A preparation method of a ZnIn2S4 nanoflower rod-like composite fiber membrane photocatalyst in situ loaded
By growing ZnIn2S4 nanorod-like structures in situ on PAN nanofibers, the problems of agglomeration and low recycling rate of ZnIn2S4 photocatalysts were solved, and a ZnIn2S4 nanorod-like composite fiber membrane with high efficiency photocatalytic performance and easy recycling was achieved.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- ZHEJIANG SCI-TECH UNIV
- Filing Date
- 2026-03-13
- Publication Date
- 2026-06-02
Smart Images
Figure CN122124866A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of photocatalyst preparation, specifically relating to a method for preparing an in-situ supported ZnIn2S4 nanoflower rod-shaped composite fiber membrane photocatalyst. Background Technology
[0002] With the increasing prominence of energy crises and environmental problems, the development and utilization of clean and sustainable solar photocatalysis technology provides an effective path to alleviate the dual challenges of energy shortages and environmental pollution. Two-dimensional layered ZnIn2S4, as a typical visible-light-responsive photocatalyst, possesses outstanding advantages such as simple synthesis, a wide light absorption range, and a suitable band structure, making it one of the preferred photocatalytic materials in the fields of energy conversion and environmental governance. However, pure ZnIn2S4 photocatalysts still have many shortcomings in practical applications: Firstly, ZnIn2S4 nanoparticles are prone to agglomeration and sedimentation to the bottom of water. The catalytic process is usually accompanied by stirring or ultrasound, during which external mechanical forces may damage the morphology of the photocatalyst, affecting the stability of the material, increasing the concentration and turbidity of the solution, and thus causing a decline in photocatalytic performance. Secondly, the low recycling rate of powdered ZnIn2S4 easily causes secondary pollution, which greatly limits its practical application.
[0003] To address the aforementioned issues, researchers have proposed a loading modification method, loading ZnIn2S4 onto flexible polymer nanofiber supports, which can effectively solve the problems of its aggregation and difficult recycling. For example, Zhang... [1] and Zheng [2] Researchers prepared ZnIn2S4 / PAN photocatalytic composite nanofiber membranes by co-spinning PAN and ZnIn2S4 powders. This method effectively solved the problems of particle agglomeration and low recycling rate. However, co-spinning easily caused uneven distribution of ZnIn2S4 nanoparticles, and some active sites were coated by polymer, which hindered their direct contact with aqueous solution. Moreover, the advantages of the layered structure of ZnIn2S4 were not fully utilized, resulting in problems such as reduced light absorption capacity and insufficient reaction sites, which limited its catalytic potential in practical applications. Summary of the Invention
[0004] The purpose of this invention is to provide a method for preparing an in-situ supported ZnIn2S4 nanofiber composite photocatalyst. Addressing the problems existing in the prior art, this method utilizes an in-situ growth method to directly support ZnIn2S4 on the surface of PAN nanofibers. The prepared composite nanofibers are PAN nanofiber-ZnIn2S4 (PAN / ZnIn2S4) core-shell nanofiber rod-like structures. This catalyst has significant advantages, including fully exposed active sites, effective preservation of the ZnIn2S4 layered structure, and uniform loading distribution. The material is not only highly hydrophilic, but the catalytic process requires no mechanical stirring and is easy to recover.
[0005] To solve the above-mentioned technical problems, the following technical solution is adopted:
[0006] A method for preparing an in-situ supported ZnIn2S4 nanoflower rod-shaped composite fiber film photocatalyst includes the following steps:
[0007] (1) Polyacrylonitrile powder is mixed with organic solvent N,N-dimethylformamide to prepare PAN spinning solution, and PAN nanofiber membrane is spun by electrospinning device.
[0008] (2) Dissolve the zinc source, indium source and sulfur source in deionized water and mix them evenly, then pour the mixture into the polytetrafluoroethylene liner;
[0009] (3) Take the PAN nanofiber membrane from step (1), add it into the polytetrafluoroethylene liner from step 2, and put it into an oven for hydrothermal reaction;
[0010] (4) After the reaction in step (3) is completed, rinse with deionized water and ethanol alternately, and then air dry to obtain PAN / ZnIn2S4 nanofiber membrane material.
[0011] After optimization, in step (1), the mass percentage concentration of the PAN spinning solution is 10~14w.
