CN114849660A - Cyclodextrin-based nano-porous composite adsorption material and preparation method thereof - Google Patents
Cyclodextrin-based nano-porous composite adsorption material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a cyclodextrin-based nano-porous composite adsorbing material and a preparation method thereof, which comprises the steps of firstly preparing a high-molecular polymer electrostatic spinning solution with a certain concentration, preparing a high-molecular electrostatic nanofiber membrane under a certain electrostatic spinning condition, then immersing a plurality of layers of electrostatic nanofiber membranes into a cyclodextrin derivative mixed solution with carbon-carbon double bonds, carrying out in-situ crosslinking polymerization reaction under a certain condition, compounding layer by layer, and preparing the cyclodextrin-based nano-porous composite adsorbing material after freeze dryingAnd (3) compounding the adsorption material. The cyclodextrin-based nano-porous composite adsorbing material prepared by the invention has a three-dimensional porous structure, a large specific surface area and various active binding sites on the surface, and can be used for dyeing and finishing dyes Methylene Blue (MB) and heavy metal antimony ions (Sb) in wastewater 3+ ) Lead ion (Pb) 2+ ) Efficient removal of the active species.
Description
Technical Field
The invention belongs to the field of functional nano composite materials, and particularly relates to a preparation method of a cyclodextrin-based nano porous composite adsorption material.
Background
In recent years, cyclodextrin, which is a cyclic oligosaccharide having a specific cavity structure, is biodegradable and available simply. Is gradually and widely applied to the fields of food, environment, medicine, polymer synthesis, cosmetics, chemical detection and the like. In the field of environmental water treatment research, more and more domestic and foreign scholars research and develop various water-insoluble cyclodextrin-based functional materials aiming at the defect that cyclodextrin dissolves water, and apply the materials to the removal of pollutants in sewage so as to realize the efficient and low-cost treatment of sewage.
Firstly, preparing high molecular polymer nanofiber membranes with different microstructures, then placing the high molecular polymer nanofiber membranes into Cyclodextrin (CD) derivative mixed solution with reactive functional groups, and compounding the nanofiber membranes and the cyclodextrin derivatives layer by layer through in-situ cross-linking polymerization reaction to prepare the nanocomposite material with a three-dimensional porous structure and controllable structural performance.
Disclosure of Invention
The invention aims to solve the technical problem of providing a cyclodextrin-based nano-porous composite adsorbing material and a preparation method thereof, synthesizing the nano-porous composite adsorbing material with large specific surface area, multiple active functional group binding sites and controllable three-dimensional pore structure, and realizing the aim of controlling dye Methylene Blue (MB) and heavy metal antimony ions (Sb) in dyeing and finishing wastewater 3+ ) Lead ion (Pb) 2+ ) Is removed efficiently。
The invention relates to a preparation method of a cyclodextrin-based nano-porous composite adsorbing material, which comprises the following steps:
s1, fully dissolving a certain amount of high molecular polymer in a certain volume of solvent, preparing high molecular polymer electrostatic spinning solution, regulating and controlling electrostatic spinning conditions, and preparing the electrostatic nanofiber membrane with controllable microstructure;
s2, placing the cyclodextrin derivative containing the carbon-carbon double bond into N, N-Dimethylformamide (DMF) solution at normal temperature, stirring until the cyclodextrin derivative is fully dissolved, then placing a certain amount of catalyst into the mixed solution, stirring until the catalyst is fully dissolved, placing a certain amount of nanofiber membranes into the cyclodextrin derivative mixed solution containing the carbon-carbon double bond, and then irradiating for 5-20 min by a high-pressure xenon lamp to carry out in-situ cross-linked polymer reaction;
and S3, after the reaction of the step S2 is finished, putting the reaction solid product into deionized water, dialyzing for 24-72 h, and freeze-drying the obtained product at-70 to-30 ℃ for 24-48 h to obtain the cyclodextrin-based nano porous composite adsorbing material.
Preferably, in step S1, the high molecular polymer is cellulose and/or polyvinyl alcohol (PVA).
Preferably, in step S2, the cyclodextrin derivative is one of vinyl- α -cyclodextrin, vinyl- β -cyclodextrin, and vinyl- γ -cyclodextrin.
Preferably, in step S2, the catalyst is one of ammonium persulfate and Azobisisobutyronitrile (AIBN).
