An interface coordination and covalent dual-anchored zeolite gel and a preparation method thereof

Abstract

The application discloses an interface coordination and covalent double-anchored zeolite gel and a preparation method thereof, and belongs to the technical field of gel material synthesis. The zeolite gel comprises the following materials in parts by mass: ZSM-5 zeolite 2-4 parts, APTES 0.2-0.5 parts, anhydrous toluene 10 parts, 3,4-DHBA 0.01-0.04 parts, ascorbic acid 0.1-0.2 parts, ferrous chloride tetrahydrate 0.03 parts, hydrogen peroxide 0.2 parts, sodium thiosulfate 0.2 parts, gel monomer 0.8-1.2 parts, 2-bromoisobutyryl bromide 0.4 parts, triethylamine 0.2-0.5 parts, carboxyethyl methacrylate 0.1 parts, cuprous bromide 0.01 parts, 2,2-bipyridine 0.01-0.05 parts and dimethylformamide 20.02 parts. Through innovative modification, anchoring and functional design, the utilization rate of zeolite, the interface stability, the adsorption performance and the cycle life are synergistically improved, and the industrial application of the zeolite gel composite material in the field of wastewater treatment and the like is promoted.

Description

Technical Field

[0001] This invention belongs to the field of gel material synthesis technology, specifically relating to a zeolite gel with interfacial coordination and covalent dual anchoring and its preparation method. Background Technology

[0002] Zeolites, with their regular microporous structure, excellent adsorption selectivity, and chemical stability, have broad application prospects in heavy metal ion adsorption and wastewater treatment. Gel materials, with their interconnected macroporous structure, good hydrophilicity, and deformation ability, can serve as carriers for the dispersion and fixation of functional particles. The zeolite-gel composite material formed by combining the two is expected to combine the high adsorption efficiency of zeolites with the mass transfer advantages of gels, becoming a research hotspot for novel high-efficiency adsorption materials. Currently, the composite of zeolites and gels is mostly prepared by physical blending or single chemical bond anchoring. Physical blending is simple to operate, but zeolite particles are prone to random aggregation in the gel matrix, leading to blockage of the microporous structure and insufficient exposure of adsorption sites, significantly reducing the adsorption utilization rate of zeolites and the adsorption capacity of the material. At the same time, the binding strength of physical adsorption is extremely low, easily resulting in zeolite detachment and gel structure damage during use, seriously affecting the service life and stability of the material.

[0003] While single chemical bond anchoring methods (such as single covalent or coordinate bonds) can improve the bonding strength between zeolite and gel and reduce zeolite agglomeration to some extent, they still have significant limitations: On the one hand, zeolite surface modification is mostly single functional group modification, lacking multiple reaction sites and failing to achieve multifunctional synergy such as adsorption, cross-linking, and response; on the other hand, single anchoring interfaces lack adaptive stress buffering capacity, and interfacial stress is easily generated during adsorption due to changes in zeolite particle volume, leading to chemical bond breakage and subsequent zeolite detachment. Furthermore, in existing zeolite-gel composites, metal ions (such as Fe) used to enhance adsorption performance... 2+ The adsorption sites are mostly introduced by simple doping, which can only serve as single adsorption sites and cannot achieve multifunctionality. At the same time, the materials lack effective redox gating mechanisms, and are prone to desorption and leakage after adsorbing heavy metal ions, causing secondary pollution. Furthermore, the adsorption sites are difficult to achieve efficient self-cleaning and regeneration, resulting in poor recycling performance of the materials and failing to meet the needs of practical engineering applications.

[0004] To address the technical pain points of existing technologies, such as zeolite agglomeration, pore blockage, low interfacial bonding strength, single function, and poor cycle stability, there is an urgent need to develop a novel zeolite-gel composite structure. Through innovative modification, anchoring, and functional design, the utilization rate of zeolite, interfacial stability, adsorption performance, and cycle life can be synergistically improved, thereby promoting the industrial application of zeolite-gel composite materials in wastewater treatment and other fields. Summary of the Invention

[0005] To overcome the shortcomings of the prior art, the present invention aims to provide a zeolite gel with interfacial coordination and covalent dual anchoring, and its preparation method. This involves introducing amino-catechol dual sites on the zeolite surface using a silane coupling agent, and utilizing Fe... 2+ Chelation achieves molecular rivet functional coupling—combining metal adsorption active sites, coordination crosslinking anchoring, and Fe... 2+ / Fe 3+ The triple action of redox cycles overcomes the problems of zeolite agglomeration and pore blockage caused by traditional physical blending; through in-situ photopolymerization, zeolite is covalently anchored to the inner wall of the gel macropores in a "honeycomb array," which, unlike physical embedding, preserves the interconnected pores while giving the zeolite complete accessibility; the coordination-covalent dual-anchoring interface has high bonding strength and adaptive stress buffering capacity; Fe 2+ It can catalyze the Fenton reaction in situ to achieve self-cleaning and regeneration of adsorption sites, solving the problem of traditional materials being difficult to regenerate after saturation and extending their service life.

