A TiO2@SnSe x S 2-x A TiO2@SnO2 bifunctional composite structure and a preparation method thereof

Abstract

This invention belongs to the field of nanomaterials technology, specifically relating to a TiO2@SnSe x S 2‑x The method for preparing the @SnO2 bifunctional composite structure includes the following steps: preparation of titanium dioxide nanotubes; dissolving a certain amount of tin tetrachloride, sodium selenite, and thioacetamide in ethanol and acetic acid solutions, then adding TiO2 nanotubes to form a mixed solution B; adding the prepared mixed solution B to a reaction vessel, placing the reaction vessel in a constant temperature chamber, and reacting at a certain temperature for several hours to obtain TiO2@SnSe x S 2‑x Tubular sheet structure; the obtained TiO2@SnSe x S 2‑x The tubular layered structure was annealed in a muffle furnace at a certain temperature for several minutes to obtain TiO2@SnSe. x S 2‑x @SnO2 bifunctional tubular sheet composite structure. This method has a simple preparation process, yields a uniform and novel product with a large specific surface area, tunable energy levels, and excellent catalytic performance, exhibiting superior adsorption and catalytic properties for heavy metal ions, which can meet the needs of various applications.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of nanomaterials, and particularly relates to a TiO2@SnSe x S 2-x @SnO2 dual-functional composite structure and a preparation method thereof. BACKGROUND

[0002] At present, the environmental problem is relatively severe, and among many environmental treatment methods, a catalyst is one of relatively effective methods. Among many catalytic materials, TiO2 is relatively mature and is researched more. However, TiO2 also has defects, for example, a wide band gap is not conducive to light absorption catalysis. Although the existing methods have improved the above problems, the effects are not good. For example, SnS2 or SnO2 is selected instead, or the existing method adopts TiO2@SnO2 or TiO2@SnS2 composite to improve the band gap, but the effects are not good.

[0003] Among many improvements, a transition metal sulfide is a MX2 type compound, M is a transition metal element in the fourth, fifth and sixth periods of the periodic table, and X represents an oxygen family element S, Se or Te. The TMDs are direct band gap materials, and the band gap width can be adjusted according to the layer thickness. And it has the advantages of rich reserves, low price, high photocatalytic efficiency and large energy storage capacity, and can be effectively applied to the improvement of TiO2.

[0004] Therefore, the application attempts to prepare a TiO2@SnSe x S 2-x @SnO2 dual-functional composite structure by a liquid phase method, and the material has high photocatalytic and heavy metal ion adsorption properties. SUMMARY

[0005] The primary technical problem to be solved by the application is to provide a preparation method of a TiO2@SnSe x S 2-x @SnO2 dual-functional composite structure, which has the advantages of simple process, low cost, short reaction period, uniformity, high catalytic performance and stability.

[0006] A preparation method of a TiO2@SnSe x S 2-x @SnO2 dual-functional composite structure, which has the advantages of simple process, low cost, short reaction period, uniformity, high catalytic performance and stability.

[0007] Step one, preparing TiO2 nanotubes;

[0008] Step two, dissolving a certain amount of tin tetrachloride, sodium selenite and thioacetamide in a certain proportion of ethanol and acetic acid solution, and then adding the TiO2 nanotubes to form a mixed solution B;

[0009] Step three, the prepared mixed solution B is added into the tetrafluoroethylene reactor, the reactor is placed in the thermostat, and the reaction is carried out at a certain temperature for several hours to obtain TiO2@SnSe x S 2-x Tubular sheet structure; the application further improves the band gap by improving SnSe x S 2-x , avoids the single band gap of single SnSe2 or SnS2, and can effectively meet different needs.

[0010] Step four, the obtained TiO2@SnSe x S 2-x tubular sheet structure is annealed in a muffle furnace at a certain temperature for several minutes to obtain TiO2@SnSe x S 2-x @SnO2 dual functional tubular sheet composite structure, 0<x<2.

[0011] The molar ratio of sodium selenite to thioacetamide in step two is 1:2-1:40; the amount of tin tetrachloride is 0.21-2.1g; the volume ratio of ethanol to acetic acid is 30:1-10:1; and the amount of TiO2 is 0.05-0.5g.

[0012] The reaction temperature of step three is 160-240℃; and the reaction time is 12-30h.

[0013] The reaction temperature of step four is 200-500℃; and the reaction time is 5-20min.

