CN110903509A - Preparation method of molecularly imprinted nanocomposite membrane for selectively separating atrazine - Google Patents

Preparation method of molecularly imprinted nanocomposite membrane for selectively separating atrazine Download PDF

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CN110903509A
CN110903509A CN201911129765.4A CN201911129765A CN110903509A CN 110903509 A CN110903509 A CN 110903509A CN 201911129765 A CN201911129765 A CN 201911129765A CN 110903509 A CN110903509 A CN 110903509A
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atrazine
membrane
mixed solution
ethanol
preparing
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CN110903509B (en
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邢文东
吴易霖
李春香
闫永胜
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Jiangsu University
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Abstract

The invention belongs to the technical field of functional material preparation, and particularly relates to a preparation method of a molecular imprinting nano composite membrane for selectively separating atrazine; the method comprises the following steps: the method is characterized in that an atrazine molecular imprinting composite membrane is prepared by adopting a method of synergistically modifying biomass activated carbon nanoparticles and silicon dioxide nanoparticles, taking atrazine as a template, methacrylic acid as a functional monomer, ethylene glycol dimethacrylate as a cross-linking agent and azobisisobutyronitrile as an initiator and combining a nano material doping technology and a molecular imprinting polymerization technology; the atrazine molecular imprinting nano composite membrane prepared by the method adopting the synergistic modification of the silicon dioxide and the activated carbon nano particles has higher specific adsorption capacity and recognition separation capacity on atrazine, so that the separation efficiency of the atrazine molecular imprinting nano composite membrane on the atrazine in a complex mixed system is greatly improved.

Description

Preparation method of molecularly imprinted nanocomposite membrane for selectively separating atrazine
Technical Field
The invention belongs to the technical field of functional material preparation, and particularly relates to a preparation method of a molecular imprinting nano composite membrane for selectively separating atrazine.
Background
Membrane Separation Technology (MST) is a separation technology that has received much attention in recent years, and is also a separation means with high efficiency in modern separation technologies. Membrane separation is a process of separating components by means of a membrane under the action of a certain driving force by utilizing the difference of permeation rates of the components in a fluid to the membrane. Compared with traditional separation modes such as distillation and extraction, the membrane separation process has the advantages of high separation efficiency, low energy consumption, no phase change, simple and convenient operation, no secondary pollution, easy recovery of separated products, high automation degree and the like. However, for the separation process on the molecular layer level, conventional microfiltration membranes, nanofiltration membranes, etc. lack the selective separation capability for specific molecules, thus limiting the wider application of membrane separation technology.
Molecular Imprinting (MIT) is a technology of great interest developed in recent years, and the occurrence of MIT well solves the problem of non-selectivity of membrane materials for specific molecules. The principle is that under the condition of template molecule, polymer is formed through the polymerization process between functional monomer and cross-linking agent, and finally the molecular template is removed by means of extraction or acid hydrolysis. Holes which are completely matched with the template molecules in three-dimensional space and have good selectivity to the template molecules are left on the surface of the polymer, and then when the target molecules and the analogues thereof are contacted with the imprinted polymer again, the imprinted sites on the imprinted polymer can specifically adsorb the target molecules and simultaneously do not adsorb non-target molecules, so that the selective separation of single-class molecules is realized. The Molecularly Imprinted Membrane (MIM) prepared by combining MST and MIT has the advantages of easiness in operation, low separation energy consumption, strong single selectivity and the like. In addition, compared with the traditional imprinted microspheres, the blocky imprinted polymers and the like, the MIM has the advantages of stable property, simple preparation process, wide application range, regular form and the like, and is a separation material with good application prospect. Currently, with the rapid development of MST, MIM has been widely used in many fields such as chemical industry, food, medicine, and the like.
Atrazine is a cheap and efficient herbicide, and is one of the most sold herbicides in the world at present. In recent thirty years, atrazine is considered to be a safe and effective product and widely applied to agricultural production. However, in recent years, atrazine has been found to be an endocrine disruptor, and has the harmful effects of immunosuppression, abnormal reproduction, cancer, hormone disorder and the like. Because of stable chemical properties and slow degradation speed, the pesticide is often left in agricultural products and water, and seriously harms the ecological system and human health. But atrazine has stable chemical structure and poor biodegradability, and the existing water treatment technologies such as ozone oxidation, electrolysis, biological treatment, adsorption and the like have poor treatment effect on atrazine and are difficult to meet the stricter environmental standards at present. Therefore, it is of great significance to develop a more selective and reliable atrazine removal strategy.
Researches find that the nano particles are introduced into the porous membrane material to improve the pore structure, the permeation flux and the specific recognition capability of the molecularly imprinted membrane, and the molecularly imprinted nano composite membrane with excellent performance is prepared, so that people pay attention to the molecularly imprinted nano composite membrane. In the application of the invention, degradable biomass material cellulose acetate and chitosan are used as base membrane materials, and the molecular imprinting composite membrane with high-efficiency selective recognition and separation capability on atrazine is prepared through the synergistic modification effect of silicon dioxide and biomass active carbon nano particles and a molecular imprinting technology.
Disclosure of Invention
The invention aims to overcome the technical defects in the prior art, prepare the molecularly imprinted membrane for efficiently separating the atrazine pollutants, and provide a new idea for solving the problems of low selectivity, poor membrane flux and the like of the traditional molecularly imprinted membrane.