Preferably, in step S1, the high molecular polymer electrospinning solution is prepared to have a concentration of 10% to 25% by mass. The electrospinning speed is 0.3-1.5 ml/h.
Preferably, in the step S2, the feeding mass ratio of the catalyst to the cyclodextrin derivative is 1-3:1, and the number of the nanofiber membranes is 1-10.
Preferably, in the step S1, the thickness of the nanofiber membrane prepared is 0.5 to 5 mm.
Preferably, in step S1, the electrospinning conditions are that the diameter of the needle is 1.0mm and the distance between the needle and the receiving plate is 10-20 cm. The voltage is 15kV, the temperature is 20-30 ℃, and the humidity is 25-35%.
A cyclodextrin-based nanoporous composite adsorbent material, prepared using any of the methods.
Preferably, the dye is Methylene Blue (MB) and heavy metal antimony ions (Sb) applied to dyeing and finishing wastewater 3+ ) Lead ion (Pb) 2 + ) Efficient removal of the active species.
According to the invention, a proper high molecular polymer is required to be selected to prepare the nanofiber membrane, so that the nanofiber membrane has good stability in an N, N-dimethylformamide solution. The solid product needs to be put into flowing deionized water for dialysis to ensure that the small molecular substances are completely dialyzed.
Compared with the prior art, the invention has the beneficial effects that:
the cyclodextrin-based nano-porous composite adsorbing material prepared by the invention is formed by compounding a plurality of layers of nano-fiber membranes and cyclodextrin cross-linked polymers layer by layer, has large specific surface area and abundant active functional group binding sites, and is applied to dye Methylene Blue (MB) and heavy metal antimony ions (Sb) in dyeing and finishing wastewater 3+ ) Lead ion (Pb) 2+ ) The high-efficiency removal is realized, and the adsorption rate reaches more than 98 percent.
Drawings
FIG. 1 is a reaction schematic diagram of a cyclodextrin-based nanoporous composite adsorbent material.
Detailed Description
The molecular structure and the composition of the finally synthesized cyclodextrin-based nano-porous composite adsorbing material are measured by a nuclear magnetic resonance spectrometer 13 C NMR、 1 H NMR) and Fourier transform infrared spectrometer (FTIR) for test analysis; analyzing the specific surface area, the pore size and the distribution range of the cyclodextrin-based nano-porous composite adsorbing material through a BET (BET test); the adsorption effect of the cyclodextrin-based nano-porous composite adsorption material on heavy metal ions in wastewater is tested and analyzed by an atomic energy spectrometer (ICP), and the test method specifically comprises the following steps: sb with the mass concentration of 100 mg/L-1000 mg/L is respectively prepared 3+ And Pb 2+ Respectively taking 20mg of cyclodextrin-based nano-porous composite adsorption solutionRespectively putting the materials into 20ml heavy metal ion solutions with different concentrations, stirring and adsorbing the materials in a water bath shaking table for 24 hours at room temperature under the condition that the PH value is 1-10, and measuring Sb in the solutions before and after adsorption by using an atomic energy spectrometer 3+ And Pb 2+ The concentration content of (A); analyzing the adsorption effect of the cyclodextrin-based nano-porous composite adsorption material on the dye in the wastewater by using an ultraviolet spectrophotometer, wherein the test method specifically comprises the following steps: preparing methylene blue solutions with different concentrations (100mol/L,200mol/L,400mol/L,800mol/L and 1000mol/L), respectively taking 20mg of cyclodextrin-based nano-porous composite adsorbing materials, respectively putting the cyclodextrin-based nano-porous composite adsorbing materials into 20ml of dye solutions with different concentrations, then putting the dye solutions into a constant temperature oscillator, and carrying out adsorption oscillation for 12 hours at room temperature to enable the dye solutions to reach adsorption balance, and testing the absorbance of the dye in the solutions before and after adsorption by using an ultraviolet-visible spectrophotometer to obtain the adsorption efficiency of the material on the dye.
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention can be made by those skilled in the art after reading the teaching of the present invention, and these equivalents also fall within the scope of the claims appended to the present application.
