Hollow tubular indium zinc sulfide photocatalytic material as well as preparation method and application thereof

Abstract

The invention discloses a hollow tubular indium zinc sulfide photocatalytic material as well as a preparation method and application thereof, and belongs to the field of photocatalysis. According to the preparation method, rod-shaped MIL-68 (In)-NH2 is taken as a template, a ZnIn2S4 sheet layer is grown on the MIL-68 (In)-NH2 in situ through a one-pot hydrothermal method, and under the hydrothermal condition, the MIL-68 (In)-NH2 structure is decomposed from the inside under the combined action of Zn < 2 + >, In < 3 + >, S < 2-> and water molecules, so that the hollow tubular ZnIn2S4 photocatalytic material is prepared. The hollow tubular structure can promote penetration and reflection of light, provide a large number of contactable reaction sites and accelerate diffusion of reactants and products. The photocatalytic material is used for photocatalytic oxygen reduction to generate H2O2 under visible light, has the advantages of simple preparation method and high visible light catalytic activity, and provides a green and sustainable way for generation of H2O2 through oxygen reduction.

Description

Technical Field

[0001] The present invention relates to the field of photocatalysis, and particularly to the application of a hollow tubular zinc indium sulfide photocatalytic material for visible light photocatalytic preparation of H2O2. Background Art

[0002] As a ternary metal sulfide, zinc indium sulfide (ZnIn2S4) has been widely studied in recent years due to its suitable band gap width, good stability, and adjustable morphology structure. Generally, ZnIn2S4 prepared by conventional methods presents a spherical morphology composed of aggregated lamellae, resulting in limited available reaction sites and being unfavorable for light absorption and mass transfer processes. The hollow tubular morphology can fully expose the reaction sites, promote light transmission and reflection, and is beneficial to the diffusion of reactants and products. Metal-organic framework materials (MOFs) are constructed by metal nodes and organic ligands through coordination bonds. Among them, MIL-68(In)-NH2 is a rod-shaped MOF material. The present invention uses MIL-68(In)-NH2 as a template and ingeniously synthesizes ZnIn2S4 with a hollow tubular structure, Zn 2+ , In 3+ and S 2- and the combined action of water molecules cause the structure of MIL-68(In)-NH2 to disintegrate from the inside, thereby preparing a hollow tubular ZnIn2S4 photocatalytic material.

[0003] Hydrogen peroxide (H2O2) is a widely used and environmentally friendly oxidant. Due to its high reactivity, sustainability, and operational safety, it has been widely used in environmental remediation, industrial production, and medical and health fields. In addition, as a carbon-neutral liquid fuel alternative, H2O2 provides a potential solution in alleviating climate change and environmental pollution. However, currently, the industrial production of H2O2 mainly relies on the anthraquinone process, which has high energy consumption, large raw material requirements, and is harmful to the environment. Visible light in sunlight accounts for about 46%, and generating H2O2 through visible light photocatalytic oxygen reduction reaction is a green and sustainable technology, which is of great significance for promoting the application of photocatalysis in energy regeneration. Summary of the Invention

[0004] The technical problem to be solved by the present invention is to provide a catalytic material capable of efficiently photocatalytically generating H2O2 under visible light and its preparation method.

[0005] The technical solution of the present invention is to provide a photocatalytic material, characterized in that: the photocatalytic material is hollow tubular zinc indium sulfide.

[0006] The present invention also provides a preparation method of the above photocatalytic material, comprising the following steps:

[0007] Step 1: Dissolve In(NO3)3·xH2O and 2-aminoterephthalic acid in N,N-dimethylformamide and stir for 2 - 3 h to obtain solution A.

[0008] Step 2: Place solution A in an oven for solvothermal reaction at 100 - 150 °C for 3 - 8 h to obtain MIL-68(In)-NH2.

[0009] Step 3: Mix a certain amount of deionized water and glycerol to obtain solution B.