A preparation method of a molecular imprinting nano composite membrane for selectively separating atrazine comprises the following steps:
s1, surface activation modification of the silica nanoparticles:
mixing silicon dioxide (SiO)2) Washing the nano particles with alcohol, centrifuging and drying in vacuum to obtain dry SiO2(ii) a Preparing mixed solution of ethanol and water, adding dry SiO2Reacting with gamma- (methacryloyloxy) propyl trimethoxy silane (kh570) in a water bath heating way, taking out a product after the reaction is finished, cleaning the product with ethanol and deionized water, centrifuging and drying in vacuum to obtain modified SiO2；
S2, activation modification of the surface of the biomass activated carbon nano particles:
washing the biomass activated carbon nano-particles with alcohol, centrifuging, and drying in vacuum to obtain dried activated carbon nano-particles; preparing a mixed solution of ethanol and water, adding dried biomass active carbon nano particles and gamma- (methacryloyloxy) propyl trimethoxy silane (kh570), then carrying out water bath heating reaction, taking out a product after the reaction is finished, cleaning the product with ethanol and deionized water, and then centrifuging and drying in vacuum to obtain modified biomass active carbon nano particles;
s3, preparing the cellulose/chitosan hybrid membrane synergistically modified by the two nanoparticles:
firstly, adding cellulose acetate, chitosan, polyvinyl alcohol, polyvinylpyrrolidone and S1 modified SiO into dimethyl sulfoxide2And the biomass activated carbon nano-particles modified by S2 to obtain a mixed solution; after the mixed solution is subjected to ultrasonic treatment, adding a certain amount of glutaraldehyde; and then carrying out water bath heating and mechanical stirring to prepare a casting solution, standing for defoaming, preparing a membrane by adopting a phase inversion method, washing the prepared membrane by using deionized water, and airing at room temperature to obtain the nanoparticle modified cellulose/chitosan hybrid membrane.
S4, preparing an atrazine molecular imprinting nano composite membrane (AMINMs):
firstly, adding atrazine, methacrylic acid and ethylene glycol dimethacrylate into ethanol to obtain a mixed solution; then, properly cutting the nanoparticle modified cellulose/chitosan hybrid membrane prepared in the step S3, immersing the membrane into a mixed solution, and adding azobisisobutyronitrile after uniformly magnetically stirring; and then carrying out imprinting polymerization reaction under the condition of nitrogen protection to obtain an imprinted membrane, washing with ethanol, washing with eluent, and airing to obtain the atrazine molecular imprinting nano composite membrane, which is marked as AMINMs.
Preferably, in step S1, the ratio of the silica nanoparticles, γ - (methacryloyloxy) propyltrimethoxysilane, and the mixed solution is 0.5 to 1.5 g: 3mL of: 100 mL; the volume ratio of ethanol to water in the mixed solution is 4: 1.
Preferably, in step S2, the biomass activated carbon nanoparticles, the gamma- (methacryloyloxy) propyltrimethoxysilane, and the mixed solution are used in a ratio of 1.0 g: 3mL of: 100 mL; the volume ratio of ethanol to water in the mixed solution is 4: 1.
Preferably, in the steps S1 and S2, the heating temperature is 70-80 ℃ and the time is 20-24 hours; the centrifugation condition is 8000 revolutions per minute, and the time is 5-10 min; the vacuum drying temperature is 60-70 ℃.
Preferably, in step S3, the cellulose acetate, chitosan, polyvinyl alcohol, polyvinyl pyrrolidone, and modified SiO are used2The dosage ratio of the modified biomass active carbon nano particles to the dimethyl sulfoxide is 3 g: 0.1 g: 0.5 g: 0.2 g: 0.4 g: 0.5 g: 40 mL; the volume ratio of the glutaraldehyde to the dimethyl sulfoxide is 1: 20.
Preferably, in step S3, the water bath heating temperature is 50 ℃ and the time is 12 hours; the coagulating bath in the phase inversion process is pure water.
Preferably, in step S4, the size of the nanoparticle-modified cellulose/chitosan hybrid membrane after being properly cut is 35 × 35 × 0.2mm, and the dosage is 3 pieces;
preferably, in step S4, the usage ratio of atrazine, methacrylic acid, ethylene glycol dimethacrylate and ethanol solution is 0.2 to 0.8 mmol: 1.5-2.5 mmol: 8-12 mmol: 50 mL; the dosage ratio of the azodiisobutyronitrile to the ethanol solution is 15-25 mg:50 mL.
Preferably, in step S4, the blotting polymerization reaction specifically comprises: the reaction was carried out at 50 ℃ for 6h and then at 60 ℃ for 24 h.
Preferably, in step S4, the eluent is a mixed solution of acetic acid and methanol at a volume ratio of 95: 5; the elution mode is that the shaking is carried out at room temperature, the eluent is changed every 3h, and the elution process lasts for 2 d.
The cellulose acetate and the chitosan in the technical scheme are used as raw materials for preparing the basement membrane.
The biomass activated carbon nano-particles and the silicon dioxide nano-particles in the technical scheme act as nano-doping materials.
The gamma- (methacryloyloxy) propyl trimethoxy silane in the technical scheme is used as a nanoparticle surface modification reagent.
The atrazine in the above technical scheme has the function of acting as a template molecule.
The methacrylic acid in the technical scheme is used as a functional monomer.
The ethylene glycol dimethacrylate in the technical scheme is used as a cross-linking agent.
The azobisisobutyronitrile in the technical scheme has the function of an initiator.
The ethanol in the technical scheme is used as a solvent.
The acetic acid in the technical scheme is used as an eluent raw material.
The invention also comprises the application of the atrazine molecular imprinting nano-composite membrane in the selective adsorption and separation of atrazine, in particular to the selective adsorption and separation of atrazine in a mixed solution of atrazine and structural analogues (ametryn and terbuthylazine).
