Antibacterial composite material for water treatment and preparation method thereof

Abstract

The invention discloses an antibacterial composite material for water treatment and a preparation method thereof in the technical field of composite materials, and the antibacterial composite material is prepared from the following components in parts by weight: 20-25 parts of a magnetic nano material, 19-22 parts of acrylic acid, 6-9 parts of allylamine, 1.8-2.2 parts of N, N '-methylene bisacrylamide, 1.3-1.6 parts of azodiisobutyronitrile and 4.3-5.5 parts of plant polyphenol. Cobalt ferrite is used as a magnetic core to prepare a magnetic nano material to improve the recovery rate, acrylic acid and allylamine are used as polymeric monomers to form a polymer layer with high adsorption capacity, and plant polyphenols are combined on the surface, so that the adsorption performance and the catalytic decomposition performance are enhanced, and the antibacterial effect of the material is improved at the same time; further, the composite material with the functions of adsorbing heavy metal ions, decomposing organic pollutants and resisting and inhibiting bacteria is obtained.

Description

Technical Field

[0001] The invention belongs to the technical field of composite materials, and specifically refers to an antibacterial composite material for water treatment and a preparation method thereof. Background Art

[0002] Water treatment is the process of removing pollutants from water bodies through physical, chemical, biological and other methods to make it meet the standards for discharge or reuse. Its core goal is to protect the water environment, maintain ecological balance and ensure human health. With the development of society, the increase in sewage discharge and the increasingly severe water resource crisis, the water treatment industry has become the focus of attention in the world today. The main sources of sewage are: 1. industrial pollution, 2. agricultural pollution, and 3. domestic pollution. Sewage discharge causes long-term accumulation of organic pollutants, heavy metal ions and microbial pathogens in water bodies, which seriously threatens human health.

[0003] Polyacrylic acid is a water-soluble high molecular polymer. Due to the high reactivity, strong adsorption and dispersibility of its groups, it can chelate with heavy metal ions to form stable complexes. It has a variety of applications in sewage treatment, especially in adsorption, dispersion, scale inhibition, flocculation and other aspects. However, high molecular weight polyacrylic acid has poor degradability and may cause secondary pollution. It is difficult to reuse, resulting in high costs, and has poor adsorption effect on organic pollutants.

[0004] Plant polyphenols are a class of natural compounds widely found in plants, mainly including gallic acid, ferulic acid, etc. They generally have antioxidant, chelating, antibacterial and adsorption properties, and show unique potential in wastewater treatment, especially in the fields of heavy metal removal, organic pollutant degradation, antibacterial disinfection and flocculation sedimentation. However, their development is restricted by shortcomings such as poor stability, limited selectivity, high risk of secondary pollution and difficulty in large-scale application.

[0005] The existing technologies currently have the following main problems: the water treatment materials currently used have single functions, poor effects and are difficult to reuse. Summary of the invention

[0006] In view of the above situation, in order to overcome the defects of the prior art, the present invention provides an antibacterial composite material for water treatment and a preparation method thereof. In order to solve the problem that water treatment materials are difficult to reuse, the present invention proposes to use cobalt ferrite as the magnetic core to prepare magnetic nanomaterials to improve the recovery rate, use acrylic acid and acrylamine as polymerization monomers to form a polymer layer with a high adsorption amount, and combine plant polyphenols on the surface to enhance the adsorption performance and catalytic decomposition performance while improving the antibacterial effect of the material, thereby obtaining a composite material with the functions of adsorbing heavy metal ions, decomposing organic pollutants and antibacterial and antibacterial.

[0007] In order to achieve the above-mentioned purpose, the technical scheme adopted by the present invention is as follows: The present invention proposes an antibacterial composite material for water treatment, which is prepared by comprising the following components in parts by weight: 20-25 parts of magnetic nanomaterials, 19-22 parts of acrylic acid, 6-9 parts of acrylamine, 1.8-2.2 parts of N,N'-methylenebisacrylamide, 1.3-1.6 parts of azobisisobutyronitrile and 4.3-5.5 parts of plant polyphenols.

