Gadolinium and sulfur defect co-modified indium zinc sulfide-based composite photocatalytic material as well as preparation method and application thereof
By introducing gadolinium and sulfur defects on the surface of indium zinc sulfide-based catalytic material, a composite indium zinc sulfide-co-modified photocatalytic material with gadolinium and sulfur defects was prepared, which solved the problem of low visible photocatalytic activity of indium zinc sulfide photocatalysts in the absence of high visible photocatalytic activity and achieved higher photocatalytic efficiency and stability.
Patent Information
- Application Number
- CN202510244558.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-03-03
- Publication Date
- 2025-07-08
AI Technical Summary
The existing indium zinc sulfide photocatalysts have shortcomings in visible photocatalytic activity and photogenerated carrier recombination rate, resulting in low efficiency in practical applications.
By introducing gadolinium and sulfur defects on the surface of indium zinc sulfide-based catalytic material, a specific preparation method is adopted, including mixing ZnCl2, InCl3·4H2O and TAA in ethylene glycol solution, adding gadolinium nitrate and reacting in an electric constant temperature blowing drying chamber to form an indium zinc sulfide composite photocatalytic material comodified with gadolinium and sulfur defects.
It significantly improves the visible light response range and photocatalytic activity of the material, has good reuse performance, simple preparation process, mild conditions, and easy operation.
Smart Images
Figure CN120268418A_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the technical field of the preparation of industrial catalytic materials, and particularly relates to a gadolinium and sulfur defect co-modified zinc indium sulfide-based composite photocatalytic material, and also relates to a preparation method of the gadolinium and sulfur defect co-modified zinc indium sulfide-based composite photocatalytic material. Background Art
[0002] ZnIn2S4 (zinc indium sulfide) is a ternary metal sulfide belonging to the AB2X4 family, which has unique optical and electronic properties. Compared with traditional photocatalysts, ZnIn2S4 has a relatively narrow band gap, which can be adjusted between about 2.06 and 2.85 eV, and has thermodynamically suitable conduction band and valence band positions, and can be used for photocatalytic CO2 reduction, and has strong light response in the visible light region. In addition, ZnIn2S4 has many advantages, such as strong structural stability, simple chemical composition, easy preparation, wide distribution of raw materials, high visible light absorption ability, etc., thus receiving extensive research attention. Although ZnIn2S4 has a suitable visible light response band gap, conduction band and valence band positions, and currently many methods for preparing ZnIn2S4 have been reported, the photocatalytic activity of intrinsic ZnIn2S4 is still not high. There are still problems in the actual application of ZnIn2S4-based photocatalysts, such as serious recombination of photo-generated carriers and low utilization rate, and too high adsorption energy barrier of S atoms to reaction intermediates. Aiming at the defects or deficiencies of ZnIn2S4 photocatalytic materials, using a modification strategy to modify it, and then developing a new material with high visible light catalytic activity and stable performance is the key to practical application. Summary of the Invention
[0003] The first object of the present invention is to provide a gadolinium and sulfur defect co-modified zinc indium sulfide-based composite photocatalytic material to solve the problem of low visible light catalytic activity of zinc indium sulfide.
[0004] To achieve the above object, the present invention discloses a gadolinium and sulfur defect co-modified zinc indium sulfide-based composite photocatalytic material, which is composed of a zinc indium sulfide-based catalytic material and gadolinium and sulfur defects introduced on the surface of the zinc indium sulfide-based catalytic material; the molar amount of gadolinium is 0.5%-20% of the molar amount of the zinc indium sulfide-based catalytic material.
[0005] The technical solution of the present invention also has the following characteristics:
[0006] As a preferred technical solution of the present invention, it is applied in photocatalytic reduction of carbon dioxide.
[0007] The second object of the present invention is to provide a preparation method of a gadolinium and sulfur defect co-modified zinc indium sulfide-based composite photocatalytic material for preparing the above-mentioned gadolinium and sulfur defect co-modified zinc indium sulfide-based composite photocatalytic material.
