A hydrophobic indium zinc sulfide-based photocatalytic material for use in a two-phase system reaction and a preparation method thereof

Abstract

The application discloses a kind of hydrophobic indium zinc sulfide-based photocatalytic materials for two-phase system reaction and preparation method thereof, belong to photocatalysis field.The application constructs a kind of water-toluene two-phase system, and there is reactant benzyl alcohol in toluene phase, and hydrophobic Zn3In2S6-based photocatalytic material (Zn3In2S6 / MIL-53-NH2) is prepared for photocatalytic preparation H2O2 and benzaldehyde simultaneously.Hydrophobic Zn3In2S6 / MIL-53-NH2 and generated benzaldehyde exist in toluene phase, and generated H2O2 exists in water phase.The photocatalytic system not only makes full use of photo-generated electrons and holes, promotes the separation of carriers, but also realizes the spontaneous separation of product, the preparation of high value-added chemical benzaldehyde while inhibiting the decomposition of H2O2.The photocatalytic material has the advantages of simple preparation method, high visible light catalytic activity, provides a kind of green, efficient, energy-saving and sustainable way for the preparation of oxygen reduction H2O2 and high value-added chemicals.

Description

Technical Field

[0001] This invention relates to the field of photocatalysis, specifically to a hydrophobic indium zinc sulfide-based photocatalytic material used in a two-phase system for the simultaneous visible light photocatalytic preparation of H2O2 and benzaldehyde. Background Technology

[0002] Hydrogen peroxide (H2O2) is a versatile and environmentally friendly oxidant, widely used in environmental remediation, industrial production, and healthcare due to its high reactivity, sustainability, and operational safety. However, current industrial H2O2 production primarily relies on the anthraquinone process, which is energy-intensive, requires large amounts of raw materials, and is environmentally harmful. Visible light accounts for approximately 46% of sunlight; therefore, photocatalytic oxygen reduction (O2) to produce H2O2 under visible light is a green and sustainable technology, significant for promoting the application of photocatalysis in energy regeneration. To achieve highly efficient photocatalytic H2O2 production, alcohol sacrificial agents are often added to the reaction system, but this introduces new problems: 1) increased production costs; 2) difficulties in product separation. Furthermore, the further photocatalytic decomposition of the generated H2O2 also limits the efficiency of photocatalytic H2O2 production. Therefore, new reaction systems need to be developed to address these issues.

[0003] Zinc indium sulfide (Zn3In2S6), a two-dimensional ternary metal sulfide, has been widely studied in recent years due to its excellent visible light absorption, suitable band structure, and good stability. This invention constructs a water-toluene biphase system, with benzyl alcohol present in the toluene phase, and prepares a hydrophobic Zn3In2S6-based photocatalyst (Zn3In2S6 / MII-53-NH2) for the simultaneous photocatalytic preparation of H2O2 and benzaldehyde. The hydrophobic Zn3In2S6 / MII-53-NH2 and the generated benzaldehyde exist in the toluene phase, while the generated H2O2 exists in the aqueous phase. This achieves spontaneous separation of the products, preparation of the high-value-added chemical benzaldehyde, and inhibition of H2O2 decomposition—a truly "three birds with one stone" approach. Summary of the Invention

[0004] The technical problem to be solved by the present invention is to provide a catalytic material and its preparation method that can efficiently photocatalyze the simultaneous preparation of H2O2 and benzaldehyde in a two-phase system under visible light.

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

[0006] The present invention also provides a method for preparing the above-mentioned photocatalytic material, comprising the following steps:

[0007] Step 1: Dissolve AlCl3·6H2O and 2-aminoterephthalic acid in deionized water and sonicate for 5-15 min to obtain solution A;

[0008] Step 2: Dissolve a certain amount of urea in solution A, and sonicate for 5-15 minutes to obtain solution B;

[0009] Step 3: Place solution B in an oven and perform a solvothermal reaction at 120-180℃ for 3-7 hours to obtain MIL-53-NH2;

[0010] Step 4: Disperse MIL-53-NH2 in deionized water by sonication for 20-40 min and stir for 20-40 min to obtain solution C;

[0011] Step 5: Add ZnSO4·7H2O, InCl3·4H2O and thioacetamide to solution C in sequence, stir for 20-40 min to obtain solution D;

[0012] Step 6: Add hexadecyltrimethylammonium bromide to solution D and stir for 20-40 minutes to obtain solution E;

[0013] Step 7: Place solution E in an oven and perform a solvothermal reaction at 150-210℃ for 8-16 hours to obtain the photocatalytic material.