[0008] Preferably, the plant polyphenol is one of tannic acid, catechin, oleuropein, gallic acid and quercetin;

[0009] Furthermore, the plant polyphenol is tannic acid.

[0010] Preferably, the nanomagnetic material is prepared from the following components in parts by weight: 21-23 parts of cobalt chloride hexahydrate, 33-38 parts of ferric chloride hexahydrate, 3-5 parts of ammonium hydroxide, 8-10 parts of tetraethyl orthosilicate, 4-6 parts of butyl titanate and 6-8 parts of 3-(methacryloyloxy)propyltrimethoxysilane.

[0011] Preferably, the method for preparing the nanomagnetic material comprises the following steps:

[0012] (1) adding cobalt chloride hexahydrate to deionized water, and then adding ferric chloride hexahydrate, mixing well to obtain a transparent solution;

[0013] (2) adding 3.5 wt % sodium hydroxide solution dropwise into the transparent solution obtained in step (1) until the pH value is 12.5, then transferring the solution into an autoclave, heating the temperature to 230° C. at room temperature at a heating rate of 3-4° C. / min, then cooling to room temperature, washing and drying to obtain magnetic cobalt ferrite;

[0014] (3) adding the magnetic cobalt ferrite obtained in step (2) to a 75 wt% ethanol solution, followed by adding ammonium hydroxide and ethyl orthosilicate, stirring in a water bath, cooling to room temperature, adding butyl titanate, stirring at 600 rpm for 3 h, standing for 20 h, centrifuging, washing and collecting the precipitate, and baking at high temperature to obtain a magnetic nanocatalyst;

[0015] (4) Add the magnetic nanocatalyst obtained in step (3) to anhydrous ethanol, add 3-(methacryloyloxy)propyltrimethoxysilane, stir in a water bath, filter, remove non-magnetic and weak magnetic components through magnetic separation, and dry to obtain a magnetic nanomaterial.

[0016] The core of the magnetic nanomaterial is magnetic cobalt ferrite, the outer layer is a silicon dioxide and titanium dioxide coating layer, and 3-(methacryloyloxy)propyltrimethoxysilane is combined with the coating layer to form a nanomaterial with a double bond shell layer.

[0017] Preferably, in step (1), the amount of cobalt chloride hexahydrate added to deionized water is 0.04-0.05 g / mL.

[0018] Preferably, in step (3), the amount of the magnetic cobalt ferrite obtained in step (2) added to the 75 wt % ethanol solution is 0.08-0.12 g / mL.

[0019] Preferably, in step (3), the water bath stirring temperature is 40-50°C, the speed is 60-80 rpm, and the time is 12-16 hours.

[0020] Preferably, in step (3), the high temperature baking temperature is 500-600° C. and the time is 3-5 hours.

[0021] Preferably, in step (4), the amount of the magnetic nanocatalyst obtained in step (3) added to anhydrous ethanol is 0.02-0.03 g / mL.

[0022] Preferably, in step (4), the water bath stirring temperature is 30-40°C, the speed is 20-30 rpm, and the time is 2-3 h.

[0023] The present invention also provides a method for preparing an antibacterial composite material for water treatment, which specifically comprises the following steps:

[0024] S1. Add the nano-magnetic material to an acetonitrile solution, disperse it by ultrasonication, add acrylic acid, acrylamine and N,N'-methylenebisacrylamide, then add azobisisobutyronitrile and mix well, heat in a water bath, wash and perform magnetic separation to obtain a magnetic composite material;

[0025] S2, adding the magnetic composite material obtained in S1 to a tris(hydroxymethyl)aminomethane hydrochloride buffer solution with a pH of 8.5 to obtain a dispersion A, and adding the plant polyphenols to anhydrous ethanol to obtain a solution B;

[0026] S3. Add solution B obtained in S2 to dispersion A, stir in a water bath, soak for 3-4 hours, filter, and dry at 80° C. for 3 hours to obtain an antibacterial composite material for water treatment.

