Indium sulfide loaded UIO-66-NH2 heterojunction photocatalyst as well as preparation method and application thereof

Abstract

The invention discloses an indium sulfide loaded UIO-66-NH2 heterojunction photocatalyst as well as a preparation method and application of the indium sulfide loaded UIO-66-NH2 heterojunction photocatalyst. According to the photocatalyst, a heterostructure is formed by a metal organic framework material UIO-66-NH2 and indium sulfide nanoparticles, wherein indium sulfide is uniformly distributed on the surface of the UIO-66-NH2. During preparation, UIO-66-NH2 is synthesized through a solvothermal method, indium sulfide grows on the surface of UIO-66-NH2 in situ through a hydrothermal method, and a compact heterogeneous interface is constructed. According to the heterostructure, visible light absorption is remarkably enhanced, and the efficiency of photocatalytic production of hydrogen peroxide is greatly improved by promoting effective separation of photo-induced electrons and holes and enhancing adsorption and activation of oxygen molecules. The catalyst is simple and convenient in preparation process, high in catalytic activity and environment-friendly, and has important application value in the fields of green energy synthesis and environmental restoration.

Description

Technical Field

[0001] This invention relates to the field of photocatalytic materials and environmental energy catalysis technology, specifically to a UIO-66-NH2 / indium sulfide composite photocatalytic material and its preparation method, as well as its application in photocatalytic hydrogen peroxide production. Background Technology

[0002] Hydrogen peroxide (H2O2), commonly known as hydrogen peroxide solution, is an important inorganic compound. Its significance is broadly reflected in various fields such as industry, medicine, environmental protection, and aerospace, stemming from its unique chemical properties—an unstable strong oxidizing agent that decomposes into water and oxygen, leaving no harmful residues. Hydrogen peroxide is a key chemical raw material and bleaching agent in industrial production processes. A 3% hydrogen peroxide solution is a common medical disinfectant and can also be used in household applications such as laundry and daily care. High concentrations of hydrogen peroxide are important cleaning and etching agents in high-precision manufacturing. Furthermore, hydrogen peroxide can serve as a core reagent in advanced oxidation processes, achieving the goals of purifying water and improving air quality through the efficient degradation of pollutants. As a "clean" chemical product that only produces water and oxygen after a reaction, it not only drives the development of various industries but also aligns with today's green and sustainable development concepts, and its importance will continue to stand out.

[0003] Hydrogen peroxide synthesis methods have evolved from the traditional industrial anthraquinone process to include direct hydrogen-oxygen synthesis and electrochemical methods. Compared to the high energy consumption and risks associated with these processes, photocatalytic hydrogen peroxide production is an emerging technology that uses light energy to drive a chemical reaction to synthesize hydrogen peroxide (H₂O₂). Its core advantages lie in its green and sustainable nature and its potential for in-situ applications, providing a highly attractive alternative to traditional synthesis methods. However, most reported photocatalysts still suffer from narrow light absorption ranges, low absorption utilization rates, and rapid recombination of photogenerated electrons and holes, resulting in low efficiency in hydrogen peroxide production that fails to meet the requirements for industrial application, thus limiting the industrial use of photocatalysis. Therefore, exploring novel and highly efficient photocatalysts has been a continuous research hotspot in this field. Recent research on photocatalyst materials mainly includes graphitic carbon nitride, metal oxides, metal sulfides, and organic frameworks.

[0004] Indium sulfide (ILS) is a semiconductor material with a narrow band gap (approximately 2.0-2.3 eV), good visible light absorption, and high electron mobility, thus possessing potential applications in photocatalysis. However, the high recombination rate of photogenerated carriers and insufficient surface active sites of ILS limit its widespread application in the photocatalytic production of hydrogen peroxide.