And (3) testing the material performance:
(1) selective adsorption experiment
Respectively weighing 7 parts of AMIMs, putting the AMINMs into a glass test tube, respectively adding 10mL of atrazine, ametryn and terbuthylazine mixed solution with the concentration of 5,10,15,20,40,60,100mg/L, standing and adsorbing for 180min at room temperature, measuring the concentration of the atrazine, ametryn and terbuthylazine which are not adsorbed in the solution by a high performance liquid chromatograph after the adsorption is finished, and calculating the adsorption capacity (Qe, mg/g) according to the result:
Q＝ (C0- Ce) × V / m (1)
wherein C is0(mg/L) and Ce(mg/L) is the concentration of the same substance in the solution before and after adsorption, V (mL) is the volume of the adsorption solution, and m (g) is the mass of the AMINMs added.
(2) Selective permeability test
A self-made combined H-shaped glass infiltration device is characterized in that the middle of the device is disconnected into two ground branch pipes, AMINMs are fixed between ground ports of two glass pools, a joint is sealed by using a degreasing adhesive tape and a waterproof adhesive tape to ensure that the device has no leakage, a mixed solution of atrazine, ametryn and terbuthylazine with the same concentration (60mg/L) is added into a sample pool on one side, an isometric solvent is added into a sample pool on the other side, two magnetons are respectively placed into the two sample pools and stirred at room temperature, sampling is carried out after different infiltration times (5,10,15,30,45,60,90,120 and 180min), the concentration of each substance penetrating through a molecular imprinting nano-composite membrane is measured by a high performance liquid chromatograph, and the infiltration amount is calculated according to the concentration.
The invention has the advantages and technical effects that:
(1) compared with the traditional molecularly imprinted membrane materials such as polyvinylidene fluoride and polysulfone, the invention based on the biomass membrane materials chitosan and cellulose has good biodegradability, so the invention is also an environment-friendly membrane material.
(2) The biomass activated carbon material used in the invention is a renewable resource, has wide source and simple preparation process, has more delicate and rich pore structure and huge specific surface area, and has the characteristics of strong adsorption capacity, strong chemical stability, high mechanical strength, convenient regeneration and the like; the method is applied to the molecularly imprinted membrane, and the comprehensive performance of the imprinted membrane is improved.
(3) According to the invention, the synergistic modification method of the silicon dioxide and the biomass activated carbon nanoparticles can be obtained through comparison experiment results, and the prepared AMINMs have the advantage of strong selective adsorption capacity, so that the separation efficiency of the AMINMs on the atrazine in a complex mixed system is greatly improved.
(4) By optimizing the proportion of the template molecule, the functional monomer and the cross-linking agent, the optimal imprinting effect is realized in the imprinting polymerization process, the target molecule specificity recognition capability of the atrazine molecular imprinting nano composite membrane is further improved, and the separation performance of the atrazine to the molecular imprinting nano composite membrane is enhanced.
Drawings
In fig. 1, (a) and (b) are scanning electron microscope images of the silica and biomass activated carbon nanoparticles in example 2, respectively, and (c) and (d) are scanning electron microscope images of the nanoparticle synergistically modified cellulose/chitosan hybrid membrane and the atrazine molecularly imprinted nanocomposite membrane in example 2, respectively.
In fig. 2(a) and (b) are the selective adsorption and selective permeation curves, respectively, for the AMINMs prepared in example 1.
In fig. 3 (a) and (b) are the selective adsorption and selective permeation curves, respectively, for the AMINMs prepared in example 2.
In fig. 4(a) and (b) are the selective adsorption and selective permeation curves, respectively, for the AMINMs prepared in example 3.
Detailed Description
The biomass active carbon nano-particles used in the invention are purchased from Beijing Deke island gold science and technology Co., Ltd, and the average particle size is 500 nm; the invention is further described with reference to the drawings and the detailed description.
Comparative example 1:
s1, preparing silicon dioxide nano particles and carrying out surface activation modification;
first, 50mL of solution A (4.0mL of tetraethylorthosilicate and 46mL of ethanol) was added to 50mL of solution B (9.0mL of ammonia, 16mL of ethanol and 25mL of distilled water) and stirred at 500r/min for 2h to prepare SiO2A nanoparticle; the prepared SiO2Washing the nanoparticles with alcohol for three times, centrifuging at 8000 rpm for 5min, and vacuum drying at 65 deg.C; taking 1g of dried SiO2Dispersing the mixture and 3mL of kh570 in 100mL of mixed solution containing ethanol and water (4:1), and heating the mixed solution in a water bath at the temperature of 80 ℃ for reaction for 24 h; after the reaction is finished, washing the product with ethanol and deionized water, finally centrifugally separating the product, and drying in vacuum to obtain modified SiO2；
S2, preparation of a silica modified cellulose/chitosan hybrid membrane:
firstly, adding 3g of cellulose acetate, 0.1g of chitosan, 0.5g of polyvinyl alcohol, 0.2g of polyvinylpyrrolidone and 0.9g of modified silica nanoparticles into 40mL of dimethyl sulfoxide; after the mixture is treated by ultrasonic for 30min, 2mL of glutaraldehyde is added; then the mixture system was heated in a 50 ℃ water bath and mechanically stirred for 12h to prepare a casting solution; standing for defoaming, preparing a membrane by adopting a phase inversion method, finally cleaning the prepared membrane by using deionized water, and airing at room temperature to obtain a nanoparticle modified cellulose/chitosan hybrid membrane;
s3, preparation of the silica modified atrazine molecular imprinting nano composite membrane:
firstly, adding 0.2mmol of atrazine, 1.5mmol of methacrylic acid and 8mmol of ethylene glycol dimethacrylate into 50mL of ethanol to obtain a mixed solution; then the silicon dioxide modified cellulose/chitosan hybrid membrane prepared in the step S2 is properly cut, and the size is 35 multiplied by 0.2 mm; cutting, immersing 3 base films into the mixed solution, uniformly stirring by magnetism, and adding 15mg of azodiisobutyronitrile; and then reacting at 50 ℃ for 6 hours under the protection of nitrogen, reacting at 60 ℃ for 24 hours, taking out the imprinted membrane, washing with ethanol for three times, then placing the imprinted membrane in 100mL of eluent composed of methanol and acetic acid (the methanol is 95mL of acetic acid and is 5mL), oscillating at room temperature, changing the eluent once every 3 hours, continuing the elution process for 2 days, washing the eluent to remove template molecules, and drying at room temperature to obtain the final silica modified atrazine molecularly imprinted nano composite membrane.