[0027] Preferably, in S1, the amount of the nanomagnetic material added to the acetonitrile solution is 3-4 mg / mL.

[0028] Preferably, in S2, the amount of the magnetic composite material obtained in S1 added to the tris(hydroxymethyl)aminomethane hydrochloride buffer solution at pH 8.5 is 0.5-0.6 g / mL.

[0029] Preferably, in S2, the amount of plant polyphenols added to anhydrous ethanol is 0.02-0.03 mg / mL.

[0030] The beneficial effects achieved by the present invention are as follows: the present invention uses cobalt ferrite as a magnetic core to prepare a recyclable multifunctional water treatment material, uses cobalt ferrite as a core to give the material magnetism to achieve the purpose of recyclability, uses tetraethyl orthosilicate and butyl titanate to prepare a coating layer on the surface of the magnetic material, and obtains a magnetic nanocatalyst that can catalytically decompose organic pollutants in water under light conditions; uses 3-(methacryloyloxy)propyltrimethoxysilane to modify the surface of the magnetic nanocatalyst, thereby improving the dispersibility of the magnetic material and reducing aggregation, and at the same time providing polymerizable double bonds, so that acrylic acid and acrylamine undergo polymerization reaction on the surface of the magnetic nanomaterial and are firmly combined, and a large number of carboxyl groups and amino groups are introduced on the surface of the material, further improving the adsorption performance of the material, and finally, through the Michael addition of primary amines and phenols and the Schiff base reaction, tannic acid is fixed on the surface of the composite material to form a tannic acid network, while improving the regeneration performance, further improving the bactericidal effect of the material and the ability to decompose organic pollutants. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 The result diagram of lead ion adsorption rate of Examples 1-3 and Comparative Examples 1-3 of the present invention;

[0032] Figure 2 The result diagram of the material regeneration rate of Examples 1-3 and Comparative Examples 1-2 of the present invention;

[0033] Figure 3 The result diagram of methyl orange removal rate of Examples 1-3 and Comparative Example 3;

[0034] Figure 4 It is the result diagram of the sterilization rate of Examples 1-3 and Comparative Example 3.

[0035] The accompanying drawings are used to provide further understanding of the present invention and constitute a part of the specification. They are used to explain the present invention together with the embodiments of the present invention and do not constitute a limitation of the present invention. DETAILED DESCRIPTION

[0036] The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all the embodiments; based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0037] Unless otherwise defined, all professional and scientific terms used herein have the same meanings as those familiar to those skilled in the art. In addition, any methods and materials similar or equivalent to those described herein may be applied to the present invention. The preferred implementation methods and materials described herein are for demonstration purposes only and are not intended to limit the content of this application.

[0038] The experimental methods in the following examples are conventional methods unless otherwise specified; the experimental materials and test strains used in the following examples are purchased from commercial channels unless otherwise specified.

[0039] Example 1

[0040] An antibacterial composite material for water treatment is prepared by comprising the following components in parts by weight: 20 parts of nanomagnetic material, 19 parts of acrylic acid, 6 parts of acrylamine, 1.8 parts of N,N'-methylenebisacrylamide, 1.3 parts of azobisisobutyronitrile and 4.3 parts of tannic acid.

[0041] The nano-magnetic material is prepared from the following components in parts by weight: 21 parts of cobalt chloride hexahydrate, 33 parts of ferric chloride hexahydrate, 3 parts of ammonium hydroxide, 8 parts of tetraethyl orthosilicate, 9 parts of butyl titanate and 6 parts of 3-(methacryloyloxy)propyltrimethoxysilane.

