CN115007128B - SrTiO 3 /TiO 2 Heteroepitaxial photocatalyst and preparation method and application thereof - Google Patents

SrTiO 3 /TiO 2 Heteroepitaxial photocatalyst and preparation method and application thereof Download PDF

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CN115007128B
CN115007128B CN202210740867.5A CN202210740867A CN115007128B CN 115007128 B CN115007128 B CN 115007128B CN 202210740867 A CN202210740867 A CN 202210740867A CN 115007128 B CN115007128 B CN 115007128B
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CN115007128A (en
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郑昭科
李蓓
黄柏标
王泽岩
刘媛媛
王朋
程合锋
张倩倩
张晓阳
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Shandong University
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Abstract

The application discloses SrTiO 3 /TiO 2 Heteroepitaxial photocatalyst, and preparation method and application thereof, comprising the following steps: the titanium oxysulfate and hydrofluoric acid are adopted to carry out hydrothermal reaction to prepare the micron-sized TiO 2 A single crystal; the micron-sized TiO 2 Dispersing the monocrystal in solvent, and performing hydrothermal reaction with strontium hydroxide, alkali liquor, polyethylene glycol and water in inert atmosphere to obtain TiO 2 The molar ratio of the catalyst to strontium hydroxide is 0.5-2:0.5-2, and the catalyst is TiO at micron level 2 (001) and/or 101) crystal planes 3 And (3) mesogenic. SrTiO 3 /TiO 2 The-0.5 h epitaxial heterojunction is in TiO 2 {001} crystal face topology epitaxial growth SrTiO 3 Mesogenic, wherein (1) SrTiO 3 And TiO 2 The highly ordered epitaxial interface of the {001} crystal face can reduce interface defects of the heterojunction and improve the service life of carriers; (2) The matched energy band structure provides additional driving force for efficient carrier transport; (3) Ordered mesogenic superstructures add active sites that enable charge transfer between adjacent nanoparticles.

Description

SrTiO 3 /TiO 2 Heteroepitaxial photocatalyst and preparation method and application thereof
Technical Field
The application belongs to the technical field of preparation of monocrystalline hetero-epitaxial mesogenic materials and photocatalysis, and in particular relates to SrTiO 3 /TiO 2 Heteroepitaxial photocatalyst, preparation method and application thereof, and the catalyst can be applied to photocatalytic degradation of tetracycline.
Background
The statements herein merely provide background information related to the present disclosure and may not necessarily constitute prior art.
Tetracyclines are one of the most commonly used antibiotics in the poultry and aquaculture industries. In recent years, the abuse of tetracyclines poses a great threat to the aqueous environment and human health. The clean and efficient photocatalysis technology is utilized to degrade the tetracycline in the water body, so that the method is an effective water purifying method.
Titanium dioxide (TiO) 2 ) Is one of the most widely used photocatalytic materials. It is of great interest because of its good chemical stability, non-toxicity, good photoelectric properties and low cost. Wherein, the decahedral titanium dioxide monocrystal has high activity crystal faces, so that electron-hole migration to {101} and {001} crystal faces respectively is promoted, and separation of carriers is promoted. However, due to TiO 2 The photocatalyst has the defects of a large number of bulk defects, weak surface adsorption capacity, easiness in recombination of carriers in the bulk and the like, so that the photocatalytic activity is not ideal. Strontium titanate (SrTiO) 3 ) Is a perovskite structure semiconductor, the higher conduction band position of the perovskite structure is favorable for charge to an electron acceptor TiO 2 Thereby forming a charge transport network. However, byIn TiO 2 When the lattice constant difference of the three dimensions of the space is larger and the lattice structure of the titanium dioxide and the strontium titanate is larger, a large number of defects and dislocation are inevitably formed at the interface, the stability of the heterojunction is affected, and the photocatalytic activity of the material is limited.
Disclosure of Invention
In view of the shortcomings of the prior art, the application aims to provide SrTiO 3 /TiO 2 Heteroepitaxial photocatalyst, preparation method and application thereof, and application of the material in photodegradation of tetracycline.