[0008] To achieve the above object, the present invention discloses a preparation method of a gadolinium and sulfur defect co-modified indium zinc sulfide-based composite photocatalytic material, which is specifically implemented according to the following steps:
[0009] Step 1, measure ZnCl2, InCl3·4H2O and TAA (thioacetamide) according to a molar ratio of 1:2:8 respectively. First, dissolve the measured ZnCl2 in an ethylene glycol solution, then add the measured InCl3·4H2O to the ethylene glycol solution, and finally add the measured TAA (thioacetamide) and stir until a transparent solution is obtained;
[0010] Step 2, add gadolinium nitrate with a molar ratio of 0.5%-20% to the transparent solution obtained in Step 1 to obtain a mixed solution A, and then stir the mixed solution A.
[0011] Step 3, first transfer the mixed solution A obtained in Step 2 into a reaction kettle and seal it, then place the reaction kettle in an electrothermal constant temperature blast drying oven for reaction to obtain a mixed solution B. After the reaction is completed, naturally cool the mixed solution B to room temperature, and then obtain the gadolinium and sulfur defect co-modified indium zinc sulfide composite photocatalytic material after centrifugal separation, washing and vacuum drying.
[0012] The technical solution of the present invention also has the following characteristics:
[0013] As a preferred solution of the present invention, in Step 3, the reaction temperature in the electrothermal constant temperature blast drying oven is 180°C - 200°C, and the time is 20h - 30h.
[0014] As a preferred solution of the present invention, in Step 3, the temperature for vacuum drying is 60°C - 100°C, and the time is 6h - 12h.
[0015] As a preferred solution of the present invention, in Step 3, the reaction kettle is a stainless steel reaction kettle lined with Teflon.
[0016] Compared with the prior art, the gadolinium and sulfur defect co-modified indium zinc sulfide-based composite photocatalytic material obtained by the preparation method of the present invention has no agglomeration, a wide visible light response range, significantly improved photocatalytic activity compared with pure indium zinc sulfide, good reuse performance, and a simple preparation process, mild conditions, good controllability and convenient operation. BRIEF DESCRIPTION OF THE DRAWINGS
[0017] Figure 1 is the X-ray powder diffraction pattern of pure indium zinc sulfide photocatalytic material, the gadolinium and sulfur defect co-modified indium zinc sulfide-based composite photocatalytic material obtained by the preparation method of the present invention, and gadolinium sulfide;
[0018] Figure 2 It is the scanning electron microscope image of the pure indium zinc sulfide photocatalytic material and the gadolinium and sulfur defect co-modified indium zinc sulfide-based composite photocatalytic material obtained by the preparation method of the present invention;
[0019] Figure 3 It is the transmission electron microscope image of the pure indium zinc sulfide photocatalytic material and the gadolinium and sulfur defect co-modified indium zinc sulfide-based composite photocatalytic material obtained by the preparation method of the present invention;
[0020] Figure 4 It is the energy dispersive X-ray spectroscopy element mapping image of the gadolinium and sulfur defect co-modified indium zinc sulfide-based composite photocatalytic material obtained by the preparation method of the present invention;
[0021] Figure 5 It is the specific surface area and pore size distribution diagram of the pure indium zinc sulfide photocatalytic material and the gadolinium and sulfur defect co-modified indium zinc sulfide-based composite photocatalytic material obtained by the preparation method of the present invention;
[0022] Figure 6 It is the solid ultraviolet-visible absorption spectrum diagram, band gap, valence band and energy band structure diagram of the pure indium zinc sulfide photocatalytic material and the gadolinium and sulfur defect co-modified indium zinc sulfide-based composite photocatalytic material obtained by the preparation method of the present invention;
[0023] Figure 7 It is the electron paramagnetic resonance spectrum of the pure indium zinc sulfide photocatalytic material and the gadolinium and sulfur defect co-modified indium zinc sulfide-based composite photocatalytic material obtained by the preparation method of the present invention;
[0024] Figure 8 It is the visible light photocatalytic activity comparison diagram of the gadolinium and sulfur defect co-modified indium zinc sulfide-based composite photocatalytic material obtained by the preparation method of the present invention;
[0025] Figure 9 It is the performance comparison diagram of different gadolinium doping amounts of the gadolinium and sulfur defect co-modified indium zinc sulfide-based composite photocatalytic material obtained by the preparation method of the present invention;
[0026] Figure 10 It is the visible light photocatalytic activity comparison diagram of the gadolinium and sulfur defect co-modified indium zinc sulfide-based composite photocatalytic material after being used 4 times obtained by the preparation method of the present invention. Specific embodiments
[0027] The technical solution of the present invention will be further described in detail below in conjunction with specific embodiments.
