Turing structure MOF composite material and preparation method and application thereof

Abstract

The invention discloses a Turing structure MOF composite material and a preparation method and application thereof. The preparation method of the composite material comprises the following steps: dissolving a surfactant in an alcohol-water system, mixing MOF with a surfactant solution, carrying out oil bath treatment at 30-100 DEG C for 1-5 hours, then adding a metal source, continuing to carry out oil bath treatment at 30-100 DEG C for 1-5 hours, then carrying out 700-900w microwave treatment for 1-5 minutes, washing and drying to obtain the MOF / MOF composite material. The surface active agent is controlled to cut the MOF surface in a microwave-assisted manner to obtain the Tailing structure, the preparation method is simple, the yield is high, the obtained composite material has a very good catalytic effect on organic pollutants, and the degradation efficiency can reach 99.2%.

Description

Technical Field

[0001] The present invention relates to the technical field of environmental functional materials and wastewater treatment, and in particular to a Turing structure MOF composite material prepared by microwave-assisted surfactant modification and application thereof in polluted water treatment. Background Art

[0002] Photocatalytic removal of persistent organic pollutants in water is considered a promising technology. By using semiconductor photocatalysts such as TiO2, ZnO, Fe2O3, CuS, CdS, etc., various persistent organic pollutants can be degraded into easily biodegradable compounds or less toxic organic and inorganic molecules such as CO2, H2O, NO under light irradiation. 3- PO4 3- , and halide ions. However, the low solar energy conversion efficiency, susceptibility to photocorrosion, easy agglomeration, and difficulty in post-separation of these inorganic catalysts restrict the large-scale application of inorganic photocatalysts.

[0003] Metal-organic frameworks (MOFs) are coordination polymers with special pores, composed of metal nodes or clusters, which are coordinated with multidentate organic linkers to form 1- and 2-dimensional structures. As an emerging hybrid porous material, MOFs have attracted the attention of researchers in the field of catalysis due to their high porosity, large specific surface area, and adjustable structure. Moreover, the confinement effect of MOFs pores not only enhances the binding force of guest molecules, but also helps to achieve the selectivity of substrate molecules and improve catalytic activity. At the same time, open pores are conducive to the transmission of substrate molecules, allowing substrate molecules to fully contact with catalysts and improve catalytic efficiency.

[0004] In recent years, surfactant-assisted synthesis of multifunctional MOFs has attracted wide attention because it can act as an emulsifier, detergent, foaming agent, wetting agent or dispersant to change the morphological structure of various unique MOFs. During the morphological change, the ordered structure may be generated by randomness. Turing explained the emergence of steady-state patterns by invoking the interaction between activators and inhibitors with different diffusion rates. Turing's diffusion-reaction theory has proved to be very influential in many disciplines. For example, pigment patterns on shells, stripes on tropical fish, and the pure chemical system of chlorite-iodide-malonic acid have been studied as Turing patterns. In crystal morphology control, the hydrophobic long hydrocarbon chain groups of surfactants can be preferentially adsorbed on specific crystalline MOFs materials in aqueous solution, forming a periodic concentration gradient, resulting in one crystal face growing significantly slower than other crystal faces, thus forming a Turing structure. Studying this unique Turing-like morphological structure is crucial for catalytic degradation of dyes. Summary of the invention

[0005] The purpose of the present invention is to provide a Turing structure MOF composite material and its preparation method and application. The present invention uses microwave-assisted combined with surfactant modification to make the prepared MOF composite material exhibit a Turing structure, and has a larger specific surface area, which is more conducive to the catalytic reaction.

[0006] The MOF composite material with a unique Turing structure of the present invention can be used as a photocatalyst to selectively identify and bind to target molecules with high affinity, thereby improving the adsorption capacity of target pollutants and promoting efficient degradation of dyes.