In order to achieve the above object, the present application is realized by the following technical scheme:
in a first aspect, the present application provides a SrTiO 3 /TiO 2 The preparation method of the heteroepitaxial photocatalyst comprises the following steps:
the titanium oxysulfate and hydrofluoric acid are adopted to carry out hydrothermal reaction to prepare the micron-sized TiO 2 A single crystal;
the micron-sized TiO 2 Dispersing the monocrystal in solvent, and performing hydrothermal reaction with strontium hydroxide, alkali liquor, polyethylene glycol and water in inert atmosphere to obtain TiO 2 The molar ratio of the catalyst to strontium hydroxide is 0.5-2:0.5-2, and the catalyst is TiO at micron level 2 (001) and/or 101) crystal planes 3 And (3) mesogenic.
In a second aspect, the present application provides SrTiO 3 /TiO 2 Heteroepitaxial photocatalysts, prepared by the preparation method.
In a third aspect, the present application provides the SrTiO 3 /TiO 2 The application of the heteroepitaxial photocatalyst in photocatalytic degradation of tetracycline.
The beneficial effects achieved by one or more embodiments of the present application described above are as follows:
1、SrTiO 3 /TiO 2 the-0.5 h epitaxial heterojunction is in TiO 2 {001} crystal face topology epitaxial growth SrTiO 3 Mesogenic, wherein (1) SrTiO 3 And TiO 2 The highly ordered epitaxial interface of the {001} crystal face can reduce interface defects of the heterojunction and improve the service life of carriers; (2) The matched energy band structure provides additional driving force for efficient carrier transport; (3) Ordered mesogenic superstructures add active sites that enable charge transfer between adjacent nanoparticles.
2. Compared with TiO 2 ,SrTiO 3 /TiO 2 Epitaxial heterojunction exhibits more excellent photocatalytic degradation of tetracyclines with SrTiO 3 /TiO 2 -0.5h is most effective. This is due to TiO 2 The coupling effect of the crystal face effect and the heterojunction between the crystal face effect and the interface of the crystal face effect promotes the electron to TiO 2 - {101} crystal face and hole direction SrTiO 3 Transfer of the {001} crystal plane. The material has wide application prospect in the aspects of reducing the harm of antibiotics and purifying the environment.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this specification, illustrate embodiments of the application and together with the description serve to explain the application.
FIG. 1 is a schematic diagram of SrTiO prepared in the example of the present application 3 /TiO 2 X-ray diffraction pattern of epitaxial heterojunction material.
FIG. 2 shows TiO according to an embodiment of the present application 2 (FIG. 2 a), srTiO 3 /TiO 2 -0.5h (FIG. 2 b), srTiO 3 /TiO 2 -1h (FIG. 2 c), srTiO 3 /TiO 2 -24h (fig. 2 d).
FIG. 3 is SrTiO prepared in example 2 of the present application 3 /TiO 2 Low power transmission electron microscopy (fig. 3 a) and high power transmission electron microscopy (fig. 3 b) at 0.5 h.
FIG. 4 shows SrTiO prepared in example 3 of the present application 3 /TiO 2 -low power (fig. 4 a) and high power (fig. 4 b) transmission electron microscopy of 1 h.
FIG. 5 shows SrTiO prepared in the example of the present application 3 /TiO 2 -0.5h (left) and SrTiO 3 /TiO 2 -24h (right) EDS-Mapping profile.
FIG. 6 is a diagram of TiO prepared in the example 2 、SrTiO 3 /TiO 2 -0.5h(ST-T-0.5h)、SrTiO 3 X-ray photoelectron spectroscopy of (c).
FIG. 7 is a graph showing the activity of photodegradable tetracyclines of various photocatalysts prepared in the examples.
FIG. 8 is a chart showing the amounts of SrTiO of different catalyst amounts prepared in example 2 3 /TiO 2 -activity profile of photocatalytic degradation of tetracycline for 0.5 h.
FIG. 9 is SrTiO prepared in example 2 3 /TiO 2 -0.5h of cyclic stability test chart for photocatalytic degradation of tetracycline.