[0005] Metal-organic frameworks (MOFs) are a class of porous crystalline materials composed of metal ions or metal clusters and organic ligands, possessing advantages such as high specific surface area, tunable pore structure, and abundant functional groups. Among them, UIO-66-NH2 has attracted widespread attention in the fields of photocatalysis and adsorption due to its excellent chemical stability, high specific surface area, and amino-functionalized structure. The high specific surface area, porous structure, and oxygen-adsorption-friendly structural characteristics of UIO-66-NH2 can mitigate the shortcomings of indium sulfide itself. The combination of the two is beneficial for improving the separation efficiency of photogenerated carriers, enhancing oxygen adsorption capacity, and improving photocatalytic activity. Summary of the Invention

[0006] The technical problem to be solved by this invention is to provide a UIO-66-NH2 / indium sulfide composite photocatalytic material to solve the problems of severe recombination of photogenerated carriers, insufficient oxygen adsorption capacity, and low hydrogen peroxide generation efficiency in the existing photocatalytic preparation of hydrogen peroxide.

[0007] Technical solution: A UIO-66-NH2 supported indium sulfide photocatalyst for photocatalytic hydrogen peroxide production; the composite material preparation method includes the following steps:

[0008] Step 1: Dissolve zirconium tetrachloride, 2-aminoterephthalic acid and acetic acid in DMF, sonicate for 20 min and then magnetically stir at 800 r / min for 2 h to obtain a homogeneous solution.

[0009] Step 2: Transfer the mixture from Step 1 to a polytetrafluoroethylene hydrothermal reactor and carry out a hydrothermal reaction in an oven for a period of time. After cooling to room temperature, centrifuge and wash to remove residual impurities, and finally dry in a vacuum oven to obtain a pale yellow UIO-66-NH2. The hydrothermal reaction temperature is 110-120 ℃ and the hydrothermal reaction time is 23-25 ​​h.

[0010] Step 3: Dissolve the UIO-66-NH2 obtained in Step 2 in a mixed solution of glycerol and water, then add InCl3·4H2O and thioacetamide. Stir at 1200 r / min for 20 min, then transfer to a high-pressure hydrothermal reactor for the second hydrothermal reaction. After cooling to room temperature, wash and dry, the resulting orange-yellow powder is the UIO-66-NH2-supported indium sulfide photocatalyst.

[0011] As an improved technical solution of the present invention: the molar ratio of zirconium tetrachloride and acetic acid in step 1 is in the range of 1:180-1:210, and the solid-liquid ratio of zirconium tetrachloride and DMF is 46.44 mg:20 mL.

[0012] As an improved technical solution of the present invention: the centrifugation speed in step 2 is 8000 rpm and the holding time is 3 min; the washing process is washing with DMF and methanol 3 times each; the vacuum oven drying time is 11-13 h and the temperature is 60-70 ℃.

[0013] As an improved technical solution of the present invention: the temperature range of the high-temperature hydrothermal reaction in step 2 is 110-120℃, and the time range of the hydrothermal reaction is 23-25 ​​h.

[0014] As an improved technical solution of the present invention: the mass ratio of UIO-66-NH2 and indium sulfide in step 3 is in the range of 1:9-1:1; the volume ratio of glycerol and water is 1:4; the centrifugation speed is 8000 rpm and the holding time is 3 min; the washing process is washing twice with ultrapure water and ethanol respectively; the vacuum oven drying time is 11-13 h and the temperature is 60-70 ℃.

[0015] As an improved technical solution of the present invention: the temperature range of the high-temperature hydrothermal step 3 is 170-180℃, and the hydrothermal reaction time range is 23-25 ​​h.

[0016] This application also discloses that the UIO-66-NH2 supported indium sulfide photocatalyst is a petal-shaped nanosphere formed by indium sulfide encapsulating the outside of an octahedron of UIO-66-NH2.

[0017] As an improved technical solution of the present invention, the method for photocatalytic hydrogen peroxide production and concentration detection includes the following steps:

[0018] 1) Add 10 mg of UIO-66-NH2 supported indium sulfide photocatalyst to a photocatalytic tube containing 50 mL of ultrapure water. Under dark conditions, place the device on a magnetic stirring table and simultaneously introduce oxygen into the device to increase the dissolved oxygen content.

[0019] 2) A xenon lamp equipped with a 420 nm filter was used as a simulated visible light source for photocatalytic reaction. 1 mL of sample was taken every 15 min using a syringe and filtered through a 0.22 μm filter membrane for subsequent concentration testing.