[0042] The preparation method of nano magnetic material comprises the following steps:

[0043] (1) adding cobalt chloride hexahydrate at an addition amount of 0.04 g / mL to deionized water, and then adding ferric chloride hexahydrate, mixing well to obtain a transparent solution;

[0044] (2) dripping 3.5 wt % sodium hydroxide solution dropwise into the transparent solution obtained in step (1) until the pH value is 12.5, then transferring the solution into an autoclave, heating the temperature to 230° C. at room temperature at a heating rate of 3° C. / min, then cooling to room temperature, washing and drying to obtain magnetic cobalt ferrite;

[0045] (3) adding 0.08 g / mL of the magnetic cobalt ferrite obtained in step (2) to a 75 wt% ethanol solution, then adding ammonium hydroxide, stirring evenly, adding ethyl orthosilicate, stirring at 60 rpm in a 40°C water bath for 12 h, cooling to room temperature, adding butyl titanate, stirring at 600 rpm for 3 h, standing for 20 h, collecting the precipitate by centrifugation, washing, and baking at 500°C for 4 h to obtain a magnetic nanocatalyst;

[0046] (4) The magnetic nanocatalyst obtained in step (3) was added to anhydrous ethanol at an addition amount of 0.02 g / mL, and 3-(methacryloyloxy)propyltrimethoxysilane was added. The mixture was stirred at 20 rpm in a 30°C water bath for 2 h. The non-magnetic and weakly magnetic components were removed by filtering and magnetic separation, and then dried to obtain a nanomagnetic material.

[0047] The present invention also provides a method for preparing an antibacterial composite material for water treatment, which specifically comprises the following steps:

[0048] S1. Add the nanomagnetic material in an amount of 3 mg / mL to an acetonitrile solution, disperse by ultrasonication, add acrylic acid, acrylamine and N,N'-methylenebisacrylamide, then add azobisisobutyronitrile and mix well, heat in a water bath, wash, and perform magnetic separation to obtain a magnetic composite material;

[0049] S2, adding the magnetic composite material obtained in S1 in an amount of 0.5 g / mL to a tris(hydroxymethyl)aminomethane hydrochloride buffer solution with a pH of 8.5 to obtain a dispersion A, and adding tannic acid in an amount of 0.02 g / mL to anhydrous ethanol to obtain a solution B;

[0050] S3. Add solution B obtained in S2 to dispersion A, stir in a water bath, soak for 3 h, filter, and dry at 80° C. for 3 h to obtain an antibacterial composite material for water treatment.

[0051] Example 2

[0052] An antibacterial composite material for water treatment is prepared by comprising the following components in parts by weight: 25 parts of nanomagnetic material, 22 parts of acrylic acid, 9 parts of acrylamine, 2.2 parts of N,N'-methylenebisacrylamide, 1.6 parts of azobisisobutyronitrile and 5.5 parts of tannic acid.

[0053] The nano-magnetic material is prepared from the following components in parts by weight: 23 parts of cobalt chloride hexahydrate, 38 parts of ferric chloride hexahydrate, 5 parts of ammonium hydroxide, 10 parts of tetraethyl orthosilicate, 12 parts of butyl titanate and 8 parts of 3-(methacryloyloxy)propyltrimethoxysilane.

[0054] The preparation method of nano magnetic material comprises the following steps:

[0055] (1) adding cobalt chloride hexahydrate at an addition amount of 0.05 g / mL to deionized water, and then adding ferric chloride hexahydrate, mixing well to obtain a transparent solution;

[0056] (2) adding 3.5 wt % sodium hydroxide solution dropwise into the transparent solution obtained in step (1) until the pH value is 12.5, then transferring the solution into an autoclave, heating the temperature to 230° C. at room temperature at a heating rate of 4° C. / min, then cooling to room temperature, washing and drying to obtain magnetic cobalt ferrite;