[0014] Specifically, in step 1, AlCl3·6H2O and 2-aminoterephthalic acid are dissolved in deionized water and sonicated for 10 min to obtain solution A;

[0015] Step 2: Dissolve a certain amount of urea in solution A, sonicate for 10 minutes to obtain solution B;

[0016] Step 3: Place solution B in an oven and perform a solvothermal reaction at 150°C for 5 hours to obtain MIL-53(AI)-NH2;

[0017] Step 4: Disperse MIL-53-NH2 in deionized water by sonication for 30 min and stir for 30 min to obtain solution C;

[0018] Step 5: Add ZnSO4·7H2O, InCl3·4H2O and thioacetamide to solution C in sequence, stir for 30 min to obtain solution D;

[0019] Step 6: Add hexadecyltrimethylammonium bromide to solution D and stir for 30 min to obtain solution E;

[0020] Step 7: Place solution E in an oven and perform a solvothermal reaction at 180°C for 12 hours to obtain the photocatalytic material.

[0021] In the above technical solution, the molar ratio of AlCl3·6H2O, 2-aminoterephthalic acid and urea in steps 1 and 2 is 4:3:6.5;

[0022] In the above technical solution, the volume of deionized water in step 1 is 30 mL;

[0023] In the above technical solution, the volume of deionized water in step 4 is 70 mL;

[0024] In the above technical solution, the molar ratio of ZnSO4·7H2O, InCl3·4H2O, thioacetamide and hexadecyltrimethylammonium bromide in steps 5 and 6 is 4:3:12:1.8.

[0025] This invention also provides the application of the above-mentioned photocatalytic material in the simultaneous photocatalytic preparation of H2O2 and benzaldehyde under visible light in a two-phase system.

[0026] Compared with the prior art, the present invention has the following advantages after adopting the above solution:

[0027] This invention constructs a water-toluene biphase system, in which benzyl alcohol, a reactant, is present in the toluene phase. A hydrophobic Zn3In2S6-based photocatalytic material (Zn3In2S6 / MIL-53-NH2) is prepared for the simultaneous photocatalytic preparation of H2O2 and benzaldehyde. The hydrophobic Zn3In2S6 / MIL-53-NH2 and the generated benzaldehyde are present in the toluene phase, while the generated H2O2 is present in the aqueous phase. This photocatalytic system not only fully utilizes photogenerated electrons and holes and promotes carrier separation, but also achieves spontaneous product separation, the preparation of the high-value-added chemical benzaldehyde, and inhibits the decomposition of H2O2. Based on this, the prepared photocatalytic material achieves ultra-high H2O2 generation efficiency, with a maximum H2O2 yield of 12161 μmol·L after 2 hours of visible light irradiation. -1 Meanwhile, the yield of benzaldehyde was 79%. Attached Figure Description

[0028] Figure 1 a and b are the X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectra of the Zn3In2S6 / MIL-53-NH2 photocatalyst material, hydrophobic Zn3In2S6 and MIL-53-NH2 prepared in Example 2, respectively.

[0029] Figure 2 Scanning electron microscope (SEM) images and water contact angle photographs of the Zn3In2S6 / MIL-53-NH2 photocatalyst material, hydrophobic Zn3In2S6 and MIL-53-NH2 prepared in Example 2.

[0030] Figure 3a and b are performance graphs of the Zn3In2S6 / MIL-53-NH2 photocatalytic material, hydrophobic Zn3In2S6 and MIL-53-NH2 prepared in Examples 1-3, respectively, in the photocatalytic simultaneous generation of H2O2 and benzaldehyde in a two-phase system under visible light. Detailed Implementation

[0031] The present invention will be further described below with reference to specific embodiments:

[0032] Example 1

[0033] 966 mg of AlCl3·6H2O and 543 mg of 2-aminoterephthalic acid were dissolved in 30 mL of deionized water, followed by sonication for 10 min. The mixture was placed in a 100 mL high-pressure reactor and maintained at 150 °C for 5 h. After cooling to room temperature, the sample was washed with anhydrous ethanol and dried in an 80 °C oven to obtain the MIL-53-NH2 material. 69 mg of MIL-53-NH2 was placed in a beaker containing 70 mL of deionized water, sonicated for 30 min, and then 863 mg of ZnSO4·7H2O, 587 mg of InCl3·4H2O, and 902 mg of thioacetamide were added. After sonication for 30 min, 650 mg of hexadecyltrimethylammonium bromide was added. After sonication for another 30 minutes, the mixture was placed in a 100 mL high-pressure reactor and kept at 180 °C for 12 h. The sample was washed with deionized water and anhydrous ethanol and dried in an 80 °C oven to obtain Zn3In2S6 / MIL-53-NH2 material.