[0020] 3) Add KI and (NH4)2MoO4 solution to the mixture in step 2) above and mix well. Detect the absorbance at 350nm wavelength within 15 min and obtain the hydrogen peroxide concentration from the working curve.

[0021] As an improved technical solution of the present invention: the stirring speed in step 1) is 1000-1100 r / min, and the stirring time is 1.0-1.5 h.

[0022] As an improved technical solution of the present invention: the concentration ratio of potassium iodide and ammonium molybdate in step 3) is 10:1, and the volume ratio is 40:1.

[0023] Compared with the prior art, the present invention has the following advantages:

[0024] 1) This invention successfully prepared a UIO-66-NH2 supported indium sulfide photocatalyst by in-situ growing indium sulfide on the octahedral UIO-66-NH2 surface using a two-step hydrothermal method. The preparation process is simple.

[0025] 2) The UIO-66-NH2 prepared by this invention has a rich porous structure, which provides abundant oxygen adsorption sites during the catalytic process;

[0026] 3) This invention constructs a tight heterojunction structure between indium sulfide and UIO-66-NH2, forming an electron transfer path from amino groups to Zr-O clusters and then to indium sulfide, which broadens the light absorption range of the material and improves the electron-hole separation efficiency.

[0027] 4) The UIO-66-NH2 supported indium sulfide composite photocatalyst prepared in this invention exhibits high activity in photocatalytic hydrogen peroxide production under pure water conditions, which is much greater than the catalytic activity of the two single catalysts. Attached Figure Description

[0028] Figure 1 These are scanning electron microscope (SEM) and field emission electron microscope (TEM) images of the UIO-66-NH2 supported indium sulfide photocatalyst in Example 1 and Example 4 of the present invention.

[0029] Figure 2 The image shows the EDS distribution of the UIO-66-NH2 supported indium sulfide photocatalyst described in this invention; the images are, in order, the EDS distributions of Zr, C, N, O, In, and S elements.

[0030] Figure 3The figures show the XPS full spectrum of UIO-66-NH2, indium sulfide, and UIO-66-NH2-supported indium sulfide photocatalysts in Examples 1, 2, and 4 of this invention, as well as the C 1s, Zr 3d, and In 3d orbital diagrams. Figure a is the XPS full spectrum of UIO-66-NH2, indium sulfide, and UIO-66-NH2-supported indium sulfide; Figure b is the high-resolution XPS image of the Zr 3d orbitals of UIO-66-NH2 and UIO-66-NH2-supported indium sulfide photocatalysts; Figure c is the high-resolution XPS image of the C 1s orbitals of UIO-66-NH2 and UIO-66-NH2-supported indium sulfide photocatalysts; Figure d is the high-resolution XPS image of the In 3d orbitals of indium sulfide and UIO-66-NH2-supported indium sulfide photocatalysts; and Figure e is the high-resolution XPS image of the N 1s orbitals of UIO-66-NH2 and UIO-66-NH2-supported indium sulfide photocatalysts.

[0031] Figure 4 The solid-state ultraviolet diffuse reflectance spectra of UIO-66-NH2, indium sulfide, and UIO-66-NH2-supported indium sulfide photocatalysts in Examples 1, 2, and 4 of this invention are shown.

[0032] Figure 5 The graph shows the concentration of hydrogen peroxide produced by photocatalysis under pure water conditions for five photocatalysts: UIO-66-NH2, indium sulfide, and UIO-66-NH2-supported indium sulfide (10%, 20%, and 50%) in Examples 1, 2, 3, 4, and 5 of the present invention.

[0033] Figure 6 The graph shows the concentration of hydrogen peroxide produced by the photocatalytic indium sulfide photocatalyst supported on UIO-66-NH2 in different gas environments. Detailed Implementation

[0034] The present invention will be further described below with reference to the accompanying drawings and specific preferred embodiments.

[0035] Example 1: A method for preparing a UIO-66-NH2 photocatalyst, comprising the following steps:

[0036] 1) Zirconium tetrachloride, 2-aminoterephthalic acid and acetic acid in a molar ratio of 1:1:200 were dissolved in DMF solution, and after ultrasonic treatment for 20 min, the solution was magnetically stirred at 800 r / min for 2 h to obtain a homogeneous solution.