[0057] (3) adding 0.12 g / mL of the magnetic cobalt ferrite obtained in step (2) to a 75 wt% ethanol solution, then adding ammonium hydroxide, stirring evenly, adding ethyl orthosilicate, stirring at 80 rpm in a 50°C water bath for 16 h, cooling to room temperature, adding butyl titanate, stirring at 600 rpm for 3 h, standing for 20 h, collecting the precipitate by centrifugation, washing, and baking at 600°C for 54 h to obtain a magnetic nanocatalyst;

[0058] (4) The magnetic nanocatalyst obtained in step (3) was added to anhydrous ethanol at an addition amount of 0.03 g / mL, and 3-(methacryloyloxy)propyltrimethoxysilane was added. The mixture was stirred at 30 rpm in a 40°C water bath for 3 h. The non-magnetic and weakly magnetic components were removed by filtering and magnetic separation, and then dried to obtain a nanomagnetic material.

[0059] The present invention also provides a method for preparing an antibacterial composite material for water treatment, which specifically comprises the following steps:

[0060] S1. Add the nanomagnetic material in an amount of 4 mg / mL to an acetonitrile solution, disperse by ultrasonication, add acrylic acid, acrylamine and N,N'-methylenebisacrylamide, then add azobisisobutyronitrile and mix well, heat in a water bath, wash, and perform magnetic separation to obtain a magnetic composite material;

[0061] S2, adding the magnetic composite material obtained in S1 in an amount of 0.6 g / mL to a tris(hydroxymethyl)aminomethane hydrochloride buffer solution with a pH of 8.5 to obtain a dispersion A, and adding tannic acid in an amount of 0.03 g / mL to anhydrous ethanol to obtain a solution B;

[0062] S3. Add solution B obtained in S2 to dispersion A, stir in a water bath, soak for 4 h, filter, and dry at 80° C. for 3 h to obtain an antibacterial composite material for water treatment.

[0063] Example 3

[0064] An antibacterial composite material for water treatment is prepared by comprising the following components in parts by weight: 22 parts of nanomagnetic material, 20 parts of acrylic acid, 7 parts of acrylamine, 2 parts of N,N'-methylenebisacrylamide, 1.5 parts of azobisisobutyronitrile and 5 parts of tannic acid.

[0065] The nano-magnetic material is prepared from the following components in parts by weight: 22 parts of cobalt chloride hexahydrate, 35 parts of ferric chloride hexahydrate, 4 parts of ammonium hydroxide, 9 parts of tetraethyl orthosilicate, 10 parts of butyl titanate and 7 parts of 3-(methacryloyloxy)propyltrimethoxysilane.

[0066] The preparation method of nano magnetic material comprises the following steps:

[0067] (1) adding cobalt chloride hexahydrate in an amount of 0.045 g / mL to deionized water, and then adding ferric chloride hexahydrate, mixing well to obtain a transparent solution;

[0068] (2) adding 3.5 wt % sodium hydroxide solution dropwise into the transparent solution obtained in step (1) until the pH value is 12.5, then transferring the solution into an autoclave, heating the temperature to 230° C. at room temperature at a heating rate of 3.5° C. / min, then cooling to room temperature, washing and drying to obtain magnetic cobalt ferrite;

[0069] (3) adding the magnetic cobalt ferrite obtained in step (2) in an amount of 0.1 g / mL to a 75 wt% ethanol solution, then adding ammonium hydroxide, stirring evenly, adding ethyl orthosilicate, stirring at 70 rpm in a 45°C water bath for 14 h, cooling to room temperature, adding butyl titanate, stirring at 600 rpm for 3 h, standing for 20 h, collecting the precipitate by centrifugation, washing, and baking at 550°C for 4.5 h to obtain a magnetic nanocatalyst;

[0070] (4) The magnetic nanocatalyst obtained in step (3) was added to anhydrous ethanol at an addition amount of 0.025 g / mL, and 3-(methacryloyloxy)propyltrimethoxysilane was added. The mixture was stirred at 25 rpm in a 35°C water bath for 2.5 h. The non-magnetic and weakly magnetic components were removed by filtering and magnetic separation, and then dried to obtain a nanomagnetic material.