[0012] After optimization, in step (1), the electrospinning parameters are as follows: spinning temperature is 20-40℃, spinning voltage is 15-20kV, receiving distance is 10-15cm, ambient humidity is 20%-35%, flow rate is 0.8-1.6mL / h, and roller speed is 200-400r / min.
[0013] After optimization, in step (2), the zinc source is one of zinc chloride and zinc sulfate (ZnSO4), the indium source is indium chloride tetrahydrate, and the sulfur source is thioacetamide.
[0014] After optimization, in step (2), the molar ratio of zinc source, indium source and sulfur source is 1:2:4.
[0015] After optimization, in step (2), the concentration of zinc source in the solution is 0.003~0.02mol / L.
[0016] After optimization, in step (3), the oven temperature is 80~120℃ and the heat preservation time is 4~8h.
[0017] After optimization, in step (4), the water is rinsed 1 to 3 times alternately with deionized water and ethanol.
[0018] After optimization, in step (4), the natural drying temperature is 40~60℃.
[0019] The above technical solution has the following beneficial effects:
[0020] (1) The in-situ loaded ZnIn2S4 nanofiber membrane prepared in this invention achieves effective loading of ZnIn2S4 by using the hydrothermal method to grow ZnIn2S4 in situ on PAN nanofibers through the coordination interaction between cyano groups and metal ions.
[0021] (2) In this invention, hydrophilic ZnIn2S4 is loaded in situ on the PAN nanofiber membrane, so that the surface of the PAN nanofiber membrane changes from hydrophobic to hydrophilic.
[0022] (3) The preparation process of this invention is simple, low-cost, and easy to recycle, and the catalyst obtained has high purity and strong crystallinity. ZnIn2S4 retains a nano-layer structure on PAN nanofibers and is uniformly loaded. Compared with the fiber membrane prepared by blending PAN and ZnIn2S4 particles, it effectively solves the problems of catalyst coating and low light absorption capacity.
[0023] (4) The in-situ supported ZnIn2S4 nanoflower rod-shaped composite fiber membrane provided by the present invention has excellent catalytic activity without mechanical stirring during the catalytic process, effectively solves the problem of ZnIn2S4 powder being easy to aggregate and deposit at the bottom of the water, and does not cause the solution to become turbid, and has great potential for engineering applications.
[0024] (5) The in-situ supported ZnIn2S4 nanoflower rod-shaped composite fiber membrane prepared by the present invention has high mechanical strength and excellent flexibility and processability. It can be made into equipment of various shapes and sizes to meet the needs of different reaction systems.
[0025] (6) The in-situ supported ZnIn2S4 nanoflower rod-shaped composite fiber membrane prepared by the present invention has strong hydrophilicity, which can promote the full contact between the catalyst and the aqueous solution, increase the contact area of the catalytic reaction, and further improve the photocatalytic efficiency.
[0026] (7) The in-situ supported ZnIn2S4 nanoflower rod-shaped composite fiber membrane prepared by the present invention exhibits excellent catalytic performance in photocatalytic hydrogen production, treatment of dye wastewater and heavy metal pollutants. Attached Figure Description
[0027] The present invention will be further described below with reference to the accompanying drawings:
[0028] Figure 1 The X-ray powder diffraction pattern of the PAN / ZnIn2S4 composite nanofiber membrane prepared according to Example 4 shows that no other impurity peaks appeared, and the loading content of ZnIn2S4 on the PAN fibers is high.
[0029] Figure 2 The PAN / ZnIn2S4 composite nanofiber membrane was prepared according to Example 4.
[0030] Figure 3 The image shows a scanning electron microscope (SEM) image of the PAN / ZnIn2S4 composite nanofiber membrane prepared according to Example 4, which appears as a nanorod-like structure.
[0031] Figure 4 The contact angle of the PAN nanofiber membrane prepared according to Example 4 after contact with water for 1 second.
[0032] Figure 5 The contact angle of the PAN / ZnIn2S4 composite nanofiber membrane prepared according to Example 4 after contact with water for 1 second.
[0033] Figure 6 The PAN / ZnIn2S4 composite nanofiber membrane prepared according to Example 4 exhibits strong light absorption in the visible light region in its ultraviolet-visible diffuse reflectance spectrum.
[0034] Figure 7 Hydrogen evolution rate diagram of the PAN / ZnIn2S4 composite nanofiber membrane prepared according to Example 4.
