Full-spectrum response IEF-11 / WO3-xS type heterojunction and preparation method and application thereof

Abstract

The invention discloses an IEF-11 / WO3-xS type heterojunction material with full spectrum response as well as a preparation method and application of the IEF-11 / WO3-xS type heterojunction material. The heterojunction is prepared by taking squaric acid, tetrabutyl titanate and WO3-x particles as raw materials, wherein the value range of x in WO3-x is 0 < = xlt; 1. The heterojunction material creatively realizes full-spectrum response from ultraviolet to near infrared through S-type energy band structural design, the separation efficiency of photo-induced electron-hole pairs reaches 2.47 times (compared with WO3-x) and 1.57 times (compared with IEF-11) due to a unique carrier transport mechanism, and strong redox sites are synchronously reserved, so that the material can be applied to the field of photoelectron-hole separation. And compared with a single-component material, the photocatalytic performance is improved by 3.74 times (compared with WO3-x) and 1.41 times (compared with IEF-11). Experiments show that under full-spectrum irradiation, the inactivation rate of the material to escherichia coli can reach 99%, the 120-minute degradation rate of the material to tetracycline (TC) reaches 86%, the material shows broad-spectrum degradation capacity to typical organic pollutants such as chlortetracycline (CTC), rhodamine B (RhB) and methylene blue (MB) in a visible region, and the 120-minute degradation efficiency reaches 77%, 53% and 95% respectively. The heterojunction material is prepared through a simple hydrothermal method, and has important application value in the fields of environmental governance, photocatalytic disinfection and the like.

Description

Technical Field

[0001] The present invention belongs to the technical field of photocatalytic material synthesis and application, and specifically relates to a full-spectrum responsive IEF-11 / WO 3-x S-type heterojunction and its preparation method and application. Background Art

[0002] With the rapid increase in the global population and the high-speed development of social economy, the combined pollution of water bodies caused by the sharp increase in industrial wastewater emissions and the acceleration of urbanization has become a major environmental challenge. Research shows that the synergistic effect of antibiotic-resistant pathogenic microorganisms and persistent organic pollutants in water bodies not only threatens the balance of aquatic ecosystems, but also seriously endangers human health through food chain enrichment (J. Environ. Chem. Eng. 2023, 11, 110481). Traditional water treatment technologies have insufficient inactivation efficiency for antibiotic-resistant bacteria and are difficult to simultaneously remove typical organic pollutants such as tetracyclines and dyes. There is an urgent need to develop new and efficient water treatment technologies.

[0003] Heterogeneous photocatalytic technology based on semiconductor photocatalysts is recognized as one of the most promising environmental treatment means because it can utilize sunlight to achieve the dual functions of deep mineralization of pollutants and efficient inactivation of pathogenic microorganisms. Among them, the titanium-based metal-organic framework material IEF-11 exhibits significant advantages in the field of photocatalysis due to its unique three-dimensional pore structure and the synergistic photocatalytic response characteristics of titanium-oxygen clusters and squaric acid ligands (Adv. Mater. 2021, 33, 2106627). However, single IEF-11 has inherent defects: i) high recombination rate of photo-generated carriers; ii) lack of response in the near-infrared light region (accounting for 52-55% of the solar spectrum); iii) insufficient exposure of surface active sites, resulting in limited actual photocatalytic efficiency.

[0004] To address the above bottlenecks, heterojunction engineering has become the core strategy for improving photocatalytic performance. Compared with traditional type-II heterojunctions, S-type heterojunctions exhibit better photocatalytic performance by promoting the spatial separation of carriers while retaining strong redox ability through a unique energy band bending mechanism. The present invention innovatively selects WO 3-x with oxygen vacancy defects as the coupling object, and its advantages are: i) the near-infrared light response characteristics can effectively compensate for the spectral shortcoming of IEF-11; ii) the gradient energy band structure forms an ideal S-type energy band match with IEF-11; iii) surface oxygen vacancies can serve as electron capture centers to synergistically improve the carrier separation efficiency. So far, there have been no relevant studies and reports on constructing a full-spectrum responsive S-type heterojunction by loading WO 3-x on IEF-11. Summary of the Invention

[0005] In view of this, the first object of the present invention is to provide a full-spectrum responsive IEF-11 / WO3-x The S-type heterojunction is used to solve the technical problems in the prior art that the photocatalytic performance of the IEF-11 semiconductor photocatalyst needs to be improved and the light response range is narrow.