[0037] 2) Transfer the mixture from step 1) to a polytetrafluoroethylene hydrothermal reactor for hydrothermal reaction. After cooling to room temperature, centrifuge and wash to obtain a pale yellow UIO-66-NH2. The hydrothermal reaction temperature is 110-120 ℃ and the hydrothermal reaction time is 23-25 ​​h.

[0038] Example 2, a method for preparing an indium sulfide photocatalyst, comprising the following steps:

[0039] 1) Dissolve InCl3·4H2O and thioacetamide in a molar ratio of 1:5 in a mixed solution of glycerol and water, wherein the volume ratio of glycerol to water is 1:4, and stir at 1200 r / min for 20 min to obtain a homogeneous solution.

[0040] 2) Transfer the mixture obtained in step 1) to a high-pressure hydrothermal reactor for hydrothermal reaction. After cooling to room temperature, wash and dry to obtain an orange-yellow powder, which is an indium sulfide photocatalyst. The hydrothermal reaction temperature is 170-180 ℃ and the hydrothermal reaction time is 23-25 ​​h.

[0041] Example 3: A UIO-66-NH2 supported indium sulfide photocatalyst for photocatalytic hydrogen peroxide production. The synthesis of this photocatalyst includes the following steps:

[0042] 1) Zirconium tetrachloride, 2-aminoterephthalic acid and acetic acid in a molar ratio of 1:1:200 were dissolved in DMF solution, and after ultrasonic treatment for 20 min, the solution was magnetically stirred at 800 r / min for 2 h to obtain a homogeneous solution.

[0043] 2) Transfer the mixture from step 1) to a polytetrafluoroethylene hydrothermal reactor for hydrothermal reaction. After cooling to room temperature, centrifuge and wash to obtain pale yellow UIO-66-NH2. The hydrothermal reaction temperature is 110-120 ℃ and the hydrothermal reaction time is 23-25 ​​h.

[0044] 3) Dissolve the UIO-66-NH2 obtained in step 2) in a mixed solution of glycerol and water at a mass ratio of 1:9 to UIO-66-NH2 and indium sulfide. Then add InCl3·4H2O and thioacetamide. Stir at 1200 r / min for 20 min and transfer to a high-pressure hydrothermal reactor for the second hydrothermal reaction. Cool to room temperature, wash and dry to obtain an orange-yellow powder, which is the UIO-66-NH2-supported indium sulfide photocatalyst. The hydrothermal reaction temperature is 170-180 ℃ and the hydrothermal reaction time is 23-25 ​​h.

[0045] Example 4: A UIO-66-NH2 supported indium sulfide photocatalyst for photocatalytic hydrogen peroxide production. The synthesis of this photocatalyst includes the following steps:

[0046] 1) Zirconium tetrachloride, 2-aminoterephthalic acid and acetic acid in a molar ratio of 1:1:200 were dissolved in DMF solution, and after ultrasonic treatment for 20 min, the solution was magnetically stirred at 800 r / min for 2 h to obtain a homogeneous solution.

[0047] 2) Transfer the mixture from step 1) to a polytetrafluoroethylene hydrothermal reactor for hydrothermal reaction. After cooling to room temperature, centrifuge and wash to obtain pale yellow UIO-66-NH2. The hydrothermal reaction temperature is 110-120 ℃ and the hydrothermal reaction time is 23-25 ​​h.

[0048] 3) Dissolve the UIO-66-NH2 obtained in step 2) in a mixed solution of glycerol and water at a mass ratio of 1:4 to UIO-66-NH2 and indium sulfide. Then add InCl3·4H2O and thioacetamide. After stirring at 1200 r / min for 20 min, transfer to a high-pressure hydrothermal reactor for the second hydrothermal reaction. Cool to room temperature, wash and dry to obtain an orange-yellow powder, which is the UIO-66-NH2-supported indium sulfide photocatalyst. The hydrothermal reaction temperature is 170-180 ℃ and the hydrothermal reaction time is 23-25 ​​h.