[0028] A gadolinium and sulfur defect co-modified indium zinc sulfide-based composite photocatalytic material of the present invention is composed of an indium zinc sulfide-based catalytic material and gadolinium and sulfur defects introduced on the surface of the indium zinc sulfide-based catalytic material, wherein the molar amount of gadolinium is 0.5%-20% of the molar amount of the indium zinc sulfide-based catalytic material.
[0029] A preparation method of a gadolinium and sulfur defect co-modified zinc indium sulfide-based composite photocatalytic material of the present invention is specifically implemented according to the following steps:
[0030] Step 1: Measure ZnCl2, InCl3·4H2O, and TAA (thioacetamide) according to a molar ratio of 1:2:8. First, dissolve the measured ZnCl2 in an ethylene glycol solution, then add the measured InCl3·4H2O to the ethylene glycol solution, and finally add the measured TAA (thioacetamide) and stir until a transparent solution is obtained;
[0031] Step 2: Add gadolinium nitrate with a molar ratio of 0.5%-20% to the transparent solution obtained in Step 1 to obtain a mixed solution A, and then stir the mixed solution A.
[0032] Step 3: First, transfer the mixed solution A obtained in Step 2 into a reaction kettle and seal it, then place the reaction kettle in an electrothermal constant temperature forced air drying oven and react at 180°C - 200°C for 20h - 30h to obtain a mixed solution B. After the reaction is completed, naturally cool the mixed solution B to room temperature, then perform centrifugal separation and washing, and then perform vacuum drying treatment at 60°C - 100°C for 6h - 12h to obtain a gadolinium and sulfur defect co-modified zinc indium sulfide composite photocatalytic material.
[0033] The preparation of the zinc indium sulfide-based catalytic material is specifically as follows:
[0034] Step 1: Measure ZnCl2, InCl3·4H2O, and TAA (thioacetamide) according to a molar ratio of 1:2:8. First, dissolve the measured ZnCl2 in an ethylene glycol solution, then add the measured InCl3·4H2O to the ethylene glycol solution, and finally add the measured TAA (thioacetamide) and stir until a transparent solution is obtained;
[0035] Step 2: First, transfer the obtained transparent solution into a reaction kettle and seal it, then place the reaction kettle in an electrothermal constant temperature forced air drying oven and react at 180°C - 200°C for 20h - 30h to obtain a mixed solution. After the reaction is completed, naturally cool the mixed solution to room temperature, then perform centrifugal separation and washing, and then perform vacuum drying treatment at 60°C - 100°C for 6h - 12h to obtain a powdered zinc indium sulfide photocatalytic material.
[0036] Figure 1 It is the X-ray diffraction pattern of ZnIn2S4 and 7% Gd-ZnIn2S4-V S The crystal structure and composition of the prepared photocatalyst were characterized by X-ray diffraction (XRD), as Figure 1As shown. The original diffraction peaks of ZnIn2S4 correspond to hexagonal ZnIn2S4 (PDF#65-2023). 7% Gd-ZnIn2S4-V S The diffraction peaks are almost identical to those of ZnIn2S4, and no diffraction peaks of Gd2S3 are observed, indicating that Gd is successfully dispersed onto ZnIn2S4.