[0006] The second object of the present invention is to provide a full spectrum response IEF-11 / WO 3-x Method for preparing S-type heterojunction.

[0007] The third object of the present invention is to provide a full spectrum response IEF-11 / WO 3-x Applications of S-type heterojunction.

[0008] To this end, the first technical solution provided by the present invention is as follows:

[0009] A full spectrum response IEF-11 / WO 3-x S-type heterojunction, full spectrum response IEF-11 / WO 3-x The S-type heterojunction is composed of squaric acid, tetrabutyl titanate, WO 3-x Made of granules;

[0010] Among them: WO 3-x In the particles, 0≤x<1.

[0011] The full spectrum response of IEF-11 / WO 3-x S-type heterojunction, the square acid, WO 3-x The mass ratio of the particles to tetrabutyl titanate is 225:20 to 100:759.

[0012] Furthermore, the above-mentioned full spectrum response IEF-11 / WO 3-x S-type heterojunction, the WO 3-x The particles were prepared by the following method: WCl 6 Disperse in methanol and stir to make it uniform, transfer to a hydrothermal reactor and perform solvothermal reaction in a muffle furnace;

[0013] Wherein, the stirring time is 0.5 to 1 hour, and the temperature is room temperature;

[0014] The solvent thermal reaction time is 12 to 24 hours, and the temperature is 180°C;

[0015] The methanol WCl 6 The solution is 1.0~2.0mg / mL.

[0016] The second technical solution of the present invention is the above-mentioned full spectrum response IEF-11 / WO 3-x The method for preparing an S-type heterojunction comprises the following steps in sequence:

[0017] 1) Suspend the ground squaric acid solid powder in isopropyl alcohol, stir and ultrasonicate at room temperature to disperse it evenly to obtain a dispersion;

[0018] 2) Add glacial acetic acid and WO 3-x particles to the dispersion in step 1), and ultrasonically dissolve again to obtain a mixed solution;

[0019] 3) Slowly add tetrabutyl titanate to the mixed solution prepared in step 2) under heating and stirring conditions. After reacting at 40 - 60 °C for 5 - 20 minutes, an orange-brown turbid liquid is obtained, which is transferred to a hydrothermal reaction kettle and subjected to a solvothermal reaction at 100 - 150 °C in a muffle furnace for 40 - 50 hours, and then post-treated to obtain IEF-11 / WO 3-x heterojunction;

[0020] The mass ratio of the squaric acid, WO 3-x particles and tetrabutyl titanate is 225:20 - 100:759.

[0021] Furthermore, for the above-mentioned all-spectrum response IEF-11 / WO 3-x S-type heterojunction and its preparation method, the mass ratio of the squaric acid, isopropyl alcohol, and glacial acetic acid is 225:6437:6720.

[0022] Furthermore, for the above-mentioned all-spectrum response IEF-11 / WO 3-x Application of the S-type heterojunction as a photocatalytic microbial bactericide; or application as a catalyst for catalytic degradation of pollutants.

[0023] Furthermore, for the above-mentioned all-spectrum response IEF-11 / WO 3-x Application of the S-type heterojunction for catalytic degradation of organic pollutants, wherein the microorganisms include at least one of bacteria, viruses, and fungi; the pollutants include at least one of antibiotics and organic dyes.

[0024] Furthermore, for the above-mentioned all-spectrum response IEF-11 / WO 3-x S-type heterojunction and its preparation method and application, the antibiotics include at least one of tetracycline and chlortetracycline; the bacteria include Escherichia coli.