[0071] The present invention also provides a method for preparing an antibacterial composite material for water treatment, which specifically comprises the following steps:

[0072] S1. Add the nanomagnetic material in an amount of 3.5 mg / mL to an acetonitrile solution, disperse by ultrasonication, add acrylic acid, acrylamine and N,N'-methylenebisacrylamide, then add azobisisobutyronitrile and mix well, heat in a water bath, wash, and perform magnetic separation to obtain a magnetic composite material;

[0073] S2, adding the magnetic composite material obtained in S1 in an amount of 0.55 g / mL to a tris(hydroxymethyl)aminomethane hydrochloride buffer solution with a pH of 8.5 to obtain a dispersion A, and adding tannic acid in an amount of 0.025 g / mL to anhydrous ethanol to obtain a solution B;

[0074] S3. Add solution B obtained in S2 to dispersion A, stir in a water bath, soak for 3.5 hours, filter, and dry at 80° C. for 3 hours to obtain an antibacterial composite material for water treatment.

[0075] Comparative Example 1

[0076] This comparative example provides a composite material, which differs from Example 1 only in that 3-(methacryloyloxy)propyltrimethoxysilane is replaced by 3-aminopropyltriethoxysilane in the components, and the remaining components and component contents are the same as those in Example 1.

[0077] Comparative Example 2

[0078] This comparative example provides a composite material, which is different from Example 1 only in that the component does not contain acrylamine, and the other components and component contents are the same as those in Example 1.

[0079] Comparative Example 3

[0080] This comparative example provides a composite material, which is different from Example 1 only in that the component does not contain tannic acid, and the other components and component contents are the same as those in Example 1.

[0081] Experimental example

[0082] 1. Heavy metal adsorption

[0083] 3g of the composite material obtained in Example 1-3 and Comparative Example 1-3 was added to 5L of a solution with an initial lead ion concentration of 90mg / L, stirred at 300rpm for 30min, and allowed to stand for 3h. The lead ion concentration in the waste liquid was detected and recorded as the final concentration. The adsorption rate was calculated using the following formula:

[0084] Adsorption rate = (initial concentration - final concentration) / initial concentration × 100%.

[0085] Figure 1 The result graph of the lead ion adsorption rate of Examples 1-3 and Comparative Examples 1-3 of the present invention is as shown in the figure. The lead ion adsorption rates of Examples 1-3 and Comparative Examples 1-3 are 86.3%, 83.5%, 86.6%, 78.2%, 63.3% and 67.5%, respectively; the lead ion adsorption rate of Example 1-3 is significantly higher than that of Comparative Examples 1-3, indicating that the use of 3-(methacryloyloxy)propyltrimethoxysilane, tannic acid and acrylamine effectively increases the lead ion adsorption capacity of the material.

[0086] 2. Regeneration performance

[0087] In the heavy metal adsorption experiment, the adsorption-completed examples 1-3 and comparative examples 1-2 were added to a 0.2 mol / L sodium phosphate solution for desorption for 1 h, and then washed with deionized water until the filtrate was neutral. After drying, the adsorption experiment was performed again, and the adsorption amount was calculated. This was performed 10 times in total, and the regeneration rate was calculated using the following formula:

[0088] Regeneration rate = 10th adsorption amount / 1st adsorption amount × 100%

[0089] Figure 2 This is a result graph of the regeneration rate of the materials of Examples 1-3 and Comparative Examples 1-2 of the present invention. As shown in the figure, as the number of experiments increases, the adsorption capacity of the adsorbent decreases. After 10 cycles of desorption, the regeneration rates of Examples 1-3 and Comparative Examples 1-2 are 75.2%, 72.6%, 75.4%, 41.2%, and 52.6%, respectively; the regeneration rate of Example 1-3 is higher than that of Comparative Example 1-2, indicating that the use of 3-(methacryloyloxy)propyltrimethoxysilane and acrylamine effectively improves the regeneration performance of the material.

