Turing structure MOF composite material and preparation method and application thereof

Abstract

The application discloses a Turing structure MOF composite material and a preparation method and application thereof; the preparation method of the composite material is as follows: a surfactant is dissolved in an alcohol-water system, the MOF is mixed with the surfactant solution, oil bath treatment is carried out at 30-100 DEG C for 1-5 hours, then a metal source is added, and the oil bath treatment is continued at 30-100 DEG C for 1-5 hours, then microwave treatment is carried out at 700-900w for 1-5 minutes, and washing and drying are carried out, and the composite material is obtained; the application cuts the MOF surface by microwave-assisted control of the surfactant, obtains a Turing structure, and has the advantages of simple preparation method, high yield, good catalytic effect on organic pollutants, and degradation efficiency of 99.2%.

Description

TECHNICAL FIELD

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

[0002] Photocatalytic removal of persistent organic pollutants in water is considered as a promising technology. By using semiconductor photocatalysts such as TiO2, ZnO, Fe2O3, CuS, CdS, etc. under light irradiation, various persistent organic pollutants can be degraded into easily biodegradable compounds or less toxic organic and inorganic molecules such as CO2, H2O, NO 3- , PO4 3- , and halide ions. However, the low solar energy conversion efficiency, easy photo-corrosion, 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 a kind of coordination polymers with special porosity, which are composed of metal nodes or clusters that are coordinated with polydentate organic linkers to form 1, 2-dimensional structures. As a new 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 structure adjustability. Moreover, the confinement effect of MOF pores enhances the binding force of guest molecules, and is conducive to the realization of selectivity and the improvement of catalytic activity of substrate molecules. At the same time, the open channels are conducive to the transmission of substrate molecules, so that the substrate molecules can fully contact with the catalyst and improve the catalytic efficiency.

[0004] In recent years, the method of surfactant-assisted synthesis of multifunctional MOFs has attracted widespread attention, because it can be used as emulsifier, detergent, foaming agent, wetting agent or dispersant to change various unique MOF morphology. During the morphological change, ordered structures may be generated due to randomness. Turing explained the emergence of steady-state patterns by invoking the interaction between activators and inhibitors with different diffusion rates, and Turing's diffusion-reaction theory has been proven to be extremely influential in many disciplines, for example, the pigment patterns on seashells, the stripes on tropical fish, and the pure chemical system of greenalite-iodide-malonic acid have been studied as Turing patterns. In the control of crystal morphology, the hydrophobic long hydrocarbon chain groups of surfactants can preferentially adsorb on specific crystal MOF materials in aqueous solution, forming a periodic concentration gradient, which leads to the growth of one crystal face being significantly slower than other crystal faces, thereby forming a Turing structure. Research on this unique Turing-like morphology is crucial for catalytic degradation of dyes. SUMMARY

[0005] The application aims to provide a Turing structure MOF composite material and a preparation method and application thereof.

[0006] The MOF composite material with the unique Turing structure can selectively recognize and combine target molecules with high affinity as a photocatalyst, improve the adsorption capacity of target pollutants, and promote efficient degradation of dyes.

[0007] The technical scheme of the application is as follows:

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

[0009] The surfactant is dissolved in an alcohol-water system to obtain a surfactant solution, the MOF is mixed with the surfactant solution, oil bath treatment is performed at 30-100 DEG C (preferably 70 DEG C) for 1-5 hours (preferably 1 hour), then a metal source is added, and the oil bath treatment is continued at 30-100 DEG C (preferably 70 DEG C) for 1-5 hours (preferably 2 hours), then 700-900 W (preferably 800 W) microwave treatment is performed for 1-5 minutes (preferably 3 minutes), and washing and drying are performed to obtain the Turing structure MOF composite material;

[0010] In the formula, R is a C1-C6 alkyl group, preferably a methyl group; n is 1-3, preferably 2; and m is 1-3, preferably 2.

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

[0012] The alcohol-water system is preferably a methanol-water system with a volume ratio of 1:2;

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

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

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

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

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

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

[0019] The Turing structure MOF composite material described in the application can be used in the reaction of photocatalytic oxidation degradation of organic pollutants in water.

