CN116212843B - Preparation method and application of self-template capable of realizing structural regulation and control of flower-like, hollow and solid titanium dioxide microspheres - Google Patents
Preparation method and application of self-template capable of realizing structural regulation and control of flower-like, hollow and solid titanium dioxide microspheres Download PDFInfo
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- 239000004005 microsphere Substances 0.000 title claims abstract description 64
- 239000007787 solid Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 230000033228 biological regulation Effects 0.000 title claims abstract description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims description 17
- 239000004408 titanium dioxide Substances 0.000 title description 4
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 33
- 238000001354 calcination Methods 0.000 claims abstract description 19
- 238000004729 solvothermal method Methods 0.000 claims abstract description 14
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- APQHKWPGGHMYKJ-UHFFFAOYSA-N Tributyltin oxide Chemical compound CCCC[Sn](CCCC)(CCCC)O[Sn](CCCC)(CCCC)CCCC APQHKWPGGHMYKJ-UHFFFAOYSA-N 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000001105 regulatory effect Effects 0.000 claims abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 45
- 230000001965 increasing effect Effects 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 241000276425 Xiphophorus maculatus Species 0.000 claims description 2
- 238000004108 freeze drying Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 30
- 239000000463 material Substances 0.000 abstract description 14
- 230000015556 catabolic process Effects 0.000 abstract description 10
- 238000006731 degradation reaction Methods 0.000 abstract description 10
- 238000007146 photocatalysis Methods 0.000 abstract description 9
- 239000011941 photocatalyst Substances 0.000 abstract description 4
- 230000001276 controlling effect Effects 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 25
- 239000012528 membrane Substances 0.000 description 17
- 238000000926 separation method Methods 0.000 description 11
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 238000003917 TEM image Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
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- 238000005516 engineering process Methods 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 3
- -1 polytetrafluoroethylene Polymers 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000009777 vacuum freeze-drying Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
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- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B01J35/39—
-
- B01J35/51—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention discloses a TiO capable of realizing flower shape, hollow and solid 2 Self-template preparation method for microsphere structure regulation and control by regulating and controlling H of sol-gel stage 2 O to TBOT molar ratio (R w ) The amorphous TiO with flower-like structures, hollow structures and solid structures with different sizes is prepared 2 Microsphere, at the same time realize hollow TiO 2 And regulating and controlling the diameter of the microsphere within the range of 1-1.8 um. Experimental study shows that when R w When=1.5, tiO was subjected to solvothermal reaction for 24h and calcination at 600 ℃ for 2h 2 The ultraviolet light catalytic degradation of 20mg/L phenol by the hollow sphere has the removal rate of more than 99% in 80min, has the best photocatalytic activity and is superior to commercial P25 photocatalyst. The preparation method is TiO 2 The hollow microsphere structure regulation and control research provides a certain reference experience, and provides a good material foundation for the photocatalysis water treatment application research.
Description
Technical Field
The invention relates to a method for realizing flower-like, hollow and solid TiO 2 A preparation method of a self-template for microsphere structure regulation belongs to the technical field of photocatalysis composite materials.
