A preparation method and application of a Co / V-ZnIn2S4 composite photocatalyst
Patent Information
- Application Number
- CN202510450339.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-04-02
- Publication Date
- 2026-10-16
AI Technical Summary
目前双金属元素掺杂提高半导体光催化活性的研究很少
[0018]本发明所述的一种Co/V-ZnIn2S4复合光催化剂的制备方法，通过将Co、V负载在ZnIn2S4上，有效地增大了光催化剂对可见光的利用效率，降低了载流子的复合速度。光催化剂中的光催化剂利用氙灯进行激发，通过与污染物分子接触并相互作用实现光催化反应，从而实现将废水中的氯诺昔康降解。采用本发明所述方法制备的Co/V-ZnIn2S4复合光催化剂结构稳定，原料简单易得，操作过程简单易行，是一种高效的绿色环保技术。
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Figure CN122912879A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of environmental functional materials preparation technology, specifically to a method for preparing a Co / V-ZnIn2S4 composite photocatalyst and its application in the photocatalytic degradation of lornoxicam, which falls under the field of environmental protection. Background Technology
[0002] Lornoxicam (LC), a commonly used nonsteroidal anti-inflammatory drug (NSAID), has raised concerns about environmental pollution due to its widespread use. The drug and its metabolites enter wastewater systems through excretion and are difficult to completely remove using traditional wastewater treatment processes, thus entering natural water bodies. These drug residues may not only have toxic effects on aquatic ecosystems but may also indirectly affect human health through cumulative effects in the food chain. Furthermore, the persistence and bioaccumulation of drugs like lornoxicam in the environment make them potential environmental pollutants, requiring close attention from the scientific community and environmental protection departments to explore effective detection and remediation methods to reduce their negative environmental impact.
[0003] To improve the utilization rate of sunlight, developing a semiconductor photocatalyst with visible light response is crucial. ZnIn₂S₄, as a novel semiconductor photocatalyst, has begun to attract widespread attention from researchers. The ternary metal sulfide ZnIn₂S₄ possesses a suitable band gap of 2.06–2.85 eV, with its conduction band being more negative than the reduction potential of water splitting, while its valence band is more positive than the oxidation potential of many organic pollutants. Furthermore, ZnIn₂S₄ exhibits advantages such as large specific surface area, low toxicity, low cost, and good chemical stability. However, the low light utilization efficiency and rapid recombination rate of photogenerated carriers in ZnIn₂S₄ hinder effective improvement of its photocatalytic efficiency. Common ZnIn₂S₄ modification methods to address these shortcomings include heterostructure construction, morphology control, single-metal doping, and non-metal doping. Currently, research on improving semiconductor photocatalytic activity through bimetallic element doping is limited. Therefore, preparing Co / V-ZnIn2S4 composite photocatalysts through Co and V bimetallic co-doping is an effective strategy to improve the photocatalytic performance of ZnIn2S4 photocatalysts. Summary of the Invention
[0004] [Technical Issues]
[0005] To address the existing problems, a preparation scheme for a Co / V-ZnIn2S4 composite photocatalyst is provided. This preparation scheme has low implementation cost and uses readily available and simple raw materials.
[0006] [Technical Solution]
[0007] To achieve the above objectives, a method for preparing a Co / V-ZnIn2S4 composite photocatalyst is provided according to one embodiment of the present invention, the preparation method comprising the following steps:
[0008] (1) Weigh 1 mmol Zn(CH3COO)2·2H2O, 2 mmol InCl3·4H2O and 4 mmol TAA respectively and add them to 40 mL of deionized water and stir for 30 min.
[0009] (2) Then, 0.778 mmol C4H6CoO4·4H2O and 0.778 mmol VO(C5H7O2)2 were dissolved in 15 mL of deionized water and 10 mL of anhydrous ethanol solution, respectively, and magnetically stirred until fully dissolved. The solutions prepared above were then mixed and magnetically stirred until fully mixed. The mixed solution was then transferred to a 100 mL polytetrafluoroethylene-lined reactor, which was then sealed and placed in a forced-air drying oven for constant temperature heating.
[0010] (3) After the reaction vessel is naturally cooled, the sample is taken out, the solid product is collected after centrifugation, the product is thoroughly washed with anhydrous ethanol and deionized water, and the product is dried in a forced-air drying oven for several hours to obtain a hexagonal Co / V-ZnIn2S4 composite photocatalyst.