[0014] Step one uses the electrospinning step to prepare TiO2 nanotubes.

[0015] The method for preparing TiO2 nanotubes is selected as follows: (1) tetrabutyl titanate, polyvinylpyrrolidone (PVP) and mineral oil are sequentially dissolved in an ethanol and acetic acid (in a certain proportion) solution, each time an agent is added, it needs to be stirred for several tens of minutes to form a mixed solution A; (2) the mixed solution A is subjected to electrospinning treatment; (3) after the electrospinning is completed, the fibers on the substrate are collected and subjected to annealing treatment to obtain TiO2 nanotubes. The amounts of tetrabutyl titanate, PVP and mineral oil are 0.5-2g, 0.1-1g and 0.5-12ml respectively; the volume ratio of ethanol to acetic acid is 15:1-2:1; the stirring time is 30-180min; the electrospinning parameters are as follows: the needle diameter is 0.2-2mm, the distance between the needle tip and the substrate is 10-30cm, the voltage is 5-30KV; the temperature is 30-80℃; the humidity is 10%-50%; the annealing temperature is 300-800℃; and the annealing time is 1-10h. The method of the application can be used to simply prepare uniform TiO2 nanotubes, which is beneficial to the later surface coating and can also improve the specific surface area.

[0016] A TiO2@SnSe x S 2-x bifunctional composite structure, TiO2@SnSe x S 2-x The length of the TiO2@SnO2 bifunctional composite structure is 0.5-50 μm, the inside is a nanotube structure, and the surface is a sheet structure.

[0017] The TiO2@SnSe x S 2-x bifunctional composite structure of the application, the preparation method of the TiO2@SnO2 bifunctional composite structure can be assisted by SnSe x S 2-x coated TiO2 nanotubes, the band gap is improved, the transport of photo-generated carriers in different materials is prolonged, and the carrier lifetime is prolonged, and the band gap difference is conducive to the transmission of carriers, thereby improving the light absorption capacity, and by adjusting the X range through the proportioning of different proportions of tin tetrachloride, sodium selenite and thioacetamide, a wider adjusted band gap is obtained, and different light absorption is met. Moreover, the surface stability can be obtained more simply by the SnO2 surface coating, and the catalytic performance of the material is improved. In addition, the method of the application realizes the TiO2@SnO2 x S 2-x bifunctional composite structure with uniform size, adjustable size, good dispersion, excellent catalytic performance and stability through reasonable process control. The raw materials of the application are cheap and easy to obtain, the synthesis process is simple, the cost is low, the reaction period is short, and the environment is not polluted. BRIEF DESCRIPTION OF DRAWINGS

[0018] Figure 1 is a scanning electron microscope (SEM) photo of the TiO2 nanotubes prepared in Example 1.

[0019] Figure 2 is a scanning electron microscope (SEM) photo of the TiO2@SnSe x S 2-x bifunctional composite structure prepared in Example 1. DETAILED DESCRIPTION

[0020] The method described in the application is further illustrated by specific examples below, but it does not mean that the application is limited to these examples.

[0021] Example 1:

[0022] A TiO2@SnSe x S 2-xThe preparation method of the SnO2 bifunctional composite structure comprises the following steps: step one, 1.02 g of tetrabutyl titanate, 0.4 g of PVP and 1.5 ml of mineral oil are sequentially dissolved in a mixed solution of 23.3 ml of ethanol and 11.7 ml of acetic acid, each time the reagent is added, and stirring is required for 60 min, to form a mixed solution A; step two, the mixed solution A is subjected to electrostatic spinning treatment, the electrostatic spinning parameters are as follows: the needle diameter is 0.6 mm, the distance between the needle tip and the substrate is 18 cm, the voltage is 15 KV, the temperature is 50 DEG C, and the humidity is 25 %; step three, after the spinning is completed, the fibers on the substrate are collected, and the TiO2 nanotubes are obtained by annealing at 600 DEG C for 4 h; step four, 1.5 mmol of tin tetrachloride, sodium selenite and thioacetamide with a molar ratio of 1:9 are dissolved in a mixed solution of 33.5 ml of ethanol and 1.5 ml of acetic acid, and then the TiO2 nanotubes are added to form a mixed solution B; step five, the prepared mixed solution B is added to a tetrafluoroethylene reaction kettle, the reaction kettle is placed in a thermostat, and the reaction is carried out at 200 DEG C for 24 h, then the reaction kettle is naturally cooled to room temperature, centrifuged, washed with ethanol and deionized water respectively for multiple times, and dried to obtain TiO2@SnSe x S 2-x . Step six, the TiO2@SnSe x S 2-x is placed in a muffle furnace and oxidized at 400 DEG C for 10 min to obtain TiO2@SnSe x S 2-x @SnO2 bifunctional composite structure.