Background
Suspended TiO 2 The photocatalysis-membrane separation technology is to intercept the membrane separation technology with high efficiency,The phase-change-free separation characteristic is combined with the suspension state photocatalysis technology, so that not only can the separation and recovery of the powder photocatalysis material be realized, but also the water conservancy residence time of the photocatalysis reaction can be effectively improved, and the photocatalysis technology has important value in actual application. The particle size of the photocatalytic material is closely related to the photocatalytic performance of the photocatalytic material, and the photocatalytic material has an important influence on membrane pollution. Nano TiO with high photocatalytic activity in membrane separation process 2 The particle diameter is smaller than the pore diameter of the membrane, and the membrane pore canal is easy to be blocked, so that the membrane is irreversibly polluted. Thus, in the early suspended state, tiO 2 In photocatalysis-membrane separation research, nano-photocatalysis powder materials are separated by adopting a nano-filter membrane with smaller pore diameter than that of an ultrafiltration membrane and a micro-filter membrane. It has been found that monodisperse TiO with an average diameter of 450nm 2 The low pressure MF membrane separation performance of the mesoporous microsphere is obviously superior to that of P25, and the larger particle size and the highly porous morphology greatly reduce the bulk density of a filter cake layer generated on the MF membrane during filtration. However, the formation of a cake layer of photocatalytic material on the membrane surface also results in a decrease in membrane flux, increased energy consumption and reduced separation efficiency. If the particle diameter of the material is further increased, not only can irreversible pollution be effectively prevented, but also the formation of a filter cake layer on the surface of the membrane and the increase of the thickness of the filter cake layer can be relieved, thereby improving the separation efficiency and reducing the cross-flow energy consumption. Meanwhile, tiO which has received attention in recent years 2 The hollow microsphere has the advantages of enhancing the light capturing capability, shortening the transfer distance of the photon-generated carriers and accelerating the surface reaction, effectively improves the efficiency of the photocatalysis reaction, and has good performance and wide application prospect in the fields of environmental purification, hydrogen production, solar cells and the like. Good light trapping ability of hollow structures depends on their size effect, when TiO 2 When the diameter of the hollow sphere is equal to the wavelength of the incident light, strong light scattering occurs; when the diameter of the sphere is far larger than the wavelength of incident light, multiple reflections may occur in the cavity, thereby improving the light collection efficiency. Thus, tiO 2 The further expansion of the structural size of the hollow microsphere has important significance for both photocatalytic activity and membrane separation performance.
Disclosure of Invention
The invention aims to provide a hollow and solid flower-shaped materialTiO 2 A method for preparing a self-template for microsphere structure regulation.
1. Amorphous TiO of different structures 2 Self-templating preparation of microspheres
The invention is a TiO capable of realizing flower shape, hollow and solid 2 The microsphere structure regulated self-template preparation process includes using butyl titanate (TBOT) as titanium source, methanol as solvent, sol-gel process and self-template solvothermal process, and regulating H 2 Molar ratio of O to TBOT (R w ) Is prepared by the method. The preparation method comprises the following steps:
under the protection of nitrogen, the butyl titanate is added into the vigorously stirred methanol and H dropwise 2 In the mixed solution of O, H is controlled 2 Molar ratio of O to TBOT R w Continuously stirring the mixed solution for 60min to be milky white at 0.75-3.75; transferring the mixture into a reaction kettle, keeping the filling ratio at 80%, heating to 125-135 ℃ at a heating rate of 5 ℃/min, and performing solvothermal reaction for 2-24 h; cooling to room temperature after the reaction is finished, centrifugally separating, washing the product with absolute methanol and water respectively, and freeze-drying in vacuum to obtain amorphous TiO 2 A microsphere; then calcining and crystallizing at 450-800 ℃ to obtain anatase TiO with different structures 2 And (3) microspheres.
When R is w At 0.75, performing solvothermal reaction for 2 hours to obtain sea urchin-shaped TiO with diameter of 1.5 mu m 2 A microsphere; when the solvothermal reaction is carried out for 4-8 hours, flower-shaped TiO with diameter of 2.5-5.3 mu m is obtained 2 A microsphere; carrying out solvothermal reaction for 24 hours to obtain platy TiO 2 Structure is as follows.
When R is w When the diameter is gradually increased within the range of 1.5-3, hollow TiO with the diameter gradually reduced from 1.8-1 mu m is obtained 2 And in the microsphere structure, the wall thickness of the hollow sphere is gradually thinned along with the prolongation of the solvothermal time from 2 to 24 hours.
The R is as follows w At 3.75, a solid TiO of diameter 0.83 [ mu ] m is obtained 2 Microsphere structure.
The amorphous TiO 2 Calcining the microspheres in air at 450-800 ℃ for 2 hours to convert the microspheres into anatase TiO 2 And (3) microspheres.