[0037] Figure 2 are for ZnIn2S4 and 7% Gd-ZnIn2S4-V S SEM images, where (a) and (b) represent ZnIn2S4, and (c) and (d) represent 7% Gd-ZnIn2S4-V S . Figure 2 As can be seen from (a) and (b) in, the original ZnIn2S4 presents a flower-like microsphere composed of uniform nanosheets; Figure 2 As can be seen from (c) and (d) in, the morphology and size of 7% Gd-ZnIn2S4-V S are basically the same as those of ZnIn2S4.
[0038] Figure 3 (a) shows the transmission electron microscope (TEM) image of ZnIn2S4; (b) shows the high-resolution transmission electron microscope (HR-TEM) image of ZnIn2S4; (c) shows the TEM image of 7% Gd-ZnIn2S4-V S ; (d) shows the HR-TEM image of 7% Gd-ZnIn2S4-V S . From Figure 3 (a) in, it can be seen that ZnIn2S4 is a flower-like microsphere composed of nanosheets. From Figure 4 (b) in, it can be seen that the crystal plane with an interplanar spacing of 0.321 nm is consistent with the (102) crystal plane spacing of ZnIn2S4. In Figure 3 (d), the crystal plane with an interplanar spacing of 0.323 nm is consistent with the (102) crystal plane spacing of 7% Gd-ZnIn2S4-V S (the marked part of the curve), indicating that Gd is successfully doped and highly dispersed on the surface of ZnIn2S4.
[0039] Figure 4 (a) is the total elemental mapping spectrum of the catalyst, (b) represents Zn, (c) represents In, (d) represents S, and (e) represents Gd. From Figure 4 it can be seen that the presence of Zn, In, S, and Gd elements indicates that Gd is uniformly dispersed on the surface of the indium zinc sulfide microspheres.
[0040] Figure 5 (a) and (b) are for ZnIn2S4 and 7% Gd-ZnIn2S4-VS Comparative analysis of the adsorption-desorption isotherms. As can be seen from Figure (a), both materials exhibit an H4-type hysteresis loop. Although the adsorption curve of 7% Gd-ZnIn2S4-V S is very similar to that of ZnIn2S4, the adsorption capacity of 7% Gd-ZnIn2S4-V S is slightly lower at all relative pressures, resulting in a significantly smaller hysteresis loop area. This indicates that ZnIn2S4 has a higher specific surface area and a more complex pore structure. The pore size distribution data (Figure (b)) further confirm that ZnIn2S4 has a wide pore size range, large pore sizes, and exhibits a larger pore volume within a certain size range. In summary, Gd doping of ZnIn2S4 changes the electronic structure of the material, thereby improving its catalytic efficiency.
[0041] Figure 6 (a) and (b) are the UV-visible diffuse reflectance spectra and Tauc plots of ZnIn2S4 and 7% Gd-ZnIn2S4-V S . As can be seen from Figure (a), Gd doping effectively improves the absorption capacity of the sample in the visible light range. The band gaps of ZnIn2S4 (2.69 eV) and 7% Gd-ZnIn2S4-V S (2.63 eV) were determined according to the Tauc plot (Figure (b)). The reduction in the band gap of the composite can be attributed to the introduction of new energy levels by Gd doping. In the context of N-type doping, Gd accepts electrons from the conduction band of ZnIn2S4, creating a shallow "acceptor level" near the bottom of the conduction band. This helps photo-generated electrons to more easily transition from the conduction band to this new acceptor level, thereby reducing the band gap. Figure (c) is the valence band XPS of ZnIn2S4 and 7% Gd-ZnIn2S4-V S . It can be seen that the valence bands of ZnIn2S4 and 7% Gd-ZnIn2S4-V S are 1.33 eV and 1.19 eV, respectively. Figure (c) shows the energy band structure diagrams of ZnIn2S4 and 7% Gd-ZnIn2S4-V S . It can be seen that Gd doping narrows the band gap of ZnIn2S4.
[0042] Figure 7 are the electron paramagnetic resonance (EPR) spectra of ZnIn2S4 and 7% Gd-ZnIn2S4-V S . As can be seen from Figure 7 them, the EPR signal of ZnIn2S4 is very weak, with a g value of 2.002, indicating the presence of surface sulfur defects, while for 7% Gd-ZnIn2S4-V S the EPR signal is very strong, indicating that 7% Gd-ZnIn2S4-V SThe concentration of surface sulfur defects is significantly higher than that of ZnIn2S4.