[0035] Figure 8 The photocatalytic degradation performance of the PAN / ZnIn2S4 composite nanofiber membrane prepared according to Example 4 on methylene blue under visible light irradiation was tested.
[0036] Figure 9 The photocatalytic degradation performance of potassium dichromate by the PAN / ZnIn2S4 composite nanofiber membrane prepared according to Example 4 was tested under visible light irradiation. Detailed Implementation
[0037] This invention utilizes an in-situ growth method to directly load ZnIn2S4 onto the surface of PAN nanofibers. The prepared composite nanofibers are PAN nanofiber-ZnIn2S4 (PAN / ZnIn2S4) core-shell nanorod structures. This catalyst has significant advantages, including fully exposed active sites, effective preservation of the ZnIn2S4 layered structure, and uniform loading distribution. The material is not only highly hydrophilic, but the catalytic process requires no mechanical stirring and is easily recoverable.
[0038] The present invention will be further described below with reference to specific embodiments. Unless otherwise specified, the reagents and materials used in the following embodiments can be obtained commercially.
[0039] Example 1:
[0040] This embodiment describes a method for preparing an in-situ supported ZnIn2S4 nanorod-shaped composite fiber film photocatalyst. The specific preparation steps are as follows:
[0041] (1) Using N,N-dimethylformamide (DMF) as solvent and PAN powder (molecular weight 150,000) as solute, a 12%wt PAN spinning solution was prepared. The solution was mixed evenly at 35°C on a magnetic stirrer and spun into PAN nanofiber membranes by an electrospinning device. The membranes were then dried at 60°C. The electrospinning conditions were: spinning temperature 25°C, spinning voltage 18kV, receiving distance 15cm, ambient humidity 30%, flow rate 1.2mL / h, and roller speed 200r / min.
[0042] (2) Dissolve 0.1 mmol of ZnCl2, 0.2 mmol of InCl3·4H2O and 0.4 mmol of thioacetamide (TAA) in 25 mL of deionized water at a molar ratio of 1:2:4 and stir for 30 min.
[0043] (3) Pour the mixed solution in step (2) into the polytetrafluoroethylene liner, cut the PAN nanofiber membrane prepared in step (1) into an appropriate size, add it to the polytetrafluoroethylene liner, and put it in an oven for hydrothermal reaction at 85°C for 8 hours.
[0044] (4) After the reaction is complete, rinse with deionized water and ethanol alternately, and dry naturally at 60°C to obtain PAN / ZnIn2S4 composite nanofiber membrane.
[0045] Example 2:
[0046] This embodiment describes a method for preparing an in-situ supported ZnIn2S4 nanorod-shaped composite fiber film photocatalyst. The specific preparation steps are as follows:
[0047] (1) Using N,N-dimethylformamide (DMF) as solvent and PAN powder (molecular weight 150,000) as solute, a 12%wt PAN spinning solution was prepared. The solution was mixed evenly at 35°C on a magnetic stirrer and spun into PAN nanofiber membranes by an electrospinning device. The membranes were then dried at 60°C. The electrospinning conditions were: spinning temperature 25°C, spinning voltage 18kV, receiving distance 15cm, ambient humidity 30%, flow rate 1.2mL / h, and roller speed 200r / min.
[0048] (2) Dissolve 0.2 mmol of ZnCl2, 0.4 mmol of InCl3·4H2O and 0.8 mmol of thioacetamide (TAA) in 25 mL of deionized water at a molar ratio of 1:2:4 and stir for 30 min.
[0049] (3) Pour the mixed solution in step (2) into the polytetrafluoroethylene liner, cut the PAN nanofiber membrane prepared in step (1) into an appropriate size, add it to the polytetrafluoroethylene liner, and put it in an oven for hydrothermal reaction at 85°C for 8 hours.
[0050] (4) After the reaction is complete, rinse with deionized water and ethanol alternately, and dry naturally at 60°C to obtain PAN / ZnIn2S4 composite nanofiber membrane.
