Cl-doped Zn3In2S6 photocatalyst, its preparation method, and applications
By preparing Cl-doped Zn3In2S6 photocatalysts, the problems of slow photogenerated electron migration rate and photocorrosion in the photocatalytic synthesis of hydrogen peroxide by bimetallic sulfide photocatalysts were solved, realizing efficient hydrogen peroxide synthesis and showing good industrial application potential.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- JIANGSU UNIV
- Filing Date
- 2025-02-26
- Publication Date
- 2026-05-12
AI Technical Summary
Existing bimetallic sulfide photocatalysts suffer from slow photogenerated electron migration rates and severe photocorrosion during the photocatalytic synthesis of hydrogen peroxide, limiting their application in the field of photocatalysis.
A method for preparing Cl-doped Zn3In2S6 photocatalyst was adopted. Cl-doped Zn3In2S6 was prepared by a one-step solvothermal method. The band structure and the formation of a local built-in electric field were controlled by Cl element doping, which improved the separation efficiency of photogenerated carriers and broadened the visible light absorption range.
It effectively improves the efficiency of photocatalytic synthesis of hydrogen peroxide, overcomes the problems of slow photogenerated electron migration rate and photocorrosion, and has a simple and low-cost preparation method with good prospects for industrial application.
Smart Images
Figure CN119951596B_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of photocatalytic materials technology, and in particular to a Cl-doped Zn3In2S6 photocatalyst, its preparation method, and its application. Background Technology
[0002] Hydrogen peroxide (H2O2) is an environmentally friendly oxidant widely used in medical treatment, disinfection, wastewater treatment, and chemical synthesis, with demand continuously increasing. Currently, over 95% of H2O2 is produced via the anthraquinone process, which relies on a noble metal palladium catalyst. This method is not only energy-intensive but also produces toxic byproducts. Photocatalysis can synthesize H2O2 in situ through the photocatalytic reduction of O2, representing a promising green and sustainable method for H2O2 production. However, photocatalysts suffer from limitations in the photocatalytic synthesis of H2O2, including weak oxygen adsorption and activation capabilities, low photoresponsiveness, and limited active sites. Therefore, developing a high-performance semiconductor photocatalyst for efficient H2O2 synthesis is of significant scientific importance and practical application value.
[0003] Bimetallic sulfides are considered promising photocatalytic materials due to their excellent visible light absorption, tunable electronic structure, and abundant active sites. However, their slow photogenerated electron migration rate and severe photocorrosion problems limit their widespread application in the field of photocatalysis. Summary of the Invention
[0004] The purpose of this invention is to provide a Cl-doped Zn3In2S6 photocatalyst, its preparation method, and its application, which solves the problems of slow photogenerated electron migration rate and severe photocorrosion of bimetallic sulfides, thus restricting their application in the field of photocatalysis.
[0005] To achieve the above objectives, this invention provides a method for preparing a Cl-doped Zn3In2S6 photocatalyst, comprising the following steps:
[0006] Zinc sulfate, indium nitrate tetrahydrate, thioacetamide and hydroxylamine hydrochloride were weighed separately and placed in deionized water. The mixture was then magnetically stirred at room temperature to disperse the solution and obtain a mixed solution.
[0007] The resulting mixed solution was transferred to a hydrothermal reactor for reaction.
[0008] After the reaction product is allowed to stand, it is centrifuged, washed, and dried to obtain the Cl-doped Zn3In2S6 photocatalyst.
[0009] Among them, in the section "Weigh out zinc sulfate, indium nitrate tetrahydrate, thioacetamide and hydroxylamine hydrochloride respectively, place them in deionized water, and disperse them by magnetic stirring at room temperature to obtain a mixed solution";
[0010] The mass ratio of zinc sulfate, indium nitrate tetrahydrate, thioacetamide, hydroxylamine hydrochloride, and deionized water is 0.242–0.726: 0.301–0.903: 0.451–1.353: 0.421–1.261: 30–60.
[0011] Among them, in the section "Weigh out zinc sulfate, indium nitrate tetrahydrate, thioacetamide and hydroxylamine hydrochloride respectively, place them in deionized water, and disperse them by magnetic stirring at room temperature to obtain a mixed solution";
[0012] The stirring time is 30 to 90 minutes.
[0013] Among them, in the section "transferring the obtained mixed solution to a hydrothermal reactor for reaction";
[0014] The reaction temperature is 140℃-200℃, and the reaction time is 8h-16h.
