Preparation method of HOF / WO3 S type heterojunction composite photocatalyst
By forming C–O–W coordination between HOF and WO3 nanorods, an S-type heterojunction with a built-in electric field was constructed, which solved the problem of weak interfacial interaction in HOF-based heterojunctions and improved the photocatalytic hydrogen evolution performance.
Patent Information
- Application Number
- CN202511300821.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-09-12
- Publication Date
- 2025-12-30
AI Technical Summary
The existing HOF-based heterojunctions have weak interfacial interactions and unstable structures, which limits the improvement of photocatalytic hydrogen evolution performance.
A one-pot self-assembly strategy was adopted to synthesize WO3 nanorods via hydrothermal method. These nanorods were then dispersed with HOF building blocks to form C–O–W coordination and S-shaped heterostructure in situ, thereby enhancing the efficiency of interfacial charge separation and migration.
The photocatalytic hydrogen evolution performance was significantly improved, and the material exhibited excellent photocatalytic activity and stability under visible light.
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Figure CN121222489A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The application relates to a preparation method of a heterojunction photocatalyst based on a hydrogen-bonded organic framework (HOF) and tungsten trioxide (WO3), and relates to the technical field of photocatalyst material preparation. BACKGROUND
[0002] With the continuous advancement of global energy crisis and carbon neutralization goals, developing clean energy conversion technology driven by solar energy has become an important direction for building a sustainable energy system. Among them, the photocatalytic water splitting to produce hydrogen technology based on semiconductor materials is widely considered as one of the ideal paths to realize the conversion of solar energy to hydrogen energy, because of its green environmental protection, mild reaction conditions, clean and non-polluted products, etc.
[0003] Hydrogen-bonded organic frameworks (HOFs) are a new type of semiconductor photocatalytic material, which has been widely studied in recent years. They have high crystallinity and mild synthesis conditions, and are easy to build adjustable pore structures, and show excellent light absorption properties. The ordered pi-pi stacking and hydrogen bond network in the material cooperatively form an electron delocalization channel, which effectively promotes the migration and transmission of photo-generated carriers. These unique advantages make it stand out among many catalytic materials. However, due to the poor intrinsic conductivity and energy level structure, the photo-generated carriers in single HOF material are rapidly recombined and the separation efficiency is low, which seriously restricts the photocatalytic hydrogen evolution performance.
[0004] Building a heterojunction is considered an effective strategy to improve the photocatalytic performance of HOFs, which is expected to inhibit carrier recombination, improve charge separation efficiency and enhance material stability. However, the HOF-based heterojunctions reported so far generally face the problems of weak interfacial coupling and insufficient stability of heterojunction structure, which limits the further breakthrough of catalytic performance. SUMMARY
[0005] The purpose of the present application is to solve the problems of weak interfacial interaction and unstable heterojunction structure of the existing synthesis of HOF-based heterojunctions, and to provide a preparation method of HOF / WO3 S-type heterojunction composite photocatalyst.
[0006] The preparation method of HOF / WO3 S-type heterojunction composite photocatalyst is as follows:
[0007] I. Preparation of WO3 nanorods:
[0008] Dissolve 2.0615 g of sodium tungstate dihydrate (Na2WO4·2H2O) and 1.45 g of sodium chloride (NaCl) in 50 mL of deionized water, and magnetically stir for 30 min;
[0009] Slowly add hydrochloric acid solution (HCl) with a concentration of 1 mol / L to adjust the pH value to 2.0, and continue to magnetically stir for 1 h;
[0010] The resulting solution was transferred to a 100 mL polytetrafluoroethylene-lined high-pressure reactor and kept at 180 °C for 18 h.
[0011] After the reaction was completed, the product was naturally cooled to room temperature. The product was centrifuged at 12,000 rpm for 5 min, and the gray solid precipitate was collected. It was washed three times with deionized water and anhydrous ethanol, respectively. The sample was then placed in a vacuum freeze dryer and dried for 24 h to obtain WO3 powder.
[0012] II. Preparation of HOF / WO3 composite materials:
[0013] 30 mg of H4TBAPy (1,3,6,8-tetra(4-carboxyphenyl)pyrene) ligand and 3 mg of WO3 powder were dispersed in 4.5 mL of DMF (N,N-dimethylformamide) and sonicated for 5 min.
