A full spectrum response IEF-11 / WO 3-x S-type heterojunction and preparation method and application thereof

Abstract

The application discloses an IEF-11 / WO 3‑x An S-type heterojunction material, a preparation method and application thereof. The heterojunction is prepared from square acid, tetrabutyl titanate and WO 3‑x particles as raw materials, wherein the WO 3‑x The value range of x is 0<=x<1. The heterojunction material is innovatively designed through an S-type energy band structure, realizes full-spectrum response from ultraviolet to near-infrared, and has a unique carrier transport mechanism, so that the separation efficiency of photo-generated electron-hole pairs reaches 2.47 times (compared with WO 3‑x ) and 1.57 times (compared with IEF-11), and meanwhile, strong redox sites are reserved, and the photocatalytic performance is improved by 3.74 times (compared with WO 3‑x ) and 1.41 times (compared with IEF-11) compared with single-component materials. Experiments show that the inactivation rate of the material on escherichia coli under full-spectrum irradiation can reach 99%, the 120-minute degradation rate of tetracycline (TC) can reach 86%, and the material shows broad-spectrum degradation ability on typical organic pollutants such as chlortetracycline (CTC), rhodamine B (RhB) and methylene blue (MB) in the visible light region, and the 120-minute degradation efficiencies are 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 and photocatalytic disinfection.

Description

Technical Field

[0001] This invention belongs to the field of photocatalytic material synthesis technology and application, specifically relating to a full-spectrum responsive IEF-11 / WO 3-x S-type heterojunctions, their preparation methods, and applications. Background Technology

[0002] With the rapid global population growth and socio-economic development, the surge in industrial wastewater discharge and the compound pollution of water bodies caused by accelerated urbanization have become major environmental challenges. Studies have shown that the synergistic effect of drug-resistant pathogens and persistent organic pollutants in water bodies not only threatens the balance of aquatic ecosystems but also seriously endangers human health through bioaccumulation in the food chain (J. Environ. Chem. Eng. 2023, 11, 110481). Traditional water treatment technologies are insufficient inactivating antibiotic-resistant bacteria and struggle to simultaneously remove typical organic pollutants such as tetracyclines and dyes, necessitating the development of novel and efficient water treatment technologies.

[0003] Heterogeneous photocatalysis based on semiconductor photocatalysts is widely recognized as one of the most promising environmental remediation methods due to its dual function of deep mineralization of pollutants and efficient inactivation of pathogenic microorganisms using sunlight. Among them, titanium-based metal-organic framework material IEF-11 has shown significant advantages in the field of photocatalysis due to its unique three-dimensional porous structure and the synergistic photoresponse characteristics of titanium oxide clusters-squaric acid ligands (Adv. Mater. 2021, 33, 2106627). However, IEF-11 alone has inherent defects: i) high photogenerated carrier recombination rate; ii) lack of response in the near-infrared region (accounting for 52-55% of the solar spectrum); iii) insufficient exposure of surface active sites, which limits its actual photocatalytic efficiency.

[0004] To address the aforementioned bottlenecks, heterojunction engineering has become a core strategy for improving photocatalytic performance. Compared to traditional type II heterojunctions, type S heterojunctions, through a unique band bending mechanism, promote carrier spatial separation while retaining strong redox capabilities, exhibiting superior photocatalytic performance. This invention innovatively selects WO3 with oxygen vacancy defects. 3-x As a coupling object, its advantages are: i) its near-infrared light response characteristics can effectively compensate for the spectral shortcomings of IEF-11; ii) its gradient band structure forms an ideal S-shaped band match with IEF-11; iii) its surface oxygen vacancies can serve as electron trapping centers, synergistically improving carrier separation efficiency. To date, no information has been found regarding IEF-11 loaded with WO. 3-x Research and reports on the construction of full-spectrum responsive S-type heterojunctions. Summary of the Invention

[0005] In view of this, the first objective of the present invention is to provide a full-spectrum responsive IEF-11 / WO3-x S-type heterojunctions are used to address the technical problems of insufficient photocatalytic performance and narrow light response range of IEF-11 semiconductor photocatalysts in existing technologies.

[0006] The second objective of this invention is to provide a full-spectrum responsive IEF-11 / WO 3-x Preparation method of S-type heterojunction.

[0007] The third objective of this invention is to provide a full-spectrum responsive IEF-11 / WO 3-x Application of S-shaped heterojunctions.