[0051] Example 3:
[0052] This embodiment describes a method for preparing an in-situ supported ZnIn2S4 nanorod-shaped composite fiber film photocatalyst. The specific preparation steps are as follows:
[0053] (1) Using N,N-dimethylformamide (DMF) as solvent and PAN powder (molecular weight 150,000) as solute, a 12%wt PAN spinning solution was prepared. The solution was mixed evenly at 35°C on a magnetic stirrer and spun into PAN nanofiber membranes by an electrospinning device. The membranes were then dried at 60°C. The electrospinning conditions were: spinning temperature 25°C, spinning voltage 18kV, receiving distance 15cm, ambient humidity 30%, flow rate 1.2mL / h, and roller speed 200r / min.
[0054] (2) Dissolve 0.3 mmol of ZnCl2, 0.6 mmol of InCl3·4H2O and 1.2 mmol of thioacetamide (TAA) in 25 mL of deionized water at a molar ratio of 1:2:4 and stir for 30 min.
[0055] (3) Pour the mixed solution in step (2) into the polytetrafluoroethylene liner, cut the PAN nanofiber membrane prepared in step (1) into an appropriate size, add it to the polytetrafluoroethylene liner, and put it in an oven for hydrothermal reaction at 85°C for 8 hours.
[0056] (4) After the reaction is complete, rinse with deionized water and ethanol alternately, and dry naturally at 60°C to obtain PAN / ZnIn2S4 composite nanofiber membrane.
[0057] Example 4:
[0058] This embodiment describes a method for preparing an in-situ supported ZnIn2S4 nanorod-shaped composite fiber film photocatalyst. The specific preparation steps are as follows:
[0059] (1) Using N,N-dimethylformamide (DMF) as solvent and PAN powder (molecular weight 150,000) as solute, a 12%wt PAN spinning solution was prepared. The solution was mixed evenly at 35°C on a magnetic stirrer and spun into PAN nanofiber membranes by an electrospinning device. The membranes were then dried at 60°C. The electrospinning conditions were: spinning temperature 25°C, spinning voltage 18kV, receiving distance 15cm, ambient humidity 30%, flow rate 1.2mL / h, and roller speed 200r / min.
[0060] (2) Dissolve 0.4 mmol of ZnCl2, 0.8 mmol of InCl3·4H2O and 1.6 mmol of thioacetamide (TAA) in deionized water at a molar ratio of 1:2:4, pour into 25 mL of deionized water and stir for 30 min;
[0061] (3) Pour the mixed solution in step (2) into the polytetrafluoroethylene liner, cut the PAN nanofiber membrane prepared in step (1) into an appropriate size, add it to the polytetrafluoroethylene liner, and put it in an oven for hydrothermal reaction at 85°C for 8 hours.
[0062] (4) After the reaction is complete, rinse with deionized water and ethanol alternately, and dry naturally at 60°C to obtain PAN / ZnIn2S4 composite nanofiber membrane.
[0063] Example 5:
[0064] This embodiment describes a method for preparing an in-situ supported ZnIn2S4 nanorod-shaped composite fiber film photocatalyst. The specific preparation steps are as follows:
[0065] (1) A 12%wt PAN spinning solution was prepared using N,N-dimethylformamide (DMF) as solvent and PAN powder (molecular weight 150,000) as solute. The solution was mixed evenly at 35°C on a magnetic stirrer and spun into PAN nanofiber membranes using an electrospinning device. The membranes were then dried at 60°C. The electrospinning conditions were as follows: spinning temperature 25°C, spinning voltage 18kV, receiving distance 15cm, ambient humidity 30%, flow rate 1.2mL / h, and roller speed 200r / min.
[0066] (2) Dissolve 0.4 mmol of ZnCl2, 0.8 mmol of InCl3·4H2O and 1.6 mmol of thioacetamide (TAA) in deionized water at a molar ratio of 1:2:4, pour into 25 mL of deionized water and stir for 30 min.
[0067] (3) Pour the mixed solution in step (2) into the polytetrafluoroethylene liner, cut the PAN nanofiber membrane prepared in step (1) into an appropriate size, add it to the polytetrafluoroethylene liner, and put it in an oven for hydrothermal reaction at 90°C for 6 hours.
[0068] (4) After the reaction is complete, rinse with deionized water and ethanol alternately, and dry naturally at 60°C to obtain PAN / ZnIn2S4 composite nanofiber membrane.