[0020] The Turing structure MOF composite material is added into wastewater containing organic pollutants, hydrogen peroxide is used as an oxidant, and the degradation reaction is carried out under the conditions of light, 20-60 DEG C, system pH = 3.0-7.0, and stirring rate 100-200 r / min, and the degradation of the organic pollutants is tested by absorbance.

[0021] Preferably, the addition amount of the Turing structure MOF composite material in the wastewater is 0.1-0.5 g / L.

[0022] The organic pollutants are, for example, reactive dyes, antibiotics, organic pesticides, etc.

[0023] The technical principle and beneficial effects of the application are as follows:

[0024] The application innovatively combines microwave assistance with surfactant modification, the MOF edge prepared can be observed to have a Turing structure, and the modified MOF has high photocatalytic performance. From the principle point of view, the hydrophobic groups on the surfactant can be adsorbed on the MOF surface to form a periodic concentration, and the surfactant is controlled to cut the MOF surface (etch the surface structure) through microwave assistance to form a Turing structure, increase the specific surface, expose more active sites, and enhance the photocatalytic oxidation efficiency.

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

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

[0027] Figure 2 : Degradation effect of the composite catalyst modified by sodium dodecyl sulfate on pollutants in Example 1 of the application. DETAILED DESCRIPTION

[0028] The application will be described in detail below in combination with specific examples, but the application is not limited to the following examples, and changes in implementation should be included in the technical scope of the application without departing from the content and scope of the application.

[0029] Example 1:

[0030] The sodium dodecyl sulfate is weighed, dissolved in a methanol-water system (V / V = 1:2), and configured into a solution with a concentration of 0.2 mol / L. 0.08 g of Ce-BDC and 20 mL of the sodium dodecyl sulfate solution are thoroughly mixed, and oil bath treatment is performed at 70°C for 1 h. After the oil bath, the solution is mixed with ferrocene, the mass concentration of the ferrocene is 5 g / L, and oil bath treatment is continued at 70°C for 2 h. The reaction mixture after the oil bath is transferred to a polytetrafluoroethylene tank, and microwave treatment is performed at a power of 800 w for 3 min. The product obtained by microwave treatment is washed with deionized water for 3 times, and dried at 60°C for 24 h. After drying, the photocatalytic composite material is obtained. It can be measured through experiments that the sample has good light Fenton catalytic capacity, and has good decomposition capacity for organic dyes and antibiotics.

[0031] Example 2:

[0032] The sodium dodecyl sulfate is weighed, dissolved in a methanol-water system (V / V = 1:2), and configured into a solution with a concentration of 0.2 mol / L. 0.08 g of Ce-BTC and 20 mL of the sodium dodecyl sulfate solution are thoroughly mixed, and oil bath treatment is performed at 70°C for 1 h. After the oil bath, the solution is mixed with ferrocene, the mass concentration of the ferrocene is 5 g / L, and oil bath treatment is continued at 70°C for 2 h. The reaction mixture after the oil bath is transferred to a polytetrafluoroethylene tank, and microwave treatment is performed at a power of 800 w for 3 min. The product obtained by microwave treatment is washed with deionized water for 3 times, and dried at 60°C for 24 h. After drying, the photocatalytic composite material is obtained. It can be measured through experiments that the sample has good light Fenton catalytic capacity, and has good decomposition capacity for organic dyes and antibiotics.

[0033] Example 3:

[0034] The cetyltrimethylammonium bromide is weighed, dissolved in a methanol-water system (V / V = 1:2), and configured into a solution with a concentration of 0.2 mol / L. 0.08 g of Ce-BDC and 20 mL of the cetyltrimethylammonium bromide solution are thoroughly mixed, and oil bath treatment is performed at 70°C for 1 h. After the oil bath, the solution is mixed with ferrocene, the mass concentration of the ferrocene is 5 g / L, and oil bath treatment is continued at 70°C for 2 h. The reaction mixture after the oil bath is transferred to a polytetrafluoroethylene tank, and microwave treatment is performed at a power of 800 w for 3 min. The product obtained by microwave treatment is washed with deionized water for 3 times, and dried at 60°C for 24 h. After drying, the photocatalytic composite material is obtained. It can be measured through experiments that the sample has good light Fenton catalytic capacity, and has good decomposition capacity for organic dyes and antibiotics.