[0010] Step 4: Ultrasonically disperse MIL-68(In)-NH2 in solution B for 10 - 30 min and stir for 10 - 30 min to obtain solution C.

[0011] Step 5: Add ZnCl2, InCl3·4H2O and thioacetamide to solution C in sequence and stir for more than 30 min to obtain solution D.

[0012] Step 6: Place solution D in an oven for solvothermal reaction at 150 - 200 °C for more than 10 h to obtain the photocatalytic material.

[0013] Specifically, in Step 1, dissolve In(NO3)3·xH2O and 2-aminoterephthalic acid in DMF and stir for 2.5 h to obtain solution A.

[0014] Step 2: Place solution A in an oven for solvothermal reaction at 125 °C for 5 h to obtain MIL-68(In)-NH2.

[0015] Step 3: Mix a certain amount of deionized water and glycerol to obtain solution B.

[0016] Step 4: Ultrasonically disperse MIL-68(In)-NH2 in solution B for 15 min and stir for 15 min to obtain solution C.

[0017] Step 5: Add ZnCl2, InCl3·4H2O and thioacetamide to solution C in sequence and stir for 30 min to obtain solution D.

[0018] Step 6: Place solution D in an oven for solvothermal reaction at 180 °C for 12 h to obtain the photocatalytic material.

[0019] In the above technical solution, the molar ratio of In(NO3)3·xH2O to 2-aminoterephthalic acid in Step 1 is 1.5:1;

[0020] In the above technical solution, the volume of N,N-dimethylformamide in Step 1 is 60 mL;

[0021] In the above technical solution, the volume of deionized water in step 3 is 32 mL, and the volume of glycerol is 8 mL;

[0022] In the above technical solution, the ratio of the amount of ZnCl2, InCl3·4H2O and thioacetamide in step 5 is 1:2:4;

[0023] The present invention also provides the use of the above-mentioned photocatalytic material in photocatalytically preparing H2O2 under visible light.

[0024] Compared with the prior art, the present invention has the following advantages after adopting the above scheme:

[0025] The present invention uses MIL-68(In)-NH2 as a template to ingeniously synthesize ZnIn2S4 with a hollow tubular structure. Compared with conventional ZnIn2S4, the hollow tubular ZnIn2S4 can promote the penetration and reflection of light, provide a large number of accessible reaction sites, and accelerate the diffusion of reactants and products, which is conducive to the photocatalytic reaction. The hollow tubular ZnIn2S4 can be used for photocatalytic generation of H2O2 under visible light. After 2h of visible light irradiation, the maximum H2O2 yield reaches 1153μmol·L -1 , which is 3.6 times the output of conventional ZnIn2S4. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 X-ray diffraction (XRD) patterns of the hollow tubular ZnIn2S4 material, conventional ZnIn2S4 material and MIL-68(In)-NH2 material prepared in Example 2;

[0027] Figure 2 Scanning electron microscope (SEM) images of the hollow tubular ZnIn2S4 material, conventional ZnIn2S4 material and MIL-68(In)-NH2 material prepared in Example 2;

[0028] Figure 3 Performance diagram of the hollow tubular ZnIn2S4 material, conventional ZnIn2S4 material and MIL-68(In)-NH2 material prepared in Examples 1-3 for photocatalytic generation of H2O2 under visible light; DETAILED DESCRIPTION

[0029] The present invention will be further described below with regard to specific embodiments:

[0030] Example 1

[0031] Dissolve 1.794 g of In(NO3)3·xH2O and 0.702 g of 2-aminoterephthalic acid in 60 mL of N,N-dimethylformamide, and then stir for 2.5 h. Place the mixture in a 100 mL autoclave and maintain it at 125 °C for 5 h. After cooling to room temperature, wash the sample with absolute ethanol and dry it in an oven at 80 °C to obtain the MIL-68(In)-NH2 material. Place 72 mg of MIL-68(In)-NH2 in a beaker containing 32 mL of deionized water and 8 mL of glycerol, sonicate for 15 min, stir for 15 min, and then add 0.1632 g of ZnCl2, 0.7032 g of InCl3·4H2O, and 0.36 g of thioacetamide. After stirring for another 30 min, place the mixture in a 100 mL autoclave and maintain it at 180 °C for 12 h. Wash the sample with deionized water and absolute ethanol and dry it in an oven at 80 °C to obtain the hollow tubular ZnIn2S4 material.