[0015] Among them, in the section "After the obtained reaction product is allowed to stand, centrifuged, washed, and dried, the Cl-doped Zn3In2S6 photocatalyst can be obtained";
[0016] The washing reagent used is distilled water, the centrifugation speed is 10000 rpm, and the number of washing cycles is 3-5.
[0017] Among them, in the section "After the obtained reaction product is allowed to stand, centrifuged, washed, and dried, the Cl-doped Zn3In2S6 photocatalyst can be obtained";
[0018] The drying temperature is 60℃ and the drying time is 12 hours.
[0019] The present invention also includes a Cl-doped Zn3In2S6 photocatalyst, which is prepared by the method described above for preparing the Cl-doped Zn3In2S6 photocatalyst.
[0020] This invention also includes the application of a Cl-doped Zn3In2S6 photocatalyst. The Cl-doped Zn3In2S6 photocatalyst is used in the photocatalytic production of H2O2, specifically including the following steps:
[0021] Weigh 20 mg of Cl-doped Zn3In2S6 photocatalyst and place it in a 50 mL photoreaction flask;
[0022] Add 18 mL of deionized water and 2 mL of isopropanol to the light reaction flask, and stir magnetically for 30 min at 20 °C in the dark to allow the reaction system to reach adsorption equilibrium.
[0023] After the dark reaction is complete, turn on the light source and take 1 mL of sample every 10 minutes. After centrifugation, use the DPD method to test the concentration of H2O2.
[0024] This invention discloses a Cl-doped Zn3In2S6 photocatalyst, its preparation method, and its application. The invention employs a one-step solvothermal method to prepare Cl-doped Zn3In2S6 (Cl-ZIS). By doping with Cl, the absorption range of Zn3In2S6 for visible light is effectively broadened, thereby enhancing the ability of bimetallic sulfide materials to synthesize H2O2 under visible light irradiation. On one hand, Cl doping can modulate the band structure of Zn3In2S6, enhancing its visible light absorption capacity and thus improving its photocatalytic H2O2 synthesis performance. On the other hand, Cl doping can create a locally built-in electric field within Zn3In2S6, thereby improving the separation efficiency of photogenerated carriers.
[0025] Compared with the prior art, the significant advantages of this invention are: by doping with Cl, the photocatalytic synthesis efficiency of H2O2 from Zn3In2S6 (Cl-ZIS) with a hydrangea-like structure can be effectively promoted; and the preparation method of this invention is simple, highly controllable, and low in cost, and has excellent prospects for industrial application. Attached Figure Description
[0026] To more clearly illustrate the technical solutions in the embodiments of this application or the prior art, the accompanying drawings used in the description of the embodiments or the prior art will be briefly introduced below.
[0027] Figure 1 SEM image of the Cl-doped Zn3In2S6 photocatalyst prepared in this invention;
[0028] Figure 2 The XRD pattern of the Cl-doped Zn3In2S6 photocatalyst prepared in this invention;
[0029] Figure 3 This is a solid-state ultraviolet diffuse reflectance image of the Cl-doped Zn3In2S6 photocatalyst prepared in this invention;
[0030] Figure 4 Photocurrent diagram of the Cl-doped Zn3In2S6 photocatalyst prepared in this invention;
[0031] Figure 5 The image shows the performance of the Cl-doped Zn3In2S6 photocatalyst for the photocatalytic production of H2O2 prepared in this invention.
[0032] Figure 6 This is a flowchart of the preparation method of the Cl-doped Zn3In2S6 photocatalyst of the present invention.
[0033] Figure 7 This is a flowchart illustrating the application of the Cl-doped Zn3In2S6 photocatalyst in the photocatalytic production of H2O2. Detailed Implementation
[0034] The embodiments of the present invention are described in detail below. Examples of the embodiments are shown in the accompanying drawings. The embodiments described below with reference to the accompanying drawings are exemplary and intended to explain the present invention, but should not be construed as limiting the present invention.
[0035] S101: Weigh out zinc sulfate, indium nitrate tetrahydrate, thioacetamide and hydroxylamine hydrochloride respectively and place them in deionized water. Disperse them by magnetic stirring at room temperature to obtain a mixed solution.
[0036] S102: Transfer the resulting mixed solution to a hydrothermal reactor for reaction;
[0037] S103: After the obtained reaction product is allowed to stand, it is centrifuged, washed, and dried to obtain the Cl-doped Zn3In2S6 photocatalyst.
[0038] Example 1:
[0039] 0.484 g zinc sulfate (ZnSO4), 0.602 g indium nitrate tetrahydrate (In(NO3)3·4H2O), 0.902 g thioacetamide (CH3CSNH2), and 0.420 g hydroxylamine hydrochloride (HONH2·HCl) were placed in a beaker containing 60 mL of deionized water and dispersed by magnetic stirring at room temperature for 60 min to obtain a mixed solution.