[0035] Example 4:

[0036] Take octadecyl trimethyl ammonium bromide, dissolved in methanol-water system (V / V = 1:2), configured into a concentration of 0.2mol / L solution. 0.08g Ce-BDC and 20mL octadecyl trimethyl ammonium bromide solution is mixed thoroughly, oil bath treatment at 70℃ for 1h. After oil bath, the solution is mixed with ferrocene, the mass concentration of ferrocene is 5g / L, continue oil bath treatment at 70℃ for 2h, the reaction mixture after oil bath is transferred to a polytetrafluoroethylene tank, microwave treatment at 800w power for 3min. The product obtained by microwave treatment is washed with deionized water for 3 times, dried at 60℃ for 24h, the dried product is the photocatalytic composite material. Through the experiment can be measured, this sample has good light Fenton catalytic ability, has good decomposition ability to organic dyes and antibiotics.

[0037] Example 5:

[0038] Take sodium dodecyl sulfate, dissolved in methanol-water system (V / V = 1:2), configured into a concentration of 0.2mol / L solution. 0.08g Cu-BDC and 20mL sodium dodecyl sulfate solution is mixed thoroughly, oil bath treatment at 70℃ for 1h. After oil bath, the solution is mixed with ferrocene, the mass concentration of ferrocene is 5g / L, continue oil bath treatment at 70℃ for 2h, the reaction mixture after oil bath is transferred to a polytetrafluoroethylene tank, microwave treatment at 800w power for 3min. The product obtained by microwave treatment is washed with deionized water for 3 times, dried at 60℃ for 24h, the dried product is the photocatalytic composite material. Through the experiment can be measured, this sample has good light Fenton catalytic ability, has good decomposition ability to organic dyes and antibiotics.

[0039] Example 6:

[0040] Take sodium dodecyl sulfate, dissolved in methanol-water system (V / V = 1:2), configured into a concentration of 0.2mol / L solution. 0.08g Al-BDC and 20mL sodium dodecyl sulfate solution is mixed thoroughly, oil bath treatment at 70℃ for 1h. After oil bath, the solution is mixed with ferrocene, the mass concentration of ferrocene is 5g / L, continue oil bath treatment at 70℃ for 2h, the reaction mixture after oil bath is transferred to a polytetrafluoroethylene tank, microwave treatment at 800w power for 3min. The product obtained by microwave treatment is washed with deionized water for 3 times, dried at 60℃ for 24h, the dried product is the photocatalytic composite material. Through the experiment can be measured, this sample has good light Fenton catalytic ability, has good decomposition ability to organic dyes and antibiotics.

[0041] Example 7:

[0042] The sodium dodecyl sulfate is weighed, dissolved in a methanol-water system (V / V = 1:2), and configured into a solution with a concentration of 0.2 mol / L. 0.08 g of Ce-BDC and 20 mL of the sodium dodecyl sulfate solution are thoroughly mixed, and oil bath treatment is performed at 30°C for 1 h. After the oil bath, the solution is mixed with ferrocene with a mass concentration of 5 g / L, and oil bath treatment is continued at 30°C for 2 h. The reaction mixture after the oil bath is transferred to a polytetrafluoroethylene tank, and microwave treatment is performed at a power of 800 w for 3 min. The product obtained by microwave treatment is washed with deionized water for 3 times, and dried at 60°C for 24 h. The photocatalytic composite material obtained after drying is obtained. It can be measured through experiments that this sample has good light Fenton catalytic capacity, and has good decomposition capacity for organic dyes and antibiotics.

