Composite TiO2 / ZnIn2S4 for removing bisphenol A and cooperatively generating hydrogen peroxide as well as preparation method and application of composite TiO2 / ZnIn2S4

Abstract

The invention relates to the technical field of photocatalyst nano materials, in particular to a composite material TiO2 / ZnIn2S4 for removing bisphenol A and cooperatively generating hydrogen peroxide as well as a preparation method and application of the composite material TiO2 / ZnIn2S4. Wherein the composite material is TiO2 / ZnIn2S4 which is formed by TiO2 and ZnIn2S4 and has a nano flower ball structure. By using the composite material TiO2 / ZnIn2S4 provided by the invention, bisphenol A removal and hydrogen peroxide generation can be realized, bisphenol A removal does not depend on large-scale instruments and equipment and specific professional places, the composite material can adapt to complex and changeable actual environments, and sewage after removal can be effectively reutilized.

Description

Technical Field

[0001] The invention relates to the technical field of photocatalyst nanomaterials, and in particular to a composite material TiO2 / ZnIn2S4 for removing synergistically generated hydrogen peroxide from bisphenol A, and a preparation method and application thereof. Background Art

[0002] Bisphenol A (BPA) is an important industrial raw material for a variety of daily necessities. It is mainly used in the production of polymer materials such as polycarbonate and epoxy resin, and can also be used in the production of consumer products such as building materials, can coatings, medical equipment, plastic containers and thermal paper. As one of the most widely used chemicals in industry, more than 100 tons of BPA are released into the environment every year around the world, and enter the ecosystem through industrial wastewater and sewage discharge, causing a variety of negative effects, such as interfering with the action process of hormones in organisms, causing abnormal growth, development and reproduction of organisms, and destroying the balance of the ecosystem. BPA has environmental, bioaccumulative and strong biological toxicity, posing a huge threat to human health. Because it is difficult to degrade under natural conditions, it has a certain degree of easy enrichment and persistence. The corresponding risk assessment results show that the environmental and health risks caused by the current BPA concentration cannot be ignored.

[0003] At present, organic wastewater is generally treated by methods such as adsorption, oxidation, biological treatment and advanced oxidation processes (AOPs). Among these methods, AOPs are widely used because they have a relatively high treatment efficiency for different types of sewage, and photocatalysis is a representative process. Compared with other treatment methods, the reaction conditions of photocatalysis are usually milder and more environmentally friendly, and the energy conversion efficiency is also more efficient, but there are also some defects. For example, the current research on the photocatalytic mechanism is still not in-depth enough, and the photochemical conversion efficiency is not ideal. In addition, in most cases, in order to more thoroughly degrade pollutants, reagents such as hydrogen peroxide (H2O2) are usually added to the reaction to produce sufficient active oxygen. However, the need for additional reagent addition may lead to a more complicated technical preparation process or additional transportation costs. In this case, it is crucial to find a suitable strategy to meet the demand for oxidants in the reaction while treating pollutants. Summary of the invention

[0004] In view of the above-mentioned deficiencies in the prior art, the object of the present invention is to provide a composite material TiO2 / ZnIn2S4 for removing synergistically generated hydrogen peroxide from bisphenol A and a preparation method and application thereof.

[0005] In order to achieve the above-mentioned object of the invention, the technical solution adopted by the present invention is:

[0006] In a first aspect, a composite material TiO2 / ZnIn2S4 for removing bisphenol A and synergistically generating hydrogen peroxide is provided, which is TiO2 / ZnIn2S4 having a nano-flower ball structure formed by TiO2 and ZnIn2S4.

[0007] In a second aspect, a method for preparing a composite material TiO2 / ZnIn2S4 for removing bisphenol A from synergistically generated hydrogen peroxide is provided, which comprises the following steps:

[0008] Dissolve TiO2 in H2O, adjust the pH to 1.5-3, add thioacetamide, ZnCl2, InCl3·4H2O, and stir to form a homogeneous solution; then put it in an 80°C oil bath and stir to react for 2-3 hours, centrifuge, wash and dry the obtained product to obtain a composite material TiO2 / ZnIn2S4.

[0009] Furthermore, the preparation method of TiO2 specifically comprises the following steps:

[0010] Ammonia water is added to anhydrous ethanol to form a homogeneous solution, tetraethyl silicate is added to react to form a precipitate, the precipitate is centrifuged, washed and dried to obtain white SiO2 balls;

[0011] SiO2 balls were dispersed in ethanol and ammonium hydroxide was added and stirred evenly at room temperature. Then tetrabutyl titanate was added at room temperature and stirred in a water bath at 45°C for 24 hours. The reaction generated a precipitate, which was centrifuged, washed and dried. After calcination, the solid was treated with HF solution to obtain TiO2 hollow balls.