[0040] The resulting mixed solution was transferred to a 100 mL hydrothermal reactor and placed in a constant temperature oven at 160 °C for 12 h.
[0041] After the reaction vessel was allowed to cool naturally to room temperature, it was centrifuged at 10000 rpm for 3 min, washed 4 times with deionized water, and dried in a constant temperature oven at 60℃ for 12 h to obtain Cl-doped Zn3In2S6 photocatalyst (2Cl-ZIS).
[0042] Example 2:
[0043] 0.484 g zinc sulfate (ZnSO4), 0.602 g indium nitrate tetrahydrate (In(NO3)3·4H2O), 0.902 g thioacetamide (CH3CSNH2), and 0.841 g hydroxylamine hydrochloride (HONH2·HCl) were placed in a beaker containing 60 mL of deionized water and dispersed by magnetic stirring at room temperature for 60 min to obtain a mixed solution.
[0044] The resulting mixed solution was transferred to a 100 mL hydrothermal reactor and placed in a constant temperature oven at 160 °C for 12 h.
[0045] After the reaction vessel was allowed to cool naturally to room temperature, it was centrifuged at 10,000 rpm for 3 min, washed 4 times with deionized water, and dried in a constant temperature oven at 60℃ for 12 h to obtain Cl-doped Zn3In2S6 photocatalyst (4Cl-ZIS).
[0046] Example 3:
[0047] 0.484 g zinc sulfate (ZnSO4), 0.602 g indium nitrate tetrahydrate (In(NO3)3·4H2O), 0.902 g thioacetamide (CH3CSNH2), and 1.682 g hydroxylamine hydrochloride (HONH2·HCl) were placed in a beaker containing 60 mL of deionized water and dispersed by magnetic stirring at room temperature for 60 min to obtain a mixed solution.
[0048] The resulting mixed solution was transferred to a 100 mL hydrothermal reactor and placed in a constant temperature oven at 160 °C for 12 h.
[0049] After the reaction vessel was allowed to cool naturally to room temperature, it was centrifuged at 10,000 rpm for 3 min, washed 4 times with deionized water, and dried in a constant temperature oven at 60℃ for 12 h to obtain Cl-doped Zn3In2S6 photocatalyst (8Cl-ZIS).
[0050] Figure 1 The images show scanning electron microscope (SEM) images of the Cl-doped Zn3In2S6 photocatalyst (Cl-ZIS) and Zn3In2S6 (ZIS) prepared in this embodiment. The images show that the prepared samples are hydrangea-like structures assembled from nanosheets. With increasing Cl doping, the clustering degree of the nanosheets decreases, and the thickness of the nanosheets also decreases.
[0051] Figure 2 The X-ray diffraction patterns of the Cl-doped Zn3In2S6 photocatalyst (Cl-ZIS) and Zn3In2S6 (ZIS) prepared in this embodiment are shown. The diffraction peak positions of Cl-ZIS and ZIS do not change significantly, indicating that Cl doping has little effect on the ZIS crystal phase. However, as the Cl doping increases, the crystallinity of the sample decreases, which is due to the disruption of the ZIS crystal structure caused by Cl doping.
[0052] Figure 3 The images show the solid-state UV diffuse reflectance spectra of the Cl-doped Zn3In2S6 photocatalyst (Cl-ZIS) and Zn3In2S6 (ZIS) prepared in this embodiment. Compared to ZIS, Cl-ZIS exhibits a significant blue shift in its light absorption edge. Furthermore, the degree of blue shift becomes more pronounced with increasing Cl doping concentration.
[0053] Figure 4The images show the photocurrent of the Cl-doped Zn3In2S6 photocatalyst (Cl-ZIS) and Zn3In2S6 (ZIS) prepared in this embodiment. Compared to ZIS, the photoresponse signal of Cl-ZIS is significantly enhanced, indicating that Cl doping improves the separation efficiency of photogenerated charges in ZIS. Among them, 4Cl-ZIS shows the highest photoresponse intensity, indicating that it has the highest separation efficiency of photogenerated charges.