2. TiO (titanium dioxide) 2 Structural characterization of microspheres
1. Electron microscope (SEM and TEM) image analysis
FIG. 1 is R w SEM images (scale length 500nm, inset TEM image) of ATS samples obtained at 0.75 (A), 1.50 (B), 2.25 (C), 3.00 (D), 3.75 (E) and heat of solution at 130℃for 8h, respectively, and R w Correlation with diameter and wall thickness. As can be seen from FIG. 1, the synthesis proceeds through the sol-gel stage R w Can prepare TiO with flower-like structure, hollow structure and solid structure 2 And (3) microspheres.
In the synthesis method of the invention, R w And (3) in the range of 0-3.75, heating the sample by using a methanol solvent for 8 hours to obtain a sample, and calcining and crystallizing the sample at 600 ℃. When R is w When=0, no precipitated product was obtained after solvothermal, indicating that methanol could not undergo dehydration reaction at 130 ℃ under solvothermal conditions, whereas TiO 2 The microspheres are all added with H before solvothermal 2 O is generated. When R is w When=0.75 (fig. 1a, f), the product is sheet TiO 2 (average wall thickness 60.52 nm) assembled flower ball structure, microsphere average diameter 5.23 um. When R is w When=1.5 to 3 (fig. 1B-D, H-J), the product is a hollow sphere structure with smooth and dense surface, and follows R w Average diameters of 1.82, 1.34 and 1.01um, respectively, and wall thicknesses of 116, 53 and 67nm, respectively. When R is w When=3.75 (fig. 1e, k), the product is TiO with an average diameter of 0.83um 2 Solid microspheres. Meanwhile, TEM image also shows that the sample can still keep the original structure form after calcination, and has good stability. From the high resolution HRTEM image, as shown in FIGS. 3 and 4, different R' s w TiO of (C) 2 The microsphere has two lattice distances of about 0.346nm and 0.232nm, which respectively correspond to anatase TiO 2 {101} and {004} crystal planes. Thus, by the sol-gel stage R in the preparation process of the invention w Can prepare TiO with flower-like structure, hollow structure and solid structure 2 Microsphere, simultaneously realizing hollow TiO 2 And regulating the diameter of the microsphere within the range of 1-1.8 um. And the microstructure is not destroyed after calcination at 600 ℃.
FIG. 2 shows a different R w TEM image of structural morphology during solvothermal process under conditions. When R is w When the value of the ratio is =0.75,and (3) forming sea urchin-shaped spherical particles with diameters of 1-1.5 um (shown in fig. 2A) in the solvothermal reaction for 2h, reacting for 4-8 h, developing needle-shaped protrusions on the surfaces of the particles into flakes, forming a flower ball structure with a complete structure, and increasing the diameters to about 2.5um (shown in fig. 2B) and 5.3um (shown in fig. 1F) respectively. The solvothermal time was continued to be extended to 24h, and the growing sheet structure continued to make the flower-ball feature disappear (fig. 2C). When R is w At =1.50, solvothermal for 2h forms TiO with an average diameter of about 1.8um and a wall thickness of about 800nm 2 Hollow sphere structure (fig. 2D), and the hollow sphere surface has a distinct porous structure. The solvothermal time continued to extend to 4H (FIG. 2E) and 8H (FIG. 1H), the hollow sphere diameter was unchanged but the surface was smoother, and the wall thickness was gradually reduced to 180nm and 116nm. And the solvothermal reaction is carried out for 24 hours, the wall thickness of the hollow sphere structure is gradually reduced to 50nm, and the surface of the microsphere is smooth and compact. And when R is w TiO at solvothermal 2 h=3.75 2 The solid sphere shape is irregular and the change in gray scale inside the sphere in the TEM image indicates that the sphere center is more dense (fig. 2G). As the solvothermal extension was increased to 4H and 8H, the spherical surface integrity and spatial uniformity gradually improved and tended to be dense at the surface (fig. 2H). When the solvent heats for 24 hours, tiO is formed on the surface of the sphere 2 The dense layer is more clearly contoured (fig. 2I).