Example 1
(1) Mixing polyvinyl alcohol (M) w 195000, 10g) are fully dissolved in 50ml of deionized water, an electrostatic spinning solution with the concentration of 20 percent is prepared, the electrostatic spinning speed is controlled to be 0.5ml/h, the diameter of a needle is 1.0mm, the distance between the needle and a receiving plate is 15cm, the voltage is 10kV, the temperature is 25 ℃, the humidity is 30 percent, and an electrostatic nanofiber membrane with the thickness of 0.5mm is prepared for standby. Putting vinyl-beta-cyclodextrin (5g) into 50ml of N, N-Dimethylformamide (DMF) solution at normal temperature, stirring until the vinyl-beta-cyclodextrin is fully dissolved, then putting ammonium persulfate (5g) into the mixed solution, and stirring until the ammonium persulfate is fully dissolved. 5 pieces of nanofiber membranes with the thickness of 0.5mm are placed in the mixed solution at the normal temperature. And then irradiating for 10min by a high-pressure xenon lamp to carry out in-situ crosslinking polymer reaction.
(2) And (2) after the reaction in the step (1) is finished, putting the reaction solid product into deionized water, dialyzing for 48 hours, and freeze-drying the obtained product at-70 ℃ for 48 hours to obtain the cyclodextrin-based nano porous composite adsorbing material.
The cyclodextrin-based nano-porous composite adsorbing material has the specific surface area S BET ＝443.39m 2 (ii) in terms of/g. The absorption rate of the sample to methylene blue is as high as 99.9 percent, and the heavy metal ions Sb 3+ And Pb 2+ The adsorption rates of the adsorbent are respectively as high as 98.5 percent and 99.1 percent.
Example 2
(1) Mixing polyvinyl alcohol (M) w 195000, 7.5g) is fully dissolved in 50ml of deionized water, an electrostatic spinning solution with the concentration of 15 percent is prepared, the electrostatic spinning speed is controlled to be 0.3ml/h, the diameter of a needle is 1.0mm, the distance between the needle and a receiving plate is 15cm, the voltage is 14kV, the temperature is 25 ℃, the humidity is 30 percent, and an electrostatic nanofiber membrane with the thickness of 0.5mm is prepared for standby. Putting vinyl-beta-cyclodextrin (5g) into 50ml of N, N-Dimethylformamide (DMF) solution at normal temperature, stirring until the vinyl-beta-cyclodextrin is fully dissolved, then putting ammonium persulfate (5g) into the mixed solution, and stirring until the ammonium persulfate is fully dissolved. At normal temperature, 10 sheets of nanofiber membrane with thickness of 0.5mm were placed in the above mixed solution. And then irradiating for 10min by a high-pressure xenon lamp to carry out in-situ crosslinking polymer reaction.
(2) And (2) after the reaction in the step (1) is finished, putting the reaction solid product into deionized water, dialyzing for 48 hours, and freeze-drying the obtained product at-70 ℃ for 48 hours to obtain the cyclodextrin-based nano porous composite adsorbing material.
The cyclodextrin-based nano-porous composite adsorbing material has the specific surface area S BET ＝453.62m 2 (ii) in terms of/g. The absorption rate of the sample to methylene blue is as high as 99.9 percent, and the heavy metal ions Sb 3+ And Pb 2+ The adsorption rates of the adsorbent are respectively as high as 99.1 percent and 99.6 percent.
Example 3
(1) Mixing polyvinyl alcohol (M) w 195000, 10g) are fully dissolved in 50ml of deionized water to prepare electrostatic spinning solution with the concentration of 20 percent, the electrostatic spinning speed is controlled to be 1.0ml/h, the diameter of a needle is 1.0mm, the distance between the needle and a receiving plate is 15cm, the voltage is 15kV, the temperature is 25 ℃, the humidity is 30 percent,preparing the electrostatic nanofiber membrane with the thickness of 0.5mm for later use. Putting vinyl-beta-cyclodextrin (5g) into 50ml of N, N-Dimethylformamide (DMF) solution at normal temperature, stirring until the vinyl-beta-cyclodextrin is fully dissolved, then putting ammonium persulfate (5g) into the mixed solution, and stirring until the ammonium persulfate is fully dissolved. 5 pieces of nanofiber membranes with the thickness of 0.5mm are placed in the mixed solution at the normal temperature. And then irradiating for 20min by a high-pressure xenon lamp to carry out in-situ crosslinking polymer reaction.
(2) And (2) after the reaction in the step (1) is finished, putting the reaction solid product into deionized water, dialyzing for 48 hours, and freeze-drying the obtained product at-70 ℃ for 48 hours to obtain the cyclodextrin-based nano porous composite adsorbing material.