[0043] In summary, it is proved that gadolinium and sulfur defects have been successfully introduced into the surface of ZnIn2S4, and finally a gadolinium and sulfur defect co-modified indium zinc sulfide-based composite photocatalytic material is obtained.
[0044] The gadolinium and sulfur defect co-modified indium zinc sulfide-based composite photocatalytic material prepared by the present invention can be used for photocatalytic CO2 reduction. The rapid growth of the global economy, the excessive growth of the population and the large-scale burning of fossil fuels have led to a significant increase in the concentration of carbon dioxide in the atmosphere. This is mainly due to the extensive development of fossil fuels. Developing efficient carbon dioxide conversion technology to capture, store and utilize carbon dioxide can alleviate these problems.
[0045] To date, many methods for CO2 conversion have been studied, including thermal catalysis, electrocatalysis, and photocatalysis. Thermal catalysis generally shows high efficiency for CO2 reduction, but often requires harsh conditions of high temperature and pressure, resulting in considerable energy costs and safety issues. Electrocatalysis is carried out under an external electric field, in which there is a trade-off between catalytic activity and selectivity due to excessively high overpotentials. In contrast, photocatalysis relies on solar energy to reduce CO2, with the advantages of mild operating conditions, low energy consumption, and ready availability. This approach not only helps mitigate climate change, but also provides the opportunity to produce renewable fuels, making it an attractive solution in future sustainable development strategies. Therefore, photocatalytic CO2 reduction has attracted tremendous research interest since 1979 when Inoue's team reduced CO2 to value-added chemicals and fuels by illuminating an aqueous suspension of titanium dioxide powder.
[0046] The experimental conditions are as follows: Photocatalytic carbon dioxide reduction (CO2RR) was carried out in a 100 mL quartz reactor. In a typical photocatalytic experiment, the sample was evenly dispersed in 10 mL of a mixed solvent (CH3CN:H2O=9:1, v / v). Before illumination, the reaction mixture was evacuated to remove dissolved gases, and then the photocatalytic reactor was filled with atmospheric pressure of high-purity carbon dioxide. A 300 W Xe lamp (using a standard AM 1.5G filter to simulate visible light, with an irradiation density of approximately 150 mW cm -2 ) was used as the light source. During the reaction, the temperature of the reaction solution was maintained at 25°C. The generated products were detected and quantified by gas chromatography (GC).
[0047] Figure 8 The photocatalytic CO2 reduction performance diagram is shown in Figure 2. Figure 8 It can be seen that 7% Gd-ZnIn2S4-V SIts photocatalytic CO2 reduction activity is higher than that of ZnIn2S4 alone. After illumination, the CO2 reduction products are syngas composed of CO and H2.
[0048] Figure 9 It is the performance diagram of different gadolinium doping amounts. It can be seen that as the gadolinium content increases, the ratio of syngas (CO:H2) changes from 1:3 to 1:1, realizing the regulation of the syngas ratio, and the performance is the highest when the doping amount is 7%, and the syngas ratio is close to 1:1.
[0049] Figure 10 It is 7% Gd-ZnIn2S4-V S It is the performance diagram of the photocatalytic carbon dioxide reduction cycle experiment. It can be seen that after 4 repeated uses, the activity of 7% Gd-ZnIn2S4-V S decreases slightly, indicating that the material has stable performance and good reusability.
[0050] Example 1
[0051] A preparation method of a gadolinium and sulfur defect co-modified zinc indium sulfide-based composite photocatalytic material of the present invention is specifically implemented according to the following steps:
[0052] Step 1, measure ZnCl2, InCl3·4H2O and TAA (thioacetamide) according to a molar ratio of 1:2:8. First, dissolve the measured ZnCl2 in an ethylene glycol solution, then add the measured InCl3·4H2O to the ethylene glycol solution, and finally add the measured TAA (thioacetamide) and stir until a transparent solution is obtained;
[0053] Step 2, add gadolinium nitrate with a molar ratio of 0.5% to the transparent solution obtained in Step 1 to obtain a mixed solution A, and then stir the mixed solution A.