2. X-ray diffraction (XRD) analysis
FIG. 3 is a graph showing the results of hollow spheres (R w =1.5) samples. R is shown in FIG. 3 w XRD patterns of hollow spheres obtained at 24h solvothermal time=1.5 and calcined at 450 ℃,600 ℃, 700 ℃ and 800 ℃ respectively for the sample. The uncalcined hollow sphere sample (r.t.) in the figure shows no distinct characteristic diffraction peak, indicating 24h solvothermal TiO 2 The hollow sphere is still in an amorphous state. The XRD patterns of the samples calcined at 450-800 ℃ show characteristic diffraction peaks at 25.84 degrees, 38.14 degrees, 48.52 degrees, 54.36 degrees, 55.81 degrees, 63.00 degrees and the like, and the characteristic diffraction peaks are respectively shifted to a certain degree compared with diffraction peaks of (101), (004), (200), (105), (211) and (204) crystal faces of an anatase standard spectrum (JCPDS, NO. 21-2172), wherein the (101) crystal face is shifted to a high angle, and the other crystal faces are shifted to a low angle. At the same time withThe intensity of diffraction peak is gradually increased when the calcination temperature is increased, and the grain sizes are respectively as follows: 8.9nm, 9.9nm, 13.2nm and 14.5nm, i.e. the crystallinity is gradually increased and the crystal grains are gradually grown up as the calcination temperature is increased.
FIG. 4 is a different R w XRD pattern of the sample calcined at 600 ℃. Different R w Similar shifts in diffraction peaks in the XRD pattern occur after calcination at 600 ℃. R is R w The corresponding grain sizes are respectively 0.75, 1.50, 2.25, 3.00 and 3.75: 9.3nm, 9.9nm, 11.8nm, 10.0nm, 11.7nm. The shift in diffraction peaks is often caused by inter-grain stresses that limit grain growth and the transformation of anatase to the rutile phase, which also accounts for the different R' s w Amorphous TiO of (C) 2 Microspheres have formed a dense structure.
3. TiO (titanium dioxide) 2 Photocatalytic activity of microsphere materials
FIG. 5 is R calcined at different temperatures w Photocatalytic activity profile of hollow sphere samples with solvothermal 24 h=1.5. As can be seen from FIG. 5, the degradation rate of phenol of the 600℃calcined sample was > 99% and the removal rates of the 450℃calcined sample, 700℃calcined sample and 800℃calcined sample were 47.34%, 77.53% and 64.49%, respectively, at 80min of the photocatalytic reaction. In combination with XRD analysis, the calcination temperature was increased from 450 to 600℃and the grain size (from 8.9nm to 9.9 nm) was all < 10nm, while the significant increase in crystallinity was the main cause of the increase in photocatalytic activity. When the temperature was raised to 700℃and 800℃respectively, the crystallinity and the grain size increased to grow up (13.2 nm and 14.5nm, respectively), resulting in a decrease in photocatalytic activity.
FIG. 6R at different solvothermal conditions w Photocatalytic activity profile of hollow sphere samples calcined at 600 ℃. The solvothermal time is prolonged from 2 hours to 24 hours, and the degradation rate of phenol is gradually increased from 82.28% to more than 99% in 80 minutes of the photocatalytic reaction. The thinner wall thickness of the hollow spheres promotes the separation of electron-hole pairs as the solvothermal time is extended.
From FIG. 7, for different R w TiO synthesized by calcining at 600 ℃ for 2h after solvothermal treatment for 24h under the condition 2 Microsphere photocatalytic activity profile. R is R w 80min phenol degradation rate of hollow sphere of=1.5 is higher than R w TiO of=0.75 2 Ball structure (91.39%), R w TiO of=3.75 2 Solid spheres and commercial P25 photocatalyst (92.75%). At the same time, along with R of the hollow sphere w Increasing to 2.25 and 3.00 and decreasing degradation to 91.01% and 77.36%, respectively. This proves that when R w At=1.5, tiO calcined with solvothermal for 24h and 600 °c 2 The hollow sphere degradation 20mg/L phenol solution has optimal photocatalytic activity and is superior to commercial P25 photocatalyst.