Detailed Description
It should be noted that the following detailed description is illustrative and is intended to provide further explanation of the application. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
In a first aspect, the present application provides a SrTiO 3 /TiO 2 The preparation method of the heteroepitaxial photocatalyst comprises the following steps:
the titanium oxysulfate and hydrofluoric acid are adopted to carry out hydrothermal reaction to prepare the micron-sized TiO 2 A single crystal;
the micron-sized TiO 2 Dispersing the monocrystal in solvent, and performing hydrothermal reaction with strontium hydroxide, alkali liquor, polyethylene glycol and water in inert atmosphere to obtain TiO 2 The molar ratio of the catalyst to strontium hydroxide is 0.5-2:0.5-2, and the catalyst is TiO at micron level 2 (001) and/or 101) crystal planes 3 And (3) mesogenic.
The micron-sized TiO prepared by the method 2 The monocrystal is micron-sized decahedron TiO 2 And (3) single crystals.
The application is realized by the method that the catalyst is prepared by the method of preparing the catalyst in TiO 2 The crystal face selectively builds an epitaxial heterojunction, so that effective and directional electron-hole migration is realized, and carrier separation is promoted. In TiO 2 Topological epitaxy on single crystals to build SrTiO 3 /TiO 2 The interface heterojunction can optimize the surface microstructure and the interface electronic structure. And since the orientation of the epitaxial layer is determined by the initial crystal orientation, a highly ordered heteroepitaxial layer can be formed. In addition, the height isThe ordered epitaxial structure is beneficial to reducing interface defects of the heterojunction and improving the service life and mobility of carriers. The material has the advantages of simple and controllable preparation method, environmental friendliness, no pollution, low price and easy obtainment of the material and the like. Therefore, the material has good application value.
The hydrothermal reaction is carried out in inert atmosphere, so that CO in the air can be avoided 2 Enter a reaction system and Sr (OH) 2 Hydrothermal reaction to form SrCO 3 And (5) impurities.
During the reaction, the catalyst is preferentially added in TiO 2 Epitaxial growth of SrTiO on {001} crystal face 3 Mesogen, then in TiO 2 SrTiO grows on both {001} and {101} crystal planes 3 And (3) mesogenic.
In some embodiments, the temperature at which the titanyl sulfate and hydrofluoric acid are subjected to the hydrothermal reaction is 170-190 ℃ and the hydrothermal reaction time is 10-15 hours.
Preferably, the temperature of the hydrothermal reaction of the titanyl sulfate and hydrofluoric acid is 180 ℃, and the hydrothermal reaction time is 12 hours.
For example, the temperature of the hydrothermal reaction may be 170 ℃, 171 ℃, 172 ℃, 173 ℃, 174 ℃, 175 ℃, 176 ℃, 177 ℃, 178 ℃, 179 ℃, 180 ℃, 181 ℃, 182 ℃, 183 ℃, 184 ℃, 185 ℃, 186 ℃, 187 ℃, 188 ℃, 189 ℃, 190 ℃.
The hydrothermal reaction time is 10h, 11h, 12h, 13h, 14h, 15h.
In some embodiments, the concentration of hydrofluoric acid is 110-130 mmol.L -1 Preferably 120 mmol.L -1 The method comprises the steps of carrying out a first treatment on the surface of the The concentration of hydrofluoric acid may be: 110 mmol.L -1 、111mmol·L -1 、112mmol·L -1 、113mmol·L -1 、114mmol·L -1 、115mmol·L -1 、116mmol·L -1 、117mmol·L -1 、118mmol·L -1 、119mmol·L -1 、120mmol·L -1 、121mmol·L -1 、122mmol·L -1 、123mmol·L -1 、124mmol·L -1 、125mmol·L -1 、126mmol·L -1 、127mmol·L -1 、128mmol·L -1 、129mmol·L -1 、130mmol·L -1
Preferably, the molar ratio of titanyl sulfate to hydrofluoric acid is 0.8-1:9-10, preferably 0.813:9.6.
During the reaction, the titanyl sulfate needs to be completely dissolved in hydrofluoric acid under stirring until the solution is clear and transparent.
In some embodiments, the TiO 2 The molar ratio of the catalyst to the strontium hydroxide is 0.7-1.5:0.7-1.5, preferably 1:1.