[0034] Example 2:

[0035] 966 mg of AlCl3·6H2O and 543 mg of 2-aminoterephthalic acid were dissolved in 30 mL of deionized water, followed by sonication for 10 min. The mixture was placed in a 100 mL high-pressure reactor and maintained at 150 °C for 5 h. After cooling to room temperature, the sample was washed with anhydrous ethanol and dried in an 80 °C oven to obtain the MIL-53-NH2 material. 154 mg of MIL-53-NH2 was placed in a beaker containing 70 mL of deionized water, sonicated for 30 min, and then 863 mg of ZnSO4·7H2O, 587 mg of InCl3·4H2O, and 902 mg of thioacetamide were added. After sonication for 30 min, 650 mg of hexadecyltrimethylammonium bromide was added. After sonication for another 30 minutes, the mixture was placed in a 100 mL high-pressure reactor and kept at 180 °C for 12 h. The sample was washed with deionized water and anhydrous ethanol and dried in an 80 °C oven to obtain Zn3In2S6 / MIL-53-NH2 material.

[0036] Example 3;

[0037] 966 mg of AlCl3·6H2O and 543 mg of 2-aminoterephthalic acid were dissolved in 30 mL of deionized water, followed by sonication for 10 min. The mixture was placed in a 100 mL high-pressure reactor and maintained at 150 °C for 5 h. After cooling to room temperature, the sample was washed with anhydrous ethanol and dried in an 80 °C oven to obtain the MIL-53-NH2 material. 265 mg of MIL-53-NH2 was placed in a beaker containing 70 mL of deionized water, sonicated for 30 min, and then 863 mg of ZnSO4·7H2O, 587 mg of InCl3·4H2O, and 902 mg of thioacetamide were added. After sonication for 30 min, 650 mg of hexadecyltrimethylammonium bromide was added. After sonication for another 30 minutes, the mixture was placed in a 100 mL high-pressure reactor and kept at 180 °C for 12 h. The sample was washed with deionized water and anhydrous ethanol and dried in an 80 °C oven to obtain Zn3In2S6 / MIL-53-NH2 material.

[0038] Figure 1 a and b are the XRD and FTIR spectra of the Zn3In2S6 / MIL-53-NH2 photocatalyst material and the hydrophobic Zn3In2S6 prepared in Example 2; as can be seen from the figures, the hydrophobic Zn3In2S6-based photocatalyst material was successfully prepared.

[0039] Figure 2 The SEM images and water contact angle photographs of the Zn3In2S6 / MIL-53-NH2 photocatalyst material and the hydrophobic Zn3In2S6 prepared in Example 2 further demonstrate the successful preparation of the hydrophobic Zn3In2S6-based photocatalyst material.

[0040] The photocatalytic test conditions are as follows:

[0041] Photocatalytic H2O2 generation test: 15 mg of hydrophobic Zn3In2S6-based photocatalyst material was placed in 15 mL of deionized water and 15 mL of 0.025 mmol·L⁻¹ hydrochloric acid. -1 The benzyl alcohol / toluene solution was used. The mixed suspension was stirred in the dark for 30 min, and then placed under a 300W xenon lamp (wavelength range: 400-780 nm) equipped with a filter for photocatalytic reaction. During the photocatalytic reaction, samples were taken from both the upper and lower layers at regular intervals, and the catalyst was filtered through a 0.22 μm filter. The filtrate samples were collected. The H₂O₂ concentration of the lower layer sample was determined by iodometric titration at 350 nm using a UV-Vis spectrophotometer, and the benzaldehyde yield of the upper layer sample was determined by gas chromatography.

[0042] The example demonstrates the photocatalytic simultaneous generation of H2O2 and benzaldehyde in a two-phase system under visible light. Figure 3The hydrophobic Zn3In2S6-based photocatalytic material provided by this invention exhibits excellent photocatalytic performance. In Example 2, after 2 hours of visible light irradiation, the yield of H2O2 reached 12161 μmol·L⁻¹. -1 Meanwhile, the yield of benzaldehyde was 79%.