[0007] The technical solution of the present invention is as follows:

[0008] A method for preparing a Turing structure MOF composite material comprises the following steps:

[0009] Dissolve the surfactant in an alcohol-water system to obtain a surfactant solution, mix the MOF with the surfactant solution, treat in an oil bath at 30-100° C. (preferably 70° C.) for 1-5 h (preferably 1 h), then add a metal source, continue the oil bath treatment at 30-100° C. (preferably 70° C.) for 1-5 h (preferably 2 h), then treat in a microwave at 700-900 W (preferably 800 W) for 1-5 min (preferably 3 min), wash, and dry to obtain a Turing structure MOF composite material;

[0010] in,

[0011] The surfactant is selected from one or more of hexadecyltrimethylammonium bromide, sodium dodecyl sulfate, and octadecyltrimethylammonium bromide, preferably sodium dodecyl sulfate;

[0012] The preferred alcohol-water system is a system of methanol-water V / V=1:2;

[0013] The concentration of the surfactant solution is preferably 0.05 to 0.25 mol / L;

[0014] MOF is selected from one or more of Ce-BDC, Ce-BTC, Al-BDC, and Cu-BDC, preferably Ce-BDC and Ce-BTC;

[0015] The preferred mass volume ratio of MOF to surfactant solution is 0.05-0.1:20, g / mL;

[0016] The metal source is selected from one or more of ferrocene, cobaltocene, and nickelocene, preferably ferrocene;

[0017] The concentration of the metal source in the reaction mixture is 4-8 g / L, preferably 5 g / L.

[0018] The invention relates to a Turing structure MOF composite material prepared by the preparation method.

[0019] The Turing structure MOF composite material of the present invention can be used in the photo-Fenton catalytic oxidation reaction to degrade organic pollutants in water. The specific application method is as follows:

[0020] The Turing structure MOF composite material was added to wastewater containing organic pollutants, and the degradation reaction was carried out under the conditions of light, 20-60°C, system pH=3.0-7.0, and stirring rate of 100-200r / min. The degradation of organic pollutants was tested by absorbance.

[0021] The preferred amount of Turing structure MOF composite material added to wastewater is 0.1-0.5 g / L;

[0022] Organic pollutants such as: reactive dyes, antibiotics, organic pesticides, etc.

[0023] The technical principle and beneficial effects of the present invention are:

[0024] The present invention innovatively combines microwave assistance with surfactant modification, and the Turing structure can be observed at the edge of the prepared MOF, and the modified MOF has efficient photocatalytic performance. From the perspective of principle, the hydrophobic groups on the surfactant can be adsorbed on the MOF surface to form a periodic concentration. The surfactant is controlled by microwave assistance to cut the MOF surface (etching the surface structure) to form a Turing structure, increase the specific surface area, expose more active sites, and enhance the photocatalytic oxidation efficiency.

[0025] The preparation method of the invention is simple and has a high yield. The formed Turing structure MOF composite material has an excellent catalytic effect on organic pollutants, and the degradation efficiency can reach 99.2%. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 : TEM electron microscope photo of SDS / Fc / Ce-BDC in Example 1 of the present invention.

[0027] Figure 2 : The degradation effect of the composite catalyst modified with sodium dodecyl sulfate on pollutants in Example 1 of the present invention. DETAILED DESCRIPTION

[0028] The present invention is described in detail below in conjunction with specific embodiments, but the present invention is not limited to the following embodiments. Without departing from the content and scope of the present invention, changes in implementation should be included in the technical scope of the present invention.

[0029] Embodiment 1:

[0030] Weigh sodium dodecyl sulfate and dissolve it in a methanol-water system (V / V=1:2) to prepare a solution with a concentration of 0.2 mol / L. Mix 0.08 g Ce-BDC and 20 mL sodium dodecyl sulfate solution thoroughly and treat it in an oil bath at 70°C for 1 h. After the oil bath, mix the solution with ferrocene, the mass concentration of ferrocene is 5 g / L, and continue to treat it in an oil bath at 70°C for 2 h. Transfer the reaction mixture after the oil bath to a polytetrafluoroethylene tank and treat it in a microwave at a power of 800w for 3 min. Wash the product obtained by microwave treatment with deionized water 3 times, dry it at 60°C for 24 h, and the photocatalytic composite material is obtained after drying. It can be measured experimentally that this sample has good photo-Fenton catalytic ability and has good decomposition ability for organic dyes and antibiotics.