And (3) testing the selective adsorption performance of the silicon dioxide modified atrazine molecular imprinting nano composite membrane:
the prepared silicon dioxide modified molecular imprinting membrane is adopted to carry out selective adsorption experiments, and the experimental result shows that the adsorption capacity of the mixed solution with the concentration of 5,10,15,20,40,60,100mg/L for 3h for atrazine, ametryn and terbuthylazine is respectively 0.87,2.13,2.64,3.27,4.14,4.65 and 4.91 mg/g; 0.87,1.31,1.42,1.57,1.94,2.03,2.14 mg/g; 0.61,1.43,1.76,1.93,2.04,2.36,2.47 mg/g; the experimental result shows that the adsorption capacity of the prepared atrazine molecular imprinting composite membrane on atrazine is higher than that of ametryn and terbuthylazine in a mixed solution with the concentration of 5-150 mg/L, namely the prepared atrazine molecular imprinting composite membrane has the function of selective adsorption and separation on atrazine. And the results of this experiment were compared with the results of selective adsorption in example 2.
Example 1:
s1, surface activation modification of the silicon dioxide nano particles;
first, 50mL of solution A (4.0mL of tetraethylorthosilicate and 46mL of ethanol) was added to 50mL of solution B(9.0mL of ammonia water, 16mL of ethanol and 25mL of distilled water), and stirring at the rotating speed of 500r/min for 2 hours to prepare SiO2A nanoparticle;
the prepared SiO2Washing the nanoparticles with alcohol for three times, centrifuging at 8000 rpm for 5min, and vacuum drying at 65 deg.C; 0.5g of dried SiO was taken2Dispersing the mixture and 3mL of kh570 in 100mL of mixed solution containing ethanol and water (4:1), and heating the mixed solution in a water bath at the temperature of 80 ℃ for reaction for 24 h; after the reaction is finished, washing the product with ethanol and deionized water, finally centrifugally separating the product, and drying in vacuum to obtain modified SiO2；
S2, surface activation modification of biomass activated carbon nano particles;
washing the biomass active carbon nanoparticles with alcohol for three times, centrifuging at 8000 rpm for 5min, and vacuum drying at 65 deg.C; taking 1g of dried SiO2Dispersing the mixture and 3mL of kh570 in 100mL of mixed solution containing ethanol and water (4:1), and heating the mixed solution in a water bath at the temperature of 80 ℃ for reaction for 24 h; after the reaction is finished, washing the product by using ethanol and deionized water, finally centrifugally separating the product, and drying in vacuum to obtain modified biomass activated carbon nano particles;
s3, preparing the cellulose/chitosan hybrid membrane synergistically modified by the two nanoparticles:
firstly, adding 3g of cellulose acetate, 0.1g of chitosan, 0.5g of polyvinyl alcohol, 0.2g of polyvinylpyrrolidone, 0.5g of modified biomass activated carbon nanoparticles and 0.4g of modified silica nanoparticles into 40mL of dimethyl sulfoxide; after the mixture is treated by ultrasonic for 30min, 2mL of glutaraldehyde is added; then the mixture system was heated in a 50 ℃ water bath and mechanically stirred for 12h to prepare a casting solution; standing for defoaming, preparing a membrane by adopting a phase inversion method, finally cleaning the prepared membrane by using deionized water, and airing at room temperature to obtain a nanoparticle modified cellulose/chitosan hybrid membrane;
s4, preparing an atrazine molecular imprinting nano composite membrane (AMINMs):
firstly, adding 0.2mmol of atrazine, 1.5mmol of methacrylic acid and 8mmol of ethylene glycol dimethacrylate into 50mL of ethanol to obtain a mixed solution; then properly cutting the nanoparticle modified cellulose/chitosan hybrid membrane prepared in the step S3 to have the size of 35 multiplied by 0.2 mm; cutting, immersing 3 base films into the mixed solution, uniformly stirring by magnetism, and adding 15mg of azodiisobutyronitrile; and then reacting at 50 ℃ for 6 hours under the protection of nitrogen, reacting at 60 ℃ for 24 hours, taking out the imprinted membrane, washing with ethanol for three times, then placing the imprinted membrane in 100mL of eluent composed of methanol and acetic acid (the methanol: the acetic acid is 95 mL: 5mL), oscillating at room temperature, changing the eluent once every 3 hours, continuing the elution process for 2 days, washing the eluent to remove template molecules, and drying at room temperature to obtain the final atrazine molecular imprinting nano composite membrane which is marked as AMINs.