In conclusion, the invention controls the H of the sol-gel stage 2 Molar ratio of O to TBOT (R w ) Under the condition of 125-135 ℃ methanol solvothermal, the amorphous TiO with different sizes of flower-like structures, hollow structures and solid structures is prepared 2 Microsphere, at the same time realize hollow TiO 2 And regulating and controlling the diameter of the microsphere within the range of 1-1.8 um. Calcining and crystallizing for 2 hours at the temperature of 450-800 ℃ to obtain anatase TiO with different structures 2 And (3) microspheres. Experimental study shows that when R w When=1.5, tiO was subjected to solvothermal reaction for 24h and calcination at 600 ℃ for 2h 2 The ultraviolet light catalytic degradation of 20mg/L phenol by the hollow sphere has the removal rate of more than 99% in 80min, has the best photocatalytic activity and is superior to commercial P25 photocatalyst. The preparation method is TiO 2 The hollow microsphere structure regulation and control research provides a certain reference experience, and provides a good material foundation for the photocatalysis water treatment application research.
Drawings
FIG. 1 is R w SEM images (scale length 500nm, inset TEM image) of ATS samples obtained at 0.75 (A), 1.50 (B), 2.25 (C), 3.00 (D), 3.75 (E) and heat of solution at 130℃for 8h, respectively, and R w Correlation with diameter and wall thickness.
FIG. 2 is R w TEM image of solvothermal 2H (A, D, G), 4H (B, E, H) 24H (C, F, I) samples at 0.75,1.5,3.75, respectively
FIG. 3 is a graph showing the results of hollow spheres (R w =1.5) XRD pattern of the sample.
FIG. 4 is a different R w XRD pattern of the sample calcined at 600 ℃.
FIG. 5R is calcined at different temperatures w Photocatalytic activity profile of hollow sphere samples with solvothermal 24 h=1.5.
FIG. 6R for different solvothermal values w Photocatalytic activity profile of hollow sphere samples calcined at 600 ℃.
FIG. 7 is a different R w TiO synthesized by calcining at 600 ℃ for 2h after solvothermal treatment for 24h under the condition 2 Microsphere photocatalytic activity profile.
Detailed Description
The TiO of the invention is described below by way of specific examples 2 The synthesis and properties of the microsphere materials are further described.
Example 1
（1）TiO 2 Preparation of microsphere materials: under the protection of nitrogen, H 2 Molar ratio of O to TBOT R w =0.75, 2.5 ml TBOT was added drop-wise to vigorously stirred 80 ml methanol and H 2 The mixed solution of O is continuously stirred for 60min, the mixture is transferred into a polytetrafluoroethylene lining of a 100 ml reaction kettle, the temperature is increased to 130 ℃ at 5 ℃ per minute, and the temperature is kept for 24h; after the reaction is finished, cooling to room temperature in air, centrifugally separating white precipitate, washing with absolute methanol and water for 3 times respectively, and vacuum freeze-drying to obtain amorphous TiO 2 A microsphere; calcining and crystallizing for 2 hours at 600 ℃ to obtain TiO 2 Flower-like microspheres (SEM image shown in fig. 1 (a)).
（2）TiO 2 Photocatalytic activity of flower-like microspheres: the photocatalytic degradation of the phenol is 20mg/L, and the degradation rate of the phenol is 91.39% after 80 minutes.