[0031] Embodiment 2:

[0032] Weigh sodium dodecyl sulfate and dissolve it in a methanol-water system (V / V=1:2) to prepare a solution with a concentration of 0.2 mol / L. Mix 0.08 g Ce-BTC and 20 mL sodium dodecyl sulfate solution thoroughly and treat it in an oil bath at 70°C for 1 h. After the oil bath, mix the solution with ferrocene, the mass concentration of ferrocene is 5 g / L, and continue the oil bath treatment at 70°C for 2 h. Transfer the reaction mixture after the oil bath to a polytetrafluoroethylene tank and microwave it at a power of 800 w for 3 min. Wash the product obtained by microwave treatment with deionized water 3 times, dry it at 60°C for 24 h, and the photocatalytic composite material is obtained after drying. It can be measured experimentally that this sample has good photo-Fenton catalytic ability and has good decomposition ability for organic dyes and antibiotics.

[0033] Embodiment 3:

[0034] Weigh hexadecyltrimethylammonium bromide, dissolve it in a methanol-water system (V / V=1:2), and prepare a solution with a concentration of 0.2mol / L. Mix 0.08g Ce-BDC and 20mL hexadecyltrimethylammonium bromide solution thoroughly and treat it in an oil bath at 70℃ for 1h. After the oil bath, mix the solution with ferrocene, the mass concentration of ferrocene is 5g / L, and continue the oil bath treatment at 70℃ for 2h. Transfer the reaction mixture after the oil bath to a polytetrafluoroethylene tank and microwave it at a power of 800w for 3min. Wash the product obtained by microwave treatment with deionized water 3 times, dry it at 60℃ for 24h, and the photocatalytic composite material is obtained after drying. It can be measured through experiments that this sample has good photo-Fenton catalytic ability and has good decomposition ability for organic dyes and antibiotics.

[0035] Embodiment 4:

[0036] Weigh octadecyltrimethylammonium bromide, dissolve it in a methanol-water system (V / V=1:2), and prepare a solution with a concentration of 0.2mol / L. Mix 0.08g Ce-BDC and 20mL octadecyltrimethylammonium bromide solution thoroughly and treat it in an oil bath at 70℃ for 1h. After the oil bath, mix the solution with ferrocene, the mass concentration of ferrocene is 5g / L, and continue the oil bath treatment at 70℃ for 2h. Transfer the reaction mixture after the oil bath to a polytetrafluoroethylene tank and microwave it at a power of 800w for 3min. Wash the product obtained by microwave treatment with deionized water 3 times, dry it at 60℃ for 24h, and the photocatalytic composite material is obtained after drying. It can be measured through experiments that this sample has good photo-Fenton catalytic ability and has good decomposition ability for organic dyes and antibiotics.

[0037] Embodiment 5:

[0038] Weigh sodium dodecyl sulfate and dissolve it in a methanol-water system (V / V=1:2) to prepare a solution with a concentration of 0.2 mol / L. Mix 0.08 g Cu-BDC and 20 mL sodium dodecyl sulfate solution thoroughly and treat it in an oil bath at 70°C for 1 h. After the oil bath, mix the solution with ferrocene, the mass concentration of ferrocene is 5 g / L, and continue to treat it in an oil bath at 70°C for 2 h. Transfer the reaction mixture after the oil bath to a polytetrafluoroethylene tank and treat it in a microwave at a power of 800w for 3 min. Wash the product obtained by microwave treatment with deionized water 3 times, dry it at 60°C for 24 h, and the photocatalytic composite material is obtained after drying. It can be measured experimentally that this sample has good photo-Fenton catalytic ability and has good decomposition ability for organic dyes and antibiotics.