[0012] In a third aspect, the application of the composite material TiO2 / ZnIn2S4 in the removal of bisphenol A is provided.

[0013] Furthermore, hydrogen peroxide may be co-generated during the bisphenol A removal process.

[0014] The beneficial effects of the present invention are:

[0015] The composite material TiO2 / ZnIn2S4 prepared by the present invention generates hydrogen peroxide during the catalytic degradation of the pollutant BPA, which can further promote the degradation of BPA in the system, making its BPA degradation performance better than that of commercial TiO2 materials and ZnIn2S4 materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 Schematic diagram of the preparation process of the composite material TiO2 / ZnIn2S4 in the embodiment (a); SEM image of TiO2 / ZnIn2S4 (b); TEM image (cd); analysis of the composition of each element in TiO2 / ZnIn2S4 (ej);

[0017] Figure 2The X-ray diffraction (XRD) pattern of the composite material TiO2 / ZnIn2S4 prepared in Example;

[0018] Figure 3 This is the performance diagram of the composite material TiO2 / ZnIn2S4, commercial TiO2 material and ZnIn2S4 material in the test example for degrading the organic pollutant BPA;

[0019] Figure 4 This is a graph of hydrogen peroxide generation concentration during the degradation of the organic pollutant BPA by the composite material TiO2 / ZnIn2S4, commercial TiO2 material and ZnIn2S4 material in the experimental example. DETAILED DESCRIPTION

[0020] The specific implementation modes of the present invention are described below so that those skilled in the art can understand the present invention. However, it should be clear that the present invention is not limited to the scope of the specific implementation modes. For those of ordinary skill in the art, as long as various changes are within the spirit and scope of the present invention as defined and determined by the attached claims, these changes are obvious, and all inventions and creations utilizing the concept of the present invention are protected.

[0021] Unless otherwise specified, the materials and reagents used in the following examples can be obtained from commercial sources.

[0022] Example

[0023] This embodiment provides a composite material TiO2 / ZnIn2S4, the preparation process of which is as follows:

[0024] Preparation of SiO2 balls: Add 24 mL of ammonia water (28%) to 81 mL of anhydrous ethanol to form a homogeneous solution. Add 4.2 mL of tetraethyl silicate dropwise. After stirring for 1 hour, white SiO2 balls are obtained, which are washed several times with deionized water and ethanol. Finally, the SiO2 balls are dried for later use.

[0025] Preparation of hollow TiO2 spheres: 0.2 g SiO2 spheres were added to 150 ml ethanol, 1 ml ammonium hydroxide was added, the mixed solution was stirred at room temperature for 60 min, then 2 mL tetrabutyl titanate was added at room temperature, and the mixture was stirred and reacted at 45 ° C for 24 hours. The mixture was washed with deionized water and ethanol, centrifuged 3 times, vacuum dried at 60 ° C for 10 hours, and calcined at 550 ° C for 2 hours to obtain SiO2 / TiO2. The SiO2 / TiO2 spheres were treated with 5% HF solution to remove SiO2. Finally, the obtained TiO2 was centrifuged, washed with deionized water and ethanol 3 times, and vacuum dried at 60 ° C for 10 hours for use.

[0026] Synthesis of core-shell TiO2 / ZnIn2S4 nanospheres: 95 mg of TiO2 hollow spheres were added to 100 mL of H2O, pH was adjusted to 1.5-3, and 0.2 mmol of thioacetamide, 0.2 mmol of ZnCl2 and 0.4 mmol of InCl3·4H2O were added after stirring for 20 minutes. The resulting mixture was stirred for 10 minutes and then placed in an oil bath at 80°C under continuous stirring. After reacting for 2 hours, the resulting product was centrifuged, washed and dried to obtain core-shell TiO2 / ZnIn2S4 nanospheres, i.e., composite material TiO2 / ZnIn2S4.

[0027] from Figure 1 It can be seen that the composite material TiO2 / ZnIn2S4 presents a nano-flower spherical structure under a microscope. Through transmission electron microscopy, it can be seen that TiO2 and ZnIn2S4 are closely connected together. The XRD pattern ( Figure 2 ) shows that the prepared TiO2 / ZnIn2S4 material was successfully synthesized to form a relatively tightly bonded TiO2 / ZnIn2S4 metal composite material.