[0049] The materials prepared above were characterized by scanning electron microscopy (SEM) and field emission electron microscopy (TEM). Figure 1 It can be seen that the synthesized composite material exhibits a core-shell monomer structure in which indium sulfide encapsulates the octahedral UIO-66-NH2.

[0050] Figure 2 This is the EDS elemental distribution diagram of the catalyst. The uniform distribution of elements such as Zr, C, N, and O indicates the successful synthesis of UIO-66-NH2. In addition, the distribution of In and S elements is concentrated on the periphery, which is strong evidence of the formation of the core-shell structure.

[0051] The materials prepared above were characterized by XPS analysis. Figure 3 The XPS full spectrum of a shows that UIO-66-NH2-supported indium sulfide contains elements such as Zr, C, N, O, In, and S. The binding energy peaks of C 1s, N 1s, O 1s, Zr 3d, In 3d, and S 2p are 285.16 eV, 400.70 eV, 532.11 eV, 183.42 eV, 444.96 eV, and 161.80 eV, respectively. Figure 3 The high-resolution spectrum of Zr3d b shows two peaks at 182.56 eV and 184.92 eV, corresponding to Zr3d 5 / 2 and Zr 3d 3 / 2 The binding energy of the composite material is shifted towards lower binding energy compared to single UIO-66-NH2. Figure 3 The peaks at 288.67 eV, 286.22 eV, and 284.8 eV in the high-resolution C 1s spectrum of c represent the three coordination environments of OC=O, CN, and CC, respectively, indicating that the recombination process did not change its coordination environment. Figure 3 In 3d appears in the high-resolution spectrum of In 3d. 5 / 2 (444.47 eV) and In 3d 3 / 2 The two peaks (452.16 eV) indicate that In exists in the form of In. 3+ For indium sulfide alone, the binding energy of In also shifts towards lower binding energy after compositing. Figure 3 In the high-resolution N 1s spectrum of e, the binding energy of the material after recombination shifts to a higher region; the above results indicate that at the heterojunction interface of UIO-66-NH2-loaded indium sulfide, an electron redistribution occurs, with the amino group acting as an electron donor and the starting point of electron transfer, and Zr-O acting as an electron buffer; finally, electrons converge at In2S3, leading to a decrease in the In peak position.

[0052] The prepared materials were characterized using solid-state ultraviolet diffuse reflectance analysis, based on... Figure 4 The results showed that the light absorption edge of the material was in the range of 600-700 nm.

[0053] Example 5: A UIO-66-NH2 supported indium sulfide photocatalyst for photocatalytic hydrogen peroxide production. The synthesis of this photocatalyst includes the following steps:

[0054] 1) Zirconium tetrachloride, 2-aminoterephthalic acid and acetic acid in a molar ratio of 1:1:200 were dissolved in DMF solution, and after ultrasonic treatment for 20 min, the solution was magnetically stirred at 800 r / min for 2 h to obtain a homogeneous solution.

[0055] 2) Transfer the mixture from step 1) to a polytetrafluoroethylene hydrothermal reactor for hydrothermal reaction. After cooling to room temperature, centrifuge and wash to obtain pale yellow UIO-66-NH2. The hydrothermal reaction temperature is 110-120 ℃ and the hydrothermal reaction time is 23-25 ​​h.

[0056] 3) Dissolve the UIO-66-NH2 obtained in step 2) in a mixed solution of glycerol and water at a mass ratio of 1:1 to UIO-66-NH2 and indium sulfide. Then add InCl3·4H2O and thioacetamide. Stir at 1200 r / min for 20 min and transfer to a high-pressure hydrothermal reactor for the second hydrothermal reaction. Cool to room temperature, wash and dry to obtain an orange-yellow powder, which is the UIO-66-NH2-supported indium sulfide photocatalyst. The hydrothermal reaction temperature is 170-180 ℃ and the hydrothermal reaction time is 23-25 ​​h.