[0043] Example 8:

[0044] The sodium dodecyl sulfate is weighed, dissolved in a methanol-water system (V / V = 1:2), and configured into a solution with a concentration of 0.2 mol / L. 0.08 g of Ce-BDC and 20 mL of the sodium dodecyl sulfate solution are thoroughly mixed, and oil bath treatment is performed at 30°C for 1 h. After the oil bath, the solution is mixed with ferrocene with a mass concentration of 5 g / L, and oil bath treatment is continued at 30°C for 2 h. The reaction mixture after the oil bath is transferred to a polytetrafluoroethylene tank, and microwave treatment is performed at a power of 800 w for 3 min. The product obtained by microwave treatment is washed with deionized water for 3 times, and dried at 60°C for 24 h. The photocatalytic composite material obtained after drying is obtained. It can be measured through experiments that this sample has good light Fenton catalytic capacity, and has good decomposition capacity for organic dyes and antibiotics.

[0045] Example 9:

[0046] The sodium dodecyl sulfate is weighed, dissolved in a methanol-water system (V / V = 1:2), and configured into a solution with a concentration of 0.2 mol / L. 0.08 g of Ce-BDC and 20 mL of the sodium dodecyl sulfate solution are thoroughly mixed, and oil bath treatment is performed at 30°C for 1 h. After the oil bath, the solution is mixed with ferrocene with a mass concentration of 5 g / L, and oil bath treatment is continued at 30°C for 2 h. The reaction mixture after the oil bath is transferred to a polytetrafluoroethylene tank, and microwave treatment is performed at a power of 800 w for 3 min. The product obtained by microwave treatment is washed with deionized water for 3 times, and dried at 60°C for 24 h. The photocatalytic composite material obtained after drying is obtained. It can be measured through experiments that this sample has good light Fenton catalytic capacity, and has good decomposition capacity for organic dyes and antibiotics.

[0047] Example 10:

[0048] Sodium dodecyl sulfate was weighed, dissolved in a methanol-water system (V / V = 1:2), and configured into a solution with a concentration of 0.2 mol / L. 0.08 g of Ce-BDC and 20 mL of the sodium dodecyl sulfate solution were thoroughly mixed, and oil bath treatment was performed at 70°C for 1 h. After the oil bath, the solution was mixed with ferrocene, the mass concentration of the ferrocene was 5 g / L, and oil bath treatment was continued at 70°C for 1 h. The reaction mixture after the oil bath was transferred to a polytetrafluoroethylene tank, and microwave treatment was performed at a power of 800 w for 3 min. The product obtained by microwave treatment was washed with deionized water 3 times, and dried at 60°C for 24 h. After drying, the photocatalytic composite material was obtained. It can be measured through experiments that this sample has good light Fenton catalytic capacity, and has good decomposition capacity for organic dyes and antibiotics.

[0049] Example 11:

[0050] Sodium dodecyl sulfate was weighed, dissolved in a methanol-water system (V / V = 1:2), and configured into a solution with a concentration of 0.2 mol / L. 0.08 g of Ce-BDC and 20 mL of the sodium dodecyl sulfate solution were thoroughly mixed, and oil bath treatment was performed at 70°C for 1 h. After the oil bath, the solution was mixed with ferrocene, the mass concentration of the ferrocene was 5 g / L, and oil bath treatment was continued at 70°C for 1 h. The reaction mixture after the oil bath was transferred to a polytetrafluoroethylene tank, and microwave treatment was performed at a power of 800 w for 3 min. The product obtained by microwave treatment was washed with deionized water 3 times, and dried at 60°C for 24 h. After drying, the photocatalytic composite material was obtained. It can be measured through experiments that this sample has good light Fenton catalytic capacity, and has good decomposition capacity for organic dyes and antibiotics.

[0051] Example 12:

[0052] Sodium dodecyl sulfate was weighed, dissolved in a methanol-water system (V / V = 1:2), and configured into a solution with a concentration of 0.2 mol / L. 0.08 g of Ce-BDC and 20 mL of the sodium dodecyl sulfate solution were thoroughly mixed, and oil bath treatment was performed at 70°C for 1 h. After the oil bath, the solution was mixed with ferrocene, the mass concentration of the ferrocene was 5 g / L, and oil bath treatment was continued at 70°C for 1 h. The reaction mixture after the oil bath was transferred to a polytetrafluoroethylene tank, and microwave treatment was performed at a power of 800 w for 3 min. The product obtained by microwave treatment was washed with deionized water 3 times, and dried at 60°C for 24 h. After drying, the photocatalytic composite material was obtained. It can be measured through experiments that this sample has good light Fenton catalytic capacity, and has good decomposition capacity for organic dyes and antibiotics.