[0039] Embodiment 6:

[0040] Weigh sodium dodecyl sulfate and dissolve it in a methanol-water system (V / V=1:2) to prepare a solution with a concentration of 0.2 mol / L. Mix 0.08 g Al-BDC and 20 mL sodium dodecyl sulfate solution thoroughly and treat it in an oil bath at 70°C for 1 h. After the oil bath, mix the solution with ferrocene, the mass concentration of ferrocene is 5 g / L, and continue the oil bath treatment at 70°C for 2 h. Transfer the reaction mixture after the oil bath to a polytetrafluoroethylene tank and microwave it at a power of 800 w for 3 min. Wash the product obtained by microwave treatment with deionized water 3 times, dry it at 60°C for 24 h, and the photocatalytic composite material is obtained after drying. It can be measured experimentally that this sample has good photo-Fenton catalytic ability and has good decomposition ability for organic dyes and antibiotics.

[0041] Embodiment 7:

[0042] Weigh sodium dodecyl sulfate and dissolve it in a methanol-water system (V / V=1:2) to prepare a solution with a concentration of 0.2 mol / L. Mix 0.08 g Ce-BDC and 20 mL sodium dodecyl sulfate solution thoroughly and treat it in an oil bath at 30°C for 1 h. After the oil bath, mix the solution with ferrocene, the mass concentration of ferrocene is 5 g / L, and continue to treat it in an oil bath at 30°C for 2 h. Transfer the reaction mixture after the oil bath to a polytetrafluoroethylene tank and treat it in a microwave at a power of 800w for 3 min. Wash the product obtained by microwave treatment with deionized water 3 times, dry it at 60°C for 24 h, and the photocatalytic composite material is obtained after drying. It can be measured experimentally that this sample has good photo-Fenton catalytic ability and has good decomposition ability for organic dyes and antibiotics.

[0043] Embodiment 8:

[0044] Weigh sodium dodecyl sulfate and dissolve it in a methanol-water system (V / V=1:2) to prepare a solution with a concentration of 0.2 mol / L. Mix 0.08 g Ce-BDC and 20 mL sodium dodecyl sulfate solution thoroughly and treat it in an oil bath at 50°C for 1 h. After the oil bath, mix the solution with ferrocene, the mass concentration of ferrocene is 5 g / L, and continue to treat it in an oil bath at 50°C for 2 h. Transfer the reaction mixture after the oil bath to a polytetrafluoroethylene tank and treat it in a microwave at a power of 800w for 3 min. Wash the product obtained by microwave treatment with deionized water 3 times, dry it at 60°C for 24 h, and the photocatalytic composite material is obtained after drying. It can be measured experimentally that this sample has good photo-Fenton catalytic ability and has good decomposition ability for organic dyes and antibiotics.

[0045] Embodiment 9:

[0046] Weigh sodium dodecyl sulfate and dissolve it in a methanol-water system (V / V=1:2) to prepare a solution with a concentration of 0.2 mol / L. Mix 0.08 g Ce-BDC and 20 mL sodium dodecyl sulfate solution thoroughly and treat it in an oil bath at 100 ° C for 1 hour. After the oil bath, mix the solution with ferrocene, the mass concentration of ferrocene is 5 g / L, and continue to treat it in an oil bath at 100 ° C for 2 hours. Transfer the reaction mixture after the oil bath to a polytetrafluoroethylene tank and microwave it at a power of 800w for 3 minutes. Wash the product obtained by microwave treatment with deionized water 3 times, dry it at 60 ° C for 24 hours, and the photocatalytic composite material is obtained after drying. It can be measured through experiments that this sample has good photo-Fenton catalytic ability and has good decomposition ability for organic dyes and antibiotics.

[0047] Embodiment 10:

[0048] Weigh sodium dodecyl sulfate and dissolve it in a methanol-water system (V / V=1:2) to prepare a solution with a concentration of 0.2 mol / L. Mix 0.08 g Ce-BDC and 20 mL sodium dodecyl sulfate solution thoroughly and treat it in an oil bath at 70°C for 1 h. After the oil bath, mix the solution with ferrocene, the mass concentration of ferrocene is 5 g / L, and continue to treat it in an oil bath at 70°C for 1 h. Transfer the reaction mixture after the oil bath to a polytetrafluoroethylene tank and treat it in a microwave at a power of 800w for 3 min. Wash the product obtained by microwave treatment with deionized water 3 times, dry it at 60°C for 24h, and the photocatalytic composite material is obtained after drying. It can be measured experimentally that this sample has good photo-Fenton catalytic ability and has good decomposition ability for organic dyes and antibiotics.