In some embodiments, the lye is sodium hydroxide solution at a concentration of 0.5-2 mol.L -1 Preferably 0.8 to 1.2 mol.L -1 . The concentration thereof may be: 0.5 mol.L -1 、0.6mol·L -1 、0.7mol·L -1 、0.8mol·L -1 、0.9mol·L -1 、1.0mol·L -1 、1.1mol·L -1 、1.2mol·L -1 、1.3mol·L -1 、1.4mol·L -1 、1.5mol·L -1 、1.6mol·L -1 、1.7mol·L -1 、1.8mol·L -1 、1.9mol·L -1 、2mol·L -1
In some embodiments, the mass fraction of polyethylene glycol in the reaction system is 0.5 to 1wt%, preferably 0.7 to 0.9wt%. The mass fraction of the material can be as follows: 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1wt%.
In some embodiments, the TiO 2 The temperature of the hydrothermal reaction with strontium hydroxide, alkali liquor, polyethylene glycol and water is 190-210 ℃, and the hydrothermal time is 0.5-72 h.
The temperature of the hydrothermal reaction may be: 190 ℃, 191 ℃, 192 ℃, 193 ℃, 194 ℃, 195 ℃, 196 ℃, 197 ℃, 198 ℃, 199 ℃, 201 ℃, 202 ℃, 203 ℃, 204 ℃, 205 ℃, 206 ℃, 207 ℃, 208 ℃, 209 ℃, 210 ℃.
The hydrothermal reaction time was 0.5h, 1h, 1.5h, 2h, 2.5h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h, 24h, 25h, 26h, 27h, 28h, 29h, 30h, 31h, 32h, 33h, 34h, 35h, 36h, 37h, 38h, 39h, 40h, 41h, 42h, 43h, 44h, 45h, 46h, 47h, 48h, 49h, 50h, 51h, 52h, 53h, 54h, 55h, 56h, 57h, 58h, 59h, 60h, 61h, 62h, 63h, 64h, 65h, 66h, 67h, 68h, 69h, 70h, 71 h.
In a second aspect, the present application provides SrTiO 3 /TiO 2 Heteroepitaxial photocatalysts, prepared by the preparation method.
The catalyst material is mainly characterized by SrTiO 3 Selective epitaxial growth of micron-sized TiO 2 The {001} crystal face of the single crystal can be epitaxially grown on TiO 2 Is provided. And micron-sized TiO 2 In contrast, srTiO 3 /TiO 2 The heteroepitaxial material has the advantages of high photocatalytic degradation efficiency, mild reaction condition and the like, and the photocatalytic degradation efficiency of tetracycline is far higher than that of pure TiO under the irradiation of ultraviolet-visible light 2
In a third aspect, the present application provides the SrTiO 3 /TiO 2 The application of the heteroepitaxial photocatalyst in photocatalytic degradation of tetracycline.
In some embodiments, the SrTiO is 3 /TiO 2 The heteroepitaxial photocatalyst is uniformly dispersed in the tetracycline solution, and is subjected to photodegradation after dark treatment.
Before illumination, the reaction system formed by the photocatalyst and the tetracycline solution is required to be subjected to dark treatment, and the dark treatment time is 30-60min so as to reach adsorption-desorption balance.
Preferably, the photodegradable light source is a xenon lamp.
Preferably, the photodegradation reaction system has a temperature of 12 to 30℃and preferably 15 ℃. The reaction temperature was controlled by circulating water.
In order to enable those skilled in the art to more clearly understand the technical scheme of the present application, the technical scheme of the present application will be described in detail below with reference to specific examples and comparative examples.
The test materials used in the examples below are all conventional in the art and are commercially available.
Example 1
Micron-sized decahedron TiO 2 A method for producing a single crystal comprising the steps of:
130mg of titanium oxysulfate (TiOSO) 4 ·xH 2 SO 4 ·xH 2 O,FW:159.9g mol -1 ) The powder was dissolved in 80ml HF solution (120 mmol L) -1 ) The solution was stirred until it was clear and transparent. The solution was transferred to a polytetrafluoroethylene-lined hydrothermal reaction kettle with a total volume of 100 mL. The mixture was kept in an oven at 180℃for 12 hours. And centrifugally collecting the white precipitate, repeatedly washing the white precipitate with deionized water and ethanol for a plurality of times, and removing soluble ion impurities. And then dried at 80℃for 12 hours.