[0032] Example 2:

[0033] Dissolve 1.794 g of In(NO3)3·xH2O and 0.702 g of 2-aminoterephthalic acid in 60 mL of N,N-dimethylformamide, and then stir for 2.5 h. Place the mixture in a 100 mL autoclave and maintain it at 125 °C for 5 h. After cooling to room temperature, wash the sample with absolute ethanol and dry it in an oven at 80 °C to obtain the MIL-68(In)-NH2 material. Place 288 mg of MIL-68(In)-NH2 in a beaker containing 32 mL of deionized water and 8 mL of glycerol, sonicate for 15 min, stir for 15 min, and then add 0.1632 g of ZnCl2, 0.7032 g of InCl3·4H2O, and 0.36 g of thioacetamide. After stirring for another 30 min, place the mixture in a 100 mL autoclave and maintain it at 180 °C for 12 h. Wash the sample with deionized water and absolute ethanol and dry it in an oven at 80 °C to obtain the hollow tubular ZnIn2S4 material.

[0034] Example 3:

[0035] 1.794 g of In(NO3)3·xH2O and 0.702 g of 2-aminoterephthalic acid were dissolved in 60 mL of N,N-dimethylformamide, and then stirred for 2.5 h. The mixed solution was placed in a 100 mL autoclave and maintained at 125 °C for 5 h. After cooling to room temperature, the sample was washed with absolute ethanol and dried in an oven at 80 °C to obtain the MIL-68(In)-NH2 material. 576 mg of MIL-68(In)-NH2 was placed in a beaker containing 32 mL of deionized water and 8 mL of glycerol, sonicated for 15 min, and after stirring for 15 min, 0.1632 g of ZnCl2, 0.7032 g of InCl3·4H2O and 0.36 g of thioacetamide were added. After stirring for another 30 min, the mixed solution was placed in a 100 mL autoclave and maintained at 180 °C for 12 h. The sample was washed with deionized water and absolute ethanol and dried in an oven at 80 °C to obtain the hollow tubular ZnIn2S4 material.

[0036] Figure 1 XRD pattern of the hollow tubular ZnIn2S4 material prepared in Example 2; it can be seen from the figure that the diffraction peaks of the hollow tubular ZnIn2S4 are consistent with those of the conventional ZnIn2S4, indicating the successful preparation of the ZnIn2S4 material.

[0037] Figure 2 SEM images of the conventional ZnIn2S4, MIL-68(In)-NH2 and the hollow tubular ZnIn2S4 prepared in Example 2; it can be seen from the figure that the ZnIn2S4 with a hollow tubular structure was successfully prepared.

[0038] The parameters of the photocatalytic test conditions are as follows:

[0039] Photocatalytic production of H2O2 test: 20 mg of the hollow tubular ZnIn2S4 was placed in 20 mL of deionized water. The mixed suspension was first stirred in the dark for 30 min, and then the reaction solution was placed under a 300 W xenon lamp equipped with a filter (light wavelength range: 400 - 780 nm) for photocatalytic reaction. During the photocatalytic reaction, samples were taken at regular intervals, filtered through a 0.22 μm nylon 66 filter head to remove the catalyst, and the filtrate samples were collected. The concentration of H2O2 was determined by iodometry at 350 nm using a UV-visible spectrophotometer.

[0040] The results of the visible-light photocatalytic preparation of H2O2 in the examples show that ( Figure 3 ), the performance of the hollow tubular ZnIn2S4 provided by the present invention is significantly better than that of the conventional ZnIn2S4 (318 μmol·L -1 ). Among them, in Example 2, after 2 h of visible-light irradiation, the yield of H2O2 reached 1153 μmol·L -1 .