[0049] Embodiment 11:

[0050] Weigh sodium dodecyl sulfate and dissolve it in a methanol-water system (V / V=1:2) to prepare a solution with a concentration of 0.2 mol / L. Mix 0.08 g Ce-BDC and 20 mL sodium dodecyl sulfate solution thoroughly and treat it in an oil bath at 70°C for 1 h. After the oil bath, mix the solution with ferrocene, the mass concentration of ferrocene is 5 g / L, and continue the oil bath treatment at 70°C for 3 h. Transfer the reaction mixture after the oil bath to a polytetrafluoroethylene tank and microwave it at a power of 800 w for 3 min. Wash the product obtained by microwave treatment with deionized water 3 times, dry it at 60°C for 24 h, and the photocatalytic composite material is obtained after drying. It can be measured through experiments that this sample has good photo-Fenton catalytic ability and has good decomposition ability for organic dyes and antibiotics.

[0051] Embodiment 12:

[0052] Weigh sodium dodecyl sulfate and dissolve it in a methanol-water system (V / V=1:2) to prepare a solution with a concentration of 0.2 mol / L. Mix 0.08 g Ce-BDC and 20 mL sodium dodecyl sulfate solution thoroughly and treat it in an oil bath at 70°C for 1 h. After the oil bath, mix the solution with ferrocene, the mass concentration of ferrocene is 5 g / L, and continue the oil bath treatment at 70°C for 4 h. Transfer the reaction mixture after the oil bath to a polytetrafluoroethylene tank and microwave it at a power of 800 w for 3 min. Wash the product obtained by microwave treatment with deionized water 3 times, dry it at 60°C for 24 h, and the photocatalytic composite material is obtained after drying. It can be measured experimentally that this sample has good photo-Fenton catalytic ability and has good decomposition ability for organic dyes and antibiotics.

[0053] Embodiment 13:

[0054] Weigh sodium dodecyl sulfate and dissolve it in a methanol-water system (V / V=1:2) to prepare a solution with a concentration of 0.2 mol / L. Mix 0.08 g Ce-BDC and 20 mL sodium dodecyl sulfate solution thoroughly and treat it in an oil bath at 70°C for 1 h. After the oil bath, mix the solution with ferrocene, the mass concentration of ferrocene is 5 g / L, and continue to treat it in an oil bath at 70°C for 5 h. Transfer the reaction mixture after the oil bath to a polytetrafluoroethylene tank and treat it in a microwave at a power of 800w for 3 min. Wash the product obtained by microwave treatment with deionized water 3 times, dry it at 60°C for 24 h, and the photocatalytic composite material is obtained after drying. It can be measured experimentally that this sample has good photo-Fenton catalytic ability and has good decomposition ability for organic dyes and antibiotics.

[0055] Embodiment 14:

[0056] Weigh sodium dodecyl sulfate and dissolve it in a methanol-water system (V / V=1:2) to prepare a solution with a concentration of 0.2mol / L. Mix 0.08g Ce-BDC and 20mL sodium dodecyl sulfate solution thoroughly and treat it in an oil bath at 70℃ for 1h. After the oil bath, mix the solution with nickelocene, the mass concentration of nickelocene is 5g / L, and continue the oil bath treatment at 70℃ for 2h. Transfer the reaction mixture after the oil bath to a polytetrafluoroethylene tank and microwave it at a power of 800w for 3min. Wash the product obtained by microwave treatment with deionized water 3 times, dry it at 60℃ for 24h, and the photocatalytic composite material is obtained after drying. It can be measured through experiments that this sample has good photo-Fenton catalytic ability and has good decomposition ability for organic dyes and antibiotics.