[0090] 3. Organic matter removal

[0091] Take dye wastewater with a methyl orange concentration of 20 mg / L, under a constant temperature of 25°C, detect the methyl orange concentration and record it as the original value, then add Examples 1-3 and Comparative Example 3, stir at 300 rpm for 20 min under natural light, then let it stand for 6 h, detect the methyl orange concentration and record it as the residual value, and calculate the methyl orange removal rate using the following formula:

[0092] Methyl orange removal rate = residual value / original value × 100%.

[0093] Figure 3 The result graph of methyl orange removal rate of Examples 1-3 and Comparative Example 3 is as follows. As shown in the figure, the removal rates of Examples 1-3 and Comparative Example 3 are 89.2%, 91.3%, 93.6% and 65.1%, respectively; the removal rate of Examples 1-3 is significantly higher than that of Comparative Example 3, indicating that the preparation of the polyphenol network improves the material's ability to remove organic pollutants.

[0094] 4. Antibacterial ability

[0095] The concentration is 1×10 8 CFU / mL of Escherichia coli and Staphylococcus aureus suspensions were added to Examples 1-3 and Comparative Example 3 at an addition amount of 2 mg / mL, and an equal mass of cobalt ferrite was added to the control group, and the mixture was fully mixed. The mixture was allowed to stand for sterilization for 1 h and 3 h under natural light, and then 1 mL was dropped into a test tube containing 5 mL of PBS buffer for dilution. Then 1 mL was placed in a sterile dish, culture medium was added, and culture was continued at a constant temperature. The plate count was performed and the sterilization rate was calculated using the following formula:

[0096] Sterilization rate = (number of colonies in the control group - number of colonies in the experimental group) / number of colonies in the control group × 100%.

[0097] Figure 4 It is a result graph of the sterilization rates of Examples 1-3 and Comparative Example 3. As shown in the figure, the sterilization rates of Examples 1-3 and Comparative Example 3 at 1 hour are 99.6%, 99.3%, 99.8%, and 61.1%, respectively, and the sterilization rates at 3 hours are 100%, 100%, 100%, and 76.1%, respectively; the sterilization rates of Examples 1-3 at 1 hour and 3 hours are significantly higher than those of Comparative Example 3, and the sterilization ability of Examples 1-3 is significantly better than that of Comparative Example 3, indicating that the preparation of the polyphenol network enhances the sterilization effect of the material.

[0098] While the embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that many changes, modifications, substitutions and variations can be made to the embodiments without departing from the principles and spirit of the invention.

[0099] The present invention and its implementation methods are described above, which is not restrictive. The drawings are only one of the implementation methods of the present invention, and the actual application is not limited thereto. In short, if ordinary technicians in the field are inspired by it and design methods and embodiments similar to the technical solution without creativity without departing from the purpose of the invention, they should all fall within the protection scope of the present invention.

Claims

1. An antibacterial composite material for water treatment, characterized in that: The invention comprises the following components in parts by weight: 20-25 parts of magnetic nanomaterials, 19-22 parts of acrylic acid, 6-9 parts of acrylamine, 1.8-2.2 parts of N,N'-methylenebisacrylamide, 1.3-1.6 parts of azobisisobutyronitrile and 4.3-5.5 parts of plant polyphenols; the plant polyphenols are one of tannic acid, catechin, gallic acid and quercetin.

2. The antibacterial composite material for water treatment according to claim 1, characterized in that: The plant polyphenol is tannic acid.