[0006] To achieve the above objectives, the present invention employs the following technical solution: This invention provides a zeolite gel with interfacial coordination and covalent dual anchoring, comprising the following materials in parts by weight: 2-4 parts ZSM-5 zeolite, 0.2-0.5 parts APTES, 10 parts anhydrous toluene, 0.01-0.04 parts 3,4-DHBA (3,4-dihydroxybenzoic acid), 0.1-0.2 parts ascorbic acid, 0.03 parts ferrous chloride tetrahydrate, 0.2 parts hydrogen peroxide, 0.2 parts sodium thiosulfate, 0.8-1.2 parts gel monomer, 0.4 parts 2-bromoisobutyryl bromide, 0.2-0.5 parts triethylamine, 0.1 parts carboxyethyl methacrylate, 0.01 parts cuprous bromide, 0.01-0.05 parts 2,2-bipyridine, and 20.02 parts dimethylformamide.

[0007] Furthermore, the gel monomer comprises materials in the following mass ratio: acrylic acid: hydroxyethyl methacrylate: N,N-methylenebisacrylamide: polyethylene glycol diacrylate: photoinitiator = 1-3: 0.3-0.6: 1: 0.2-0.4: 0.05-0.15.

[0008] Furthermore, the preparation method of the gel monomer includes the following steps: I. Weigh 1-3 parts of acrylic acid and add it to 0.3-0.6 parts of hydroxyethyl methacrylate. Stir at 500 r / min for 30 min to obtain a monomer solution. II. Weigh 1 part of N,N-methylenebisacrylamide and add it to the monomer solution obtained in step I. Stir at 500 r / min for 30 min. Weigh 0.2-0.4 parts of polyethylene glycol diacrylate and add it to the solution. Continue stirring at the above speed for 30 min to obtain the crosslinking solution. III. Weigh 0.05-0.15 parts of photoinitiator and add it to the crosslinking solution obtained in step II. Stir at 500 r / min for 30 min, and then irradiate with light at 300 W and 420 nm for 3 min to obtain the gel monomer.

[0009] Furthermore, the photoinitiator described in step III is Irgacure 2959.

[0010] This invention also provides a method for preparing a zeolite gel with interfacial coordination and covalent dual anchoring, the steps of which are as follows: Step 1: Weigh 2-4 parts of ZSM-5 zeolite and add it to 10 parts of anhydrous toluene. Sonicate at 25 kHz for 20 min. Weigh 0.2-0.5 parts of APTES and add it to the mixture. Stir at 350 r / min for 30 min. Add glacial acetic acid to adjust the pH to 4-5. Then heat and reflux at 90℃ for 4 h while passing nitrogen gas at a flow rate of 30 mL / min. After cooling naturally to room temperature, wash the mixture three times each with deionized water and anhydrous ethanol to obtain aminated zeolite. Step 2: Add the ammoniated zeolite obtained in Step 1 to 30 parts of deionized water, weigh out 0.01-0.04 parts of 3,4-DHBA and add it to the water, heat at 80℃ for 6 hours and stir at 500 r / min to obtain modified zeolite. Step 3: Weigh 0.02 parts of dimethylformamide and add it to 15 parts of deionized water. Stir at 500 r / min for 30 min. Add the modified zeolite obtained in Step 2 and sonicate at 25 kHz for 20 min. Add 0.2-0.5 parts of triethylamine and stir at 500 r / min for 10 min. Add 0.4 parts of 2-bromoisobutyryl bromide and heat at 90℃ for 3 h. Then cool naturally to room temperature and wash with deionized water and anhydrous ethanol three times each. Dry at 65℃ for 24 h to obtain polymerized zeolite. Step 4: Weigh 0.1 parts of carboxyethyl methacrylate, 0.01 parts of cuprous bromide, and 0.01-0.05 parts of 2,2-bipyridine and add them to 20 parts of DMF. Stir at 500 r / min for 30 min to obtain a reaction solution. Add the polymerized zeolite obtained in Step 3 to the reaction solution and heat under reflux at 80℃ for 4 h. Then, allow it to cool naturally to room temperature and wash it three times each with deionized water and anhydrous ethanol. Dry it at 65℃ for 24 h to obtain the zeolite core-polymer. Step 5: Weigh 0.03 parts of ferrous chloride tetrahydrate and add it to 30 parts of deionized water. Stir at 500 r / min for 30 min. Add the zeolite core-polymer obtained in Step 4 and sonicate at 25 kHz for 15 min. Add 0.8-1.2 parts of gel monomer and stir at 350 r / min for 30 min. Heat at 60℃ for 12 h, then cool naturally to room temperature. Wash with deionized water and anhydrous ethanol three times each. Dry at 65℃ for 24 h to obtain the basic zeolite gel. Step 6: Weigh 0.1-0.2 parts of ascorbic acid and add it to 20 parts of deionized water. Stir at 500 r / min for 30 min to obtain solution A. Weigh 0.2 parts of hydrogen peroxide and add it to 10 parts of deionized water. Stir at 500 r / min for 30 min to obtain solution B. Weigh 0.2 parts of sodium thiosulfate and add it to 20 parts of deionized water. Stir at 500 r / min for 30 min to obtain solution C. Let the basic zeolite gel obtained in Step 5 stand for 20 min each in solutions A, B, and C. Wash it three times each with deionized water and anhydrous ethanol, and dry it at 65℃ for 24 h to obtain a zeolite gel with interfacial coordination and covalent double anchoring.

