CN101891248A - Titania nanotube/nanorod microspheres with hierarchical structure and preparation method thereof - Google Patents
Titania nanotube/nanorod microspheres with hierarchical structure and preparation method thereof Download PDFInfo
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- CN101891248A CN101891248A CN 201010223267 CN201010223267A CN101891248A CN 101891248 A CN101891248 A CN 101891248A CN 201010223267 CN201010223267 CN 201010223267 CN 201010223267 A CN201010223267 A CN 201010223267A CN 101891248 A CN101891248 A CN 101891248A
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Abstract
The invention discloses titania nanotube/nanorod microspheres with a hierarchical structure and a preparation method thereof. The microspheres are porous spheres formed by intertwining titania nanotubes or nanorods, and are obtained by reacting a titania microsphere precursor in alkali solution, dispersing and washing in diluted acid, and annealing at the temperature of between 400 and 500 DEG C. The microspheres have a three-dimensional hierarchical structure and high specific surface area; and the microspheres have higher ultraviolet absorption capability and high catalytic activity under ultraviolet light because of a hierarchical tubular structure.
Description
Technical field
The present invention relates to a kind of graduation titanium dioxide microballoon sphere, particularly titania nanotube/nanorod microspheres of a kind of graded structure and preparation method thereof can be used for the environmental technology field of ultraviolet degradation organic pollutant.
Background technology
In recent years, environmental pollution has become serious problems that threaten human survival, and the conductor photocatalysis oxidation technology that develops rapidly becomes a kind of effective ways of administering environmental problem.In numerous conductor photocatalysis materials, titanium dioxide is most widely used a kind of photocatalyst owing to have advantages such as oxidation capacity is strong, nontoxic, chemical property is stable always.Because these excellent characteristics, titanium dioxide has widely in many fields such as deodorizing, antibiotic, water treatment and purifying airs to be used.Though titanium dioxide is kind of a generally acknowledged photocatalyst preferably, considers from practical application and commercialization, its photocatalytic activity remains further to be improved, and generally is at present to improve its catalytic activity by specific surface area and the degree of crystallinity that improves material.In addition, the titanium dioxide of practical application at present is that the form with nanometer powder exists mostly, and this makes that the difficult separation and recycling of material is bigger, and nanometer powder also more easily reunites, and easily makes catalyst deactivation.
The one or more dimensions nano material comprises nano wire, nanometer rod and nanotube etc., has the better characteristics of ratio nano powder.Have specific surface area as titania nanotube and reach the catalytic efficiency advantages of higher greatly, be well suited for being used for catalysis purifying air and sewage disposal, but the more difficult Separation and Recovery of dispersive titania nanotube has influenced its application in practice.In recent years, the material with graded structure has obtained extensive concern because of its excellent characteristic in functional materials is synthetic." JACS " (J.Am.Chem.Soc.2008,130,11256～11257) have reported that graduate titanium dioxide microballoon sphere has good effect aspect the filtration treatment sewage, but this microballoon specific surface area is less, only is 21.6m
2/ g.Therefore, synthetic graduation titanium dioxide microballoon sphere with one or more dimensions nanometer material structure (particularly nano tubular structure) will have important practical application meaning.
Summary of the invention
The purpose of this invention is to provide titania nanotube/nanorod microspheres of a kind of graded structure and preparation method thereof, this kind microballoon has tridimensional network, bigger serface and is easy to Separation and Recovery.
A kind of titania nanotube/nanorod microspheres of graded structure, microballoon are the porous balls that the nanometer rod by the titania nanotube of diameter 10～12nm, length 2～6 μ m or diameter 12～15nm, length 40～60nm is interwoven.
Above-mentioned microsphere diameter is 4～6 μ m, and specific surface area is 61.1～215.8m
2/ g, pore volume is 0.29～0.42cm
3/ g, average pore diameter is 7.85～18.71nm, is a kind of micron order functional materials of bigger serface, relatively is fit to degradable organic pollutant in actual applications.