[0054] Figure 5 The activity diagrams for the photocatalytic production of H2O2 by the Cl-doped Zn3In2S6 photocatalyst (Cl-ZIS) and Zn3In2S6 (ZIS) prepared in this embodiment are shown. The specific steps included: 20 mg of the Cl-doped Zn3In2S6 photocatalyst (Cl-ZIS) was weighed and placed in a 50 mL photocatalytic reaction flask, along with 18 mL of deionized water and 2 mL of isopropanol. The mixture was magnetically stirred for 30 min in the dark at 20°C until adsorption equilibrium was reached. After the dark reaction was complete, the light source (a 300 W xenon lamp with λ>420 nm) was turned on, and 1 mL of sample was taken every 10 min. After centrifugation, the concentration of H2O2 was measured using the DPD method. The results showed that ZIS produced almost no H2O2, while the Cl-doped Zn3In2S6 photocatalyst (Cl-ZIS) produced significant amounts of H2O2. Among them, 4Cl-ZIS showed the highest H2O2 production rate.
[0055] Figure 6 This is a flowchart of the preparation method of the Cl-doped Zn3In2S6 photocatalyst of the present invention.
[0056] Figure 7 This is a flowchart illustrating the application of the Cl-doped Zn3In2S6 photocatalyst in the photocatalytic production of H2O2.
[0057] The above-disclosed embodiments are merely one or more preferred embodiments of this application and should not be construed as limiting the scope of this application. Those skilled in the art can understand that all or part of the processes for implementing the above embodiments and equivalent changes made in accordance with the claims of this application still fall within the scope of this application.
Claims
1. A method for preparing a Cl-doped Zn3In2S6 photocatalyst, characterized in that, Includes the following steps: Zinc sulfate, indium nitrate tetrahydrate, thioacetamide and hydroxylamine hydrochloride were weighed separately and placed in deionized water. The mixture was then magnetically stirred at room temperature to disperse the solution and obtain a mixed solution. The resulting mixed solution was transferred to a hydrothermal reactor for reaction. After the reaction product is allowed to stand, it is centrifuged, washed, and dried to obtain the Cl-doped Zn3In2S6 photocatalyst. The Cl-doped Zn3In2S6 photocatalyst has a hydrangea-like structure assembled from nanosheets; the light absorption edge of the Cl-doped Zn3In2S6 photocatalyst exhibits a blue shift compared to undoped Zn3In2S6. The mass ratio of zinc sulfate, indium nitrate tetrahydrate, thioacetamide, hydroxylamine hydrochloride, and deionized water is 0.484~0.726:0.602~0.903:0.902~1.353:0.841~1.261:30~60.
2. The preparation method of the Cl-doped Zn3In2S6 photocatalyst as described in claim 1, characterized in that, In the process of "weighing zinc sulfate, indium nitrate tetrahydrate, thioacetamide and hydroxylamine hydrochloride separately and placing them in deionized water, then dispersing them with magnetic stirring at room temperature to obtain a mixed solution"; The stirring time is 30~90 min.
3. The preparation method of the Cl-doped Zn3In2S6 photocatalyst as described in claim 1, characterized in that, In the section "Transfer the resulting mixed solution to a hydrothermal reactor for reaction"; The reaction temperature is 140℃-200℃, and the reaction time is 8 h-16 h.
4. The preparation method of the Cl-doped Zn3In2S6 photocatalyst as described in claim 1, characterized in that, In the statement "After the obtained reaction product is allowed to stand, centrifuged, washed, and dried, the Cl-doped Zn3In2S6 photocatalyst can be obtained"; The washing reagent used is distilled water, the centrifugation rate is 10,000 rpm, and the number of washing cycles is 3-5.
5. The preparation method of the Cl-doped Zn3In2S6 photocatalyst as described in claim 4, characterized in that, In the statement "After the obtained reaction product is allowed to stand, centrifuged, washed, and dried, the Cl-doped Zn3In2S6 photocatalyst can be obtained"; The drying temperature was 60℃ and the drying time was 12 hours.
6. A Cl-doped Zn3In2S6 photocatalyst, characterized in that, It was prepared using the preparation method of Cl-doped Zn3In2S6 photocatalyst as described in any one of claims 1-5.
7. An application of a Cl-doped Zn3In2S6 photocatalyst, characterized in that, The Cl-doped Zn3In2S6 photocatalyst as described in claim 6 is used in the photocatalytic production of H2O2. Specifically... Includes the following steps: Weigh 20 mg of Cl-doped Zn3In2S6 photocatalyst and place it in a 50 mL photoreaction flask; Add 18 mL of deionized water and 2 mL of isopropanol to the light reaction flask, and stir magnetically for 30 min at 20°C in the dark to allow the reaction system to reach adsorption equilibrium. After the dark reaction is complete, turn on the light source and take 1 mL of sample every 10 min. After centrifugation, use the DPD method to test the concentration of H2O2.