The cyclodextrin-based nano-porous composite adsorbing material has the specific surface area S BET ＝430.58m 2 (ii) in terms of/g. The absorption rate of the sample to methylene blue is as high as 99.9 percent, and the heavy metal ions Sb 3+ And Pb 2+ The adsorption rates of the adsorbent are respectively as high as 98.6 percent and 98.9 percent.
Example 4
(1) Mixing polyvinyl alcohol (M) w 195000, 10g) are fully dissolved in 50ml of deionized water, an electrostatic spinning solution with the concentration of 20 percent is prepared, the electrostatic spinning speed is controlled to be 1.0ml/h, the diameter of a needle is 1.0mm, the distance between the needle and a receiving plate is 15cm, the voltage is 18kV, the temperature is 25 ℃, the humidity is 30 percent, and an electrostatic nanofiber membrane with the thickness of 0.5mm is prepared for standby. Putting vinyl-beta-cyclodextrin (5g) into 50ml of N, N-Dimethylformamide (DMF) solution at normal temperature, stirring until the vinyl-beta-cyclodextrin is fully dissolved, then putting ammonium persulfate (5g) into the mixed solution, and stirring until the ammonium persulfate is fully dissolved. At normal temperature, 10 sheets of nanofiber membrane with thickness of 0.5mm were placed in the above mixed solution. And then irradiating for 20min by a high-pressure xenon lamp to carry out in-situ crosslinking polymer reaction.
(2) And (2) after the reaction in the step (1) is finished, putting the reaction solid product into deionized water, dialyzing for 48 hours, and freeze-drying the obtained product at-70 ℃ for 48 hours to obtain the cyclodextrin-based nano porous composite adsorbing material.
The cyclodextrin-based nano-porous composite adsorbing material has the specific surface area S BET ＝446.47m 2 (ii) in terms of/g. The absorption rate of the sample to methylene blue is as high as 99.9 percent, and the heavy metal ions Sb 3+ And Pb 2+ The adsorption rates of the adsorbent are respectively as high as 98.9% and 99.2%.
Example 5
(1) Mixing polyvinyl alcohol (M) w 195000, 7.5g) is fully dissolved in 50ml of deionized water, an electrostatic spinning solution with the concentration of 15 percent is prepared, the electrostatic spinning speed is controlled to be 0.5ml/h, the diameter of a needle is 1.0mm, the distance between the needle and a receiving plate is 15cm, the voltage is 13kV, the temperature is 25 ℃, the humidity is 30 percent, and an electrostatic nanofiber membrane with the thickness of 1.0mm is prepared for standby. Putting vinyl-beta-cyclodextrin (5g) into 50ml of N, N-Dimethylformamide (DMF) solution at normal temperature, stirring until the vinyl-beta-cyclodextrin is fully dissolved, then putting ammonium persulfate (5g) into the mixed solution, and stirring until the ammonium persulfate is fully dissolved. 5 pieces of 1.0mm thick nanofiber membrane were placed in the above mixed solution at room temperature. And then irradiating for 10min by a high-pressure xenon lamp to carry out in-situ crosslinking polymer reaction.
(2) And (2) after the reaction in the step (1) is finished, putting the reaction solid product into deionized water, dialyzing for 48 hours, and freeze-drying the obtained product at-70 ℃ for 48 hours to obtain the cyclodextrin-based nano porous composite adsorbing material.
The cyclodextrin-based nano-porous composite adsorbing material has the specific surface area S BET ＝445.68m 2 (ii) in terms of/g. The absorption rate of the sample to methylene blue is as high as 99.9 percent, and the heavy metal ions Sb 3+ And Pb 2+ The adsorption rates of the adsorbent are respectively as high as 98.6 percent and 99.1 percent.
Example 6
(1) Mixing polyvinyl alcohol (M) w 195000, 10g) are fully dissolved in 50ml of deionized water, an electrostatic spinning solution with the concentration of 20 percent is prepared, the electrostatic spinning speed is controlled to be 0.5ml/h, the diameter of a needle is 1.0mm, the distance between the needle and a receiving plate is 15cm, the voltage is 15kV, the temperature is 25 ℃, the humidity is 35 percent, and an electrostatic nanofiber membrane with the thickness of 1.0mm is prepared for standby. Placing 5g of vinyl-beta-cyclodextrin (vinyl-beta-cyclodextrin) in 50ml of N, N-Dimethylformamide (DMF) solution at normal temperature, stirring until the vinyl-beta-cyclodextrin is fully dissolved, then placing 5g of ammonium persulfate in the mixed solution, and stirring until the ammonium persulfate is fully dissolvedFully dissolving. Under the condition of normal temperature, 8 pieces of nanofiber membranes with the thickness of 1.0mm are placed in the mixed solution. And then irradiating for 10min by a high-pressure xenon lamp to carry out in-situ crosslinking polymer reaction.