[0011] In step (2), the magnetic stirring time is 30 min to 50 min; the molar ratio of C4H6CoO4·4H2O and VO(C5H7O2)2 is any multiple of 0.778 mmol:0.778 mmol.
[0012] In step (2), the temperature of the drying oven is set to 160℃~200℃; the sample is heated in the forced-air drying oven for 8h~16h.
[0013] According to one embodiment of the present invention, a Co / V-ZnIn2S4 composite photocatalyst prepared by the above preparation method is provided, and the prepared Co / V-ZnIn2S4 composite photocatalyst is used to degrade lornoxicam in the aquatic environment.
[0014] Material source
[0015] Zinc acetate dihydrate, indium chloride dihydrate, thioacetamide, cobalt acetate tetrahydrate, and vanadium acetylacetone oxide were all analytical grade and provided by Maclean's and Aladdin's.
[0016] [Beneficial Effects]
[0017] In summary, the present invention has the following beneficial effects:
[0018] This invention discloses a method for preparing a Co / V-ZnIn2S4 composite photocatalyst. By loading Co and V onto ZnIn2S4, the photocatalyst's utilization efficiency for visible light is effectively increased, while reducing the recombination rate of charge carriers. The photocatalyst is excited using a xenon lamp and achieves a photocatalytic reaction through contact and interaction with pollutant molecules, thereby degrading lornoxicam in wastewater. The Co / V-ZnIn2S4 composite photocatalyst prepared using this method has a stable structure, uses readily available and simple raw materials, and is easy to operate, representing a highly efficient and environmentally friendly technology. Attached Figure Description
[0019] Figure 1 These are SEM images of (a) Co / V-ZnIn2S4, (b) Co-ZnIn2S4, (c) V-ZnIn2S4, and (d) ZnIn2S4.
[0020] Figure 2 X-ray diffraction patterns of Co / V-ZnIn2S4, Co-ZnIn2S4, V-ZnIn2S4, and ZnIn2S4.
[0021] Figure 3 (a) Overall XPS spectrum; (b) XPS spectrum of Zn 2p; (c) XPS spectrum of In 3d; (d) XPS spectrum of S 2p; (e) XPS spectrum of Co 3d; (f) XPS spectrum of V 2p.
[0022] Figure 4 The image shows the photocatalytic degradation effect of Co / V-ZnIn2S4, Co-ZnIn2S4, V-ZnIn2S4, and ZnIn2S4 on lornoxicam in water.
[0023] Figure 5 UV-Vis absorption spectra of lornoxicam degradation by Co / V-ZnIn2S4 under different illumination times.
[0024] Figure 6 (a) Transient photocurrents of ZnIn2S4 and Co / V-ZnIn2S4; (b) Electrochemical impedance spectroscopy of ZnIn2S4 and Co / V-ZnIn2S4. Detailed Implementation
[0025] The photocatalytic performance of the Co / V-ZnIn2S4 composite photocatalyst prepared in this invention was evaluated by its visible light degradation performance of lornoxicam in water. The pre-prepared ZnIn2S4, Co-ZnIn2S4, V-ZnIn2S4, and Co / V-ZnIn2S4 composite photocatalysts were respectively placed in 100 mL of 20 mg / L lornoxicam aqueous solution. Under magnetic stirring, the solutions were placed in the dark for 30 min for adsorption. Then, they were irradiated with visible light from a 300 W xenon lamp. Every 10 min, 3–4 mL of solution was collected, filtered, and the concentration was determined spectrophotometrically at λ = 376 nm using diphenylcarbazide. Each experiment was repeated three times to ensure accuracy. Figure 4 The image shows the photocatalytic degradation effects of four ZnIn2S4 photocatalysts. (Refer to...) Figure 4 It can be seen that after 30 minutes of visible light irradiation, the degradation rate of lornoxicam by the Co / V-ZnIn2S4 composite photocatalyst reached 98.47%, indicating that the photocatalyst has a good degradation effect on lornoxicam.
[0026] To enable those skilled in the art to better understand the present invention, the present invention will be further described in detail below with reference to embodiments. However, it should be understood that the following embodiments are only preferred embodiments of the present invention, and the scope of protection claimed by the present invention is not limited thereto.