The preparation method of the titania nanotube/nanorod microspheres of above-mentioned graded structure, step is as follows:
(1) synthesize the titanium dioxide microballoon sphere presoma with existing universal method, this presoma is made up of random nano particle, and diameter is 4～6 μ m;
(2) get above-mentioned presoma and put into the alkaline solution that concentration is 5～15M, magnetic agitation 0.5～0.8h mixes, mixed solution put into have the teflon-lined autoclave, react 24～48h down at 130～200 ℃, behind the naturally cooling, cooled product is dispersed in the dilute hydrochloric acid again, magnetic agitation 12h, to neutral, can obtain graduation titanium dioxide microballoon sphere that diameter be 4～6 μ ms behind suction filtration, 40 ℃ of dry 5h through deionized water wash;
(3) subsequently this microballoon is annealed at 400～500 ℃, can obtain a kind of titania nanotube/nanorod microspheres of graded structure.
The described alkaline solution of above-mentioned steps (2) is sodium hydroxide or potassium hydroxide solution, and consumption is 0.5g presoma 50mL alkaline solution; The concentration of dilute hydrochloric acid is 0.1M, and consumption is 0.5g presoma 600mL acid solution.
Titanium dioxide microballoon sphere of the present invention has the following advantages:
1, have unique three-dimensional graded structure, microsphere diameter is 4～6 μ m, and spheroid is by diameter 10～12nm, and the nanometer rod of the titania nanotube of length 2～6 μ m or diameter 12～15nm, length 40～60nm is formed; This microballoon is the anatase octahedrite phase.
2, this microballoon has high-specific surface area, has vesicular structure simultaneously, is suitable for being used for photocatalysis degradation organic contaminant;
3, owing to be micro-sphere structure, this catalyzer is easy to separate, thereby is easy in actual applications recycle;
4, owing to graduate vesicular structure, this microballoon has stronger uv-absorbing ability, apparently higher than the titanium dioxide (Degussa P25) of commercial applications.
5, catalytic activity height under the UV-light is apparently higher than the titanium dioxide (Degussa P25) of commercial applications.
6, this method for preparing catalyst is simple, and preparation productive rate height has great industrialization value.
Can carry out with the following method the photocatalytic activity test that the present invention proposes:
Photochemical catalysis test (transverse section 30cm in glass beaker
2, high 5cm) carry out under the normal temperature and pressure.Light source is selected the 500W xenon lamp for use.Come the photocatalytic activity of assess sample with tropeolin-D.Take by weighing 0.1g sample dispersion (20mg/L) in the 100mL methyl orange solution.Before the light-catalyzed reaction test, lucifuge magnetic agitation 30min makes tropeolin-D reach adsorption equilibrium at catalyst surface, and every 5min sampling 5mL, supernatant liquor measurement of ultraviolet-visible spectrophotometer absorbancy is got in centrifugation behind the logical light.As a comparison, under equal experiment condition, carried out the photocatalytic activity test with P25 with commercial.
Test through photochemical catalysis, the titania nanotube microballoon of graded structure can be intact with methyl orange degradation at 30min, the titanium dioxide nano-rod microballoon of graded structure can be intact with methyl orange degradation at 40min, and commercially need the 50min could methyl orange degradation is complete with P25.As seen the photocatalytic activity of the titania nanotube/nanorod microspheres of graded structure will be higher than and commercial uses P25, and microballoon is easy to sedimentation, through the just separable recycling of natural subsidence.
Description of drawings
Fig. 1 is the X-ray diffractogram of the embodiment of the invention 1 product;
Fig. 2 is the SEM and the TEM figure of the embodiment of the invention 1 product;
Fig. 3 is that the UV, visible light diffuse-reflectance of the embodiment of the invention 1 product and P25 absorbs figure;
Fig. 4 is the X-ray diffractogram of the embodiment of the invention 2 products;
Fig. 5 is the SEM and the TEM figure of the embodiment of the invention 2 products;
Embodiment:
Embodiment 1
At first under hydrothermal condition, synthesize the titanium dioxide microballoon sphere presoma: the 5.1g tetrabutyl titanate is under agitation splashed in the 75mL dehydrated alcohol with universal method, add the 0.33mL vitriol oil (98%) and 0.3mL deionized water subsequently, with mixture put into volume be 110mL have a teflon-lined autoclave, at 180 ℃ of reaction 4h, naturally cool to room temperature, take out and filter, standby behind 40 ℃ of dry 5h.This presoma is made up of random nano particle, and diameter is 4～6 μ m; Get 0.5g microballoon presoma and put into the sodium hydroxide solution that 50mL concentration is 10M, magnetic agitation 0.5h, with mixed solution put into volume be 80mL have a teflon-lined autoclave, at 150 ℃ of reaction 24h, naturally cool to room temperature, take out and filter, deionized water wash is to neutral, product is dispersed in the dilute hydrochloric acid that 600mL concentration is 0.1M again, stirring at room 12h, to neutral, at 40 ℃ of dry 5h, can obtain diameter is the nanotube-shaped titanium dioxide microballoon sphere of 4～6 μ m through deionized water wash.This microballoon at 400 ℃ of annealing 1h, can be obtained the titania nanotube microballoon of the graded structure of anatase octahedrite phase.