[0023] The Figure 1 and 2 are SEM images of the TiO2 nanotubes and the TiO2@SnSe x S 2-x @SnO2 bifunctional composite structure prepared in the embodiment, respectively, and it can be seen from the images that the prepared TiO2@SnSe x S 2-x @SnO2 bifunctional composite structure has good dispersity and uniform size.

[0024] Comparative example:

[0025] TiO2@SnSe2@SnO2 and TiO2@SnS2@SnO2 are respectively prepared, and the catalytic performance and stability are tested, and it is shown that the TiO2@SnSe x S 2-x @SnO2 material prepared in the application has higher catalytic performance. This is because the SnSe x S 2-xThe band gap adjustment improvement can further improve the band gap, expand the light absorption range, improve the light absorption energy, and prolong the transport of photo-generated carriers in different materials, thereby prolonging the carrier lifetime, improving the catalytic performance, and improving the stability of SnO2 due to the increase in the surface area of the nanotube surface sheet structure. Thus, the material prepared by the method of the present application has high catalytic performance and stability.

[0026] Example 2:

[0027] The difference between this example and Example 1 is that the amount of tetrabutyl titanate in step one is changed to 1.36 g, and the others are the same as Example 1, as follows: Step one, 1.36 g of tetrabutyl titanate, 0.4 g of PVP and 1.5 ml of mineral oil were sequentially dissolved in a mixed solution of 23.3 ml of ethanol and 11.7 ml of acetic acid, and each reagent was stirred for 60 min. A mixed solution A was formed; Step two, the mixed solution A was subjected to electrospinning treatment, and the electrospinning parameters were as follows: the needle diameter was 0.6 mm, the distance between the needle tip and the substrate was 18 cm, the voltage was 15 KV, the temperature was 50°C, and the humidity was 25%; Step three, after the electrospinning was completed, the fibers on the substrate were collected, and annealing was performed at 600°C for 4 h to obtain TiO2 nanotubes; Step four, 1.5 mmol of tin tetrachloride, sodium selenite and thioacetamide with a molar ratio of 1:9 were dissolved in a mixed solution of 33.5 ml of ethanol and 1.5 ml of acetic acid, and then TiO2 nanotubes were added to form a mixed solution B; Step five, the prepared mixed solution B was added to a tetrafluoroethylene reaction kettle, the reaction kettle was placed in a constant temperature oven, and reaction was performed at 200°C for 24 h. After the reaction kettle was naturally cooled to room temperature, centrifugation, ethanol and deionized water were washed several times, and drying was performed to obtain TiO2@SnSe x S 2-x Step six, TiO2@SnSe x S 2-x was placed in a muffle furnace and oxidized at 400°C for 10 min to obtain a TiO2@SnSe x S 2-x @SnO2 bifunctional composite structure.

[0028] Example 3:

[0029] The embodiment is different from embodiment 1 in that the amount of ethanol and acetic acid in step one is changed to 28ml and 7ml respectively, and the others are the same as embodiment 1, as follows: step one, 1.02g of tetrabutyl titanate, 0.4g of PVP and 1.5ml of mineral oil are sequentially dissolved in a mixed solution of 28ml of ethanol and 7ml of acetic acid, and each reagent needs to be stirred for 60min, forming a mixed solution A; step two, the mixed solution A is subjected to electrospinning treatment, and the electrospinning parameters are as follows: the needle diameter is 0.6mm, the distance between the needle tip and the substrate is 18cm, the voltage is 15KV, the temperature is 50℃, and the humidity is 25%; step three, after the electrospinning is completed, the fibers on the substrate are collected, and annealing is performed at 600℃ for 4h, thereby obtaining TiO2nanotubes; step four, 1.5mmol of tin tetrachloride, sodium selenite and thioacetamide with a molar ratio of 1:9 are dissolved in a mixed solution of 33.5ml of ethanol and 1.5ml of acetic acid, and then TiO2nanotubes are added to form a mixed solution B; step five, the prepared mixed solution B is poured into a tetrafluoroethylene reaction kettle, the reaction kettle is placed in a constant temperature oven, and reaction is performed at 200℃ for 24h, then the reaction kettle is naturally cooled to room temperature, centrifuged, washed with ethanol and deionized water for multiple times, and dried, thereby obtaining TiO2@SnSe x S 2-x . Step six, TiO2@SnSe x S 2-x is placed in a muffle furnace and oxidized at 400℃ for 10min, thereby obtaining TiO2@SnSe x S 2-x @SnO2bifunctional composite structure.