Example 2
（1）TiO 2 Preparation of microsphere materials: r is under the protection of nitrogen w 2.5 ml TBOT was added drop wise to vigorously stirred 80 ml methanol and H =1.5 2 The mixed solution of O is continuously stirred for 60min, the mixture is transferred into a polytetrafluoroethylene lining of a 100 ml reaction kettle, the temperature is increased to 130 ℃ at 5 ℃ per minute, and the temperature is kept for 24h; after the reaction is finished, cooling to room temperature in air, centrifugally separating white precipitate, washing with absolute methanol and water for 3 times respectively, and vacuum freeze-drying to obtain amorphous TiO 2 A microsphere; calcining and crystallizing for 2 hours at 600 ℃ to obtain TiO 2 Hollow microspheres (SEM image as in fig. 1 (B)).
（2）TiO 2 Photocatalytic activity of hollow microspheres: the photocatalytic degradation of 20mg/L phenol is carried out, and the degradation rate of phenol is more than 99% after 80 minutes.
Example 3
（1）TiO 2 Preparation of microsphere materials: r is under the protection of nitrogen w =3.75, 2.5 ml TBOT was added drop-wise to vigorously stirred 80 ml methanol and H 2 The mixed solution of O is continuously stirred for 60min, the mixture is transferred into a polytetrafluoroethylene lining of a 100 ml reaction kettle, the temperature is increased to 130 ℃ at 5 ℃ per minute, and the temperature is kept for 24h; after the reaction is finished, cooling to room temperature in air, centrifugally separating white precipitate, washing with absolute methanol and water for 3 times respectively, and vacuum freeze-drying to obtain amorphous TiO 2 A microsphere; calcining and crystallizing for 2 hours at 600 ℃ to obtain TiO 2 Solid microspheres (SEM image as in fig. 1 (E)).
（2）TiO 2 Photocatalytic activity of solid microspheres: the photocatalytic degradation of the phenol is 20mg/L, and the degradation rate of the phenol is 63.44% after 80 minutes.
Claims (3)
1. Can realize flower form, hollow and solid TiO 2 The microsphere structure regulated self-template preparation process includes adding butyl titanate dropwise into vigorously stirred methanol and H under nitrogen protecting condition with butyl titanate TBOT as titanium source and methanol as solvent 2 In the mixed solution of O, H is controlled 2 Molar ratio of O to TBOT R w Continuously stirring the mixed solution for 60min to be milky white at 0.75-3.75; then transferring the mixture into a reaction kettle, heating to 125-135 ℃ at a heating rate of 5 ℃/min, and performing solvothermal reaction for 2-24 hours; cooling to room temperature after the reaction is finished, centrifugally separating, washing the product with absolute methanol and water respectively, and freeze-drying in vacuum to obtain amorphous TiO 2 A microsphere; then calcining and crystallizing at 450-800 ℃ to obtain anatase TiO with different structures 2 A microsphere;
when R is w At 0.75, performing solvothermal reaction for 2 hours to obtain sea urchin-shaped TiO with diameter of 1.5 mu m 2 A microsphere; when the solvothermal reaction is carried out for 4-8 hours, flower-shaped TiO with diameter of 2.5-5.3 mu m is obtained 2 A microsphere; carrying out solvothermal reaction for 24 hours to obtain platy TiO 2 A structure;
when R is w When the diameter is gradually increased within the range of 1.5-3, hollow TiO with the diameter gradually reduced from 1.8-1 mu m is obtained 2 The microsphere structure is characterized in that the wall thickness of the hollow sphere is gradually thinned along with the prolongation of the solvothermal time from 2 to 24 hours;
when R is w At 3.75, a solid TiO of diameter 0.83 [ mu ] m is obtained 2 Microsphere structure.
2. A method for producing flower-like, hollow and solid TiO according to claim 1 2 The preparation method of the self-template for microsphere structure regulation is characterized by comprising the following steps: the amorphous TiO 2 Calcining the microspheres in air at 450-800 ℃ for 2 hours to convert the microspheres into anatase TiO 2 And (3) microspheres.
3. TiO prepared according to the method of claim 1 2 The application of the microsphere in photocatalytic degradation of phenol.
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