[0025] Another technical solution of the present invention is a method for photocatalytic degradation of pollutants by an all-spectrum response IEF-11 / WO 3-x S-type heterojunction. Add the IEF-11 / WO 3-x S-type heterojunction to the system containing pollutants, and photocatalytically degrade the pollutants under all-spectrum light irradiation.

[0026] Another technical solution of the present invention is an all-spectrum response IEF-11 / WO 3-xMethod for photocatalytic killing of microorganisms by S-type heterojunction. Add the IEF-11 / WO 3-x S-type heterojunction into a system containing microorganisms, and photocatalytically kill the microorganisms under full-spectrum light irradiation.

[0027] Compared with the prior art, the technical solution provided by the present invention has the following advantages and beneficial effects:

[0028] 1) The full-spectrum responsive IEF-11 / WO 3-x S-type heterojunction with response in the near-infrared region of WO 3-x makes the light response range of the IEF-11 / WO 3-x S-type heterojunction broaden to the full-spectrum region, improving the utilization rate of sunlight.

[0029] 2) The full-spectrum responsive IEF-11 / WO 3-x S-type heterojunction has a high separation efficiency of photo-generated carriers and strong redox ability, and has excellent photocatalytic performance for killing E. coli and degrading TC under full-spectrum irradiation.

[0030] 3) The IEF-11 / WO 3-x heterojunction provided by the present invention has universality for degrading common organic pollutants in water under visible light, and has good degradation performance for TC, CTC, RhB and MB.

[0031] 4) The heterojunction preparation method provided by the present invention is simple, low-cost, high-productivity, easy to scale up production, and suitable for popularization and application. Description of the Drawings

[0032] Figure 1 Scanning electron microscope image of the IEF-11 / WO 3-x -33 heterojunction prepared in Example 2;

[0033] Figure 2 X-ray diffraction pattern of the sample;

[0034] Figure 3 Ultraviolet diffuse reflection, band gap, valence band and energy band structure diagrams of the sample;

[0035] Figure 4 Effect of the IEF-11 / WO 3-x -33 heterojunction prepared in Example 2 on the growth state of E. coli on an agar plate under different light sources;

[0036] Figure 5 Inactivation efficiency of the IEF-11 / WO 3-x -33 heterojunction prepared in Example 2 on E. coli under different light sources;

[0037] Figure 6 It is the degradation efficiency diagram of TC for the sample under the irradiation of a full-spectrum light source;

[0038] Figure 7 It is the degradation efficiency diagram of other common organic pollutants in water body by the IEF-11 / WO 3-x -33 heterojunction prepared in Example 2 under visible light irradiation. Detailed implementation manners

[0039] The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are some, but not all, of the embodiments of the present invention. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0040] Example 1

[0041] This example provides an IEF-11 / WO 3-x -17 heterojunction, which is prepared successively through the following steps:

[0042] Suspend 255 mg of ground squaric acid solid powder in 8.2 mL of isopropanol, magnetically stir at a speed of 450 rpm for 5 minutes at room temperature, and then ultrasonically treat for 5 minutes in an ultrasonic bath at 35 kHz; then add 6.4 mL of glacial acetic acid and 20 mg of WO 3-x particles, and ultrasonically treat again for 15 minutes. Then, slowly add 0.762 mL of tetrabutyl titanate under stirring to obtain an orange suspension heated at 50 °C for 15 minutes; then transfer the orange suspension to a polytetrafluoroethylene-lined hydrothermal reaction kettle for sealing, heat it to 120 °C at a heating rate of 1.5 °C / min, keep it for 48 hours, and finally cool it to room temperature at a cooling rate of 1.5 °C / min to obtain an orange-brown solid. Wash the orange-brown solid with isopropanol, then centrifuge to separate and collect the solid, and dry the collected solid at 30 °C and 0.9 MPa in vacuum for 12 hours.

[0043] Among them, the WO 3-x particles are prepared by the following method: Disperse 50 mg of WCl 6 in 50 mL of methanol and stir at room temperature for 30 minutes, then transfer it to a hydrothermal reaction kettle and carry out a solvothermal reaction in a muffle furnace;

[0044] Among them, the stirring time is 0.5 hour and the temperature is room temperature;

[0045] The solvothermal reaction time is 12 hours and the temperature is 180 °C;

[0046] Among them: 0≤x<1 in the WO 3-x particles.