[0011] Compared with the prior art, the present invention has the following beneficial effects: This invention introduces amino groups and grafts catechol groups onto the surface of zeolite using a silane coupling agent, constructing an amino-catechin dual reaction site; and utilizes Fe 2+ Chelating with catechols enables multifunctional molecular coupling—serving as an active site for metal ion adsorption, as a dynamic cross-linking agent for coordination anchoring at the zeolite-gel interface, and via Fe... 2+ / Fe 3+ Reversible switching of valence states enables adsorption-reduction cycles in redox reactions. This dual-anchoring mechanism overcomes the problems of zeolite agglomeration and pore blockage caused by traditional physical blending.

[0012] This invention covalently anchors zeolite to the inner wall of the macropores of a gel in a "honeycomb array" structure through in-situ photopolymerization, which differs from traditional physical embedding methods. This structure retains the open channels of the gel while giving the zeolite complete accessibility; the coordination-covalent dual-anchoring interface makes the binding strength higher than that of physical adsorption, while also giving the interface an adaptive stress buffering capacity, enhancing the mechanical stability of the material.

[0013] This invention utilizes Fe 2+Its in-situ catalytic properties can trigger the Fenton reaction to achieve self-cleaning and regeneration of adsorption sites, solving the problem that traditional adsorption materials are difficult to regenerate after saturation and extending the service life of the materials. Attached Figure Description

[0014] Figure 1 This is a diagram illustrating the preparation method of the zeolite gel with interfacial coordination and covalent dual anchoring proposed in this application; Figure 2 A photograph of the interfacial coordination and covalently anchored zeolite gel prepared in this application; Figure 3 Degradation test diagrams of interfacial coordination and covalently anchored zeolite gels prepared for examples and comparative examples in RhB.

[0015] The accompanying drawings are provided to further illustrate the invention and form part of the specification. They are used together with the embodiments of the invention to explain the invention and do not constitute a limitation thereof. Detailed Implementation

[0016] To enable those skilled in the art to understand the features and effects of the present invention, the terms and expressions used in the specification and claims are explained and defined in general below. Unless otherwise specified, all technical and scientific terms used herein have the ordinary meaning understood by those skilled in the art regarding the present invention, and in case of conflict, the definitions in this specification shall prevail.

[0017] In this document, all features defined by numerical ranges or percentage ranges, such as numerical values, quantities, contents, and concentrations, are for the sake of brevity and convenience only. Accordingly, descriptions of numerical ranges or percentage ranges should be considered as covering and specifically disclosing all possible sub-ranges and individual numerical values ​​(including integers and fractions) within those ranges.

[0018] In this article, unless otherwise specified, “contains,” “includes,” “containing,” “has,” or similar terms cover the meanings of “composed of” and “mainly composed of,” for example, “A contains a” covers the meanings of “A contains a and others” and “A contains only a.”

[0019] For the sake of brevity, not all possible combinations of the technical features in each implementation scheme or embodiment are described herein. Therefore, as long as there is no contradiction in the combination of these technical features, the technical features in each implementation scheme or embodiment can be combined arbitrarily, and all possible combinations should be considered within the scope of this specification.

[0020] This invention provides a zeolite gel with interfacial coordination and covalent dual anchoring, and a method for its preparation. The specific process of the preparation method is as follows: Figure 1 As shown.

[0021] The present invention will be further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Furthermore, it should be understood that after reading the teachings of this invention, those skilled in the art can make various alterations or modifications to the invention, and these equivalent forms also fall within the scope defined by the appended claims.

