and Liquid earlier, the clear solution of getting the upper strata then carries out the mensuration of absorbance.
(c) by the degradation rate of the change calculations methylene blue of methylene blue concentration in the system.The degradation rate of methylene blue and UV-irradiation time relation are as shown in Figure 4.When shining 4 h, the degradation rate of methylene blue is 88.6%.

Claims (2)

1. a high voidage and high specific area TiO 2The preparation method of microballoon is characterized in that carrying out according to following step:
(1) be 1～5 to mix tetrabutyl titanate and acetylacetone,2,4-pentanedione by the amount of substance ratio, stirring reaction 0.5 h prepares oil phase liquid;
(2) get a certain amount of this oil phase liquid and under condition of stirring, join in the aqueous solution of water or DBSA, form milky dispersion; The oil phase that adds and the volume ratio of water are 0.05～0.5;
(3) above-mentioned dispersion is transferred in the agitated reactor that has cup in the polytetrafluoroethylene (PTFE) reaction 24 h under 100～200 ℃ temperature;
(4) reacted product is after processes such as centrifugation, water washing and washing with alcohol, dry 2 h under 100 ℃ temperature;
(5) at last with sample 550 ℃ of heat treatment 0.5 h in Muffle furnace, can obtain TiO 2Microspherical catalyst.
2. a kind of high voidage according to claim 1 and high specific area TiO 2The preparation method of microballoon is characterized in that wherein the concentration of the aqueous solution of the described DBSA of step (1) is 72-800mg/L.
CN201210173399.4A 2012-05-29 2012-05-29 Method for synthesizing TiO2 microsphere with high voidage and high specific surface area Expired - Fee Related CN102716732B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104549193A (en) * 2015-01-08 2015-04-29 常州大学 Low-density TiO2/SiO2 composite microsphere and preparation method thereof

Citations (5)

* 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
CN102249301A (en) * 2011-05-13 2011-11-23 常州大学 Method for controlling surface morphology of TiO2 through ambient humidity
CN102276159A (en) * 2011-05-13 2011-12-14 常州大学 Method for producing bionics TiO2 film by taking ammonium salt as inductive agent

Patent Citations (5)

* 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
CN102249301A (en) * 2011-05-13 2011-11-23 常州大学 Method for controlling surface morphology of TiO2 through ambient humidity
CN102276159A (en) * 2011-05-13 2011-12-14 常州大学 Method for producing bionics TiO2 film by taking ammonium salt as inductive agent

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104549193A (en) * 2015-01-08 2015-04-29 常州大学 Low-density TiO2/SiO2 composite microsphere and preparation method thereof

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