[0047] Example 2

[0048] This example provides an IEF-11 / WO 3-x -33 heterojunction, which is prepared by the following steps in sequence:

[0049] Suspend 255 mg of ground squaric acid solid powder in 8.2 mL of isopropanol, magnetically stir at a speed of 450 rpm for 5 minutes at room temperature, and then ultrasonically treat for 5 minutes in an ultrasonic bath at 35 kHz; then add 6.4 mL of glacial acetic acid and 50 mg of WO 3-x particles, and ultrasonically treat again for 15 minutes. Then, slowly add 0.762 mL of tetrabutyl titanate under stirring to obtain an orange suspension heated at 50 °C for 15 minutes; then transfer the orange suspension to a polytetrafluoroethylene-lined hydrothermal reaction kettle for sealing, heat it to 120 °C at a heating rate of 1.5 °C / min, keep it for 48 hours, and finally cool it to room temperature at a cooling rate of 1.5 °C / min to obtain an orange-brown solid. Wash the orange-brown solid with isopropanol, then centrifuge to separate and collect the solid, and vacuum-dry the collected solid at 0.9 MPa and 30 °C for 12 hours.

[0050] Among them, the WO 3-x particles are prepared by the following method: Disperse 50 mg of WCl 6 in 50 mL of methanol and stir at room temperature for 30 minutes, then transfer it to a hydrothermal reaction kettle and carry out a solvothermal reaction in a muffle furnace;

[0051] Among them, the stirring time is 0.5 hours and the temperature is room temperature;

[0052] The solvothermal reaction time is 12 hours and the temperature is 180 °C;

[0053] Among them: 0 ≤ x < 1 in the WO 3-x particles.

[0054] Example 3

[0055] This example provides a preparation method of an IEF-11 / WO 3-x -50 heterojunction, and the specific steps are as follows:

[0056] Suspend 255 mg of ground squaric acid solid powder in 8.2 mL of isopropanol, magnetically stir at a speed of 450 rpm for 5 minutes at room temperature, and then ultrasonically treat for 5 minutes in an ultrasonic bath at 35 kHz; then add 6.4 mL of glacial acetic acid and 100 mg of WO 3-xThe particles were sonicated again for 15 minutes. Then, 0.762 mL of tetrabutyl titanate was slowly added under stirring to obtain an orange suspension heated at 50 °C for 15 minutes; the orange suspension was then transferred to a polytetrafluoroethylene-lined hydrothermal reactor, sealed, heated to 120 °C at a heating rate of 1.5 °C / min, maintained for 48 hours, and finally cooled to room temperature at a cooling rate of 1.5 °C / min to obtain an orange-brown solid. The orange-brown solid was washed with isopropanol, and then the solid was collected by centrifugation. The collected solid was vacuum dried at 0.9 MPa and 30 °C for 12 hours.

[0057] Among them, WO 3-x The particles were prepared by the following method: 50 mg of WCl 6 was dispersed in 50 mL of methanol and stirred at room temperature for 30 minutes, then transferred to a hydrothermal reactor and subjected to a solvothermal reaction in a muffle furnace;

[0058] Among them, the stirring time was 0.5 hours and the temperature was room temperature;

[0059] The solvothermal reaction time was 12 hours and the temperature was 180 °C;

[0060] Among them: WO 3-x In the particles, 0 ≤ x < 1.