[0022] The following examples use instruments and equipment conventional in the art. Experimental methods in the following examples, unless otherwise specified, are generally performed under conventional conditions or as recommended by the manufacturer. All raw materials used in the following examples are conventional commercially available products with specifications conventional in the art. In this specification and the following examples, unless otherwise specified, "%" refers to weight percentage, "parts" refers to parts by weight, and "ratio" refers to weight proportion.

[0023] The preparation method and characterization in the following examples are based on... Figures 1-3 Unless otherwise specified, all methods are conventional. The materials used in the following examples are all new materials purchased from the market, and the photoinitiator is Irgacure 2959.

[0024] ZSM-5 zeolite is a synthetic zeolite molecular sieve with a high silica-to-alumina ratio and a unique three-dimensional pore structure, belonging to the MFI type topology.

[0025] APTES, full name: 3 Aminopropyltriethoxysilane, Chinese name: 3 Aminopropyltriethoxysilane is a silane coupling agent.

[0026] 3,4-DHBA, Chinese name: 3,4-dihydroxybenzoic acid.

[0027] Example 1: A zeolite gel with interfacial coordination and covalent double anchoring, wherein the zeolite gel with interfacial coordination and covalent double anchoring comprises the following materials in parts by weight: 2 parts ZSM-5 zeolite, 0.2 parts APTES, 10 parts anhydrous toluene, 0.01 parts 3,4-DHBA, 0.1 parts ascorbic acid, 0.03 parts ferrous chloride tetrahydrate, 0.2 parts hydrogen peroxide, 0.2 parts sodium thiosulfate, 0.8 parts gel monomer, 0.4 parts 2-bromoisobutyryl bromide, 0.2 parts triethylamine, 0.1 parts carboxyethyl methacrylate, 0.01 parts cuprous bromide, 0.01 parts 2,2-bipyridine, and 0.02 parts dimethylformamide.

[0028] The preparation method of the gel monomer is as follows: I. Weigh 1 part of acrylic acid and add it to 0.3 parts of hydroxyethyl methacrylate. Stir at 500 r / min for 30 min to obtain a monomer solution. II. Weigh 1 part of N,N-methylenebisacrylamide and add it to the monomer solution obtained in step I. Stir at 500 r / min for 30 min. Weigh 0.2 parts of polyethylene glycol diacrylate and add it to the solution. Continue stirring at the above speed for 30 min to obtain the crosslinking solution. III. Weigh 0.05 parts of photoinitiator and add it to the crosslinking solution obtained in step II. Stir at 500 r / min for 30 min, and then irradiate with light at 300 W and 420 nm for 3 min to obtain gel monomer.

[0029] This embodiment also provides a method for preparing a zeolite gel with interfacial coordination and covalent dual anchoring, the steps of which are as follows: Step 1: Weigh 2 parts of ZSM-5 zeolite and add them to 10 parts of anhydrous toluene. Sonicate at 25 kHz for 20 min. Weigh 0.2 parts of APTES and add them to the mixture. Stir at 350 r / min for 30 min. Add glacial acetic acid to adjust the pH to 4. Then heat and reflux at 90℃ for 4 h while introducing nitrogen gas at a flow rate of 30 mL / min. After cooling naturally to room temperature, wash the mixture three times each with deionized water and anhydrous ethanol to obtain aminated zeolite. Step 2: Add the ammoniated zeolite obtained in Step 1 to 30 parts of deionized water, weigh out 0.01 parts of 3,4-DHBA and add it to the water, heat at 80℃ for 6 hours and stir at 500 r / min to obtain modified zeolite. Step 3: Weigh 0.02 parts of dimethylformamide and add it to 15 parts of deionized water. Stir at 500 r / min for 30 min. Add the modified zeolite obtained in Step 2 and sonicate at 25 kHz for 20 min. Add 0.2 parts of triethylamine and stir at 500 r / min for 10 min. Add 0.4 parts of 2-bromoisobutyryl bromide and heat at 90℃ for 3 h. Then cool naturally to room temperature and wash with deionized water and anhydrous ethanol three times each. Dry at 65℃ for 24 h to obtain polymerized zeolite. Step 4: Weigh 0.1 parts of carboxyethyl methacrylate, 0.01 parts of cuprous bromide and 0.01 parts of 2,2-bipyridine and add them to 20 parts of DMF. Stir at 500 r / min for 30 min to obtain a reaction solution. Add the polymerized zeolite obtained in Step 3 to the reaction solution and heat under reflux at 80℃ for 4 h. Then cool naturally to room temperature, wash with deionized water and anhydrous ethanol three times each, and dry at 65℃ for 24 h to obtain the zeolite core-polymer. Step 5: Weigh 0.03 parts of ferrous chloride tetrahydrate and add it to 30 parts of deionized water. Stir at 500 r / min for 30 min. Add the zeolite core-polymer obtained in Step 4 and sonicate at 25 kHz for 15 min. Add 0.8 parts of gel monomer and stir at 350 r / min for 30 min. Heat at 60℃ for 12 h, then cool naturally to room temperature. Wash with deionized water and anhydrous ethanol three times each. Dry at 65℃ for 24 h to obtain the basic zeolite gel. Step 6: Weigh 0.1 parts of ascorbic acid and add it to 20 parts of deionized water. Stir at 500 r / min for 30 min to obtain solution A. Weigh 0.2 parts of hydrogen peroxide and add it to 10 parts of deionized water. Stir at 500 r / min for 30 min to obtain solution B. Weigh 0.2 parts of sodium thiosulfate and add it to 20 parts of deionized water. Stir at 500 r / min for 30 min to obtain solution C. Let the basic zeolite gel obtained in Step 5 stand for 20 min each in solutions A, B, and C. Wash it three times each with deionized water and anhydrous ethanol, and dry it at 65℃ for 24 h to obtain a zeolite gel with interfacial coordination and covalent double anchoring.