Example 2
SrTiO 3 /TiO 2 -0.5h epitaxial heterojunction (abbreviated ST-T-0.5h; srtio 3 Mesogenic selectivity at TiO 2 {001} crystal plane epitaxial growth), comprising the steps of:
the above-mentioned 0.2g TiO 2 Dispersing in 2ml ethanol to obtain suspension. 0.66g Sr (OH) 2 ·8H 2 O was dissolved in 4mL of water to give a strontium hydroxide solution. This suspension was slowly added to the above strontium hydroxide solution under argon bubbling and stirred well. Then 2mL of NaOH solution (5M), 2mL of 8wt% polyethylene glycol solution (PEG, MW 400) and 2mL of deionized water were added. The resulting liquid was transferred to a 30 ml teflon lined hydrothermal reaction kettle and kept in an oven at 200 ℃ for 0.5 hours. After cooling, the white precipitate is centrifugally collected, repeatedly washed with deionized water and ethanol for a plurality of times, and the final powder is dried for 12 hours at 80 ℃ to obtain SrTiO 3 /TiO 2 -0.5h sample.
Example 3
SrTiO 3 /TiO 2 -T epitaxial heterojunction (abbreviated as ST-T-T h, t=1-72 h; srtio 3 Mesogen in TiO 2 {001} and {101} crystal plane epitaxial growth). The difference is that 1h, 6h, 24h, 72h, etc. are kept in an oven at 200℃as in example 1.
Product analysis and performance testing:
SrTiO 3 /TiO 2 morphology analysis and phase analysis of epitaxial heterojunction:
example SystemSrTiO of preparation 3 /TiO 2 The XRD pattern of the epitaxial heterojunction is shown in figure 1. It can be seen that SrTiO in the heterojunction over time 3 The (110) peak of (C) is gradually enhanced, which shows that SrTiO containing strontium titanate and titanium dioxide in different proportions 3 /TiO 2 Epitaxial heterojunction is gradually formed.
Micron-sized TiO prepared in example 1 2 As shown in FIG. 2 (a), both the {001} and {101} crystal planes of titanium dioxide remain clean and smooth. SrTiO prepared by partial different reaction time 3 /TiO 2 Epitaxial heterojunction (SrTiO) 3 /TiO 2 -0.5h,SrTiO 3 /TiO 2 -1h,SrTiO 3 /TiO 2 -24h are abbreviated as ST-T-0.5h, ST-T-1h, ST-T-24h, respectively, as shown in FIG. 2 (b-d). It can be seen that the epitaxial growth of strontium titanate on the crystal face of titanium dioxide is selective, and when the reaction proceeds to about 0.5h, the strontium titanate preferentially selectively grows epitaxially on the {001} crystal face of titanium dioxide to form a layer of compact small strontium titanate particles of about 50nm in size, when the reaction time is continued to be prolonged, larger strontium titanate particles grow epitaxially on the {101} crystal face of titanium dioxide, and when the reaction proceeds to about 24h, the strontium titanate coats each crystal face of titanium dioxide.
FIG. 3 shows the TiO of the low power transmission electron microscope and the high resolution transmission electron microscope 2 [001 of]The axis is parallel to SrTiO 3 [100 of]A shaft. The high-power TEMs of fig. 3 (b) and fig. 4 (b) show lattice fringe parameters that are consistent with those in the XRD pattern database.
FIG. 5 shows SrTiO prepared in the example 3 /TiO 2 -0.5h and SrTiO 3 /TiO 2 -position and content distribution of Ti, O and Sr elements for 24 h. The Sr element content at 24h in the figure is significantly higher than the element content at 0.5h, indicating that more strontium titanate is formed on the crystal face of titanium dioxide as the reaction time is prolonged.