[0061] Example 4

[0062] This example provides an IEF-11 / WO 3-x -33-T1 heterojunction, which was prepared successively by the following steps:

[0063] 255 mg of ground squaric acid solid powder was suspended in 8.2 mL of isopropanol, magnetically stirred at a rotation speed of 450 rpm at room temperature for 5 minutes, and then sonicated in an ultrasonic bath at 35 kHz for 5 minutes; then 6.4 mL of glacial acetic acid and 50 mg of WO 3-x particles were added, and sonicated again for 15 minutes. Then, 0.762 mL of tetrabutyl titanate was slowly added under stirring to obtain an orange suspension heated at 40 °C for 15 minutes; the orange suspension was then transferred to a polytetrafluoroethylene-lined hydrothermal reactor, sealed, heated to 120 °C at a heating rate of 1.5 °C / min, maintained for 48 hours, and finally cooled to room temperature at a cooling rate of 1.5 °C / min to obtain an orange-brown solid. The orange-brown solid was washed with isopropanol, and then the solid was collected by centrifugation. The collected solid was vacuum dried at 0.9 MPa and 30 °C for 12 hours.

[0064] Among them, WO 3-x The particles were prepared by the following method: 50 mg of WCl 6 was dispersed in 50 mL of methanol and stirred at room temperature for 30 minutes, then transferred to a hydrothermal reactor and subjected to a solvothermal reaction in a muffle furnace;

[0065] Among them, the stirring time is 0.5 hours and the temperature is room temperature;

[0066] The solvothermal reaction time is 12 hours and the temperature is 180 °C;

[0067] Among them: WO 3-x In the particles, 0 ≤ x < 1.

[0068] Example 5

[0069] This example provides an IEF-11 / WO 3-x -33-T2 heterojunction, which is prepared by the following steps in sequence:

[0070] Suspend 255 mg of ground squaric acid solid powder in 8.2 mL of isopropanol, magnetically stir at 450 rpm at room temperature for 5 minutes, and then ultrasonically treat in an ultrasonic bath at 35 kHz for 5 minutes; then add 6.4 mL of glacial acetic acid and 50 mg of WO 3-x particles and ultrasonically treat again for 15 minutes. Then, slowly add 0.762 mL of tetrabutyl titanate under stirring, and heat at 60 °C for 15 minutes to obtain an orange suspension; then transfer the orange suspension to a polytetrafluoroethylene-lined hydrothermal reaction kettle, seal it, heat it to 120 °C at a heating rate of 1.5 °C / min, keep it for 48 hours, and finally cool it to room temperature at a cooling rate of 1.5 °C / min to obtain an orange-brown solid. Wash the orange-brown solid with isopropanol, then centrifuge to separate and collect the solid, and vacuum-dry the collected solid at 0.9 MPa and 30 °C for 12 hours.

[0071] Among them, the WO 3-x particles are prepared by the following method: Disperse 50 mg of WCl 6 in 50 mL of methanol and stir at room temperature for 30 minutes, transfer it to a hydrothermal reaction kettle and carry out a solvothermal reaction in a muffle furnace;

[0072] Among them, the stirring time is 0.5 hours and the temperature is room temperature;

[0073] The solvothermal reaction time is 12 hours and the temperature is 180 °C;

[0074] Among them: WO 3-x In the particles, 0 ≤ x < 1.

[0075] In order to verify the IEF-11 / WO 3-x -33 heterojunction prepared in this application, the following gives the performance detection spectra, sterilization performance test experiments and experimental data of the IEF-11 / WO 3-x -33 heterojunction prepared in Example 2.

[0076] IEF-11 / WO prepared in Example 2 3-x The SEM image of the IEF-11 / WO Figure 1 -33 heterojunction is shown in Figure 1 . It can be seen that IEF-11 is a hexagonal facet crystal (diameter 85±30 nm), and WO 3-x nanoparticles (diameter 217±50 nm) are wrapped therein.

[0077] The XRD pattern of the IEF-11 / WO 3-x -33 heterojunction prepared in Example 2 is shown in Figure 2 . It can be seen from Figure 2 that the XRD pattern of the IEF-11 / WO 3-x -33 heterojunction has the typical characteristic peaks of IEF-11 and WO 3-x , proving the successful construction of the heterojunction.

[0078] The IEF-11 / WO 3-x -33 heterojunction prepared in Example 2; and the UV diffuse reflection, band gap, valence band and energy band structure diagrams of IEF-11 and WO 3-x are shown in Figure 3 . It can be judged from the energy band structure that the S-type heterojunction is successfully constructed.