[0057] Ten mg of the catalysts prepared in Examples 1, 2, 3, 4, and 5 were ultrasonically dispersed in a photocatalytic tube containing 50 mL of pure water. Before the experiment, the tube was continuously stirred for 30 min in the dark with bubbling of oxygen to achieve adsorption equilibrium between the reactants. The photocatalytic tube was then placed on a stirring table and irradiated with a 300 W xenon lamp equipped with a 420 nm filter. A 1 mL sample was taken every 15 minutes for a total of 5 times. The concentration of H2O2 was determined using a combination of iodometric titration and ultraviolet spectrophotometry. First, the sampled solution was filtered through a 0.22 μm filter to remove residual catalyst. Then, 2 mL of 0.1 M KI solution and 50 μL of 0.01 M (NH4)2MoO4 solution were added to the treated solution. Under the catalytic action of the latter, hydrogen peroxide and iodide ions could generate an equal amount of elemental iodine. The concentration was measured at 350 nm using a UV-Vis spectrophotometer based on the colorimetric reaction. The absorbance value at a wavelength of nm is equivalent to the concentration of hydrogen peroxide on the standard curve.

[0058] Figure 5 The photocatalytic hydrogen peroxide production performance of UIO-66-NH2, indium sulfide, and UIO-66-NH2 supported on indium sulfide (10%, 20%, and 50%) in pure water was tested. The hydrogen peroxide yields of UIO-66-NH2 and indium sulfide were 1.48 μM and 2.57 μM, respectively, which were negligible. However, the hydrogen peroxide yield increased significantly after UIO-66-NH2 was supported on indium sulfide. With the increase of UIO-66-NH2 content, the hydrogen peroxide yield showed a trend of first increasing and then decreasing, reaching a maximum of 202.67 μM at a mass ratio of 20%. The above results indicate that the heterojunction formed by UIO-66-NH2 supported on indium sulfide can broaden the light absorption range, promote the separation of photogenerated electrons and holes, and has excellent photocatalytic performance.

[0059] Example 6: A photocatalyst for photocatalytic hydrogen peroxide production using UIO-66-NH2 supported indium sulfide, specifically using UIO-66-NH2 supported indium sulfide as the catalyst and a xenon lamp as the light source, involves a photocatalytic reaction in pure water, including the following steps:

[0060] Three 10 mg portions of UIO-66-NH2-supported indium sulfide (20%) were weighed and ultrasonically dispersed in photocatalytic tubes containing 50 mL of ultrapure water, respectively. Three different environmental atmospheres were created for these three photocatalytic tubes: the first tube was directly exposed to air without any gas treatment; the second tube was purged with oxygen; and the third tube was purged with nitrogen. All three photocatalytic tubes were stirred in the dark for 30 min until gas adsorption equilibrium was reached. Then, the light source was turned on, and the tubes were irradiated for 1 h under simulated natural light emitted by a xenon lamp equipped with a 420 nm filter to complete the photocatalytic hydrogen peroxide production reaction. The sample solution was filtered through a 0.22 μm filter membrane to remove residual catalyst. Then, 2 mL of 0.1 M KI solution and 50 μL of 0.01 M (NH4)2MoO4 solution were added to the treated solution. The absorbance value at 350 nm was measured using a UV-Vis spectrophotometer, and this value is equivalent to the hydrogen peroxide concentration on the standard curve.

[0061] Figure 6 The figure shows the hydrogen peroxide yield of the UIO-66-NH2-supported indium sulfide described in this invention under different atmospheric conditions. As shown in the figure, negligible hydrogen peroxide yield was observed under nitrogen atmosphere. The yields of hydrogen peroxide under air and oxygen atmospheres were 551.89 μmol / g / h and 1013.35 μmol / g / h, respectively, demonstrating the importance of oxygen in the photocatalytic hydrogen peroxide production of the catalyst material.

[0062] The above description is merely a preferred embodiment of the present invention, used to illustrate the technical solution of the present invention, and is not intended to limit the scope of protection of the present invention. For those skilled in the art, various equivalent substitutions or modifications can be made to the technical solution of the present invention without departing from the technical concept and essence of the present invention, and all such substitutions or modifications should fall within the scope of protection defined by the claims of the present invention.