Ammms separation performance test:
(1) selective adsorption experiment
FIG. 2(a) is a graph showing the selective adsorption curves of the prepared AMINOMs, and the experimental results show that the 3-hour adsorption amounts of the AMINOMs to atrazine, ametryn and terbuthylazine in the mixed solution with the concentration of 5,10,15,20,40,60,100mg/L are respectively 1.52,2.68,3.31,3.98,4.82,5.13 and 5.42 mg/g; 0.97,1.31,1.54,1.55,1.78,2.04,2.24 mg/g; 1.02,1.53,1.82,1.93,2.13,2.41,2.56 mg/g; the experimental result shows that the adsorption capacity of the prepared atrazine molecular imprinting composite membrane on atrazine is higher than that of ametryn and terbuthylazine in a mixed solution with the concentration of 5-100 mg/L, namely the prepared atrazine molecular imprinting composite membrane has the function of selective adsorption and separation on atrazine.
(2) Selective permeability test
The results of the AMINMS permselective experiments in FIG. 2(b) show that in the mixed aqueous solution of atrazine, ametryn and terbuthylazine with initial concentration of 60mg/L, the atrazine concentration in the blank sample cell was measured as 0.52,0.66,0.72,0.83,0.91,1.02,1.14,1.21,1.32mg/L at sampling time of 5,10,15,30,45,60,90,120,180min, respectively, and the atrazine concentration in the blank sample cell was measured as 0.51,0.72,1.04,1.41,1.72,1.98,2.36,2.57,2.69mg/L, and the terbuthylazine concentration was measured as 0.49,0.67,0.91,1.26,1.54,1.76,2.15,2.36,2.45mg/L, respectively. The experimental results show that the prepared AMINOMs have the effect of inhibiting penetration of atrazine and have no influence on atrazine and terbuthylazine within 5-180 min, so that the selective separation of atrazine and analogues thereof is realized.
Example 2:
s1, surface activation modification of the silicon dioxide nano particles; (ii) a
First, 50mL of solution A (4.0mL of tetraethylorthosilicate and 46mL of ethanol) was added to 50mL of solution B (9.0mL of ammonia, 16mL of ethanol and 25mL of distilled water) and stirred at 500r/min for 2h to prepare SiO2A nanoparticle;
the prepared SiO2Washing the nanoparticles with alcohol for three times, centrifuging at 8000 rpm for 5min, and vacuum drying at 65 deg.C; taking 1g of dried SiO2Dispersing the mixture and 3mL of kh570 in 100mL of mixed solution containing ethanol and water (4:1), and heating the mixed solution in a water bath at the temperature of 80 ℃ for reaction for 24 h; after the reaction is finished, washing the product with ethanol and deionized water, finally centrifugally separating the product, and drying in vacuum to obtain modified SiO2(ii) a The scanning image of the modified silica nano-particles is shown as the (a) image in figure 1;
s2, surface activation modification of biomass activated carbon nano particles;
washing the biomass active carbon nanoparticles with alcohol for three times, centrifuging at 8000 rpm for 5min, and vacuum drying at 65 deg.C; taking 1g of dried SiO2Dispersing the mixture and 3mL of kh570 in 100mL of mixed solution containing ethanol and water (4:1), and heating the mixed solution in a water bath at the temperature of 80 ℃ for reaction for 24 h; after the reaction is finished, washing the product by using ethanol and deionized water, finally centrifugally separating the product, and drying in vacuum to obtain modified biomass activated carbon nano particles; the scanning image of the obtained modified biomass activated carbon nano-particles is shown as a (b) image in fig. 1;
s3, preparing the cellulose/chitosan hybrid membrane synergistically modified by the two nanoparticles:
firstly, adding 3g of cellulose acetate, 0.1g of chitosan, 0.5g of polyvinyl alcohol, 0.2g of polyvinylpyrrolidone, 0.5g of modified biomass activated carbon nanoparticles and 0.4g of modified silica nanoparticles into 40mL of dimethyl sulfoxide; after the mixture is treated by ultrasonic for 30min, 2mL of glutaraldehyde is added; then the mixture system was heated in a 50 ℃ water bath and mechanically stirred for 12h to prepare a casting solution; standing for defoaming, preparing a membrane by adopting a phase inversion method, finally cleaning the prepared membrane by using deionized water, and airing at room temperature to obtain a nanoparticle modified cellulose/chitosan hybrid membrane; the prepared hybrid membrane scanning image is shown as a graph (c) in figure 1, and the porous morphological characteristics of the hybrid membrane can be seen;
s4, preparing an atrazine molecular imprinting nano composite membrane (AMINMs):
firstly, adding 0.5mmol of atrazine, 2mmol of methacrylic acid and 10mmol of ethylene glycol dimethacrylate into 50mL of ethanol to obtain a mixed solution; then properly cutting the nanoparticle modified cellulose/chitosan hybrid membrane prepared in the step S3 to have the size of 35 multiplied by 0.2 mm; cutting, immersing 3 base films into the mixed solution, uniformly stirring by magnetism, and adding 20mg of azodiisobutyronitrile; then under the protection of nitrogen, reacting at 50 ℃ for 6 hours, reacting at 60 ℃ for 24 hours, taking out the imprinted membrane, washing with ethanol for three times, then placing the imprinted membrane in 100mL of eluent composed of methanol and acetic acid (the methanol: the acetic acid is 95 mL: 5mL), oscillating at room temperature, changing the eluent once every 3 hours, continuing the elution process for 2 days, washing the eluent to remove template molecules, drying at room temperature, and obtaining the final atrazine molecular imprinting nano composite membrane which is marked as AMINs; the scanning electron micrograph of the prepared AMINMs is shown in FIG. 1, panel (d), and it can be seen that a layer of imprinted polymer is formed on the surface of the film.