[0079] It should be noted that the detection spectra of other examples are basically similar to those of Example 2, so they are omitted here.

[0080] Test Example 1

[0081] This test example is about the photocatalytic performance of the IEF-11 / WO 3-x -33 heterojunction prepared in Example 2 for killing E. coli.

[0082] The test steps are as follows:

[0083] Take 5 mL of E. coli bacterial solution (OD 600 = 0.09 - 0.11) and mix it with 45 mL of sterilized normal saline. Add 30 mg of IEF-11 / WO 3-x -33 heterojunction to the above solution. Use a 300 W xenon lamp as the light source and set it to visible light, near-infrared light and full-spectrum light source respectively by using different filters. Under the light source irradiation, take out 100 μL of the bacterial suspension at 0, 15, 30, 45, and 60 minutes respectively, dilute it 1×10 3 times, then take 100 μL and spread it evenly on the LB solid medium, and culture it in a 37°C constant temperature incubator for 12 - 18 hours. The photocatalytic bactericidal performance of the IEF-11 / WO 3-x -33 heterojunction can be obtained through the change of the number of E. coli colonies.

[0084] Figure 4 The influence of the IEF-11 / WO 3-x -33 heterojunction on the growth state of E. coli on an agar plate under different light source irradiations. It can be seen that under the irradiations of near-infrared light, visible light, and full-spectrum light sources, the photocatalytic killing performance of the IEF-11 / WO 3-x -33 heterojunction on E. coli increases successively, indicating that the IEF-11 / WO 3-x -33 heterojunction has excellent photocatalytic killing performance on E. coli. For the corresponding E. coli efficiency diagram, refer to Figure 5 .

[0085] Test Example 2

[0086] This test example is about the photocatalytic degradation performance of IEF-11 particles, WO 3-x particles, and the IEF-11 / WO 3-x heterojunctions prepared in Examples 1 to 3 under full-spectrum light source conditions. The test steps are as follows:

[0087] Prepare 100 mL of a TC solution with a concentration of 20 mg / L. Add 10 mg of the sample to the above solution and use a 300 W xenon lamp as the light source (full-spectrum reflector). After stirring in the dark for 30 minutes, irradiate the system with the light source for 120 minutes. During this period, take 3 mL of the TC solution at regular intervals, and remove the photocatalyst in the solution with a 0.22 μm aqueous filter membrane. Measure the absorbance of TC at 357 nm using a UV-visible spectrophotometer.

[0088] The degradation efficiency of the blank control group and each group of catalysts on TC under full-spectrum conditions is as Figure 6 shown. Compared with pure IEF-11 particles and WO 3-x particles, the IEF-11 / WO 3-x heterojunctions with different mass fraction ratios have significantly improved degradation rates of TC under full-spectrum conditions. Among them, the visible-light photocatalytic degradation performance of the IEF-11 / WO 3-x -33 heterojunction is the best, and it can degrade 86% of TC within 120 minutes.

[0089] Test Example 3

[0090] This test example is about the performance test of the IEF-11 / WO 3-x -33 heterojunction prepared in Example 2 for photocatalytic degradation of other organic pollutants (CTC, RhB, MB) under visible light irradiation. The test steps are as follows:

[0091] Prepare 100 mL of an organic pollutant solution with a certain concentration. Add 10 mg of the sample to the above solution, and use a 300 W xenon lamp with a filter as the visible light source. After stirring for 30 minutes under dark conditions, irradiate the system with the light source for 120 minutes. During this period, take 3 mL of the organic pollutant solution at regular intervals, remove the photocatalyst in the solution with a 0.22 μm water-based filter membrane, and measure the absorbance of the organic pollutant at a certain wavelength using an ultraviolet spectrophotometer.

[0092] IEF-11 / WO 3-x -33 heterojunction under visible light irradiation conditions for the degradation efficiency of organic pollutants (CTC, RhB, MB) is as Figure 7 shown. It can be seen from the figure that IEF-11 / WO 3-x -33 heterojunction in 120 minutes for the degradation rates of CTC, RhB and MB are 76.7%, 52.3% and 95.4% respectively. The above results indicate that the heterojunction prepared by the present invention has universality in the application of photocatalytic degradation of common organic pollutants in water bodies.