Claims

1. A method for preparing an indium sulfide-supported UIO-66-NH2 heterojunction photocatalyst, characterized in that, Includes the following steps: Step 1: Zirconium tetrachloride, 2-aminoterephthalic acid, and acetic acid were dissolved in DMF solution at a ratio of 20.83 mg zirconium tetrachloride to 1 mL acetic acid, wherein the ratio of zirconium tetrachloride to DMF was 46.44 mg to 20 mL; the solution was ultrasonically treated for 20 min and magnetically stirred for 2 h to obtain a homogeneous solution. Step 2: Transfer the mixture from Step 1 to a polytetrafluoroethylene hydrothermal reactor and carry out a solvothermal reaction at 110-120 °C for 23-25 ​​h; after cooling to room temperature, centrifuge and wash to remove residual impurities, and finally dry in a vacuum oven to obtain a pale yellow UIO-66-NH2. Step 3: Dissolve the UIO-66-NH2 obtained in Step 2 in a mixed solution of glycerol and water, then add a certain amount of InCl3·4H2O and thioacetamide. Stir at 1200 r / min for 20 min, then transfer to a high-pressure hydrothermal reactor for the second hydrothermal reaction. After cooling to room temperature, wash and dry, the resulting orange-yellow powder is the UIO-66-NH2-supported indium sulfide photocatalyst. The hydrothermal reaction temperature is 170-180 ℃, and the hydrothermal reaction time is 23-25 ​​h.

2. The method for synthesizing the UIO-66-NH2 supported indium sulfide photocatalyst according to claim 1, characterized in that, The solid-liquid ratio of zirconium tetrachloride and acetic acid in step 1 is 20.83 mg: 1 mL.

3. The method for synthesizing the UIO-66-NH2 supported indium sulfide photocatalyst according to claim 1, characterized in that, The solid-liquid ratio of zirconium tetrachloride and DMF in step 1 is 46.44 mg: 20 mL.

4. The method for synthesizing the UIO-66-NH2 supported indium sulfide photocatalyst according to claim 1, characterized in that, In step 2, the centrifugation speed is 8000 rpm and the holding time is 3 min; the washing process involves washing with DMF and methanol 3 times each; the vacuum oven drying time is 11-13 h and the temperature is 60-70 ℃.

5. The method for synthesizing the UIO-66-NH2 supported indium sulfide photocatalyst according to claim 1, characterized in that, In step 3, the mass ratio of UIO-66-NH2 to indium sulfide is 1:9 to 1:1, and the volume ratio of glycerol to water is 1:4; the centrifugation speed is 8000 rpm, and the holding time is 3 min; the washing process involves washing twice with ultrapure water and ethanol respectively; the vacuum oven drying time is 11-13 h, and the temperature is 60-70 ℃.

6. The method according to claim 5, characterized in that, The UIO-66-NH2 supported indium sulfide photocatalyst is formed by indium sulfide encapsulating on the octahedral surface of UIO-66-NH2 to form petal-shaped nanospheres.

7. The application of a UIO-66-NH2 supported indium sulfide photocatalyst prepared by the synthesis method of claim 1 in the production of hydrogen peroxide from water under visible light.

8. The method according to any one of claims 6, characterized in that, The method for photocatalytic hydrogen peroxide production and concentration detection includes the following steps: Add 10 mg of UIO-66-NH2 supported indium sulfide photocatalyst to a photocatalytic tube containing 50 mL of ultrapure water. Under dark conditions, place the device on a magnetic stirring table and simultaneously introduce oxygen into the device to increase the dissolved oxygen content. A xenon lamp equipped with a 420 nm filter was used as a simulated visible light source for photocatalytic reaction. 1 mL of sample was taken every 15 min using a syringe and filtered through a 0.22 μm filter membrane for subsequent concentration testing. Add KI and (NH4)2MoO4 solution to the mixture in step 2) above and mix well. Detect the absorbance at 350 nm wavelength within 15 min and obtain the hydrogen peroxide concentration from the working curve.

9. The application according to claim 7, characterized in that, The stirring speed in step 1) is 1000-1100 r / min, and the stirring time is 1.0-1.5 h.

10. The application according to claim 7, characterized in that, In step 3), the concentration ratio of potassium iodide to ammonium molybdate is 10:1, and the volume ratio is 40:1.

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