[0053] Example 13:

[0054] The sodium dodecyl sulfate is weighed, dissolved in a methanol-water system (V / V = 1:2), and configured into a solution with a concentration of 0.2 mol / L. 0.08 g of Ce-BDC and 20 mL of the sodium dodecyl sulfate solution are thoroughly mixed, and oil bath treatment is performed at 70°C for 1 h. After the oil bath, the solution is mixed with ferrocene with a mass concentration of 5 g / L, and oil bath treatment is continued at 70°C for 5 h. The reaction mixture after the oil bath is transferred to a polytetrafluoroethylene tank, and microwave treatment is performed at a power of 800 w for 3 min. The product obtained by microwave treatment is washed with deionized water 3 times, and dried at 60°C for 24 h. The photocatalytic composite material obtained after drying is obtained. It can be measured through experiments that this sample has good light Fenton catalytic capacity and good decomposition capacity for organic dyes and antibiotics.

[0055] Example 14:

[0056] The sodium dodecyl sulfate is weighed, dissolved in a methanol-water system (V / V = 1:2), and configured into a solution with a concentration of 0.2 mol / L. 0.08 g of Ce-BDC and 20 mL of the sodium dodecyl sulfate solution are thoroughly mixed, and oil bath treatment is performed at 70°C for 1 h. After the oil bath, the solution is mixed with ferrocene with a mass concentration of 5 g / L, and oil bath treatment is continued at 70°C for 5 h. The reaction mixture after the oil bath is transferred to a polytetrafluoroethylene tank, and microwave treatment is performed at a power of 800 w for 3 min. The product obtained by microwave treatment is washed with deionized water 3 times, and dried at 60°C for 24 h. The photocatalytic composite material obtained after drying is obtained. It can be measured through experiments that this sample has good light Fenton catalytic capacity and good decomposition capacity for organic dyes and antibiotics.

[0057] Example 15:

[0058] The sodium dodecyl sulfate is weighed, dissolved in a methanol-water system (V / V = 1:2), and configured into a solution with a concentration of 0.2 mol / L. 0.08 g of Ce-BDC and 20 mL of the sodium dodecyl sulfate solution are thoroughly mixed, and oil bath treatment is performed at 70°C for 1 h. After the oil bath, the solution is mixed with ferrocene with a mass concentration of 5 g / L, and oil bath treatment is continued at 70°C for 5 h. The reaction mixture after the oil bath is transferred to a polytetrafluoroethylene tank, and microwave treatment is performed at a power of 800 w for 3 min. The product obtained by microwave treatment is washed with deionized water 3 times, and dried at 60°C for 24 h. The photocatalytic composite material obtained after drying is obtained. It can be measured through experiments that this sample has good light Fenton catalytic capacity and good decomposition capacity for organic dyes and antibiotics.

[0059] Example 16:

[0060] The sodium dodecyl sulfate is weighed, dissolved in a methanol-water system (V / V = 1:2), and configured into a solution with a concentration of 0.2 mol / L. 0.08 g of Ce-BDC and 20 mL of the sodium dodecyl sulfate solution are thoroughly mixed, and oil bath treatment is performed at 70°C for 1 h. After the oil bath, the solution is mixed with ferrocene, the mass concentration of the ferrocene is 4 g / L, and oil bath treatment is continued at 70°C for 2 h. The reaction mixture after the oil bath is transferred to a polytetrafluoroethylene tank, and microwave treatment is performed at a power of 800 w for 3 min. The product obtained by microwave treatment is washed with deionized water 3 times, and dried at 60°C for 24 h. After drying, the photocatalytic composite material is obtained. It can be measured through experiments that the sample has good light Fenton catalytic capacity, and has good decomposition capacity for organic dyes and antibiotics.