[0030] Example 4:

[0031] The embodiment is different from example 1 in that the stirring time in step one is changed to 30 min, and the others are the same as example 1, as follows: step one, 1.02 g of tetrabutyl titanate, 0.4 g of PVP and 1.5 ml of mineral oil are sequentially dissolved in a mixed solution of 23.3 ml of ethanol and 11.7 ml of acetic acid, and each reagent needs to be stirred for 30 min, forming a mixed solution A; step two, the mixed solution A is subjected to electrospinning treatment, and the electrospinning parameters are as follows: the needle diameter is 0.6 mm, the distance between the needle tip and the substrate is 18 cm, the voltage is 15 KV; the temperature is 50℃; and the humidity is 25%; step three, after the spinning is completed, the fibers on the substrate are collected, and annealing is performed at 600℃ for 4 h, to obtain TiO2 nanotubes; step four, 1.5 mmol of tin tetrachloride, sodium selenite and thioacetamide with a molar ratio of 1:9 are dissolved in a mixed solution of 33.5 ml of ethanol and 1.5 ml of acetic acid, and then TiO2 nanotubes are added to form a mixed solution B; step five, the prepared mixed solution B is added to a tetrafluoroethylene reaction kettle, the reaction kettle is placed in a constant temperature oven, and reaction is performed at 200℃ for 24 h, and then the reaction kettle is naturally cooled to room temperature, centrifuged, washed with ethanol and deionized water for multiple times, and dried, to obtain TiO2@SnSe x S 2-x . Step six, the TiO2@SnSe x S 2-x is placed in a muffle furnace and oxidized at 400℃ for 10 min, to obtain a TiO2@SnSe x S 2-x @SnO2 bifunctional composite structure.

[0032] Example 5:

[0033] The embodiment is different from embodiment 1 in that the distance between the needle tip and the substrate in step two is 15 cm, and the others are the same as embodiment 1, as follows: step one, 1.02 g of tetrabutyl titanate, 0.4 g of PVP and 1.5 ml of mineral oil are sequentially dissolved in a mixed solution of 23.3 ml of ethanol and 11.7 ml of acetic acid, and each reagent needs to be stirred for 60 min, forming a mixed solution A; step two, the mixed solution A is subjected to electrospinning treatment, and the electrospinning parameters are as follows: the needle diameter is 0.6 mm, the distance between the needle tip and the substrate is 15 cm, the voltage is 15 KV; the temperature is 50℃; and the humidity is 25%; step three, after the spinning is completed, the fibers on the substrate are collected, and annealing is performed at 600℃ for 4 h, thereby obtaining TiO2 nanotubes; step four, 1.5 mmol of tin tetrachloride, sodium selenite and thioacetamide with a molar ratio of 1:9 are dissolved in a mixed solution of 33.5 ml of ethanol and 1.5 ml of acetic acid, and then TiO2 nanotubes are added to form a mixed solution B; step five, the prepared mixed solution B is added to a tetrafluoroethylene reaction kettle, the reaction kettle is placed in a constant temperature oven, and reaction is performed at 200℃ for 24 h, and then the reaction kettle is naturally cooled to room temperature, centrifuged, washed with ethanol and deionized water respectively for multiple times, and dried, thereby obtaining TiO2@SnSe x S 2-x . Step six, the TiO2@SnSe x S 2-x is placed in a muffle furnace and oxidized at 400℃ for 10 min, thereby obtaining a TiO2@SnSe x S 2-x @SnO2 bifunctional composite structure.