[0014] Under vigorous stirring conditions, 18 mL of ultrapure water was rapidly added to the above dispersion, and vigorous stirring was continued for 5 min. The solution quickly turned into a bright yellow suspension.
[0015] Add 18 mL of anhydrous ethanol and continue stirring vigorously for 5 min;
[0016] The mixture was centrifuged at 15,000 rpm for 6 min, and the bright yellow solid was collected. It was washed three times with deionized water and acetone, respectively, and then freeze-dried under vacuum for 24 h to obtain the HOF / WO3 composite material (the mass ratio of HOF to WO3 was 10:1, denoted as HOF / WO3-10%).
[0017] The preparation method of HOF / WO3 S-type heterojunction composite photocatalyst is as follows:
[0018] I. Preparation of WO3 nanorods:
[0019] Dissolve 2.0615 g of sodium tungstate dihydrate (Na2WO4·2H2O) and 1.45 g of sodium chloride (NaCl) in 50 mL of deionized water and stir magnetically for 30 min.
[0020] Slowly add 1 mol / L hydrochloric acid solution (HCl) to adjust the pH to 2.0, and continue magnetic stirring for 1 h;
[0021] The resulting solution was transferred to a 100 mL polytetrafluoroethylene-lined high-pressure reactor and kept at 180 °C for 18 h.
[0022] After the reaction was completed, the product was naturally cooled to room temperature. The product was centrifuged at 12,000 rpm for 5 min, and the gray solid precipitate was collected. It was washed three times with deionized water and anhydrous ethanol, respectively. The sample was then placed in a vacuum freeze dryer and dried for 24 h to obtain WO3 powder.
[0023] II. Preparation of HOF / WO3 composite materials:
[0024] 30 mg H4TBAPy ligand and 5 mg WO3 powder were dispersed in 4.5 mL DMF and sonicated for 5 min.
[0025] Under vigorous stirring conditions, 18 mL of ultrapure water was rapidly added to the above dispersion, and vigorous stirring was continued for 5 min. The solution quickly turned into a bright yellow suspension.
[0026] Add 18 mL of anhydrous ethanol and continue stirring vigorously for 5 min;
[0027] The mixture was centrifuged at 15,000 rpm for 6 min, and the bright yellow solid was collected. It was washed three times with deionized water and acetone, respectively, and then freeze-dried under vacuum for 24 h to obtain the HOF / WO3 composite material (the mass ratio of HOF to WO3 was 6:1, denoted as HOF / WO3-16.7%).
[0028] The preparation method of HOF / WO3 S-type heterojunction composite photocatalyst is as follows:
[0029] I. Preparation of WO3 nanorods:
[0030] Dissolve 2.0615 g of sodium tungstate dihydrate (Na2WO4·2H2O) and 1.45 g of sodium chloride (NaCl) in 50 mL of deionized water and stir magnetically for 30 min.
[0031] Slowly add 1 mol / L hydrochloric acid solution (HCl) to adjust the pH to 2.0, and continue magnetic stirring for 1 h;
[0032] The resulting solution was transferred to a 100 mL polytetrafluoroethylene-lined high-pressure reactor and kept at 180 °C for 18 h.
[0033] After the reaction was completed, the product was naturally cooled to room temperature. The product was centrifuged at 12,000 rpm for 5 min, and the gray solid precipitate was collected. It was washed three times with deionized water and anhydrous ethanol, respectively. The sample was then placed in a vacuum freeze dryer and dried for 24 h to obtain WO3 powder.
[0034] II. Preparation of HOF / WO3 composite materials:
[0035] 30 mg H4TBAPy ligand and 10 mg WO3 powder rod were dispersed in 4.5 mL DMF and sonicated for 5 min.
[0036] Under vigorous stirring conditions, 18 mL of ultrapure water was rapidly added to the above dispersion, and vigorous stirring was continued for 5 min. The solution quickly turned into a bright yellow suspension.
[0037] Add 18 mL of anhydrous ethanol and continue stirring vigorously for 5 min;
[0038] The mixture was centrifuged at 15,000 rpm for 6 min, and the bright yellow solid was collected. It was washed three times with deionized water and acetone, respectively, and then freeze-dried under vacuum for 24 h to obtain the HOF / WO3 composite material (the mass ratio of HOF to WO3 was 3:1, denoted as HOF / WO3-33.3%).