[0027] Example 1:
[0028] The Co / V-ZnIn2S4 composite photocatalyst according to the present invention is prepared by the following method:
[0029] (1) Weigh 1 mmol Zn(CH3COO)2·2H2O, 2 mmol InCl3·4H2O and 4 mmol TAA respectively and add them to 40 mL of deionized water and stir for 30 min.
[0030] (2) Then, 0.778 mmol C4H6CoO4·4H2O and 0.778 mmol VO(C5H7O2)2 were dissolved in 15 mL of deionized water and 10 mL of anhydrous ethanol solution, respectively. The mixture was magnetically stirred until fully dissolved. The solutions were then magnetically stirred for 30 min until fully mixed. The mixed solution was transferred to a 100 mL polytetrafluoroethylene-lined reactor, which was then sealed and placed in a 200 °C drying oven for 12 hours.
[0031] (3) After the reaction vessel is naturally cooled, the sample is taken out, the solid product is collected after centrifugation, the product is thoroughly washed with anhydrous ethanol and deionized water, and the product is dried in a forced-air drying oven for several hours to obtain Co / V-ZnIn2S4 composite photocatalyst.
[0032] Example 2:
[0033] The preparation method was similar to that in Example 1, except that in (2), only 0.778 mmol of C4H6CoO4·4H2O was weighed and dissolved in 15 mL of deionized water solution. The solution was magnetically stirred until fully dissolved. The final sample was recorded as Co-ZnIn2S4 composite photocatalyst.
[0034] Example 3:
[0035] The preparation method was similar to that in Example 1, except that in (2), only 0.778 mmol VO(C5H7O2)2 was weighed and dissolved in 10 mL of anhydrous ethanol solution, and magnetically stirred until fully dissolved. The final sample was recorded as V-ZnIn2S4 composite photocatalyst.
[0036] Example 4:
[0037] The preparation method was similar to that in Example 1, except that Co source and V source were not added in (2). The solution prepared in (1) was directly used to prepare the sample through methods (2) and (3). The final sample was denoted as ZnIn2S4 composite photocatalyst.
[0038] Example 5:
[0039] The catalysts Co / V-ZnIn2S4, Co-ZnIn2S4, V-ZnIn2S4, and ZnIn2S4, prepared according to the same steps in Examples 1-4 above, showed degradation rates of LC of 98.47%, 9.42%, 94.67%, and 94.74% respectively within 30 min.
Claims
1. A method for preparing a Co / V-ZnIn2S4 composite photocatalyst, comprising the following steps: (1) Weigh 1 mmol Zn(CH3COO)2·2H2O, 2 mmol InCl3·4H2O and 4 mmol TAA and add them to 40 mL of deionized water and stir for 30 min; (2) Then, 0.778 mmol C4H6CoO4·4H2O and 0.778 mmol VO(C5H7O2)2 were dissolved in 15 mL of deionized water and 10 mL of anhydrous ethanol solution, respectively, and magnetically stirred until fully dissolved. Then, the solutions prepared above were mixed and magnetically stirred for 40 min until the solutions were fully mixed and homogeneous. The homogeneous solution was transferred to a 100 mL polytetrafluoroethylene-lined reactor, which was then sealed and placed in a 200 °C drying oven for constant heating for 12 h. (3) After the reaction vessel is naturally cooled, the sample is taken out, the solid product is collected after centrifugation, the product is thoroughly washed with anhydrous ethanol and deionized water, and the product is dried in a forced-air drying oven for several hours to obtain a hexagonal Co / V-ZnIn2S4 composite photocatalyst.
2. The preparation method according to claim 1, characterized in that, In step (2), the magnetic stirring time is 30 min to 50 min.
3. The preparation method according to claim 1, characterized in that, In step (2), the molar ratio of C4H6CoO4·4H2O and VO(C5H7O2)2 is any multiple of 0.778mmol:0.778mmol.
4. The preparation method according to claim 1, characterized in that, In step (2), the temperature of the drying oven is set to 160℃~200℃.
5. The preparation method according to claim 1, characterized in that, In step (2), the sample is heated in a forced-air drying oven for 8 to 16 hours.
6. The ZnIn2S4 composite photocatalyst prepared by the synthesis method of claim 1 is applied to the degradation of the pharmaceutical pollutant lornoxicam in the aquatic environment.