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

[0009] A full-spectrum response IEF-11 / WO 3-x S-type heterojunction, the full-spectrum response IEF-11 / WO 3-x S-type heterojunction is composed of squaric acid, tetrabutyl titanate, and WO3. 3-x Made from granules;

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

[0011] The above-mentioned full-spectrum response IEF-11 / WO 3-x S-type heterojunction, the aforementioned squaric acid, WO3 3-x The mass ratio of particles to tetrabutyl titanate is 225:20 to 100:759.

[0012] Furthermore, the aforementioned full-spectrum response of IEF-11 / WO 3-x S-type heterojunction, the WO 3-x The particles were prepared by dispersing WCl6 in methanol and stirring until homogeneous, then transferring it to a hydrothermal reactor and carrying out a solvothermal reaction in a muffle furnace.

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

[0014] The solvothermal reaction time is 12–24 hours, and the temperature is 180°C;

[0015] The methanol-WCl6 solution has a concentration of 1.0–2.0 mg / mL.

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

[0017] 1) The finely ground squaric acid solid powder is suspended in isopropanol, and stirred and sonicated at room temperature to disperse it evenly to obtain a dispersion.

[0018] 2) Add glacial acetic acid and WO3 to the dispersion from step 1). 3-x The particles were dissolved again by ultrasonication to obtain a mixed solution.

[0019] 3) Under heating and stirring conditions, tetrabutyl titanate is slowly added to the mixed solution prepared in step 2). After reacting at 40–60°C for 5–20 minutes, the resulting orange-brown turbid liquid is transferred to a hydrothermal reactor and subjected to a solvothermal reaction at 100–150°C for 40–50 hours in a muffle furnace. Post-treatment yields IEF-11 / WO. 3-x Heterogeneous junction;

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

[0021] Furthermore, the aforementioned full-spectrum response IEF-11 / WO 3-x The S-type heterojunction and its preparation method, wherein the mass ratio of squaric acid, isopropanol and glacial acetic acid is 225:6437:6720.

[0022] Furthermore, the aforementioned full-spectrum response IEF-11 / WO 3-x S-type heterojunctions can be used as photocatalytic microbial bactericides or as catalysts for the degradation of pollutants.

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

[0024] Furthermore, the aforementioned full-spectrum response IEF-11 / WO 3-x S-type heterojunctions, their preparation methods and applications, wherein the antibiotic includes at least one of tetracycline and chlortetracycline; and the bacteria include Escherichia coli.

[0025] Another technical solution of this invention is a full-spectrum response IEF-11 / WO 3-x The method of photocatalytic degradation of pollutants using S-type heterojunctions, using IEF-11 / WO 3-x When an S-shaped heterojunction is added to a system containing pollutants, it photocatalytically degrades the pollutants under full-spectrum light irradiation.

[0026] Another technical solution of this invention is a full-spectrum response IEF-11 / WO 3-xThe method of S-type heterojunction photocatalytic killing of microorganisms, using IEF-11 / WO 3-x When an S-shaped heterojunction is added to a system containing microorganisms, the microorganisms are photocatalytically killed 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 response IEF-11 / WO provided by this invention 3-x S-type heterojunctions have a WO response in the near-infrared region. 3-x The use of IEF-11 / WO 3-x The S-type heterojunction expands the optical response range to the full spectrum, improving the utilization rate of sunlight.

[0029] 2) The full-spectrum response IEF-11 / WO provided by this invention 3-x S-type heterojunctions have high photogenerated carrier separation efficiency and strong redox ability, and exhibit excellent photocatalytic killing of E. coli and degradation of TC under full-spectrum irradiation.

[0030] 3) The IEF-11 / WO provided by this invention 3-x Heterogeneous junctions are universally applicable to the degradation of common organic pollutants in water by visible light, and exhibit good degradation performance for TC, CTC, RhB and MB.

[0031] 4) The heterojunction preparation method provided by this invention is simple, low-cost, and highly productive, and is easy to scale up for production, making it suitable for widespread application. Attached Figure Description

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

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

[0034] Figure 3 The diagram shows the ultraviolet diffuse reflectance, band gap, valence band, and band structure of the sample.