[0034] Example 6:

[0035] The embodiment is different from embodiment 1 in that the voltage is changed to 18KV in step two, and the others are the same as embodiment 1, as follows: step one, 1.02g of tetrabutyl titanate, 0.4g of PVP and 1.5ml of mineral oil are sequentially dissolved in a mixed solution of 23.3ml of ethanol and 11.7ml of acetic acid, and each reagent needs to be stirred for 60min, forming a mixed solution A; step two, the mixed solution A is subjected to electrostatic spinning treatment, and the electrostatic spinning parameters are as follows: the needle diameter is 0.6mm, the distance between the needle tip and the substrate is 18cm, the voltage is 18KV; the temperature is 50℃; and the humidity is 25%; step three, after the spinning is completed, the fibers on the substrate are collected, and annealing is performed at 600℃ for 4h, thereby obtaining TiO2nanotubes; step four, 1.5mmol of tin tetrachloride, sodium selenite and thioacetamide with a molar ratio of 1:9 are dissolved in a mixed solution of 33.5ml of ethanol and 1.5ml of acetic acid, and then TiO2nanotubes are added, forming a mixed solution B; step five, the prepared mixed solution B is added to a tetrafluoroethylene reaction kettle, the reaction kettle is placed in a constant temperature oven, and reaction is performed at 200℃ for 24h, and then the reaction kettle is naturally cooled to room temperature, centrifuged, washed with ethanol and deionized water respectively for multiple times, and dried, thereby obtaining TiO2@SnSe x S 2-x . Step six, the TiO2@SnSe x S 2-x is placed in a muffle furnace and oxidized at 400℃ for 10min, thereby obtaining a TiO2@SnSe x S 2-x @SnO2 bifunctional composite structure.

[0036] Example 7:

[0037] The embodiment is different from embodiment 1 in that the annealing temperature in step three is changed to 500℃, and the others are the same as embodiment 1, as follows: step one, 1.02g of tetrabutyl titanate, 0.4g of PVP and 1.5ml of mineral oil are sequentially dissolved in a mixed solution of 23.3ml of ethanol and 11.7ml of acetic acid, and stirring is required for 60min after each addition of reagent to form a mixed solution A; step two, the mixed solution A is subjected to electrostatic spinning treatment, and the electrostatic spinning parameters are as follows: the needle diameter is 0.6mm, the distance between the needle tip and the substrate is 18cm, the voltage is 15KV, the temperature is 50℃, and the humidity is 25%; step three, after the spinning is completed, the fibers on the substrate are collected, and annealing is performed at 500℃ for 4h to obtain TiO2nanotubes; step four, 1.5mmol of tin tetrachloride, sodium selenite and thioacetamide with a molar ratio of 1:9 are dissolved in a mixed solution of 33.5ml of ethanol and 1.5ml of acetic acid, and then TiO2nanotubes are added to form a mixed solution B; step five, the prepared mixed solution B is added to a tetrafluoroethylene reaction kettle, the reaction kettle is placed in a thermostat, and reaction is performed at 200℃ for 24h, and then the reaction kettle is naturally cooled to room temperature, centrifuged, washed with ethanol and deionized water for multiple times, and dried to obtain TiO2@SnSe x S 2-x . Step six, TiO2@SnSe x S 2-x is placed in a muffle furnace and oxidized at 400℃ for 10min to obtain TiO2@SnSe x S 2-x @SnO2bifunctional composite structure.

[0038] Example 8:

[0039] The embodiment is different from embodiment 1 in that the annealing time in step three is changed to 2h, and the others are the same as embodiment 1, as follows: step one, 1.02g of tetrabutyl titanate, 0.4g of PVP and 1.5ml of mineral oil are sequentially dissolved in a mixed solution of 23.3ml of ethanol and 11.7ml of acetic acid, and stirring is required for 60min after each addition of reagent to form a mixed solution A; step two, the mixed solution A is subjected to electrospinning treatment, and the electrospinning parameters are as follows: the needle diameter is 0.6mm, the distance between the needle tip and the substrate is 18cm, the voltage is 15KV, the temperature is 50℃, and the humidity is 25%; step three, after the electrospinning is completed, the fibers on the substrate are collected, and annealing is performed at 600℃ for 2h to obtain TiO2nanotubes; step four, 1.5mmol of tin tetrachloride, sodium selenite and thioacetamide with a molar ratio of 1:9 are dissolved in a mixed solution of 33.5ml of ethanol and 1.5ml of acetic acid, and then TiO2nanotubes are added to form a mixed solution B; step five, the prepared mixed solution B is added to a tetrafluoroethylene reaction kettle, the reaction kettle is placed in a thermostat, and reaction is performed at 200℃ for 24h, and then the reaction kettle is naturally cooled to room temperature, centrifuged, washed with ethanol and deionized water for multiple times, and dried to obtain TiO2@SnSe x S 2-x . Step six, TiO2@SnSe x S 2-x is placed in a muffle furnace and oxidized at 400℃ for 10min to obtain TiO2@SnSe x S 2-x @SnO2bifunctional composite structure.