[0028] Test example

[0029] In this test example, simulated wastewater was used to carry out a bisphenol A degradation test, and the degradation effects of the composite material TiO2 / ZnIn2S4 prepared in the example, the commercial TiO2 material and the ZnIn2S4 material were compared.

[0030] Dissolve 1 mg BPA in 50 ml deionized water (PH=11) to make the BPA concentration 20 mg / L to form simulated wastewater. Prepare 3 portions of simulated wastewater with the same BPA concentration according to the above method, and add the composite material TiO2 / ZnIn2S4 prepared in Example 1, commercial TiO2 material and ZnIn2S4 material into the 3 portions of simulated wastewater, respectively, with the dosage of 1 g / L, and the total dosage of each portion of simulated wastewater is 50 mg. React under visible light for 3 hours, and take samples at regular intervals to monitor the concentration of BPA and hydrogen peroxide in the simulated wastewater.

[0031] Figure 3 The results show that after 3 hours of reaction time, BPA in the simulated wastewater added with commercial TiO2 material is degraded by 10%, and BPA in the simulated wastewater added with commercial ZnIn2S4 material is degraded by 90%. The simulated wastewater added with the composite material TiO2 / ZnIn2S4 prepared in the example catalytically degrades more than 99% of BPA within 3 hours.

[0032] Figure 4The results show that after 3 hours of reaction time, only 88 μmol / L of hydrogen peroxide was generated in the simulated wastewater with the addition of commercial TiO2 material, 1147 μmol / L of hydrogen peroxide was generated in the simulated wastewater with the addition of commercial ZnIn2S4 material, and the simulated wastewater with the addition of the composite material TiO2 / ZnIn2S4 prepared in the example catalytically generated hydrogen peroxide concentration of 1441 μmol / L within 3 hours.

[0033] In summary, the composite material TiO2 / ZnIn2S4 prepared by the present invention can achieve the removal of bisphenol A and the synergistic generation of hydrogen peroxide, and make the water after removal treatment reusable, and BPA removal can be carried out on any commercial photocatalytic reaction device (or any other device that can simultaneously have sufficient light and water), so that the removal of bisphenol A does not rely on large-scale instruments and equipment and specific professional places, can adapt to complex and changeable actual environments, and truly realize the effective treatment and reuse of BPA-containing wastewater.

[0034] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the present invention can be implemented in other specific forms without departing from the spirit or essential features of the present invention. Therefore, the embodiments should be considered exemplary and non-restrictive in all respects, and the scope of the present invention is defined by the appended claims rather than the above description, and it is intended that all changes falling within the meaning and scope of the equivalent elements of the claims be included in the present invention.

[0035] In addition, it should be understood that although the present specification is described according to implementation modes, not every implementation mode contains only one independent technical solution. This description of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment may also be appropriately combined to form other implementation modes that can be understood by those skilled in the art.

Claims

1. A composite material TiO2 / ZnIn2S4 for removing synergistically generated hydrogen peroxide from bisphenol A, characterized in that: The composite material is TiO2 / ZnIn2S4 formed by TiO2 and ZnIn2S4 and having a nano flower ball structure.

2. A method for preparing a composite material TiO2 / ZnIn2S4 for removing bisphenol A from synergistically generated hydrogen peroxide, characterized in that: The following steps are involved: Dissolve TiO2 in H2O, adjust the pH to 1.5-3, add thioacetamide, ZnCl2, InCl3·4H2O, and stir to form a homogeneous solution; then put it in an 80°C oil bath and stir to react for 2-3 hours, centrifuge, wash and dry the obtained product to obtain a composite material TiO2 / ZnIn2S4.

3. The preparation method according to claim 1, characterized in that: The preparation method of TiO2 specifically comprises the following steps: Ammonia water is added to anhydrous ethanol to form a homogeneous solution, tetraethyl silicate is added to react to form a precipitate, the precipitate is centrifuged, washed and dried to obtain white SiO2 balls; SiO2 balls were dispersed in ethanol and ammonium hydroxide was added and stirred evenly at room temperature. Then tetrabutyl titanate was added at room temperature and stirred in a 45°C water bath for 24 hours. The reaction generated a precipitate, which was centrifugally washed and dried. After calcination, the solid was treated with HF solution to obtain TiO2 hollow balls.

4. Use of the composite material TiO2 / ZnIn2S4 according to claim 1 or the composite material TiO2 / ZnIn2S4 prepared by the method described in any one of claims 2 to 3 in the removal of bisphenol A.

5. The application according to claim 4, characterized in that: Can co-generate hydrogen peroxide during the bisphenol A removal process.

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