[0039] Tungsten trioxide (WO3) is a classic n-type semiconductor with excellent photochemical stability and carrier trapping ability. Its surface readily forms stable coordination bonds with oxygen-containing functional groups. This strong interaction can significantly enhance carrier transport between heterojunctions and induce a strong built-in electric field (IEF), thereby driving the spatially selective separation and migration of photogenerated electron-hole pairs.
[0040] This invention provides an S-shaped heterojunction composite photocatalyst based on HOF / WO3 and its preparation method. This method, for the first time, utilizes a one-pot self-assembly strategy to synthesize WO3 nanorods via a hydrothermal method. HOF building blocks and WO3 nanorods are co-dispersed, and WO3 nanorods are introduced in situ during HOF crystal growth, inducing C–O–W coordination and an S-shaped heterostructure. This significantly enhances interfacial charge separation and migration efficiency. The heterojunction is formed in situ during crystallization via a one-pot self-assembly strategy. The composite material is obtained after centrifugation, washing, and freeze-drying. This method induces C–O–W coordination at the HOF / WO3 interface, constructing an S-shaped heterojunction with a built-in electric field, significantly improving photogenerated charge separation and migration efficiency. The preparation process of this invention is mild and simple, and the obtained material exhibits excellent photocatalytic hydrogen evolution activity and stability under visible light.
[0041] Compared with existing HOF-based photocatalytic materials and their preparation methods, the material obtained by this invention has the following advantages:
[0042] (1) The one-pot self-assembly method achieved close interfacial contact between HOF and WO3 at the nanoscale, forming a stable rod-rod heterostructure;
[0043] (2) The C–O–W coordination bonds formed at the interface effectively enhance the built-in electric field and promote the efficient spatial separation and migration of photogenerated carriers;
[0044] (3) The constructed HOF / WO3S heterojunction significantly improves the photocatalytic hydrogen evolution performance. Attached Figure Description
[0045] Figure 1 This is a schematic diagram of the preparation method of the HOF / WO3S type heterojunction composite photocatalyst of the present invention;
[0046] Figure 2 This is a scanning electron microscope image of the HOF / WO3S heterojunction composite photocatalyst prepared according to specific implementation method two;
[0047] Figure 3 This is a transmission electron microscope image of the HOF / WO3S heterojunction composite photocatalyst prepared according to specific implementation method two;
[0048] Figure 4 This is a high-resolution transmission electron microscope image of the HOF / WO3S heterojunction composite photocatalyst prepared according to specific implementation method two.
[0049] Figure 5 The scanning transmission electron diffraction spectrum of the HOF / WO3S heterojunction composite photocatalyst prepared according to specific implementation method 2 is shown.
[0050] Figure 6 The image shows the XRD pattern of the HOF / WO3S heterojunction composite photocatalyst prepared according to specific implementation method two. Detailed Implementation
[0051] The technical solution of the present invention is not limited to the specific embodiments listed below, but also includes any combination of the specific embodiments.
[0052] Specific Implementation Method 1: The preparation method of the HOF / WO3 S-type heterojunction composite photocatalyst in this implementation method is as follows:
[0053] I. Preparation of WO3 nanorods:
[0054] Dissolve 2.0615 g of sodium tungstate dihydrate (Na2WO4·2H2O) and 1.45 g of sodium chloride (NaCl) in 50 mL of deionized water and stir magnetically for 30 min.
[0055] Slowly add 1 mol / L hydrochloric acid solution (HCl) to adjust the pH to 2.0, and continue magnetic stirring for 1 h;
[0056] The resulting solution was transferred to a 100 mL polytetrafluoroethylene-lined high-pressure reactor and kept at 180 °C for 18 h.
[0057] After the reaction was completed, the product was naturally cooled to room temperature. The product was centrifuged at 12,000 rpm for 5 min, and the gray solid precipitate was collected. It was washed three times with deionized water and anhydrous ethanol, respectively. The sample was then placed in a vacuum freeze dryer and dried for 24 h to obtain WO3 powder.
[0058] II. Preparation of HOF / WO3 composite materials:
[0059] 30 mg of H4TBAPy (1,3,6,8-tetra(4-carboxyphenyl)pyrene) ligand and 3 mg of WO3 powder were dispersed in 4.5 mL of DMF (N,N-dimethylformamide) and sonicated for 5 min.