[0040] Example 9:

[0041] The embodiment is different from embodiment 1 in that the amount of tin tetrachloride in step four is changed to 1 mmol, and the others are the same as embodiment 1, as follows: step one, 1.02 g of tetrabutyl titanate, 0.4 g of PVP and 1.5 ml of mineral oil are sequentially dissolved in a mixed solution of 23.3 ml of ethanol and 11.7 ml of acetic acid, and stirring is required for 60 min after each addition of reagent to form a mixed solution A; step two, the mixed solution A is subjected to electrostatic spinning treatment, and the electrostatic spinning parameters are as follows: the needle diameter is 0.6 mm, the distance between the needle tip and the substrate is 18 cm, the voltage is 15 KV, the temperature is 50℃, and the humidity is 25%; step three, after the spinning is completed, the fibers on the substrate are collected, and annealing is performed at 600℃ for 4 h to obtain TiO2 nanotubes; step four, 1 mmol of tin tetrachloride, sodium selenite and thioacetamide with a molar ratio of 1:9 are dissolved in a mixed solution of 33.5 ml of ethanol and 1.5 ml of acetic acid, and then TiO2 nanotubes are added to form a mixed solution B; step five, the prepared mixed solution B is added to a tetrafluoroethylene reaction kettle, the reaction kettle is placed in a thermostat, and reaction is performed at 200℃ for 24 h, and then the reaction kettle is naturally cooled to room temperature, centrifuged, washed with ethanol and deionized water for multiple times, and dried to obtain TiO2@SnSe x S 2-x . Step six, TiO2@SnSe x S 2-x is placed in a muffle furnace and oxidized at 400℃ for 10 min to obtain TiO2@SnSe x S 2-x @SnO2 bifunctional composite structure.

[0042] Example 10:

[0043] The embodiment is different from embodiment 1 in that the ethanol and acetic acid are changed to 67ml and 3ml in step four, and the others are the same as embodiment 1, as follows: step one, 1.02g of tetrabutyl titanate, 0.4g of PVP and 1.5ml of mineral oil are sequentially dissolved in a mixed solution of 23.3ml of ethanol and 11.7ml of acetic acid, and stirring is required for 60min after each addition of reagent to form a mixed solution A; step two, the mixed solution A is subjected to electrospinning treatment, and the electrospinning parameters are as follows: the needle diameter is 0.6mm, the distance between the needle tip and the substrate is 18cm, the voltage is 15KV, the temperature is 50℃, and the humidity is 25%; step three, after the electrospinning is completed, the fibers on the substrate are collected, and annealing is performed at 600℃ for 4h to obtain TiO2nanotubes; step four, 1.5mmol of tin tetrachloride, sodium selenite and thioacetamide with a molar ratio of 1:9 are dissolved in a mixed solution of 67ml of ethanol and 3ml of acetic acid, and then TiO2nanotubes are added to form a mixed solution B; step five, the prepared mixed solution B is added to a teflon reaction kettle, the reaction kettle is placed in a thermostat, and reaction is performed at 200℃ for 24h, and then the reaction kettle is naturally cooled to room temperature, centrifuged, washed with ethanol and deionized water for multiple times, and dried to obtain TiO2@SnSe x S 2-x . Step six, the TiO2@SnSe x S 2-x is placed in a muffle furnace and oxidized at 400℃ for 10min to obtain a TiO2@SnSe x S 2-x @SnO2 bifunctional composite structure.

[0044] Example 11:

[0045] The embodiment is different from embodiment 1 in that the reaction temperature in step five is changed to 180℃, and the others are the same as embodiment 1, as follows: step one, 1.02g of tetrabutyl titanate, 0.4g of PVP and 1.5ml of mineral oil are sequentially dissolved in a mixed solution of 23.3ml of ethanol and 11.7ml of acetic acid, and each reagent needs to be stirred for 60min, forming a mixed solution A; step two, the mixed solution A is subjected to electrostatic spinning treatment, and the electrostatic spinning parameters are as follows: the needle diameter is 0.6mm, the distance between the needle tip and the substrate is 18cm, the voltage is 15KV; the temperature is 50℃; and the humidity is 25%; step three, after the spinning is completed, the fibers on the substrate are collected, and annealing is performed at 600℃ for 4h, thereby obtaining TiO2nanotubes; step four, 1.5mmol of tin tetrachloride, sodium selenite and thioacetamide with a molar ratio of 1:9 are dissolved in a mixed solution of 33.5ml of ethanol and 1.5ml of acetic acid, and then TiO2nanotubes are added, forming a mixed solution B; step five, the prepared mixed solution B is added to a tetrafluoroethylene reaction kettle, the reaction kettle is placed in a thermostat, and reaction is performed at 180℃ for 24h, and then the reaction kettle is naturally cooled to room temperature, centrifuged, washed with ethanol and deionized water for multiple times, and dried, thereby obtaining TiO2@SnSe x S 2-x . Step six, TiO2@SnSe x S 2-x is placed in a muffle furnace and oxidized at 400℃ for 10min, thereby obtaining TiO2@SnSe x S 2-x @SnO2bifunctional composite structure.

[0046] Example 12:

[0047] The embodiment is different from embodiment 1 in that the reaction time in step five is changed to 18h, and the others are the same as embodiment 1, as follows: step one, 1.02g of tetrabutyl titanate, 0.4g of PVP and 1.5ml of mineral oil are sequentially dissolved in a mixed solution of 23.3ml of ethanol and 11.7ml of acetic acid, and each reagent needs to be stirred for 60min, forming a mixed solution A; step two, the mixed solution A is subjected to electrostatic spinning treatment, and the electrostatic spinning parameters are as follows: the needle diameter is 0.6mm, the distance between the needle tip and the substrate is 18cm, the voltage is 15KV; the temperature is 50℃; and the humidity is 25%; step three, after the spinning is completed, the fibers on the substrate are collected, and annealing is performed at 600℃ for 4h, thereby obtaining TiO2nanotubes; step four, 1.5mmol of tin tetrachloride, sodium selenite and thioacetamide with a molar ratio of 1:9 are dissolved in a mixed solution of 33.5ml of ethanol and 1.5ml of acetic acid, and then TiO2nanotubes are added, forming a mixed solution B; step five, the prepared mixed solution B is added to a tetrafluoroethylene reaction kettle, the reaction kettle is placed in a thermostat, and reaction is performed at 200℃ for 18h, and then the reaction kettle is naturally cooled to room temperature, centrifuged, washed with ethanol and deionized water respectively for multiple times, and dried, thereby obtaining TiO2@SnSe x S 2-x . Step six, TiO2@SnSe x S 2-x is placed in a muffle furnace and oxidized at 400℃ for 10min, thereby obtaining TiO2@SnSe x S 2-x @SnO2bifunctional composite structure.

[0048] Example 13:

[0049] The embodiment is different from embodiment 1 in that the reaction temperature in step six is changed to 420℃, and the others are the same as embodiment 1, as follows: step one, 1.02g of tetrabutyl titanate, 0.4g of PVP and 1.5ml of mineral oil are sequentially dissolved in a mixed solution of 23.3ml of ethanol and 11.7ml of acetic acid, and each reagent needs to be stirred for 60min, forming a mixed solution A; step two, the mixed solution A is subjected to electrostatic spinning treatment, and the electrostatic spinning parameters are as follows: the needle diameter is 0.6mm, the distance between the needle tip and the substrate is 18cm, the voltage is 15KV; the temperature is 50℃; and the humidity is 25%; step three, after the spinning is completed, the fibers on the substrate are collected, and annealing is performed at 600℃ for 4h, thereby obtaining TiO2nanotubes; step four, 1.5mmol of tin tetrachloride, sodium selenite and thioacetamide with a molar ratio of 1:9 are dissolved in a mixed solution of 33.5ml of ethanol and 1.5ml of acetic acid, and then TiO2nanotubes are added, forming a mixed solution B; step five, the prepared mixed solution B is added to a tetrafluoroethylene reaction kettle, the reaction kettle is placed in a thermostat, and reaction is performed at 200℃ for 24h, and then the reaction kettle is naturally cooled to room temperature, centrifuged, washed with ethanol and deionized water respectively for multiple times, and dried, thereby obtaining TiO2@SnSe x S 2-x . Step six, the TiO2@SnSe x S 2-x is placed in a muffle furnace and oxidized at 420℃ for 10min, thereby obtaining a TiO2@SnSe x S 2-x @SnO2 bifunctional composite structure.