[0093] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that: they can still modify the technical solutions recorded in the foregoing embodiments, or perform equivalent replacements on some or all of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A full spectrum response IEF-11 / WO 3-x An S-type heterojunction is characterized by: The full spectrum response IEF-11 / WO 3-x The S-type heterojunction is composed of squaric acid, tetrabutyl titanate, WO 3-x Made of granules; Among them: WO 3-x In the particles, 0≤x<1.

2. Full spectrum response IEF-11 / WO according to claim 1 3-x An S-type heterojunction is characterized by: The square acid, WO 3-x The mass ratio of the particles to tetrabutyl titanate is 225:20 to 100:

759.

3. The full spectrum response IEF-11 / WO according to claim 1 3-x An S-type heterojunction is characterized by: The WO 3-x The particles were prepared by the following method: WCl6 was dispersed in methanol and stirred to make it uniform, and then transferred to a hydrothermal reactor in a muffle furnace for solvothermal reaction; Wherein, the stirring time is 0.5 to 1 hour, and the temperature is room temperature; The solvent thermal reaction time is 12 to 24 hours, and the temperature is 180°C; The methanol WCl6 solution is 1.0-2.0 mg / mL.

4. A full spectrum response IEF-11 / WO as claimed in any one of claims 1 to 3 3-x The method for preparing an S-type heterojunction is characterized in that: The steps are as follows: 1) suspending the ground solid powder of squaric acid in isopropanol, stirring and ultrasonicating at room temperature to uniformly disperse the powder to obtain a dispersion; 2) Add glacial acetic acid and WO to the dispersion in step 1) 3-x The particles were ultrasonically dissolved again to obtain a mixed solution; 3) Tetrabutyl titanate was slowly added to the mixed solution prepared in step 2) under heating and stirring conditions, and the orange-brown turbid liquid obtained after the reaction at 40-60° C. for 5-20 minutes was transferred to a hydrothermal reactor and subjected to a solvent thermal reaction at 100-150° C. in a muffle furnace for 40-50 hours, and post-treated to obtain IEF-11 / WO 3-x Heterojunction; The square acid, WO 3-x The mass ratio of the particles to tetrabutyl titanate is 225:20 to 100:

759.

5. A full spectrum response IEF-11 / WO according to claim 4 3-x An S-type heterojunction and a method for preparing the same are characterized in that: The mass ratio of the squaric acid, isopropanol and glacial acetic acid is 225:6437:6720.

6. The full spectrum response IEF-11 / WO as claimed in claim 1 3-x The S-type heterojunction is used as a photocatalytic microbial bactericide; or as a catalyst for catalytic degradation of pollutants.

7. A full spectrum response IEF-11 / WO according to claim 6 3-x The application of the S-type heterojunction as a photocatalytic microbial bactericide or for catalytic degradation of organic pollutants is characterized in that: The microorganisms include at least one of bacteria, viruses and fungi; the pollutants include at least one of antibiotics and organic dyes.

8. A full spectrum response IEF-11 / WO according to claim 7 3-x S-type heterojunction and preparation method and application thereof, characterized in that: The antibiotics include at least one of tetracycline and chlortetracycline; and the bacteria include Escherichia coli.

9. A full spectrum response IEF-11 / WO 3-x The method for photocatalytic degradation of pollutants by S-type heterojunction is characterized in that: Will IEF-11 / WO 3-x The S-type heterojunction is added to a system containing pollutants to photocatalytically degrade the pollutants under full-spectrum light irradiation.

10. A full spectrum response IEF-11 / WO 3-x The method for killing microorganisms by photocatalysis at an S-type heterojunction is characterized in that: Will IEF-11 / WO 3-x The S-type heterojunction is added to a system containing microorganisms to photocatalytically kill the microorganisms under full-spectrum light irradiation.

Images