[0030] Example 2: A zeolite gel with interfacial coordination and covalent double anchoring, wherein the zeolite gel with interfacial coordination and covalent double anchoring comprises the following materials in parts by weight: 3 parts ZSM-5 zeolite, 0.25 parts APTES, 10 parts anhydrous toluene, 0.03 parts 3,4-DHBA, 0.15 parts ascorbic acid, 0.03 parts ferrous chloride tetrahydrate, 0.2 parts hydrogen peroxide, 0.2 parts sodium thiosulfate, 1 part gel monomer, 0.4 parts 2-bromoisobutyryl bromide, 0.35 parts triethylamine, 0.1 parts carboxyethyl methacrylate, 0.01 parts cuprous bromide, 0.03 parts 2,2-bipyridine, and 0.02 parts dimethylformamide.

[0031] The preparation method of the gel monomer is as follows: I. Weigh 2 parts of acrylic acid and add it to 0.45 parts of hydroxyethyl methacrylate. Stir at 500 r / min for 30 min to obtain a monomer solution. II. Weigh 1 part of N,N-methylenebisacrylamide and add it to the monomer solution obtained in step I. Stir at 500 r / min for 30 min. Weigh 0.3 parts of polyethylene glycol diacrylate and add it to the solution. Continue stirring at the above speed for 30 min to obtain the crosslinking solution. III. Weigh 0.1 part of photoinitiator and add it to the crosslinking solution obtained in step II. Stir at 500 r / min for 30 min, and then irradiate with light at 300 W and 420 nm for 3 min to obtain gel monomer.

[0032] This embodiment also provides a method for preparing a zeolite gel with interfacial coordination and covalent dual anchoring, the steps of which are as follows: Step 1: Weigh 3 parts of ZSM-5 zeolite and add them to 10 parts of anhydrous toluene. Sonicate at 25 kHz for 20 min. Weigh 0.25 parts of APTES and add them to the mixture. Stir at 350 r / min for 30 min. Add glacial acetic acid to adjust the pH to 4.5. Then heat and reflux at 90℃ for 4 h while passing nitrogen gas at a flow rate of 30 mL / min. After cooling naturally to room temperature, wash the mixture three times each with deionized water and anhydrous ethanol to obtain aminated zeolite. Step 2: Add the ammoniated zeolite obtained in Step 1 to 30 parts of deionized water, weigh out 0.03 parts of 3,4-DHBA and add it to the water, heat at 80℃ for 6 hours and stir at 500 r / min to obtain modified zeolite. Step 3: Weigh 0.02 parts of dimethylformamide and add it to 15 parts of deionized water. Stir at 500 r / min for 30 min. Add the modified zeolite obtained in Step 2 and sonicate at 25 kHz for 20 min. Add 0.35 parts of triethylamine and stir at 500 r / min for 10 min. Add 0.4 parts of 2-bromoisobutyryl bromide and heat at 90℃ for 3 h. Then cool naturally to room temperature and wash with deionized water and anhydrous ethanol three times each. Dry at 65℃ for 24 h to obtain polymerized zeolite. Step 4: Weigh 0.1 parts of carboxyethyl methacrylate, 0.01 parts of cuprous bromide and 0.03 parts of 2,2-bipyridine and add them to 20 parts of DMF. Stir at 500 r / min for 30 min to obtain a reaction solution. Add the polymerized zeolite obtained in Step 3 to the reaction solution and heat under reflux at 80℃ for 4 h. Then cool naturally to room temperature, wash with deionized water and anhydrous ethanol three times each, and dry at 65℃ for 24 h to obtain the zeolite core-polymer. Step 5: Weigh 0.03 parts of ferrous chloride tetrahydrate and add it to 30 parts of deionized water. Stir at 500 r / min for 30 min. Add the zeolite core-polymer obtained in Step 4 and sonicate at 25 kHz for 15 min. Add 1 part of gel monomer and stir at 350 r / min for 30 min. Heat at 60℃ for 12 h, then cool naturally to room temperature. Wash with deionized water and anhydrous ethanol three times each. Dry at 65℃ for 24 h to obtain the basic zeolite gel. Step 6: Weigh 0.15 parts of ascorbic acid and add it to 20 parts of deionized water. Stir at 500 r / min for 30 min to obtain solution A. Weigh 0.2 parts of hydrogen peroxide and add it to 10 parts of deionized water. Stir at 500 r / min for 30 min to obtain solution B. Weigh 0.2 parts of sodium thiosulfate and add it to 20 parts of deionized water. Stir at 500 r / min for 30 min to obtain solution C. Let the basic zeolite gel obtained in Step 5 stand for 20 min each in solutions A, B, and C. Wash it three times each with deionized water and anhydrous ethanol, and dry it at 65℃ for 24 h to obtain a zeolite gel with interfacial coordination and covalent double anchoring.