[0069] Example 6:
[0070] (1) A 12%wt PAN spinning solution was prepared using N,N-dimethylformamide (DMF) as solvent and PAN powder (molecular weight 150,000) as solute. The solution was mixed evenly at 35°C on a magnetic stirrer and spun into PAN nanofiber membranes using an electrospinning device. The membranes were then dried at 60°C. The electrospinning conditions were as follows: spinning temperature 25°C, spinning voltage 18kV, receiving distance 15cm, ambient humidity 30%, flow rate 1.2mL / h, and roller speed 200r / min.
[0071] (2) Dissolve 0.4 mmol of ZnSO4 precursor ZnIn2S4, 0.8 mmol of InCl3·4H2O and 1.6 mmol of thioacetamide (TAA) in deionized water at a molar ratio of 1:2:4, pour into 25 mL of deionized water and mix and stir for 30 min.
[0072] (3) Pour the mixed solution in step (2) into the polytetrafluoroethylene liner, cut the PAN nanofiber membrane prepared in step (1) into an appropriate size, add it to the polytetrafluoroethylene liner, and put it in an oven for hydrothermal reaction at 85°C for 8 hours.
[0073] (4) After the reaction is complete, rinse with deionized water and ethanol alternately, and dry naturally at 60°C to obtain PAN / ZnIn2S4 composite nanofiber membrane.
[0074] The above are merely specific embodiments of the present invention, but the technical features of the present invention are not limited thereto. Any simple changes, equivalent substitutions, or modifications made based on the present invention to solve essentially the same technical problems and achieve essentially the same technical effects are all covered within the protection scope of the present invention.
Claims
1. A method for preparing an in-situ supported ZnIn2S4 nanoflower rod-shaped composite fiber film photocatalyst, characterized in that... The process includes the following steps: (1) Mixing polyacrylonitrile powder with organic solvent N,N-dimethylformamide to form a PAN spinning solution, and spinning it into a PAN nanofiber membrane using an electrospinning device; (2) Dissolving zinc source, indium source and sulfur source in deionized water and mixing them evenly, and pouring them into a polytetrafluoroethylene liner; (3) Taking the PAN nanofiber membrane from step (1), adding it to the polytetrafluoroethylene liner from step 2, and placing it in an oven for hydrothermal reaction; (4) After the reaction in step (3) is completed, rinsing it alternately with deionized water and ethanol, and then naturally drying it to obtain the PAN / ZnIn2S4 nanofiber membrane material.
2. The method for preparing an in-situ supported ZnIn2S4 nanoflower-shaped composite fiber membrane photocatalyst according to claim 1, characterized in that: In step (1), the mass percentage concentration of the PAN spinning solution is 10~14w.
3. The method for preparing an in-situ supported ZnIn2S4 nanoflower rod-shaped composite fiber membrane photocatalyst according to claim 1, characterized in that: In step (1), the electrospinning parameters are as follows: spinning temperature is 20-40℃, spinning voltage is 15-20kV, receiving distance is 10-15cm, ambient humidity is 20%-35%, flow rate is 0.8-1.6mL / h, and roller speed is 200-400r / min.
4. The method for preparing an in-situ supported ZnIn2S4 nanoflower rod-shaped composite fiber film photocatalyst according to claim 1, characterized in that: In step (2), the zinc source is either zinc chloride or zinc sulfate, the indium source is indium chloride tetrahydrate, and the sulfur source is thioacetamide.
5. The method for preparing an in-situ supported ZnIn2S4 nanoflower-shaped composite fiber membrane photocatalyst according to claim 1, characterized in that: In step (2), the molar ratio of zinc source, indium source and sulfur source is 1:2:
4.
6. The method for preparing an in-situ supported ZnIn2S4 nanoflower rod-shaped composite fiber film photocatalyst according to claim 1, characterized in that: In step (2), the concentration of the zinc source in the solution is 0.003~0.02 mol / L.
7. The method for preparing an in-situ supported ZnIn2S4 nanoflower rod-shaped composite fiber film photocatalyst according to claim 1, characterized in that: In step (3), the oven temperature is 80~120℃ and the heat preservation time is 4~8h.
8. The method for preparing an in-situ supported ZnIn2S4 nanoflower-shaped composite fiber membrane photocatalyst according to claim 1, characterized in that: In step (4), rinse with deionized water and ethanol alternately 1 to 3 times.
9. The method for preparing an in-situ supported ZnIn2S4 nanoflower rod-shaped composite fiber membrane photocatalyst according to claim 1, characterized in that: In step (4), the natural drying temperature is 40~60℃.