[0035] Figure 4 IEF-11 / WO prepared in Example 2 under different light source irradiation conditions 3-x -33 The effect of heterojunctions on the growth status of E. coli on agar plates;

[0036] Figure 5 IEF-11 / WO prepared in Example 2 under different light source irradiation conditions 3-x -33 Heterojunction efficiency of E. coli;

[0037] Figure 6 This is a graph showing the degradation efficiency of TC by the sample under full-spectrum light source irradiation;

[0038] Figure 7 IEF-11 / WO prepared in Example 2 3-x -33 Degradation efficiency of heterojunctions for other common organic pollutants in water under visible light irradiation. Detailed Implementation

[0039] The technical solution of the present invention will now be clearly and completely described with reference to the accompanying drawings. Obviously, the described embodiments are only some, not all, of the embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0040] Example 1

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

[0042] 255 mg of finely ground squaric acid solid powder was suspended in 8.2 mL of isopropanol and magnetically stirred at 450 rpm for 5 minutes at room temperature, followed by sonication at 35 kHz in an ultrasonic bath for 5 minutes; then 6.4 mL of glacial acetic acid and 20 mg of WO3 were added. 3-x The particles were sonicated again for 15 minutes. Then, 0.762 mL of tetrabutyl titanate was slowly added with stirring, and the mixture was heated at 50 °C for 15 minutes to obtain an orange suspension. The orange suspension was then transferred to a polytetrafluoroethylene-lined hydrothermal reactor and sealed. The temperature was increased to 120 °C at a rate of 1.5 °C / min and maintained for 48 hours. Finally, the temperature was decreased to room temperature at a 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 dried under vacuum at 30 °C and 0.9 MPa for 12 hours.

[0043] Among them WO 3-x The particles were prepared by the following method: 50 mg WCl6 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.

[0044] The stirring time is 0.5 hours, and the temperature is room temperature.

[0045] The solvothermal reaction time is 12 hours, and the temperature is 180℃;

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

[0047] Example 2

[0048] This embodiment provides an IEF-11 / WO 3-x -33 heterojunction, which is prepared sequentially through the following steps:

[0049] 255 mg of finely ground squaric acid solid powder was suspended in 8.2 mL of isopropanol and magnetically stirred at 450 rpm for 5 minutes at room temperature, followed by sonication at 35 kHz in an ultrasonic bath for 5 minutes; then 6.4 mL of glacial acetic acid and 50 mg of WO3 were added. 3-x The particles were sonicated again for 15 minutes. Then, 0.762 mL of tetrabutyl titanate was slowly added with stirring, and the mixture was heated at 50 °C for 15 minutes to obtain an orange suspension. The orange suspension was then transferred to a polytetrafluoroethylene-lined hydrothermal reactor and sealed. The temperature was increased to 120 °C at a rate of 1.5 °C / min and maintained for 48 hours. Finally, the temperature was decreased to room temperature at a 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 then vacuum dried at 0.9 MPa and 30 °C for 12 hours.

[0050] Among them WO 3-x The particles were prepared by the following method: 50 mg WCl6 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.

[0051] 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℃;

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

[0054] Example 3

[0055] This embodiment provides an IEF-11 / WO 3-x The preparation method of -50 heterojunction is as follows:

[0056] 255 mg of finely ground squaric acid solid powder was suspended in 8.2 mL of isopropanol and magnetically stirred at 450 rpm for 5 minutes at room temperature, followed by sonication at 35 kHz in an ultrasonic bath for 5 minutes; then 6.4 mL of glacial acetic acid and 100 mg of WO3 were added. 3-xThe particles were sonicated again for 15 minutes. Then, 0.762 mL of tetrabutyl titanate was slowly added with stirring, and the mixture was heated at 50 °C for 15 minutes to obtain an orange suspension. The orange suspension was then transferred to a polytetrafluoroethylene-lined hydrothermal reactor and sealed. The temperature was increased to 120 °C at a rate of 1.5 °C / min and maintained for 48 hours. Finally, the temperature was decreased to room temperature at a 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 then 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 WCl6 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] The stirring time is 0.5 hours, and the temperature is room temperature.

[0059] The solvothermal reaction time is 12 hours, and the temperature is 180℃;

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

[0061] Example 4

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

[0063] 255 mg of finely ground squaric acid solid powder was suspended in 8.2 mL of isopropanol and magnetically stirred at 450 rpm for 5 minutes at room temperature, followed by sonication at 35 kHz in an ultrasonic bath for 5 minutes; then 6.4 mL of glacial acetic acid and 50 mg of WO3 were added. 3-x The particles were sonicated again for 15 minutes. Then, 0.762 mL of tetrabutyl titanate was slowly added with stirring, and the mixture was heated at 40 °C for 15 minutes to obtain an orange suspension. The orange suspension was then transferred to a polytetrafluoroethylene-lined hydrothermal reactor and sealed. The temperature was increased to 120 °C at a rate of 1.5 °C / min and maintained for 48 hours. Finally, the temperature was decreased to room temperature at a 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 then 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 WCl6 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] 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℃;

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

[0068] Example 5

[0069] This embodiment provides an IEF-11 / WO 3-x -33-T2 heterojunction, which is prepared sequentially through the following steps:

[0070] 255 mg of finely ground squaric acid solid powder was suspended in 8.2 mL of isopropanol and magnetically stirred at 450 rpm for 5 minutes at room temperature, followed by sonication at 35 kHz in an ultrasonic bath for 5 minutes; then 6.4 mL of glacial acetic acid and 50 mg of WO3 were added. 3-x The particles were sonicated again for 15 minutes. Then, 0.762 mL of tetrabutyl titanate was slowly added with stirring, and the mixture was heated at 60 °C for 15 minutes to obtain an orange suspension. The orange suspension was then transferred to a polytetrafluoroethylene-lined hydrothermal reactor and sealed. The temperature was increased to 120 °C at a rate of 1.5 °C / min and maintained for 48 hours. Finally, the temperature was decreased to room temperature at a 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 then vacuum dried at 0.9 MPa and 30 °C for 12 hours.

[0071] Among them WO 3-x The particles were prepared by the following method: 50 mg WCl6 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.

[0072] 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℃;

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

[0075] To verify the IEF-11 / WO prepared in this application 3-x -33 heterojunction, the IEF-11 / WO prepared in Example 2 is given below. 3-x -33 Heterojunction related performance test spectrum, sterilization performance test experiment and its experimental data.

[0076] IEF-11 / WO prepared in Example 2 3-x-33 SEM image of the heterojunction (see attached image). Figure 1 ,from Figure 1 As can be seen, IEF-11 is a hexagonal planar crystal (diameter 85±30nm), and WO 3-x Nanoparticles (217±50nm in diameter) are encapsulated within.

[0077] IEF-11 / WO prepared in Example 2 3-x See the XRD pattern of the -33 heterojunction. Figure 2 ,from Figure 2 It can be seen from IEF-11 / WO 3-x The XRD pattern of the -33 heterojunction shows IEF-11 and WO. 3-x The typical characteristic peaks prove that the heterostructure was successfully constructed.

[0078] IEF-11 / WO prepared in Example 2 3-x -33 heterojunction; and IEF-11 and WO 3-x See diagrams of ultraviolet diffuse reflectance, band gap, valence band, and band structure. Figure 3 The successful construction of the S-type heterojunction can be determined by the band structure.

[0079] It should be noted that the detection spectrum of the actual embodiment is basically similar to that of embodiment 2, so it is omitted here.

[0080] Test Example 1

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

[0082] The testing steps are as follows:

[0083] Take 5 mL of E. coli bacterial culture (OD) 600 =0.09~0.11) and 45mL of sterile physiological saline were mixed, and 30mg of IEF-11 / WO was added to the above solution. 3-x -33 heterojunction, using a 300W xenon lamp as the light source, with different filters configured for visible light, near-infrared light, and full-spectrum light. Under illumination, 100μL of bacterial suspension was collected at 0, 15, 30, 45, and 60 minutes, and diluted 1×10⁻⁶. 3 After doubling, 100 μL was evenly spread onto LB solid medium and incubated at 37°C for 12–18 hours. The IEF-11 / WO ratio was determined by the change in E. coli colony count. 3-x -33 heterojunction photocatalytic bactericidal performance.

[0084] Figure 4 IEF-11 / WO under different light sources3-x The influence of -33 heterojunctions on the growth state of E. coli on agar plates shows that under near-infrared light, visible light, and full-spectrum light irradiation, IEF-11 / WO 3-x The photocatalytic killing performance of the -33 heterojunction for E. coli increases sequentially, indicating that the IEF-11 / WO 3-x The -33 heterojunction pair exhibits excellent photocatalytic killing performance of E. coli. (See the corresponding E. coli efficiency diagram.) Figure 5 .

[0085] Test Example 2

[0086] This test case uses IEF-11 particles and WO3. 3-x Particles and IEF-11 / WO prepared in Examples 1-3 3-x The photocatalytic degradation performance of heterojunctions under full-spectrum light source conditions was tested using the following steps:

[0087] Prepare 100 mL of a 20 mg / L TC solution, add 10 mg of sample to the solution, and use a 300 W xenon lamp (full-spectrum reflector) as the light source. 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 TC solution periodically, remove the photocatalyst from the solution using a 0.22 μm aqueous filter membrane, and measure the TC absorbance at 357 nm using a UV spectrophotometer.

[0088] The degradation efficiency of TC by the blank control group and each catalyst group under full-spectrum conditions is as follows: Figure 6 As shown, compared with pure IEF-11 particles and WO 3-x Compared to particles, IEF-11 / WO has different mass fraction ratios. 3-x Heterojunctions significantly improved the degradation rate of TC under full-spectrum conditions. Among them, IEF-11 / WO... 3-x The -33 heterojunction exhibits the best visible light catalytic degradation performance for TC, degrading 86% of TC within 120 minutes.