The X-ray photoelectron spectrum of FIG. 6 demonstrates TiO 2 With SrTiO 3 The presence of the interface heterojunction between the atoms causes the transfer of electrons between the different atoms. Wherein SrTiO 3 /TiO 2 The binding energy peak of Ti 2p and O1s in 0.5h is shifted to the low field direction, and the binding energy peak of Sr 3d is increasedThe field direction moves, which indicates the formation of an interfacial heterojunction.
Photocatalytic degradation of tetracycline experiments:
(1) The experimental method comprises the following steps: 20mg of the catalyst (TiO 2 SrTiO of different reaction times 3 /TiO 2 Epitaxial heterojunction (SrTiO) 3 /TiO 2 -0.5h,SrTiO 3 /TiO 2 -1h is abbreviated as ST-T-0.5h, ST-T-1 h), respectively), suspended at a concentration of 20mg L -1 To 50ml of the aqueous tetracycline solution, the solution was magnetically stirred at room temperature to disperse the solution. Before photocatalytic degradation, the catalyst and the tetracycline solution are magnetically stirred in the dark for 30min to reach adsorption-desorption equilibrium. In the photocatalytic degradation process, the top of the container is irradiated by using a 300w xenon lamp irradiated by full spectrum as a light source, and the temperature of the reaction equipment is kept at 15 ℃ by using cold water circulation equipment. 4ml of the solution is taken every certain time (10 min, 20min, 30min, 40min, 60min and 90 min), and the solution is centrifuged at 1200 rpm for 2min. The supernatant was taken in a cuvette and the concentration of the supernatant was then determined by UV-visible absorption spectroscopy at 357nm (maximum absorption of tetracycline). Five cycle experiments were performed under the same conditions to examine the cycle stability of the photocatalyst. After each test, the photocatalyst was centrifuged, washed with deionized water multiple times, and dried at 60 ℃ for the next cycle.
(2) Experimental results: tiO prepared in the examples 2 、SrTiO 3 /TiO 2 The comparative experiments of the photocatalytic degradation of tetracycline activity by epitaxial heterojunction (ST-T-0.5 h, ST-T-1 h) are shown in FIG. 7. Wherein ST-T-0.5h has the highest photodegradation performance due to SrTiO of the catalyst 3 Mesogenic nanoparticles and TiO 2 Forms an interface heterojunction and is due to SrTiO 3 The conduction band position of (C) is higher than that of TiO 2 This facilitates the transfer of electrons from strontium titanate to titanium dioxide while holes are transferred from titanium dioxide to strontium titanate, thereby facilitating the separation of carriers. In addition, the highly ordered strontium titanate mesogenic superstructure is beneficial to increasing active sites and improving photocatalytic efficiency. FIG. 8 shows a different SrTiO 3 /TiO 2 -0.5h catalyst amount to photodegradation tetracycline activityThe results demonstrate that the amount of catalyst added is positively correlated with the catalytic activity. Fig. 9 demonstrates that the catalyst has good photocatalytic cycle stability.
The above description is only of the preferred embodiments of the present application and is not intended to limit the present application, but various modifications and variations can be made to the present application by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.

Claims (13)

1. SrTiO 3 /TiO 2 The application of the heteroepitaxial photocatalyst in photocatalytic degradation of tetracycline is characterized in that:
the SrTiO 3 /TiO 2 The preparation method of the heteroepitaxial photocatalyst comprises the following steps:
the micron-sized decahedron TiO is prepared by adopting titanyl sulfate and hydrofluoric acid to carry out hydrothermal reaction 2 A single crystal; the concentration of hydrofluoric acid is 110-130 mmol.L -1 The temperature of the hydrothermal reaction is 170-190 ℃, and the hydrothermal reaction time is 10-15h;
the micron-sized decahedral TiO 2 Dispersing the monocrystal in a solvent, and carrying out hydrothermal reaction with strontium hydroxide, alkali liquor, polyethylene glycol and water in an inert atmosphere, wherein the temperature of the hydrothermal reaction is 190-210 ℃ and the hydrothermal time is 0.5-1h; tiO (titanium dioxide) 2 The molar ratio of the catalyst to strontium hydroxide is 0.5-2:0.5-2, and the catalyst is micron-sized decahedral TiO 2 (001) and/or 101) crystal planes 3 And (3) mesogenic.