[0057] Embodiment 15:

[0058] Weigh sodium dodecyl sulfate and dissolve it in a methanol-water system (V / V=1:2) to prepare a solution with a concentration of 0.2 mol / L. Mix 0.08 g Ce-BDC and 20 mL sodium dodecyl sulfate solution thoroughly and treat it in an oil bath at 70°C for 1 h. After the oil bath, mix the solution with cobalt cyclopentadienyl (cobalt cyclopentadienyl) at a mass concentration of 5 g / L. Continue the oil bath treatment at 70°C for 2 h. Transfer the reaction mixture after the oil bath to a polytetrafluoroethylene tank and microwave it at a power of 800 w for 3 min. Wash the product obtained by microwave treatment with deionized water 3 times, dry it at 60°C for 24 h, and the photocatalytic composite material is obtained after drying. It can be measured experimentally that this sample has good photo-Fenton catalytic ability and has good decomposition ability for organic dyes and antibiotics.

[0059] Embodiment 16:

[0060] Weigh sodium dodecyl sulfate and dissolve it in a methanol-water system (V / V=1:2) to prepare a solution with a concentration of 0.2 mol / L. Mix 0.08 g Ce-BDC and 20 mL sodium dodecyl sulfate solution thoroughly and treat it in an oil bath at 70°C for 1 h. After the oil bath, mix the solution with ferrocene, the mass concentration of ferrocene is 4 g / L, and continue to treat it in an oil bath at 70°C for 2 h. Transfer the reaction mixture after the oil bath to a polytetrafluoroethylene tank and treat it in a microwave at a power of 800 w for 3 min. Wash the product obtained by microwave treatment with deionized water 3 times, dry it at 60°C for 24 h, and the photocatalytic composite material is obtained after drying. It can be measured through experiments that this sample has good photo-Fenton catalytic ability and has good decomposition ability for organic dyes and antibiotics.

[0061] Embodiment 17:

[0062] Weigh sodium dodecyl sulfate and dissolve it in a methanol-water system (V / V=1:2) to prepare a solution with a concentration of 0.2 mol / L. Mix 0.08 g Ce-BDC and 20 mL sodium dodecyl sulfate solution thoroughly and treat it in an oil bath at 70°C for 1 h. After the oil bath, mix the solution with ferrocene, the mass concentration of ferrocene is 6 g / L, and continue to treat it in an oil bath at 70°C for 2 h. Transfer the reaction mixture after the oil bath to a polytetrafluoroethylene tank and treat it in a microwave at a power of 800w for 3 min. Wash the product obtained by microwave treatment with deionized water 3 times, dry it at 60°C for 24 h, and the photocatalytic composite material is obtained after drying. It can be measured experimentally that this sample has good photo-Fenton catalytic ability and has good decomposition ability for organic dyes and antibiotics.

[0063] Embodiment 18:

[0064] Weigh sodium dodecyl sulfate and dissolve it in a methanol-water system (V / V=1:2) to prepare a solution with a concentration of 0.2 mol / L. Mix 0.08 g Ce-BDC and 20 mL sodium dodecyl sulfate solution thoroughly and treat it in an oil bath at 70°C for 1 h. After the oil bath, mix the solution with ferrocene, the mass concentration of ferrocene is 7 g / L, and continue to treat it in an oil bath at 70°C for 2 h. Transfer the reaction mixture after the oil bath to a polytetrafluoroethylene tank and treat it in a microwave at a power of 800w for 3 min. Wash the product obtained by microwave treatment with deionized water 3 times, dry it at 60°C for 24 h, and the photocatalytic composite material is obtained after drying. It can be measured experimentally that this sample has good photo-Fenton catalytic ability and has good decomposition ability for organic dyes and antibiotics.