[0054] Step 3, first transfer the mixed solution A obtained in Step 2 into a reaction kettle and seal it, then place the reaction kettle in an electrothermal constant temperature blast drying oven and react at 180°C for 30 h to obtain a mixed solution B. After the reaction is completed, naturally cool the mixed solution B to room temperature, then perform centrifugal separation and washing, and then perform vacuum drying treatment at 60°C for 12 h to obtain a gadolinium and sulfur defect co-modified zinc indium sulfide composite photocatalytic material.
[0055] Example 2
[0056] A preparation method of a gadolinium and sulfur defect co-modified zinc indium sulfide-based composite photocatalytic material of the present invention is specifically implemented according to the following steps:
[0057] Step 1: Measure ZnCl2, InCl3·4H2O, and TAA (thioacetamide) according to a molar ratio of 1:2:8. First, dissolve the measured ZnCl2 in an ethylene glycol solution, then add the measured InCl3·4H2O to the ethylene glycol solution, and finally add the measured TAA (thioacetamide) and stir until a transparent solution is obtained;
[0058] Step 2: Add gadolinium nitrate with a molar ratio of 5% to the transparent solution obtained in Step 1 to obtain a mixed solution A, and then stir the mixed solution A;
[0059] Step 3: First, transfer the mixed solution A obtained in Step 2 into a reaction kettle and seal it, then place the reaction kettle in an electrothermal constant temperature forced air drying oven and react at 180°C for 24 h to obtain a mixed solution B. After the reaction is completed, naturally cool the mixed solution B to room temperature, then perform centrifugal separation and washing, and then perform vacuum drying treatment at 60°C for 12 h to obtain a gadolinium and sulfur defect co-modified indium zinc sulfide composite photocatalytic material.
[0060] Example 3
[0061] A preparation method of a gadolinium and sulfur defect co-modified indium zinc sulfide-based composite photocatalytic material of the present invention is specifically implemented according to the following steps:
[0062] Step 1: Measure ZnCl2, InCl3·4H2O, and TAA (thioacetamide) according to a molar ratio of 1:2:8. First, dissolve the measured ZnCl2 in an ethylene glycol solution, then add the measured InCl3·4H2O to the ethylene glycol solution, and finally add the measured TAA (thioacetamide) and stir until a transparent solution is obtained;
[0063] Step 2: Add gadolinium nitrate with a molar ratio of 7% to the transparent solution obtained in Step 1 to obtain a mixed solution A, and then stir the mixed solution A;
[0064] Step 3: First, transfer the mixed solution A obtained in Step 2 into a reaction kettle and seal it, then place the reaction kettle in an electrothermal constant temperature forced air drying oven and react at 180°C for 24 h to obtain a mixed solution B. After the reaction is completed, naturally cool the mixed solution B to room temperature, then perform centrifugal separation and washing, and then perform vacuum drying treatment at 60°C for 12 h to obtain a gadolinium and sulfur defect co-modified indium zinc sulfide composite photocatalytic material.
[0065] Example 4
[0066] A preparation method of a gadolinium and sulfur defect co-modified indium zinc sulfide-based composite photocatalytic material of the present invention is specifically implemented according to the following steps:
[0067] Step 1: Measure ZnCl2, InCl3·4H2O and TAA (thioacetamide) according to the molar ratio of 1:2:8 respectively. First, dissolve the measured ZnCl2 in ethylene glycol solution, then add the measured InCl3·4H2O to the ethylene glycol solution, and finally add the measured TAA (thioacetamide) and stir until a transparent solution is obtained;
[0068] Step 2: Add gadolinium nitrate with a molar ratio of 10% to the transparent solution obtained in Step 1 to obtain a mixed solution A, and then stir the mixed solution A.