[0041] In this invention, rod-shaped MIL-68(In)-NH2 is used as a template, and ZnIn2S4 nanosheets are in-situ grown on MIL-68(In)-NH2 by a one-pot hydrothermal method. Under hydrothermal conditions, the combined action of Zn 2+ , In 3+ , S 2- and water molecules causes the internal disintegration of the MIL-68(In)-NH2 structure, thereby preparing hollow tubular ZnIn2S4 photocatalytic material. The hollow tubular structure can promote light penetration and reflection, provide a large number of accessible reaction sites, and accelerate the diffusion of reactants and products. The photocatalytic material is used for photocatalytic oxygen reduction to generate H2O2 under visible light, and has the advantages of simple preparation method and high visible light photocatalytic activity, providing a green and sustainable approach for oxygen reduction to generate H2O2.

[0042] The above is only an illustration of the preferred embodiments of the present invention, and it should not be construed as a limitation of the claims. Any equivalent structure or equivalent process transformation made using the specification of the present invention is included within the scope of the patent protection of the present invention.

Claims

1. A photocatalytic material, characterized in that: The photocatalytic material is hollow tubular indium zinc sulfide.

2. The preparation method of the photocatalytic material according to claim 1, characterized in that: It includes the following steps. Step 1: Dissolve In(NO3)3·xH2O and 2-aminoterephthalic acid in N,N-dimethylformamide and stir for 2 - 3 h to obtain solution A. Step 2: Place solution A in an oven for solvothermal reaction at 100 - 150 °C for 3 - 8 h to obtain MIL-68(In)-NH2. Step 3: Mix a certain amount of deionized water and glycerol to obtain solution B. Step 4: Ultrasonically disperse MIL-68(In)-NH2 in solution B for 10 - 30 min and stir for 10 - 30 min to obtain solution C. Step 5: Add ZnCl2, InCl3·4H2O, and thioacetamide to solution C in sequence and stir for more than 30 min to obtain solution D. Step 6: Place solution D in an oven for solvothermal reaction at 150 - 200 °C for more than 10 h to obtain the photocatalytic material.

3. The preparation method of the photocatalytic material according to claim 1, wherein: It includes the following steps. Step 1: Dissolve In(NO3)3·xH2O and 2-aminoterephthalic acid in DMF and stir for 2.5 h to obtain solution A. Step 2: Place solution A in an oven for solvothermal reaction at 125 °C for 5 h to obtain MIL-68(In)-NH2. Step 3: Mix a certain amount of deionized water and glycerol to obtain solution B. Step 4: Ultrasonically disperse MIL-68(In)-NH2 in solution B for 15 min and stir for 15 min to obtain solution C. Step 5: Add ZnCl2, InCl3.4H2O, and thioacetamide to solution C in sequence and stir for 30 min to obtain solution D. Step 6: Place solution D in an oven for solvothermal reaction at 180 °C for 12 h to obtain the photocatalytic material.

4. The preparation method of the photocatalytic material according to claim 3, characterized in that: The molar ratio of In(NO3)3·xH2O to 2-aminoterephthalic acid in step 1 is 1.5:

1.

5. The preparation method of the photocatalytic material according to claim 3, characterized in that: The volume of N,N-dimethylformamide in step 1 is 60 mL.

6. The preparation method of the photocatalytic material according to claim 3, wherein: The volume of deionized water in step 3 is 32 mL, and the volume of glycerol is 8 mL.

7. The preparation method of the photocatalytic material according to claim 3, characterized in that: The molar ratio of ZnCl2, InCl3·4H2O, and thioacetamide in step 5 is 1:2:

4.

8. Application of a catalyst prepared from the photocatalytic material as described in claim 1 or the preparation method of the photocatalytic material as described in any one of claims 2 - 7 in photocatalytic generation of H2O2 under visible light.

Images