[0065] Embodiment 19:

[0066] Weigh sodium dodecyl sulfate and dissolve it in a methanol-water system (V / V=1:2) to prepare a solution with a concentration of 0.2 mol / L. Mix 0.08 g Ce-BDC and 20 mL sodium dodecyl sulfate solution thoroughly and treat it in an oil bath at 70°C for 1 hour. After the oil bath, mix the solution with ferrocene, the mass concentration of ferrocene is 8 g / L, and continue to treat it in an oil bath at 70°C for 2 hours. Transfer the reaction mixture after the oil bath to a polytetrafluoroethylene tank and treat it in a microwave at a power of 800w for 3 minutes. Wash the product obtained by microwave treatment with deionized water 3 times, dry it at 60°C for 24 hours, and the photocatalytic composite material is obtained after drying. It can be measured experimentally that this sample has good photo-Fenton catalytic ability and has good decomposition ability for organic dyes and antibiotics.

[0067] Embodiment 20:

[0068] Weigh sodium dodecyl sulfate and dissolve it in a methanol-water system (V / V=1:2) to prepare a solution with a concentration of 0.2 mol / L. Mix 0.08 g Ce-BDC and 20 mL sodium dodecyl sulfate solution thoroughly and treat it in an oil bath at 70°C for 1 h. After the oil bath, mix the solution with ferrocene, the mass concentration of ferrocene is 5 g / L, and continue to treat it in an oil bath at 70°C for 2 h. Transfer the reaction mixture after the oil bath to a polytetrafluoroethylene tank and treat it in a microwave at a power of 800w for 1 min. Wash the product obtained by microwave treatment with deionized water 3 times, dry it at 60°C for 24 h, and the photocatalytic composite material is obtained after drying. It can be measured experimentally that this sample has good photo-Fenton catalytic ability and has good decomposition ability for organic dyes and antibiotics.

[0069] Embodiment 21:

[0070] Weigh sodium dodecyl sulfate and dissolve it in a methanol-water system (V / V=1:2) to prepare a solution with a concentration of 0.2 mol / L. Mix 0.08 g Ce-BDC and 20 mL sodium dodecyl sulfate solution thoroughly and treat it in an oil bath at 70°C for 1 h. After the oil bath, mix the solution with ferrocene, the mass concentration of ferrocene is 5 g / L, and continue to treat it in an oil bath at 70°C for 2 h. Transfer the reaction mixture after the oil bath to a polytetrafluoroethylene tank and treat it in a microwave at a power of 800w for 2 min. Wash the product obtained by microwave treatment with deionized water 3 times, dry it at 60°C for 24 h, and the photocatalytic composite material is obtained after drying. It can be measured experimentally that this sample has good photo-Fenton catalytic ability and has good decomposition ability for organic dyes and antibiotics.

[0071] Embodiment 22:

[0072] Weigh sodium dodecyl sulfate and dissolve it in a methanol-water system (V / V=1:2) to prepare a solution with a concentration of 0.2 mol / L. Mix 0.08 g Ce-BDC and 20 mL sodium dodecyl sulfate solution thoroughly and treat it in an oil bath at 70°C for 1 h. After the oil bath, mix the solution with ferrocene, the mass concentration of ferrocene is 5 g / L, and continue to treat it in an oil bath at 70°C for 2 h. Transfer the reaction mixture after the oil bath to a polytetrafluoroethylene tank and treat it in a microwave at a power of 800w for 4 min. Wash the product obtained by microwave treatment with deionized water 3 times, dry it at 60°C for 24 h, and the photocatalytic composite material is obtained after drying. It can be measured experimentally that this sample has good photo-Fenton catalytic ability and has good decomposition ability for organic dyes and antibiotics.

[0073] Embodiment 23:

[0074] Weigh sodium dodecyl sulfate and dissolve it in a methanol-water system (V / V=1:2) to prepare a solution with a concentration of 0.2 mol / L. Mix 0.08 g Ce-BDC and 20 mL sodium dodecyl sulfate solution thoroughly and treat it in an oil bath at 70°C for 1 h. After the oil bath, mix the solution with ferrocene, the mass concentration of ferrocene is 5 g / L, and continue to treat it in an oil bath at 70°C for 2 h. Transfer the reaction mixture after the oil bath to a polytetrafluoroethylene tank and treat it in a microwave at a power of 800w for 5 min. Wash the product obtained by microwave treatment with deionized water 3 times, dry it at 60°C for 24 h, and the photocatalytic composite material is obtained after drying. It can be measured experimentally that this sample has good photo-Fenton catalytic ability and has good decomposition ability for organic dyes and antibiotics.