2. The use according to claim 1, characterized in that: the concentration of hydrofluoric acid is 120 mmol.L -1
3. Use according to claim 1, wherein the molar ratio of titanyl sulfate to hydrofluoric acid is 0.8-1:9-10.
4. Use according to claim 3, wherein the molar ratio of titanyl sulfate to hydrofluoric acid is preferably 0.813:9.6.
5. The use according to claim 1, characterized in that: tiO (titanium dioxide) 2 The molar ratio of the catalyst to the strontium hydroxide is 0.7-1.5:0.7-1.5.
6. The use according to claim 1, characterized in that: the alkali liquor is sodium hydroxide solution with the concentration of 0.5-2 mol.L -1
7. The use according to claim 6, characterized in that: the concentration of the alkali liquor is 0.8-1.2 mol.L -1
8. The use according to claim 1, characterized in that: in the reaction system, the mass fraction of polyethylene glycol is 0.5-1wt%.
9. The use according to claim 8, characterized in that: the mass fraction of polyethylene glycol is preferably 0.7-0.9wt%.
10. The use according to claim 1, characterized in that: the SrTiO is prepared 3 /TiO 2 The heteroepitaxial photocatalyst is uniformly dispersed in the tetracycline solution, and is subjected to photodegradation after dark treatment.
11. The use according to claim 10, characterized in that: the light source for photodegradation is a xenon lamp.
12. The use according to claim 10, characterized in that: the temperature of the photodegradation reaction system is 12-30 ℃.
13. The use according to claim 12, characterized in that: the temperature of the photodegradation reaction system was 15 ℃.
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Citations (6)

* Cited by examiner, † Cited by third party
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
CN103657619A (en) * 2013-10-16 2014-03-26 江苏大学 Preparation method of titanium dioxide nanosheet photocatalytic material with controllable size
CN103861576A (en) * 2014-03-06 2014-06-18 天津大学 Heterojunction nano-tube array film photocatalysis material for exposing high-energy surface of anatase titanium dioxide, and preparation method and application of photocatalysis material
CN105032390A (en) * 2015-07-17 2015-11-11 黑龙江大学 Preparation method of SrTiO3-TiO2 porous microsphere photocatalyst
CN106955695A (en) * 2017-02-28 2017-07-18 西北师范大学 A kind of strontium titanium dioxide/strontium titanate nano heterojunction and its preparation method and application
CN112007627A (en) * 2020-08-19 2020-12-01 西安近代化学研究所 TiO 22Nanosheet, preparation method and application thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
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
CN103657619A (en) * 2013-10-16 2014-03-26 江苏大学 Preparation method of titanium dioxide nanosheet photocatalytic material with controllable size
CN103861576A (en) * 2014-03-06 2014-06-18 天津大学 Heterojunction nano-tube array film photocatalysis material for exposing high-energy surface of anatase titanium dioxide, and preparation method and application of photocatalysis material
CN105032390A (en) * 2015-07-17 2015-11-11 黑龙江大学 Preparation method of SrTiO3-TiO2 porous microsphere photocatalyst
CN106955695A (en) * 2017-02-28 2017-07-18 西北师范大学 A kind of strontium titanium dioxide/strontium titanate nano heterojunction and its preparation method and application
CN112007627A (en) * 2020-08-19 2020-12-01 西安近代化学研究所 TiO 22Nanosheet, preparation method and application thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
"Monolithic SrTiO3/titanate nanotube/TiO2 nanocomposite toward enhanced photocatalytic activity";Kenji OKADA等;Journal of the Ceramic Society of Japan;第127卷(第10期);第761-766页 *
"Rational synthesis of SrTiO3 nanodots anchored mesocrystalline anatase TiO2 submicrospheres for photocatalytic reduction of CrVI";Shengxin Gao等;Separation and Purification Technology;第275卷;第1-11页 *
"Sonochemical Deposition of Au Nanoparticles on Different Facets-Dominated Anatase TiO2 Single Crystals and Resulting Photocatalytic Performance";Kun Cheng等;J. Phys. Chem. C;第117卷;第14600−14607页 *

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