[0043] This invention constructs a water-toluene biphase system, in which the reactant benzyl alcohol is present in the toluene phase, and prepares a hydrophobic Zn3In2S6-based photocatalytic material (Zn3In2S6 / MIL-53-NH2) for the simultaneous photocatalytic preparation of H2O2 and benzaldehyde. The hydrophobic Zn3In2S6 / MIL-53-NH2 and the generated benzaldehyde exist in the toluene phase, while the generated H2O2 exists in the aqueous phase. This photocatalytic system not only fully utilizes photogenerated electrons and holes and promotes carrier separation, but also achieves spontaneous product separation, simultaneously inhibiting the decomposition of H2O2 and the preparation of the high-value-added chemical benzaldehyde. The photocatalytic material has the advantages of simple preparation method and high visible light photocatalytic activity, providing a green, efficient, energy-saving, and sustainable pathway for the oxygen reduction to generate H2O2 and the preparation of high-value-added chemicals.

[0044] The above description only illustrates preferred embodiments of the present invention and should not be construed as limiting the scope of the claims. Any equivalent structural or procedural modifications made using this specification are included within the patent protection scope of the present invention.

Claims

1. A photocatalytic material, characterized in that: The photocatalytic material is a hydrophobic indium zinc sulfide-based material.

2. The method for preparing the photocatalytic material according to claim 1, characterized in that: Includes the following steps, Step 1: Dissolve AlCl3·6H2O and 2-aminoterephthalic acid in deionized water and sonicate for 5-15 min to obtain solution A; Step 2: Dissolve a certain amount of urea in solution A, and sonicate for 5-15 minutes to obtain solution B; Step 3: Place solution B in an oven and perform a solvothermal reaction at 120-180℃ for 3-7 hours to obtain MIL-53-NH2; Step 4: Disperse MIL-53-NH2 in deionized water by sonication for 20-40 min and stir for 20-40 min to obtain solution C; Step 5: Add ZnSO4·7H2O, InCl3·4H2O and thioacetamide to solution C in sequence, stir for 20-40 min to obtain solution D; Step 6: Add hexadecyltrimethylammonium bromide to solution D and stir for 20-40 minutes to obtain solution E; Step 7: Place solution E in an oven and perform a solvothermal reaction at 150-210℃ for 8-16 hours to obtain the photocatalytic material.

3. The method for preparing the photocatalytic material according to claim 1, characterized in that: Includes the following steps, Step 1: Dissolve AlCl3·6H2O and 2-aminoterephthalic acid in deionized water and sonicate for 10 min to obtain solution A; Step 2: Dissolve a certain amount of urea in solution A, sonicate for 10 minutes to obtain solution B; Step 3: Place solution B in an oven and perform a solvothermal reaction at 150°C for 5 hours to obtain MIL-53(AI)-NH2; Step 4: Disperse MIL-53-NH2 in deionized water by sonication for 30 min and stir for 30 min to obtain solution C; Step 5: Add ZnSO4·7H2O, InCl3·4H2O and thioacetamide to solution C in sequence, stir for 30 min to obtain solution D; Step 6: Add hexadecyltrimethylammonium bromide to solution D and stir for 30 min to obtain solution E; Step 7: Place solution E in an oven and perform a solvothermal reaction at 180°C for 12 hours to obtain the photocatalytic material.

4. The method for preparing the photocatalytic material according to claim 3, characterized in that: The molar ratio of AlCl3·6H2O, 2-aminoterephthalic acid, and urea in steps 1 and 2 is 4:3:6.

5.

5. The method for preparing the photocatalytic material according to claim 3, characterized in that: The volume of deionized water in step 1 is 30 mL.

6. The method for preparing the photocatalytic material according to claim 3, characterized in that: The volume of deionized water in step 4 is 70 mL.

7. The method for preparing the photocatalytic material according to claim 3, characterized in that: The molar ratio of ZnSO4·7H2O, InCl3·4H2O, thioacetamide, and hexadecyltrimethylammonium bromide in steps 5 and 6 is 4:3:12:1.

8.

8. The application of a catalyst prepared by the photocatalytic material as described in claim 1 or by the method for preparing the photocatalytic material as described in any one of claims 2-7 in the photocatalytic simultaneous generation of H2O2 and benzaldehyde under visible light in a two-phase system.

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