[0075] Application examples:

[0076] Taking the composite material SDS / Fc / CeBDC of Example 1 as an example, the application in the photo-Fenton catalytic oxidation reaction is described. 0.01g of the composite material SDS / Fc / CeBDC of Example 1 is added to 100mL of wastewater containing 20g / mL methylene blue, and 0.05mL of 30% hydrogen peroxide is used as an oxidant. The degradation reaction is carried out under the conditions of light, 25°C, system pH=5, and stirring rate of 200r / min, and the degradation is tested by absorbance.

[0077] The composite materials of Examples 2 to 23 were used for photo-Fenton catalytic oxidation reaction in the same manner. The results are shown in Table 1:

[0078] Table 1

[0079] Example Decolorization rate % Example 1 99.2％ Example 2 99.1％ Example 3 77.2％ Example 4 77.9％ Example 5 78.2％ Example 6 72.1％ Example 7 73.5％ Example 8 78.2％ Example 9 70.9％ Example 10 80.5％ Embodiment 11 75.3％ Example 12 71.2％ Example 13 78.2％ Embodiment 14 77.1％ Embodiment 15 76.8％ Example 16 71.5％ Embodiment 17 70.5％ Embodiment 18 72.2％ Embodiment 19 82.2％ Embodiment 20 80.2％ Embodiment 21 80.0％ Embodiment 22 79.8％ Embodiment 23 78.7％

Claims

1. A method for preparing a Turing structure MOF composite material, characterized in that: The steps include: The surfactant is dissolved in an alcohol-water system to obtain a surfactant solution, the MOF and the surfactant solution are mixed, and the mixture is treated in an oil bath at 30-100°C for 1-5 hours, and then a metal source is added, and the mixture is treated in an oil bath at 30-100°C for 1-5 hours, and then the mixture is treated in a microwave at 700-900W for 1-5 minutes, and then washed and dried to obtain a Turing structure MOF composite material; in, The surfactant is selected from one or more of hexadecyltrimethylammonium bromide, sodium lauryl sulfate, and octadecyltrimethylammonium bromide; MOF is selected from one or more of Ce-BDC, Ce-BTC, Al-BDC, and Cu-BDC; The metal source is selected from one or more of ferrocene, cobaltocene and nickelocene.

2. The method for preparing the Turing structure MOF composite material according to claim 1, characterized in that: The alcohol-water system is a system of methanol-water V / V=1:

2.

3. The method for preparing the Turing structure MOF composite material according to claim 1, characterized in that: The concentration of the surfactant solution is 0.05-0.25 mol / L.

4. The method for preparing the Turing structure MOF composite material according to claim 1, characterized in that: The mass volume ratio of MOF to surfactant solution is 0.05-0.1:20, g / mL.

5. The method for preparing the Turing structure MOF composite material according to claim 1, characterized in that: The concentration of the metal source in the reaction mixture is 4-8 g / L.

6. A Turing structure MOF composite material obtained by the preparation method according to any one of claims 1 to 5.

7. Use of the Turing structure MOF composite material as claimed in claim 6 in the photo-Fenton catalytic oxidation degradation of organic pollutants in water.

8. The use according to claim 7, characterized in that The application method is as follows: The Turing structure MOF composite material was added to wastewater containing organic pollutants, and the degradation reaction was carried out under the conditions of light, 20-60°C, system pH=3.0-7.0, and stirring rate of 100-200r / min. The degradation of organic pollutants was tested by absorbance. The addition amount of Turing structure MOF composite material to wastewater is 0.1-0.5 g / L; Organic pollutants include reactive dyes, antibiotics, and organic pesticides.

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