[0060] Under vigorous stirring conditions, 18 mL of ultrapure water was rapidly added to the above dispersion, and vigorous stirring was continued for 5 min. The solution quickly turned into a bright yellow suspension.
[0061] Add 18 mL of anhydrous ethanol and continue stirring vigorously for 5 min;
[0062] The mixture was centrifuged at 15,000 rpm for 6 min, and the bright yellow solid was collected. It was washed three times with deionized water and acetone, respectively, and then freeze-dried under vacuum for 24 h to obtain the HOF / WO3 S-type heterojunction composite photocatalyst (the mass ratio of HOF to WO3 was 10:1, denoted as HOF / WO3-10%).
[0063] Specific Implementation Method Two: The preparation method of the HOF / WO3 S-type heterojunction composite photocatalyst in this implementation method is as follows:
[0064] I. Preparation of WO3 nanorods:
[0065] Dissolve 2.0615 g of sodium tungstate dihydrate (Na2WO4·2H2O) and 1.45 g of sodium chloride (NaCl) in 50 mL of deionized water and stir magnetically for 30 min.
[0066] Slowly add 1 mol / L hydrochloric acid solution (HCl) to adjust the pH to 2.0, and continue magnetic stirring for 1 h;
[0067] The resulting solution was transferred to a 100 mL polytetrafluoroethylene-lined high-pressure reactor and kept at 180 °C for 18 h.
[0068] After the reaction was completed, the product was naturally cooled to room temperature. The product was centrifuged at 12,000 rpm for 5 min, and the gray solid precipitate was collected. It was washed three times with deionized water and anhydrous ethanol, respectively. The sample was then placed in a vacuum freeze dryer and dried for 24 h to obtain WO3 powder.
[0069] II. Preparation of HOF / WO3 composite materials:
[0070] 30 mg H4TBAPy ligand and 5 mg WO3 powder were dispersed in 4.5 mL DMF and sonicated for 5 min.
[0071] Under vigorous stirring conditions, 18 mL of ultrapure water was rapidly added to the above dispersion, and vigorous stirring was continued for 5 min. The solution quickly turned into a bright yellow suspension.
[0072] Add 18 mL of anhydrous ethanol and continue stirring vigorously for 5 min;
[0073] The mixture was centrifuged at 15,000 rpm for 6 min, and the bright yellow solid was collected. It was washed three times with deionized water and acetone, respectively, and then freeze-dried under vacuum for 24 h to obtain the HOF / WO3S heterojunction composite photocatalyst (the mass ratio of HOF to WO3 was 6:1, denoted as HOF / WO3-16.7%).
[0074] Specific Implementation Method 3: The preparation method of the HOF / WO3 S-type heterojunction composite photocatalyst in this implementation method is as follows:
[0075] I. Preparation of WO3 nanorods:
[0076] Dissolve 2.0615 g of sodium tungstate dihydrate (Na2WO4·2H2O) and 1.45 g of sodium chloride (NaCl) in 50 mL of deionized water and stir magnetically for 30 min.
[0077] Slowly add 1 mol / L hydrochloric acid solution (HCl) to adjust the pH to 2.0, and continue magnetic stirring for 1 h;
[0078] The resulting solution was transferred to a 100 mL polytetrafluoroethylene-lined high-pressure reactor and kept at 180 °C for 18 h.
[0079] After the reaction was completed, the product was naturally cooled to room temperature. The product was centrifuged at 12,000 rpm for 5 min, and the gray solid precipitate was collected. It was washed three times with deionized water and anhydrous ethanol, respectively. The sample was then placed in a vacuum freeze dryer and dried for 24 h to obtain WO3 powder.
[0080] II. Preparation of HOF / WO3 composite materials:
[0081] 30 mg H4TBAPy ligand and 10 mg WO3 powder rod were dispersed in 4.5 mL DMF and sonicated for 5 min.
[0082] Under vigorous stirring conditions, 18 mL of ultrapure water was rapidly added to the above dispersion, and vigorous stirring was continued for 5 min. The solution quickly turned into a bright yellow suspension.