Ammms separation performance test:
(1) selective adsorption experiment
FIG. 3 (a) is a selective adsorption curve of the prepared AMINOMs, and the experimental results show that the 3-hour adsorption amounts of the AMINOMs to atrazine, ametryn and terbuthylazine in the mixed solution with the concentration of 5,10,15,20,40,60,100mg/L are respectively 1.64,2.92,3.47,4.13,4.97,5.38 and 5.64 mg/g; 1.01,1.42,1.63,1.75,2.02,2.19,2.31 mg/g; the experimental results show that the adsorption capacity of the prepared atrazine molecular imprinting composite membrane on atrazine is higher than that of ametryn and terbuthylazine in a mixed solution with the concentration of 5-150 mg/L, namely the prepared atrazine molecular imprinting composite membrane has the selective adsorption separation effect on atrazine. (2) Selective permeability test
The results of the AMINMS permselective experiments in FIG. 3 (b) show that in the mixed aqueous solution of atrazine, atrazine and terbuthylazine each at an initial concentration of 60mg/L, the atrazine concentration in the blank cell was measured at 0.41,0.46,0.57,0.75,0.83,0.89,0.97,1.03,1.13mg/L at sampling times of 5,10,15,30,45,60,90,120,180min, respectively, and the atrazine concentration in the blank cell was measured at 0.43,0.69,0.91,1.30,1.64,1.92,2.27,2.42,2.52mg/L, and the terbuthylazine concentration was measured at 0.48,0.51,0.73,1.15,1.46,1.74,2.05,2.16,2.26mg/L, respectively. The experimental results show that the prepared AMINOMs have the effect of inhibiting penetration of atrazine and have no influence on atrazine and terbuthylazine within 5-180 min, so that the selective separation of atrazine and analogues thereof is realized.
Example 3:
s1, preparing nanoparticles, and performing activation modification;
first, 50mL of solution A (4.0mL of tetraethylorthosilicate and 46mL of ethanol) was added to 50mL of solution B (9.0mL of ammonia, 16mL of ethanol and 25mL of distilled water) and stirred at 500r/min for 2h to prepare SiO2A nanoparticle;
the prepared SiO2Washing the nanoparticles with alcohol for three times, centrifuging at 8000 rpm for 5min, and vacuum drying at 65 deg.C; taking 1.5g of dried SiO2Dispersing the mixture and 3mL of kh570 in 100mL of mixed solution containing ethanol and water (4:1), and heating the mixed solution in a water bath at the temperature of 80 ℃ for reaction for 24 h; after the reaction is finished, washing the product with ethanol and deionized water, finally centrifugally separating the product, and drying in vacuum to obtain modified SiO2；
S2, modifying kh570 on the surface of the biomass activated carbon nano particles;
washing the activated carbon nanoparticles with alcohol for three times, centrifuging at 8000 rpm for 5min, and vacuum drying at 65 deg.C; 1g of dried Si was takenO2Dispersing the mixture and 3mL of kh570 in 100mL of mixed solution containing ethanol and water (4:1), and heating the mixed solution in a water bath at the temperature of 80 ℃ for reaction for 24 h; after the reaction is finished, washing the product by using ethanol and deionized water, finally centrifugally separating the product, and drying in vacuum to obtain modified biomass activated carbon nano particles;
s3, preparing the cellulose/chitosan hybrid membrane synergistically modified by the two nanoparticles:
firstly, adding 3g of cellulose acetate, 0.1g of chitosan, 0.5g of polyvinyl alcohol, 0.2g of polyvinylpyrrolidone, 0.5g of modified biomass activated carbon nanoparticles and 0.4g of modified silica nanoparticles into 40mL of dimethyl sulfoxide; after the mixture is treated by ultrasonic for 30min, 2mL of glutaraldehyde is added; then the mixture system was heated in a 50 ℃ water bath and mechanically stirred for 12h to prepare a casting solution; standing for defoaming, preparing a membrane by adopting a phase inversion method, finally cleaning the prepared membrane by using deionized water, and airing at room temperature to obtain a nanoparticle modified cellulose/chitosan hybrid membrane;
s4, preparing an atrazine molecular imprinting nano composite membrane (AMINMs):
firstly, adding 0.8mmol of atrazine, 2.5mmol of methacrylic acid and 12mmol of ethylene glycol dimethacrylate into 50mL of ethanol to obtain a mixed solution; then properly cutting the nanoparticle modified cellulose/chitosan hybrid membrane prepared in the step S3 to have the size of 35 multiplied by 0.2 mm; cutting, immersing 3 base films into the mixed solution, uniformly stirring by magnetism, and adding 25mg of azodiisobutyronitrile; and then reacting at 50 ℃ for 6 hours under the protection of nitrogen, reacting at 60 ℃ for 24 hours, taking out the imprinted membrane, washing with ethanol for three times, then placing the imprinted membrane in 100mL of eluent composed of methanol and acetic acid (the methanol: the acetic acid is 95 mL: 5mL), oscillating at room temperature, changing the eluent once every 3 hours, continuing the elution process for 2 days, washing the eluent to remove template molecules, and drying at room temperature to obtain the final atrazine molecular imprinting nano composite membrane which is marked as AMINs.
Ammms separation performance test:
(1) selective adsorption experiments;
FIG. 4(a) is a graph showing the selective adsorption curves of the prepared AMINOMs, and the experimental results show that the 3-hour adsorption amounts of the AMINOMs to atrazine, ametryn and terbuthylazine in the mixed solution with the concentration of 5,10,15,20,40,60,100mg/L are 1.57,2.78,3.39,4.02,4.76,5.03 and 5.34mg/g, respectively; 0.94,1.32,1.48,1.49,1.79,2.01,2.17 mg/g; 1.12,1.63,1.84,1.97,2.35,2.54,2.67 mg/g; the experimental result shows that the adsorption capacity of the prepared atrazine molecular imprinting composite membrane on atrazine is higher than that of ametryn and terbuthylazine in a mixed solution with the concentration of 5-100 mg/L, namely the prepared atrazine molecular imprinting composite membrane has the function of selective adsorption and separation on atrazine.