[0050] Example 14:

[0051] The embodiment is different from embodiment 1 in that the oxidation time in step six is changed to 5 min, and the others are the same as embodiment 1, and the specific steps are as follows: step one, 1.02 g of tetrabutyl titanate, 0.4 g of PVP and 1.5 ml of mineral oil are sequentially dissolved in a mixed solution of 23.3 ml of ethanol and 11.7 ml of acetic acid, and each reagent needs to be stirred for 60 min, forming a mixed solution A; step two, the mixed solution A is subjected to electrospinning treatment, and the electrospinning parameters are: the needle diameter is 0.6 mm, the distance between the needle tip and the substrate is 18 cm, the voltage is 15 KV; the temperature is 50℃; the humidity is 25%; step three, after the spinning is completed, the fibers on the substrate are collected, and the TiO2 nanotubes are obtained by annealing at 600℃ for 4h; step four, 1.5 mmol of tin tetrachloride, sodium selenite and thioacetamide with a molar ratio of 1:9 are dissolved in a mixed solution of 33.5 ml of ethanol and 1.5 ml of acetic acid, and then TiO2 nanotubes are added to form a mixed solution B; step five, the prepared mixed solution B is added to a tetrafluoroethylene reaction kettle, the reaction kettle is placed in a constant temperature oven, and the reaction is carried out at 200℃ for 24h, and then the reaction kettle is naturally cooled to room temperature, centrifuged, washed with ethanol and deionized water for several times, and dried to obtain TiO2@SnSe x S 2-x . Step six, the TiO2@SnSe x S 2-x is placed in a muffle furnace at 400℃ for 5 min to obtain a TiO2@SnSe x S 2-x @SnO2 bifunctional composite structure.

[0052] Only the method in the parameter range of the present application can obtain the TiO2@SnSe x S 2-x @SnO2 bifunctional composite structure composite photocatalytic material which is uniform, has good catalytic performance and stability. The parameters outside the scope of the present application cannot obtain a material with good uniformity and stability. In addition, the material of the present application can also effectively adsorb organic matter due to the coating of the nanotube surface with a sheet structure, which is beneficial to improve the catalytic treatment effect.

[0053] The above is only a preferred embodiment of the patent, and does not limit the patent in any form. Any person skilled in the art can make many possible changes and modifications to the above disclosed method and technical content without departing from the scope of the technical solution, or modify it as an equivalent embodiment. Therefore, any simple modification, equivalent change and modification made to the above embodiments according to the technical essence of the present application, without departing from the technical solution of the present application, still belongs to the protection scope of the present application.

Claims

1. A TiO2@SnSe x S 2-x A method for preparing a TiO2@SnO2 bifunctional composite structure, characterized in that, The method comprises the following steps: Step one, preparing TiO2 nanotube; Step two, dissolving a certain amount of tin tetrachloride, sodium selenite and thioacetamide in a solution of ethanol and acetic acid in a certain proportion, and then adding TiO2 nanotube to form a mixed solution B; Step three, add the prepared mixed solution B to the tetrafluoroethylene reactor, place the reactor in the thermostat, react for several hours at a certain temperature, and obtain TiO2@SnSe x S 2-x Tubular sheet structure; Step four, the obtained TiO2@SnSe x S 2-x The tubular sheet structure was annealed in a muffle furnace at a certain temperature for several minutes to obtain a TiO2@SnSe x S 2-x @SnO2 bifunctional tubular sheet composite structure, wherein 0 The molar ratio of sodium selenite to thioacetamide in step two is 1:2-1:40; the amount of tin tetrachloride is 0.21-2.1g; the volume ratio of ethanol to acetic acid is 30:1-10:1; and the amount of TiO2 is 0.05-0.5g; The reaction temperature of step three is 160-240℃; and the reaction time is 12-30h; The reaction temperature of step four is 200-500℃; and the reaction time is 5-20min.

2. TiO2@SnSe as claimed in claim 1 x S 2-x A preparation method of TiO2@SnO2 bifunctional composite structure, characterized in that: The TiO2 nanotube is prepared by the electrospinning step in step one.

3. A TiO2@SnSe composite structure prepared by the method of any one of claims 1-2 x S 2-x @SnO2 composite structure, characterized in that: TiO2@SnSe x S 2-x The length of the TiO2@SnO2 composite structure is 0.5-50 μm.

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