Accompanying drawing 1 is the X-ray diffractogram of present embodiment products therefrom, as seen from the figure, each diffraction peak of this product all with anatase octahedrite TiO mutually
2Standard card (JCPDS No.21-1272) to go up peak position corresponding, and do not have the dephasign peak and exist, illustrate that product is pure anatase octahedrite phase TiO
2Accompanying drawing 2 is the SEM of present embodiment products therefrom and TEM figure, and the diameter of gained titanium dioxide microballoon sphere is 4～6 μ m as seen from Figure 2, and this microballoon is by diameter 10～12nm, and length is that the titania nanotube of 2～6 μ m is entwined.Accompanying drawing 3 is that the UV, visible light diffuse-reflectance of present embodiment products therefrom and commercial applications titanium dioxide (Degussa P25) absorbs the figure contrast, the relative P25 of this titanium dioxide microballoon sphere has stronger uv-absorbing ability as can be seen, and this has good light scattering property owing to the graduation nano tubular structure.
Above detection and the analysis integrated product that has proved that present embodiment obtains are graduation tubulose anatase phase titanium dioxide microballoons.Adopt the titanium dioxide microballoon sphere of the inventive method preparation, the product crystal formation is intact, has both had bigger specific surface area, has one dimension tubular structure and characteristic such as easily separated again simultaneously, can be used effectively in fields such as PHOTOCATALYTIC AIR-PURIFYING and sewage; Therefore this microballoon also has tridimensional network, can carry out liquid filtering effectively, the potential using value is also arranged at filter membrane aspect disposing of sewage.
Embodiment 2
At first synthesize titanium dioxide microballoon sphere presoma (with embodiment 1) with universal method; Get 0.5g microballoon presoma and put into the sodium hydroxide solution that 50mL concentration is 10M, magnetic agitation 0.5h, with mixed solution put into volume be 80mL have a teflon-lined autoclave, at 150 ℃ of reaction 24h, naturally cool to room temperature, take out and filter, deionized water wash is to neutral, product is dispersed in the dilute hydrochloric acid that 600mL concentration is 0.1M again, stirring at room 12h, extremely neutral through deionized water wash, at 40 ℃ of dry 5h, product can obtain the titanium dioxide nano-rod microballoon of the graded structure of anatase octahedrite phase at 500 ℃ of annealing 1h.
Accompanying drawing 4 is the X-ray diffractogram of present embodiment products therefrom, and as seen from the figure, this product is pure anatase octahedrite phase TiO
2Accompanying drawing 5 is the SEM and the TEM figure of present embodiment products therefrom, the gained titanium dioxide microballoon sphere is the nanometer rod composition of diameter 12～15nm, length 40～60nm as seen from Figure 5, and this is to sinter nanometer rod into owing to higher anneal temperature makes nano tubular structure subside.
Embodiment 3
At first synthesize titanium dioxide microballoon sphere presoma (with embodiment 1) with universal method; Get 0.5g microballoon presoma and put into the sodium hydroxide solution that 50mL concentration is 5M, magnetic agitation 0.5h, with mixed solution put into volume be 80mL have a teflon-lined autoclave, at 180 ℃ of reaction 24h, naturally cool to room temperature, take out and filter, deionized water wash is dispersed in product in the dilute hydrochloric acid that 600mL concentration is 0.1M again to neutral, stirring at room 12h, to neutral, at 40 ℃ of dry 5h, product is at 400 ℃ of annealing 1h through deionized water wash.