[0069] Step 3: First, transfer the mixed solution A obtained in Step 2 into a reaction kettle and seal it, then place the reaction kettle in an electrothermal constant temperature forced air drying oven and react at 180 °C for 24 h to obtain a mixed solution B. After the reaction is completed, naturally cool the mixed solution B to room temperature, then perform centrifugal separation and washing, and then vacuum dry it at 60 °C for 12 h to obtain a gadolinium and sulfur defect co-modified indium zinc sulfide composite photocatalytic material.
[0070] Example 5
[0071] A preparation method of a gadolinium and sulfur defect co-modified indium zinc sulfide-based composite photocatalytic material of the present invention is specifically implemented according to the following steps:
[0072] Step 1: Measure ZnCl2, InCl3·4H2O and TAA (thioacetamide) according to the molar ratio of 1:2:8 respectively. First, dissolve the measured ZnCl2 in ethylene glycol solution, then add the measured InCl3·4H2O to the ethylene glycol solution, and finally add the measured TAA (thioacetamide) and stir until a transparent solution is obtained;
[0073] Step 2: Add gadolinium nitrate with a molar ratio of 20% to the transparent solution obtained in Step 1 to obtain a mixed solution A, and then stir the mixed solution A.
[0074] Step 3: First, transfer the mixed solution A obtained in Step 2 into a reaction kettle and seal it, then place the reaction kettle in an electrothermal constant temperature forced air drying oven and react at 200 °C for 20 h to obtain a mixed solution B. After the reaction is completed, naturally cool the mixed solution B to room temperature, then perform centrifugal separation and washing, and then vacuum dry it at 100 °C for 6 h to obtain a gadolinium and sulfur defect co-modified indium zinc sulfide composite photocatalytic material.
Claims
1. A gadolinium and sulfur defect co-modified zinc indium sulfide-based composite photocatalytic material, characterized in that, It consists of an indium zinc sulfide-based catalytic material and gadolinium and sulfur defects introduced on the surface of the indium zinc sulfide-based catalytic material; the molar amount of gadolinium is 0.5%-20% of the molar amount of the indium zinc sulfide-based catalytic material.
2. The gadolinium and sulfur defect co-modified indium zinc sulfide-based composite photocatalytic material according to claim 1, characterized in that, It is applied in photocatalytic reduction of carbon dioxide.
3. A preparation method of a gadolinium and sulfur defect co-modified zinc indium sulfide-based composite photocatalytic material, characterized in that, It is specifically implemented according to the following steps: Step 1, measure ZnCl2, InCl3·4H2O and TAA (thioacetamide) respectively according to a molar ratio of 1:2:
8. First, dissolve the measured ZnCl2 in an ethylene glycol solution, then add the measured InCl3·4H2O to the ethylene glycol solution, and finally add the measured TAA (thioacetamide) and stir until a transparent solution is obtained; Step 2, add gadolinium nitrate with a molar ratio of 0.5%-20% to the transparent solution obtained in Step 1 to obtain a mixed solution A, and then stir the mixed solution A. Step 3, first transfer the mixed solution A obtained in Step 2 into a reaction kettle and seal it, then place the reaction kettle in an electrothermal constant temperature blast drying oven for reaction to obtain a mixed solution B. After the reaction is completed, naturally cool the mixed solution B to room temperature, and then obtain a gadolinium and sulfur defect co-modified indium zinc sulfide composite photocatalytic material after centrifugal separation, washing and vacuum drying.
4. The preparation method of the gadolinium and sulfur defect co-modified indium zinc sulfide-based composite photocatalytic material according to claim 3, wherein, In Step 3, the temperature for reaction in the electrothermal constant temperature blast drying oven is 180°C - 200°C, and the time is 20h - 30h.
5. The preparation method of the gadolinium and sulfur defect co-modified indium zinc sulfide-based composite photocatalytic material according to claim 4, characterized in that, In Step 3, the temperature for vacuum drying is 60°C - 100°C, and the time is 6h - 12h.
6. The preparation method of the gadolinium and sulfur defect co-modified indium zinc sulfide-based composite photocatalytic material according to claim 5, characterized in that, In Step 3, the reaction kettle is a stainless steel reaction kettle lined with Teflon.