[0033] Example 3: A zeolite gel with interfacial coordination and covalent double anchoring, wherein the zeolite gel with interfacial coordination and covalent double anchoring comprises the following materials in parts by weight: 4 parts ZSM-5 zeolite, 0.5 parts APTES, 10 parts anhydrous toluene, 0.04 parts 3,4-DHBA, 0.2 parts ascorbic acid, 0.03 parts ferrous chloride tetrahydrate, 0.2 parts hydrogen peroxide, 0.2 parts sodium thiosulfate, 1.2 parts gel monomer, 0.4 parts 2-bromoisobutyryl bromide, 0.5 parts triethylamine, 0.1 parts carboxyethyl methacrylate, 0.01 parts cuprous bromide, 0.05 parts 2,2-bipyridine, and 0.02 parts dimethylformamide.

[0034] The preparation method of the gel monomer is as follows: I. Weigh 3 parts of acrylic acid and add it to 0.6 parts of hydroxyethyl methacrylate. Stir at 500 r / min for 30 min to obtain a monomer solution. II. Weigh 1 part of N,N-methylenebisacrylamide and add it to the monomer solution obtained in step I. Stir at 500 r / min for 30 min. Weigh 0.4 parts of polyethylene glycol diacrylate and add it to the solution. Continue stirring at the above speed for 30 min to obtain the crosslinking solution. III. Weigh 0.15 parts of photoinitiator and add it to the crosslinking solution obtained in step II. Stir at 500 r / min for 30 min, and then irradiate with light at 300 W and 420 nm for 3 min to obtain gel monomer.