[0061] Example 17:

[0062] The sodium dodecyl sulfate is weighed, dissolved in a methanol-water system (V / V = 1:2), and configured into a solution with a concentration of 0.2 mol / L. 0.08 g of Ce-BDC and 20 mL of the sodium dodecyl sulfate solution are thoroughly mixed, and oil bath treatment is performed at 70°C for 1 h. After the oil bath, the solution is mixed with ferrocene, the mass concentration of the ferrocene is 4 g / L, and oil bath treatment is continued at 70°C for 2 h. The reaction mixture after the oil bath is transferred to a polytetrafluoroethylene tank, and microwave treatment is performed at a power of 800 w for 3 min. The product obtained by microwave treatment is washed with deionized water 3 times, and dried at 60°C for 24 h. After drying, the photocatalytic composite material is obtained. It can be measured through experiments that the sample has good light Fenton catalytic capacity, and has good decomposition capacity for organic dyes and antibiotics.

[0063] Example 18:

[0064] The sodium dodecyl sulfate is weighed, dissolved in a methanol-water system (V / V = 1:2), and configured into a solution with a concentration of 0.2 mol / L. 0.08 g of Ce-BDC and 20 mL of the sodium dodecyl sulfate solution are thoroughly mixed, and oil bath treatment is performed at 70°C for 1 h. After the oil bath, the solution is mixed with ferrocene, the mass concentration of the ferrocene is 4 g / L, and oil bath treatment is continued at 70°C for 2 h. The reaction mixture after the oil bath is transferred to a polytetrafluoroethylene tank, and microwave treatment is performed at a power of 800 w for 3 min. The product obtained by microwave treatment is washed with deionized water 3 times, and dried at 60°C for 24 h. After drying, the photocatalytic composite material is obtained. It can be measured through experiments that the sample has good light Fenton catalytic capacity, and has good decomposition capacity for organic dyes and antibiotics.

[0065] Example 19:

[0066] The sodium dodecyl sulfate was weighed, dissolved in a methanol-water system (V / V = 1:2), and configured into a solution with a concentration of 0.2 mol / L. 0.08 g of Ce-BDC and 20 mL of the sodium dodecyl sulfate solution were thoroughly mixed, and oil bath treatment was performed at 70°C for 1 h. After the oil bath, the solution was mixed with ferrocene, the mass concentration of the ferrocene was 8 g / L, and oil bath treatment was continued at 70°C for 2 h. The reaction mixture after the oil bath was transferred to a polytetrafluoroethylene tank, and microwave treatment was performed at a power of 800 w for 3 min. The product obtained by microwave treatment was washed with deionized water 3 times, and dried at 60°C for 24 h. After drying, the photocatalytic composite material was obtained. It can be measured through experiments that this sample has good light Fenton catalytic capacity, and has good decomposition capacity for organic dyes and antibiotics.

[0067] Example 20:

[0068] The sodium dodecyl sulfate was weighed, dissolved in a methanol-water system (V / V = 1:2), and configured into a solution with a concentration of 0.2 mol / L. 0.08 g of Ce-BDC and 20 mL of the sodium dodecyl sulfate solution were thoroughly mixed, and oil bath treatment was performed at 70°C for 1 h. After the oil bath, the solution was mixed with ferrocene, the mass concentration of the ferrocene was 5 g / L, and oil bath treatment was continued at 70°C for 2 h. The reaction mixture after the oil bath was transferred to a polytetrafluoroethylene tank, and microwave treatment was performed at a power of 800 w for 1 min. The product obtained by microwave treatment was washed with deionized water 3 times, and dried at 60°C for 24 h. After drying, the photocatalytic composite material was obtained. It can be measured through experiments that this sample has good light Fenton catalytic capacity, and has good decomposition capacity for organic dyes and antibiotics.