[0089] Test Example 3

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

[0091] Prepare a 100 mL solution of organic pollutants of a specific concentration. Add 10 mg of sample to the solution and use a 300 W xenon lamp with a filter as the visible light source. Stir for 30 minutes in the dark, then irradiate the system with the light source for 120 minutes. During this period, take 3 mL of the organic pollutant solution periodically, remove the photocatalyst from the solution using a 0.22 μm aqueous filter membrane, and measure the absorbance of the organic pollutants at a specific wavelength using a UV spectrophotometer.

[0092] IEF-11 / WO 3-x The degradation efficiency of the -33 heterojunction for organic pollutants (CTC, RhB, MB) under visible light irradiation is as follows: Figure 7 As shown in the figure. It can be seen from the figure that IEF-11 / WO 3-x The -33 heterojunction exhibited degradation rates of 76.7%, 52.3%, and 95.4% for CTC, RhB, and MB, respectively, within 120 minutes. These results demonstrate the universality of the heterojunction prepared in this invention for photocatalytic degradation of common organic pollutants in water.

[0093] The above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit it. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features therein. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A full-spectrum responsive IEF-11 / WO 3-x S-shaped heterojunction, characterized in that... The full-spectrum response IEF-11 / WO 3-x S-type heterojunction is composed of squaric acid, tetrabutyl titanate, and WO3. 3-x Made from granules; Among them: WO 3-x In particles, 0 ≤ x < 1.

2. The full-spectrum response IEF-11 / WO according to claim 1 3-x S-shaped heterojunction, characterized in that... The aforementioned squaric acid, WO 3-x The mass ratio of particles to tetrabutyl titanate is 225: 20~100:

759.

3. The full-spectrum response IEF-11 / WO according to claim 1 3-x S-shaped heterojunction, characterized in that... The WO mentioned 3-x The particles were prepared by dispersing WCl6 in methanol and stirring until homogeneous, then transferring it to a hydrothermal reactor and carrying out a solvothermal reaction in a muffle furnace. The stirring time is 0.5 to 1 hour, and the temperature is room temperature; The solvothermal reaction time is 12-24 hours, and the temperature is 180 ℃; The methanol-WCl6 solution has a concentration of 1.0~2.0 mg / mL.

4. The full-spectrum response IEF-11 / WO according to any one of claims 1 to 3 3-x The method for preparing an S-type heterojunction is characterized by, The steps are as follows: 1) The finely ground squaric acid solid powder is suspended in isopropanol, and stirred and sonicated at room temperature to disperse it evenly to obtain a dispersion. 2) Add glacial acetic acid and WO3 to the dispersion from step 1). 3-x The particles were dissolved again by ultrasonication to obtain a mixed solution. 3) Under heating and stirring conditions, tetrabutyl titanate is slowly added to the mixed solution prepared in step 2). After reacting at 40-60℃ for 5-20 minutes, the resulting orange-brown turbid liquid is transferred to a hydrothermal reactor and subjected to a solvothermal reaction at 100-150℃ for 40-50 hours in a muffle furnace. Post-treatment yields IEF-11 / WO. 3-x Heterogeneous junction; The aforementioned squaric acid, WO 3-x The mass ratio of particles to tetrabutyl titanate is 225: 20~100:

759.

5. A full-spectrum response IEF-11 / WO according to claim 4 3-x The method for preparing an S-type heterojunction is characterized by, 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 described in claim 1 3-x S-type heterojunctions can be used as photocatalytic microbial bactericides or as catalysts for the degradation of pollutants.

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

8. The application according to claim 7, characterized in that, The antibiotics include at least one of tetracycline and chlortetracycline; the bacteria include Escherichia coli.

9. A full-spectrum responsive IEF-11 / WO 3-x The method for photocatalytic degradation of pollutants using an S-type heterojunction is characterized by... The IEF-11 / WO as described in claim 1 3-x When an S-shaped heterojunction is added to a system containing pollutants, it photocatalytically degrades the pollutants under full-spectrum light irradiation.

10. A full-spectrum responsive IEF-11 / WO 3-x The method for photocatalytic killing of microorganisms using S-type heterojunctions is characterized by... The IEF-11 / WO as described in claim 1 3-x When an S-shaped heterojunction is added to a system containing microorganisms, the microorganisms are photocatalytically killed under full-spectrum light irradiation.

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