[0035] This embodiment also provides a method for preparing a zeolite gel with interfacial coordination and covalent dual anchoring, the steps of which are as follows: Step 1: Weigh 4 parts of ZSM-5 zeolite and add them to 10 parts of anhydrous toluene. Sonicate at 25 kHz for 20 min. Weigh 0.5 parts of APTES and add them to the mixture. Stir at 350 r / min for 30 min. Add glacial acetic acid to adjust the pH to 5. Then heat and reflux at 90℃ for 4 h while introducing nitrogen gas at a flow rate of 30 mL / min. After cooling naturally to room temperature, wash the mixture three times each with deionized water and anhydrous ethanol to obtain aminated zeolite. Step 2: Add the ammoniated zeolite obtained in Step 1 to 30 parts of deionized water, weigh out 0.04 parts of 3,4-DHBA and add it to the water, heat at 80℃ for 6 hours and stir at 500 r / min to obtain modified zeolite. Step 3: Weigh 0.02 parts of dimethylformamide and add it to 15 parts of deionized water. Stir at 500 r / min for 30 min. Add the modified zeolite obtained in Step 2 and sonicate at 25 kHz for 20 min. Add 0.5 parts of triethylamine and stir at 500 r / min for 10 min. Add 0.4 parts of 2-bromoisobutyryl bromide and heat at 90℃ for 3 h. Then cool naturally to room temperature and wash with deionized water and anhydrous ethanol three times each. Dry at 65℃ for 24 h to obtain polymerized zeolite. Step 4: Weigh 0.1 parts of carboxyethyl methacrylate, 0.01 parts of cuprous bromide and 0.05 parts of 2,2-bipyridine and add them to 20 parts of DMF. Stir at 500 r / min for 30 min to obtain a reaction solution. Add the polymerized zeolite obtained in Step 3 to the reaction solution and heat under reflux at 80℃ for 4 h. Then cool naturally to room temperature, wash with deionized water and anhydrous ethanol three times each, and dry at 65℃ for 24 h to obtain the zeolite core-polymer. Step 5: Weigh 0.03 parts of ferrous chloride tetrahydrate and add it to 30 parts of deionized water. Stir at 500 r / min for 30 min. Add the zeolite core-polymer obtained in Step 4 and sonicate at 25 kHz for 15 min. Add 1.2 parts of gel monomer and stir at 350 r / min for 30 min. Heat at 60℃ for 12 h, then cool naturally to room temperature. Wash with deionized water and anhydrous ethanol three times each. Dry at 65℃ for 24 h to obtain the basic zeolite gel. Step 6: Weigh 0.2 parts of ascorbic acid and add it to 20 parts of deionized water. Stir at 500 r / min for 30 min to obtain solution A. Weigh 0.2 parts of hydrogen peroxide and add it to 10 parts of deionized water. Stir at 500 r / min for 30 min to obtain solution B. Weigh 0.2 parts of sodium thiosulfate and add it to 20 parts of deionized water. Stir at 500 r / min for 30 min to obtain solution C. Let the basic zeolite gel obtained in Step 5 stand for 20 min each in solutions A, B, and C. Wash it three times each with deionized water and anhydrous ethanol, and dry it at 65℃ for 24 h to obtain a zeolite gel with interfacial coordination and covalent double anchoring.

[0036] Comparative Example 1: The difference between Comparative Example 1 and Example 2 is that ferrous chloride tetrahydrate was not added; the rest is the same as Example 2.

[0037] Comparative Example 2: The difference between Comparative Example 2 and Example 2 is that no gel monomer was added; the rest is the same as Example 2.

[0038] Comparative Example 3: The difference between Comparative Example 3 and Example 2 is that ferrous chloride tetrahydrate and gel monomer were not added; the rest of the parts are the same as Example 2.

[0039] The following tests were performed on the prepared gel material: Figure 2This is a photograph of the interfacial coordination and covalently anchored zeolite gel prepared in Example 2. It can be seen that the prepared material has a uniform particle size and no large particles are present. Figure 3 The degradation test diagrams of RhB in the interfacial coordination and covalently double-anchored zeolite gels prepared in Examples 1-3 and Comparative Examples 1-3 show that the examples have higher adsorption rates than the comparative examples, and exhibit higher degradation performance under light irradiation. Meanwhile, comparing the degradation performance of Example 2 and Comparative Example 2, Fe... 2+ Not only does it act as a molecular rivet to stabilize the zeolite-gel interface, but it also serves as a catalytic active center for the Fenton reaction, through Fe 2+ +H₂O₂→Fe 3+ +OH+OH - The reaction pathway generates highly oxidizing hydroxyl radicals (·OH), which attack the chromophore structure of the RhB molecule, causing it to break down and degrade; simultaneously, Fe... 3+ It can be converted back to Fe under light or the action of a reducing agent within the system. 2+ This forms a catalytic cycle, preventing the loss and deactivation of iron ions. (The specific process involves weighing 50 mg of interfacially coordinated and covalently double-anchored zeolite gel and adding it to 200 parts of a 30 mg / L RhB solution. The reaction is carried out in the dark for 10 minutes, followed by illumination with a light for 30 minutes.)

[0040] In summary, this invention provides a zeolite gel with interfacial coordination and covalent dual anchoring, and its preparation method; it constructs dual reaction sites through dual modification of the zeolite surface with amino-catechol, and utilizes Fe... 2+ The "molecular rivet" triple function realizes the "adsorption-locking" cycle and site self-cleaning, solving the problems of traditional zeolite agglomeration and pore blockage; through in-situ photopolymerization, zeolite is covalently anchored in a honeycomb array, preserving the accessibility of the pores and zeolite, and the dual anchoring interface enhances the bonding strength and has adaptive stress buffering capability.

[0041] Obviously, the above comparative examples and embodiments are only a part of the comparative examples and embodiments of the present invention, and they, along with the comparative examples and embodiments referenced based on such examples, are all within the scope of protection of this invention.

[0042] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

[0043] The present invention and its embodiments have been described above. This description is not restrictive, and the accompanying drawings are only one embodiment of the present invention. The actual application is not limited to this. In conclusion, if those skilled in the art are inspired by this description and design similar methods and embodiments without departing from the spirit of the present invention, they should all fall within the protection scope of the present invention.