[0069] Example 21:

[0070] The sodium dodecyl sulfate was weighed, dissolved in a methanol-water system (V / V = 1:2), and configured into a solution with a concentration of 0.2 mol / L. 0.08 g of Ce-BDC and 20 mL of the sodium dodecyl sulfate solution were thoroughly mixed, and oil bath treatment was performed at 70°C for 1 h. After the oil bath, the solution was mixed with ferrocene, the mass concentration of the ferrocene was 5 g / L, and oil bath treatment was continued at 70°C for 2 h. The reaction mixture after the oil bath was transferred to a polytetrafluoroethylene tank, and microwave treatment was performed at a power of 800 w for 2 min. The product obtained by microwave treatment was washed with deionized water 3 times, and dried at 60°C for 24 h. After drying, the photocatalytic composite material was obtained. It can be measured through experiments that this sample has good light Fenton catalytic capacity, and has good decomposition capacity for organic dyes and antibiotics.

[0071] Example 22:

[0072] Sodium dodecyl sulfate was weighed, dissolved in a methanol-water system (V / V = 1:2) to prepare a solution with a concentration of 0.2 mol / L. 0.08 g of Ce-BDC and 20 mL of the sodium dodecyl sulfate solution were thoroughly mixed, and then treated in an oil bath at 70°C for 1 h. After oil bath treatment, the solution was mixed with ferrocene, and the mass concentration of ferrocene was 5 g / L. The mixture was continuously treated in an oil bath at 70°C for 2 h. The reaction mixture after oil bath treatment was transferred to a polytetrafluoroethylene tank, and then treated in a microwave at a power of 800 w for 4 min. The product obtained by microwave treatment was washed with deionized water for 3 times, and then dried at 60°C for 24 h. The photocatalytic composite material was obtained after drying. It can be measured by experiments that the sample has good light Fenton catalytic capacity, and has good decomposition capacity for organic dyes and antibiotics.

[0073] Example 23

[0074] Sodium dodecyl sulfate was weighed, dissolved in a methanol-water system (V / V = 1:2) to prepare a solution with a concentration of 0.2 mol / L. 0.08 g of Ce-BDC and 20 mL of the sodium dodecyl sulfate solution were thoroughly mixed, and then treated in an oil bath at 70°C for 1 h. After oil bath treatment, the solution was mixed with ferrocene, and the mass concentration of ferrocene was 5 g / L. The mixture was continuously treated in an oil bath at 70°C for 2 h. The reaction mixture after oil bath treatment was transferred to a polytetrafluoroethylene tank, and then treated in a microwave at a power of 800 w for 4 min. The product obtained by microwave treatment was washed with deionized water for 3 times, and then dried at 60°C for 24 h. The photocatalytic composite material was obtained after drying. It can be measured by experiments that the sample has good light Fenton catalytic capacity, and has good decomposition capacity for organic dyes and antibiotics.

[0075] Application example

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

[0077] The composite materials of Examples 2-23 were used in the light Fenton catalytic oxidation reaction in the same way, and the results are shown in Table 1.

[0078] Table 1

[0079] Examples % decolorization 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％ Example 11 75.3％ Example 12 71.2％ Example 13 78.2％ Example 14 77.1％ Example 15 76.8％ Example 16 71.5％ Example 17 70.5％ Example 18 72.2％ Example 19 82.2％ Example 20 80.2％ Example 21 80.0％ Example 22 79.8％ Example 23 78.7％

Claims

1. A method for preparing a Turing structure MOF composite material, characterized in that, Includes the following steps: The surfactant was dissolved in an alcohol-water system to obtain a surfactant solution. The MOF was mixed with the surfactant solution and treated in an oil bath at 30–100°C for 1–5 h. Then, a metal source was added and the oil bath treatment was continued at 30–100°C for 1–5 h. After that, it was microwaved at 700–900 W for 1–5 min, washed, and dried to obtain a Turing structure MOF composite material. in, The surfactant is selected from one or more of hexadecyltrimethylammonium bromide, sodium dodecyl 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, cobalt dicene, and nickel dicene.

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

3. The method for preparing the Turing structure MOF composite material as described in 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 as described in claim 1, characterized in that, The mass-to-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 as described in claim 1, characterized in that, The concentration of the metal source in the reaction mixture is 4–8 g / L.

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

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

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

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