3. The method for preparing the antibacterial composite material for water treatment according to claim 1, characterized in that: The specific steps include: S1. Add the nano-magnetic material to an acetonitrile solution, disperse it by ultrasonication, add acrylic acid, acrylamine and N,N'-methylenebisacrylamide, then add azobisisobutyronitrile and mix well, heat in a water bath, wash and perform magnetic separation to obtain a magnetic composite material; S2, adding the magnetic composite material obtained in S1 to a tris(hydroxymethyl)aminomethane hydrochloride buffer solution with a pH of 8.5 to obtain a dispersion A, and adding the plant polyphenols to anhydrous ethanol to obtain a solution B; S3. Add solution B obtained in S2 to dispersion A, stir in a water bath, soak for 3-4 hours, filter, and dry at 80° C. for 3 hours to obtain an antibacterial composite material for water treatment.

4. The method for preparing the antibacterial composite material for water treatment according to claim 1, characterized in that: The nano magnetic material is prepared from the following components in parts by weight: 21-23 parts of cobalt chloride hexahydrate, 33-38 parts of ferric chloride hexahydrate, 3-5 parts of ammonium hydroxide, 8-10 parts of tetraethyl orthosilicate, 4-6 parts of butyl titanate and 6-8 parts of 3-(methacryloyloxy)propyltrimethoxysilane.

5. The method for preparing the antibacterial composite material for water treatment according to claim 4, characterized in that: The preparation method of the nano magnetic material comprises the following steps: (1) adding cobalt chloride hexahydrate to deionized water, and then adding ferric chloride hexahydrate, mixing well to obtain a transparent solution; (2) adding 3.5 wt % sodium hydroxide solution dropwise into the transparent solution obtained in step (1) until the pH value is 12.5, then transferring the solution into an autoclave, heating the temperature to 230° C. at room temperature at a heating rate of 3-4° C. / min, then cooling to room temperature, washing and drying to obtain magnetic cobalt ferrite; (3) adding the magnetic cobalt ferrite obtained in step (2) to a 75 wt% ethanol solution, followed by adding ammonium hydroxide and ethyl orthosilicate, stirring in a water bath, cooling to room temperature, adding butyl titanate, stirring at 600 rpm for 3 h, standing for 20 h, centrifuging, washing and collecting the precipitate, and baking at high temperature to obtain a magnetic nanocatalyst; (4) Add the magnetic nanocatalyst obtained in step (3) to anhydrous ethanol, add 3-(methacryloyloxy)propyltrimethoxysilane, stir in a water bath, filter, remove non-magnetic and weak magnetic components through magnetic separation, and dry to obtain a magnetic nanomaterial.

6. The method for preparing the antibacterial composite material for water treatment according to claim 3, characterized in that: In S1, the amount of nanomagnetic material added to the acetonitrile solution is 3-4 mg / mL.

7. The method for preparing the antibacterial composite material for water treatment according to claim 3, characterized in that: In S2, the amount of the magnetic composite material obtained in S1 added to the tris(hydroxymethyl)aminomethane hydrochloride buffer solution with a pH of 8.5 is 0.5-0.6 g / mL; the amount of the plant polyphenol added to the anhydrous ethanol is 0.02-0.03 mg / mL.

8. The method for preparing the antibacterial composite material for water treatment according to claim 5, characterized in that: In step (1), the amount of cobalt chloride hexahydrate added to deionized water is 0.04-0.05 g / mL.

9. The method for preparing the antibacterial composite material for water treatment according to claim 5, characterized in that: In step (3), the amount of the magnetic cobalt ferrite obtained in step (2) added to the 75wt% ethanol solution is 0.08-0.12g / mL; the water bath stirring temperature is 40-50°C, the speed is 60-80rpm, and the time is 12-16h; the high temperature baking temperature is 500-600°C, and the time is 3-5h.

10. The method for preparing the antibacterial composite material for water treatment according to claim 5, characterized in that: In step (4), the amount of the magnetic nanocatalyst obtained in step (3) added to anhydrous ethanol is 0.02-0.03 g / mL; the water bath stirring temperature is 30-40° C., the speed is 20-30 rpm, and the time is 2-3 h.

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