Claims

1. A zeolite gel with interfacial coordination and covalent dual anchoring, characterized in that, The material comprises the following parts by weight: 2-4 parts ZSM-5 zeolite, 0.2-0.5 parts APTES, 10 parts anhydrous toluene, 0.01-0.04 parts 3,4-DHBA, 0.1-0.2 parts ascorbic acid, 0.03 parts ferrous chloride tetrahydrate, 0.2 parts hydrogen peroxide, 0.2 parts sodium thiosulfate, 0.8-1.2 parts gel monomer, 0.4 parts 2-bromoisobutyryl bromide, 0.2-0.5 parts triethylamine, 0.1 parts carboxyethyl methacrylate, 0.01 parts cuprous bromide, 0.01-0.05 parts 2,2-bipyridine, and 20.02 parts dimethylformamide; The gel monomer comprises materials in the following mass ratio: acrylic acid: hydroxyethyl methacrylate: N,N-methylenebisacrylamide: polyethylene glycol diacrylate: photoinitiator = (1-3): (0.3-0.6): 1: (0.2-0.4): (0.05-0.15).

2. The zeolite gel with interfacial coordination and covalent dual anchoring according to claim 1, characterized in that, The preparation method of the gel monomer includes the following steps: Acrylic acid was added to hydroxyethyl methacrylate and stirred to obtain a monomer solution; N,N-methylenebisacrylamide was added to the monomer solution and stirred. Then polyethylene glycol diacrylate was added and stirred to obtain a crosslinking solution. A photoinitiator was added to the crosslinking solution, stirred, and irradiated to obtain a gel monomer.

3. The zeolite gel with interfacial coordination and covalent dual anchoring according to claim 2, characterized in that, The photoinitiator is Irgacure 2959.

4. The zeolite gel with interfacial coordination and covalent dual anchoring according to claim 2, characterized in that, The illumination conditions are as follows: a light source with a power of 300 W and a wavelength of 420 nm is used for illumination, and the illumination time is 3 min.

5. A method for preparing an interfacial coordination and covalently anchored zeolite gel according to any one of claims 1-4, characterized in that, Includes the following steps: I. Add ZSM-5 zeolite to anhydrous toluene, sonicate, then add APTES, stir, add acid to adjust the pH value, perform the first heating and reflux under nitrogen, wash, and obtain aminated zeolite. II. Add the aminated zeolite to water, then add 3,4-DHBA, heat and stir to obtain the modified zeolite; III. Add dimethylformamide to water, then add the modified zeolite, sonicate, add triethylamine, stir, add 2-bromoisobutyryl bromide, heat, and obtain polymerized zeolite; IV. Add carboxyethyl methacrylate, cuprous bromide and 2,2-bipyridine to dimethylformamide, stir to obtain a reaction solution, add polymerized zeolite to the reaction solution, and heat under reflux for a second time to obtain zeolite core-polymer; V. Add ferrous chloride tetrahydrate to water, stir, then add zeolite core-polymer, sonicate, then add gel monomer, stir, and heat to obtain basic zeolite gel; VI. Add ascorbic acid to water and stir to obtain solution A; add hydrogen peroxide to water and stir to obtain solution B; add sodium thiosulfate to water and stir to obtain solution C. The basic zeolite gel was placed in solutions A, B and C in sequence, allowed to stand, and dried to obtain a zeolite gel with interfacial coordination and covalent double anchoring.

6. The method for preparing a zeolite gel with interfacial coordination and covalent dual anchoring according to claim 5, characterized in that, The acid is glacial acetic acid, and the pH value is 4-5; the temperature of the first heating reflux is 90°C, and the time is 4 hours.

7. The method for preparing a zeolite gel with interfacial coordination and covalent dual anchoring according to claim 5, characterized in that, The second heating and reflux temperature is 80°C, and the time is 4 hours.

8. The method for preparing a zeolite gel with interfacial coordination and covalent dual anchoring according to claim 5, characterized in that, The mass ratio of the dimethylformamide in step III to the dimethylformamide in step IV is 0.02:

20.

9. The method for preparing a zeolite gel with interfacial coordination and covalent dual anchoring according to claim 5, characterized in that, The mass ratio of ascorbic acid to water in solution A is (0.1-0.2):20; the mass ratio of hydrogen peroxide to water in solution B is 0.2:10; and the mass ratio of sodium thiosulfate to water in solution C is 0.2:

20.

10. The method for preparing a zeolite gel with interfacial coordination and covalent dual anchoring according to claim 5, characterized in that, The standing time for solutions A, B, and C is 20 minutes.

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