(2) Selecting a permeability experiment;
the results of the AMINMS permselective experiments in FIG. 4(b) show that in the mixed aqueous solution of atrazine, atrazine and terbuthylazine each at an initial concentration of 60mg/L, the atrazine concentration in the blank cell was measured at 0.53,0.65,0.74,0.97,1.03,1.12,1.18,1.23,1.34mg/L at 5,10,15,30,45,60,90,120,180min, respectively, and the atrazine concentration in the blank cell was measured at 0.48,0.76,1.03,1.52,1.84,2.07,2.28,2.45,2.57mg/L, and the terbuthylazine concentration was measured at 0.42,0.63,0.88,1.31,1.64,1.79,2.04,2.21,2.31mg/L, respectively. The experimental results show that the prepared AMINOMs have the effect of inhibiting penetration of atrazine and have no influence on atrazine and terbuthylazine within 5-180 min, so that the selective separation of atrazine and analogues thereof is realized.
Compared with the experimental result of comparative example 1, the imprinted membrane synergistically modified by the biomass activated carbon nanoparticles and the silica nanoparticles in the examples has obviously improved specific adsorption capacity for atrazine compared with the imprinted membrane modified by silica alone.
Description of the drawings: the above embodiments are only used to illustrate the present invention and do not limit the technical solutions described in the present invention; thus, while the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted; all such modifications and variations are intended to be included herein within the scope of this disclosure and the present invention and protected by the following claims.

Claims (9)

1. A preparation method of a molecularly imprinted nanocomposite membrane for selectively separating atrazine is characterized by comprising the following specific steps:
s1, washing the silicon dioxide nanoparticles with alcohol, centrifuging, and drying in vacuum to obtain dry silicon dioxide; preparing a mixed solution of ethanol and water, adding dried silicon dioxide and gamma- (methacryloyloxy) propyl trimethoxy silane, then carrying out water bath heating reaction, taking out a product after the reaction is finished, cleaning the product with ethanol and deionized water, and then carrying out centrifugation and vacuum drying to obtain modified silicon dioxide;
s2, washing the biomass active carbon nano-particles with alcohol, centrifuging, and drying in vacuum to obtain dried biomass active carbon nano-particles; preparing a mixed solution of ethanol and water, adding dried biomass active carbon nano particles and gamma- (methacryloyloxy) propyl trimethoxy silane, then carrying out water bath heating reaction, taking out a product after the reaction is finished, cleaning the product with ethanol and deionized water, and then centrifuging and drying in vacuum to obtain modified biomass active carbon nano particles;
s3, firstly, adding cellulose acetate, chitosan, polyvinyl alcohol, polyvinylpyrrolidone, modified silicon dioxide in S1 and modified biomass activated carbon nano-particles in S2 into dimethyl sulfoxide to obtain a mixed solution; after the mixed solution is subjected to ultrasonic treatment, adding a certain amount of glutaraldehyde; then heating in water bath and mechanically stirring to prepare a casting solution, standing for defoaming, preparing a membrane by adopting a phase inversion method, cleaning the prepared membrane by using deionized water, and airing at room temperature to obtain a nanoparticle modified cellulose/chitosan hybrid membrane;
s4, adding atrazine, methacrylic acid and ethylene glycol dimethacrylate into ethanol to obtain a mixed solution; then, properly cutting the nanoparticle modified cellulose/chitosan hybrid membrane prepared in the step S3, immersing the membrane into a mixed solution, and adding azobisisobutyronitrile after uniformly magnetically stirring; and then carrying out imprinting polymerization reaction under the protection of nitrogen to obtain an imprinted membrane, washing with ethanol, washing with eluent, and drying to obtain the atrazine molecular imprinting nano composite membrane, which is marked as AMINMs.
2. The method for preparing a molecularly imprinted nanocomposite membrane for selectively separating atrazine according to claim 1, wherein in step S1, the ratio of the silicon dioxide nanoparticles to the gamma- (methacryloyloxy) propyl trimethoxysilane to the mixed solution is 0.5-1.5 g: 3mL of: 100 mL; the volume ratio of ethanol to water in the mixed solution is 4: 1.
3. The method for preparing a molecularly imprinted nanocomposite membrane for selectively separating atrazine according to claim 1, wherein in step S2, the dosage ratio of the biomass activated carbon nanoparticles, gamma- (methacryloyloxy) propyl trimethoxysilane and the mixed solution is 1.0 g: 3mL of: 100 mL; the volume ratio of ethanol to water in the mixed solution is 4: 1.
4. The preparation method of the molecularly imprinted nanocomposite membrane for selectively separating atrazine according to claim 1, wherein in the steps S1 and S2, the heating temperature is 70-80 ℃ and the time is 20-24 hours; the centrifugation condition is 8000 revolutions per minute, and the time is 5-10 min; the vacuum drying temperature is 60-70 ℃.
5. The method for preparing the molecularly imprinted nanocomposite membrane for selectively separating atrazine according to claim 1, wherein in step S3, the cellulose acetate, chitosan, polyvinyl alcohol, polyvinylpyrrolidone and modified SiO are added2The dosage ratio of the modified biomass active carbon nano particles to the dimethyl sulfoxide is 3 g: 0.1 g: 0.5 g: 0.2 g: 0.4 g: 0.5 g: 40 mL; the volume ratio of the glutaraldehyde to the dimethyl sulfoxide is 1: 20.