Claims (5)
1. the titania nanotube/nanorod microspheres of a graded structure is characterized in that, microballoon is the porous ball of being woven and being formed by titania nanotube or nanometer rod.
2. according to the titania nanotube/nanorod microspheres of the described graded structure of claim 1, it is characterized in that described microsphere diameter is 4～6 μ m, specific surface area is 61.1～215.8m
2/ g, pore volume is 0.29～0.42cm
3/ g.
3. according to the titania nanotube/nanorod microspheres of the described graded structure of claim 1, it is characterized in that described titania nanotube diameter 10～12nm, length 2～6 μ m, the diameter 12～15nm of nanometer rod, length 40～60nm.
4. the preparation method of the titania nanotube/nanorod microspheres of the described graded structure of claim 1 is characterized in that, step is as follows:
(1) synthesis of titanium dioxide microballoon presoma;
(2) get above-mentioned presoma and put into the alkaline solution that concentration is 5～15M, magnetic agitation 0.5～0.8h mixes, mixed solution put into have the teflon-lined autoclave, react 24～48h down at 130～200 ℃, behind the naturally cooling, cooled product is dispersed in the dilute hydrochloric acid again, magnetic agitation, extremely neutral through deionized water wash then, suction filtration, drying can obtain the titanium dioxide microballoon sphere of classifying;
(3) subsequently this microballoon is annealed at 400～500 ℃, obtain the titania nanotube/nanorod microspheres of graded structure.
5. according to the preparation method of the titania nanotube/nanorod microspheres of the described graded structure of claim 4, it is characterized in that in the step (2), described alkaline solution is sodium hydroxide or potassium hydroxide solution, consumption is 0.5g presoma 50mL alkaline solution; The concentration of described dilute hydrochloric acid is 0.1M, and consumption is 0.5g presoma 600mL acid solution.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102631909A (en) * | 2012-04-13 | 2012-08-15 | 山东大学 | Titanium dioxide nano wire microsphere photocatalysis material with hydrogenated surface and preparation method thereof |
| CN104843786A (en) * | 2015-06-01 | 2015-08-19 | 山东大学 | Hierarchical titanium dioxide microspheres based on surface oriented growth nano-rods and preparation method thereof |
| CN109650439A (en) * | 2019-01-29 | 2019-04-19 | 淄博泽辰光媒科技有限公司 | Large scale self assembly titanium dioxide microballoon sphere and its preparation method and application |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101670280A (en) * | 2009-09-27 | 2010-03-17 | 山东大学 | Titanium dioxide microspheroidal photocatalyst with high active surface and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101670280A (en) * | 2009-09-27 | 2010-03-17 | 山东大学 | Titanium dioxide microspheroidal photocatalyst with high active surface and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 《Chemistry Letters》 20081115 Yanfeng Zhang et al. Self-assembly TiO2 Hierarchical Hollow Microspheres with Rutile Nanorods by Template-free Hydrothermal Method 第1264-1265页 1-5 第37卷, 第12期 2 * |
| 《硅酸盐学报》 20080331 赵谦 等 二氧化钛纳米管的合成及光催化性能 第1-5页 1-5 第36卷, 第S1期 2 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102631909A (en) * | 2012-04-13 | 2012-08-15 | 山东大学 | Titanium dioxide nano wire microsphere photocatalysis material with hydrogenated surface and preparation method thereof |
| CN102631909B (en) * | 2012-04-13 | 2014-07-16 | 山东大学 | Titanium dioxide nano wire microsphere photocatalysis material with hydrogenated surface and preparation method thereof |
| CN104843786A (en) * | 2015-06-01 | 2015-08-19 | 山东大学 | Hierarchical titanium dioxide microspheres based on surface oriented growth nano-rods and preparation method thereof |
| CN109650439A (en) * | 2019-01-29 | 2019-04-19 | 淄博泽辰光媒科技有限公司 | Large scale self assembly titanium dioxide microballoon sphere and its preparation method and application |
| CN109650439B (en) * | 2019-01-29 | 2021-03-26 | 淄博泽辰光媒科技有限公司 | Large-size self-assembled titanium dioxide microsphere and preparation method and application thereof |
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