[0083] Add 18 mL of anhydrous ethanol and continue stirring vigorously for 5 min;
[0084] The mixture was centrifuged at 15,000 rpm for 6 min, and the bright yellow solid was collected. It was washed three times with deionized water and acetone, respectively, and then freeze-dried under vacuum for 24 h to obtain the HOF / WO3S heterojunction composite photocatalyst (the mass ratio of HOF to WO3 was 3:1, denoted as HOF / WO3-33.3%).
[0085] The following experiments were used to verify the effectiveness of the invention:
[0086] Experiment 1:
[0087] HOF photocatalyst preparation method:
[0088] 30 mg of tetracarboxypyrene (H4TBAPy) ligand was dispersed in 4.5 mL of N,N-dimethylformamide (DMF) and sonicated for 5 min.
[0089] Under vigorous stirring, 18 mL of ultrapure water was quickly added to the above solution, and vigorous stirring was continued for 5 min. The solution quickly turned into a bright yellow suspension.
[0090] Add 18 mL of anhydrous ethanol to the resulting suspension and continue stirring vigorously for 5 min.
[0091] The mixture was transferred to centrifuge tubes and centrifuged at 15,000 rpm for 6 min. The bright yellow solid was collected and washed three times with deionized water and acetone, respectively.
[0092] The sample was placed in a vacuum freeze dryer and freeze-dried for 24 h to obtain HOF powder.
[0093] Experiment 2
[0094] Preparation of WO3 nanorods:
[0095] Dissolve 2.0615 g of sodium tungstate dihydrate (Na2WO4·2H2O) and 1.45 g of sodium chloride (NaCl) in 50 mL of deionized water and stir magnetically for 30 min.
[0096] Slowly add 1 mol / L hydrochloric acid solution (HCl) to adjust the pH to 2.0, and continue magnetic stirring for 1 h.
[0097] The resulting solution was transferred to a 100 mL polytetrafluoroethylene-lined high-pressure reactor and kept at 180 °C for 18 h.
[0098] After the reaction was completed, the product was allowed to cool naturally to room temperature. The product was then centrifuged at 12,000 rpm for 5 min, and the gray solid precipitate was collected and washed three times with deionized water and anhydrous ethanol, respectively.
[0099] The sample was dried in a vacuum freeze dryer for 24 h to obtain WO3 powder.
[0100] Each time, 2 mg of HOF / WO3 composite photocatalysts with different WO3 contents prepared according to specific methods one to three, HOF powder prepared in Experiment 1, and WO3 powder prepared in this experiment were weighed and added to 40 mL of 0.1 mol / L ascorbic acid aqueous solution. 60 μl of H2PtCl6 (concentration 1 mg / mL) was added, and the mixture was sonicated for 5 min. After sealing the system, Ar gas was introduced to purge air, followed by the injection of 30 mL of He as an internal standard gas. The reaction was started under 455 nm LED light source irradiation (LED power supply power 50 W), and magnetic stirring was used to ensure the homogeneity of the catalytic system. Every 60 minutes, 40 μL of gas was manually sampled using a 100 μL gas sampling needle. The collected gas was quantitatively analyzed using a Clarus-580 gas chromatograph equipped with an MS-5A column and a thermal conductivity detector (TCD). The calculated hydrogen production efficiencies for the five systems—HOF, WO3, HOF / WO3-10%, HOF / WO3-16.7%, and HOF / WO3-33.3%—were 179.7 mmol·g. -1 ·h -1 443.3 mmol·g -1 ·h -1 475.5 mmol·g -1 ·h -1 374.8 mmol·g -1 ·h -1 0.
Claims
1. A method for preparing an HOF / WO3 S-type heterojunction composite photocatalyst, characterized in that The preparation method of the HOF / WO3 S-type heterojunction composite photocatalyst is as follows: I. Preparation of WO3 nanorods: Dissolve 2.0615 g of sodium tungstate dihydrate and 1.45 g of sodium chloride in 50 mL of deionized water, and magnetically stir for 30 min; Slowly add a hydrochloric acid solution with a concentration of 1 mol / L to adjust the pH value to 2.0, and continue to magnetically stir for 1 h; Transfer the obtained solution to a 100 mL polytetrafluoroethylene-lined high-pressure reaction kettle, and keep it at 180 ℃ for 18 h; After the reaction is completed, naturally cool it to room temperature, centrifuge the product at a speed of 12000 rpm for 5 min, collect the gray solid precipitate, wash it with deionized water and anhydrous ethanol three times respectively, and then dry the sample in a vacuum freeze dryer for 24 h to obtain WO3 powder; II. Preparation of HOF / WO3 composite material: Disperse 30 mg of H4TBAPy ligand and 3 mg of WO3 powder in 4.5 mL of DMF, and ultrasonically treat for 5 min; Under the condition of vigorous stirring, quickly add 18 mL of ultrapure water to the above dispersion, continue to stir vigorously for 5 min, and the solution quickly turns into a bright yellow suspension; Add 18 mL of anhydrous ethanol, and continue to stir vigorously for 5 min; Centrifuge the mixed system at 15000 rpm for 6 min, collect the bright yellow solid, and wash it with deionized water and acetone three times respectively, and then vacuum freeze dry for 24 h to obtain the HOF / WO3 S-type heterojunction composite photocatalyst.