6. The method for preparing a molecularly imprinted nanocomposite membrane for selectively separating atrazine according to claim 1, wherein in step S3, the water bath heating temperature is 50 ℃ and the time is 12 hours; the coagulating bath used in the phase inversion process is pure water.
7. The preparation method of the molecularly imprinted nanocomposite membrane for selectively separating atrazine according to claim 1, wherein in step S4, the dosage ratio of atrazine, methacrylic acid, ethylene glycol dimethacrylate and ethanol solution is 0.2-0.8 mmol: 1.5-2.5 mmol: 8-12 mmol: 50 mL; the dosage ratio of the azodiisobutyronitrile to the ethanol solution is 15-25 mg:50 mL.
8. The method for preparing a molecularly imprinted nanocomposite membrane for selectively separating atrazine according to claim 1, wherein in step S4, the imprinting polymerization reaction comprises the following specific steps: the reaction was carried out at 50 ℃ for 6h and then at 60 ℃ for 24 h.
9. The method for preparing the molecularly imprinted nanocomposite membrane for selectively separating atrazine according to claim 1, wherein in step S4, the eluent is a mixed solution of acetic acid and methanol in a volume ratio of 95: 5; the cleaning mode is that the shaking is carried out at room temperature, the eluent is changed every 3h, and the elution process lasts for 2 d.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111871375A (en) * 2020-08-17 2020-11-03 常州大学 Preparation method and application of biochar with efficient atrazine adsorption performance

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20110035454A (en) * 2009-09-30 2011-04-06 주식회사 아모메디 Nano-fibered membrane for western blot and manufacturing method of the same
KR20120021734A (en) * 2010-08-16 2012-03-09 주식회사 아모메디 Nano-fibered membrane of hydrophile property for western blot by plasma coating and manufacturing method of the same
CN102764598A (en) * 2012-07-17 2012-11-07 西安建筑科技大学 Preparation method of molecular engram composite film for separating tryptophane isomer
CN103028331A (en) * 2013-01-03 2013-04-10 盐城工学院 Preparation method of hydroxyethyl cellulose-silicon dioxide pervaporation hybrid membrane
CN104231166A (en) * 2014-09-05 2014-12-24 江苏大学 Preparation method of bionic artemisinin molecular imprinting composite membrane
CN104759263A (en) * 2015-03-25 2015-07-08 江苏大学 A preparing method of a multiwalled carbon nanotube doped salicylic acid blend imprinted membrane
CN106881069A (en) * 2017-03-09 2017-06-23 吉林师范大学 A kind of preparation method and application of temperature response type europium ion trace composite membrane
CN108097072A (en) * 2017-12-18 2018-06-01 长春工业大学 A kind of hydrophilic modifying CPVA-PVDF ultrafiltration membranes and preparation method thereof
CN108246266A (en) * 2017-11-22 2018-07-06 广东工业大学 A kind of preparation of Atrazine surface molecule print magnetic mesoporous material and application process
CN108816058A (en) * 2018-06-27 2018-11-16 江苏大学 A kind of rheum emodin molecular engram titanium dioxide nano-particle composite membrane and the preparation method and application thereof
CN109364770A (en) * 2018-11-28 2019-02-22 江苏大学 A kind of preparation method and applications of gadolinium ion trace nano-carbon material composite membrane
WO2019090470A1 (en) * 2017-11-07 2019-05-16 蔡燕铃 Highly permeable and highly selective pva/ga/cs-m+ pervaporation film for dehydration of organic solutions

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20110035454A (en) * 2009-09-30 2011-04-06 주식회사 아모메디 Nano-fibered membrane for western blot and manufacturing method of the same
KR20120021734A (en) * 2010-08-16 2012-03-09 주식회사 아모메디 Nano-fibered membrane of hydrophile property for western blot by plasma coating and manufacturing method of the same
CN102764598A (en) * 2012-07-17 2012-11-07 西安建筑科技大学 Preparation method of molecular engram composite film for separating tryptophane isomer
CN103028331A (en) * 2013-01-03 2013-04-10 盐城工学院 Preparation method of hydroxyethyl cellulose-silicon dioxide pervaporation hybrid membrane
CN104231166A (en) * 2014-09-05 2014-12-24 江苏大学 Preparation method of bionic artemisinin molecular imprinting composite membrane
CN104759263A (en) * 2015-03-25 2015-07-08 江苏大学 A preparing method of a multiwalled carbon nanotube doped salicylic acid blend imprinted membrane
CN106881069A (en) * 2017-03-09 2017-06-23 吉林师范大学 A kind of preparation method and application of temperature response type europium ion trace composite membrane
WO2019090470A1 (en) * 2017-11-07 2019-05-16 蔡燕铃 Highly permeable and highly selective pva/ga/cs-m+ pervaporation film for dehydration of organic solutions
CN108246266A (en) * 2017-11-22 2018-07-06 广东工业大学 A kind of preparation of Atrazine surface molecule print magnetic mesoporous material and application process
CN108097072A (en) * 2017-12-18 2018-06-01 长春工业大学 A kind of hydrophilic modifying CPVA-PVDF ultrafiltration membranes and preparation method thereof
CN108816058A (en) * 2018-06-27 2018-11-16 江苏大学 A kind of rheum emodin molecular engram titanium dioxide nano-particle composite membrane and the preparation method and application thereof
CN109364770A (en) * 2018-11-28 2019-02-22 江苏大学 A kind of preparation method and applications of gadolinium ion trace nano-carbon material composite membrane

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
汪多仁: "《合成树脂与工程塑料生产技术》", 31 August 2001, 中国轻工业出版社 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111871375A (en) * 2020-08-17 2020-11-03 常州大学 Preparation method and application of biochar with efficient atrazine adsorption performance

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