2. A method for preparing an HOF / WO3 S-type heterojunction composite photocatalyst, characterized in that The preparation method of the HOF / WO3 S-type heterojunction composite photocatalyst is as follows: I. Preparation of WO3 nanorods: Dissolve 2.0615 g of sodium tungstate dihydrate and 1.45 g of sodium chloride in 50 mL of deionized water, and magnetically stir for 30 min; Slowly add a hydrochloric acid solution with a concentration of 1 mol / L to adjust the pH value to 2.0, and continue to magnetically stir for 1 h; Transfer the obtained solution to a 100 mL polytetrafluoroethylene-lined high-pressure reaction kettle, and keep it at 180 ℃ for 18 h; After the reaction is completed, naturally cool it to room temperature, centrifuge the product at a speed of 12000 rpm for 5 min, collect the gray solid precipitate, wash it with deionized water and anhydrous ethanol three times respectively, and then dry the sample in a vacuum freeze dryer for 24 h to obtain WO3 powder; II. Preparation of HOF / WO3 composite material: Disperse 30 mg of H4TBAPy ligand and 3 mg of WO3 powder in 4.5 mL of DMF, and ultrasonically treat for 5 min; Under the condition of vigorous stirring, quickly add 18 mL of ultrapure water to the above dispersion, continue to stir vigorously for 5 min, and the solution quickly turns into a bright yellow suspension; Add 18 mL of anhydrous ethanol, and continue to stir vigorously for 5 min; Centrifuge the mixed system at 15000 rpm for 6 min, collect the bright yellow solid, and wash it with deionized water and acetone three times respectively, and then vacuum freeze dry for 24 h to obtain the HOF / WO3 S-type heterojunction composite photocatalyst.
3. A method for preparing an HOF / WO3 S-type heterojunction composite photocatalyst, characterized in that The preparation method of the HOF / WO3 S-type heterojunction composite photocatalyst is as follows: I. Preparation of WO3 nanorods: Dissolve 2.0615 g of sodium tungstate dihydrate and 1.45 g of sodium chloride in 50 mL of deionized water, and magnetically stir for 30 min; Slowly add a hydrochloric acid solution with a concentration of 1 mol / L to adjust the pH value to 2.0, and continue to magnetically stir for 1 h; Transfer the obtained solution to a 100 mL polytetrafluoroethylene-lined high-pressure reaction kettle, and keep it at 180 ℃ for 18 h; After the reaction is completed, naturally cool it to room temperature, centrifuge the product at a speed of 12000 rpm for 5 min, collect the gray solid precipitate, wash it with deionized water and anhydrous ethanol three times, respectively, and then dry the sample in a vacuum freeze dryer for 24 h to obtain WO3 powder; II. Preparation of HOF / WO3 composite material: Disperse 30 mg of H4TBAPy ligand and 10 mg of WO3 powder rod in 4.5 mL of DMF, and ultrasonically treat for 5 min; Under the condition of vigorous stirring, rapidly add 18 mL of ultrapure water to the above dispersion, continue to vigorously stir for 5 min, and the solution rapidly changes into a bright yellow suspension; Add 18 mL of anhydrous ethanol, and continue to vigorously stir for 5 min; Centrifuge the mixed system at 15000 rpm for 6 min, collect the bright yellow solid, and wash it with deionized water and acetone three times, respectively, and then vacuum freeze dry for 24 h to obtain the HOF / WO3 S-type heterojunction composite photocatalyst.