(2) And (2) after the reaction in the step (1) is finished, putting the reaction solid product into deionized water, dialyzing for 48 hours, and freeze-drying the obtained product at-70 ℃ for 48 hours to obtain the cyclodextrin-based nano porous composite adsorbing material.
The cyclodextrin-based nano-porous composite adsorbing material has the specific surface area S BET ＝453.82m 2 (ii) in terms of/g. The absorption rate of the sample to methylene blue is as high as 99.9 percent, and the heavy metal ions Sb 3+ And Pb 2+ The adsorption rates of the adsorbent are respectively as high as 98.1% and 99.2%.
Example 7
(1) Mixing polyvinyl alcohol (M) w 195000, 7.5g) is fully dissolved in 50ml of deionized water, an electrostatic spinning solution with the concentration of 15 percent is prepared, the electrostatic spinning speed is controlled to be 0.3ml/h, the diameter of a needle is 1.0mm, the distance between the needle and a receiving plate is 15cm, the voltage is 15kV, the temperature is 25 ℃, the humidity is 30 percent, and an electrostatic nanofiber membrane with the thickness of 1.0mm is prepared for standby. Putting vinyl-beta-cyclodextrin (5g) into 50ml of N, N-Dimethylformamide (DMF) solution at normal temperature, stirring until the vinyl-beta-cyclodextrin is fully dissolved, then putting ammonium persulfate (5g) into the mixed solution, and stirring until the ammonium persulfate is fully dissolved. At normal temperature, 10 sheets of 1.0mm thick nanofiber membrane were placed in the above mixed solution. And then irradiating for 10min by a high-pressure xenon lamp to carry out in-situ crosslinking polymer reaction.
(2) And (2) after the reaction in the step (1) is finished, putting the reaction solid product into deionized water, dialyzing for 48 hours, and freeze-drying the obtained product at-70 ℃ for 48 hours to obtain the cyclodextrin-based nano porous composite adsorbing material.
The cyclodextrin-based nano-porous composite adsorbing material has the specific surface area S BET ＝458.69m 2 (ii) in terms of/g. The absorption rate of the sample to methylene blue is as high as 99.9 percent, and the heavy metal ions Sb 3+ And Pb 2+ The adsorption rates of the adsorbent are respectively as high as 98.1% and 99.2%.
Example 8
(1) Mixing polyvinyl alcohol (M) w 195000, 10g) are fully dissolved in 50ml of deionized water, an electrostatic spinning solution with the concentration of 20 percent is prepared, the electrostatic spinning speed is controlled to be 0.3ml/h, the diameter of a needle is 1.0mm, the distance between the needle and a receiving plate is 10cm, the voltage is 15kV, the temperature is 25 ℃, the humidity is 30 percent, and an electrostatic nanofiber membrane with the thickness of 1.0mm is prepared for standby. Putting vinyl-beta-cyclodextrin (5g) into 50ml of N, N-Dimethylformamide (DMF) solution at normal temperature, stirring until the vinyl-beta-cyclodextrin is fully dissolved, then putting ammonium persulfate (5g) into the mixed solution, and stirring until the ammonium persulfate is fully dissolved. 5 pieces of nanofiber membranes with the thickness of 1.0mm are placed in the mixed solution at the normal temperature. And then irradiating for 20min by a high-pressure xenon lamp to carry out in-situ crosslinking polymer reaction.
(2) And (2) after the reaction in the step (1) is finished, putting the reaction solid product into deionized water, dialyzing for 72h, and freeze-drying the obtained product at-70 ℃ for 48h to obtain the cyclodextrin-based nano porous composite adsorption material.
The cyclodextrin-based nano-porous composite adsorbing material has the specific surface area S BET ＝442.56m 2 (ii) in terms of/g. The absorption rate of the sample to methylene blue is as high as 99.9 percent, and the heavy metal ions Sb 3+ And Pb 2+ The adsorption rates of the adsorbent are respectively as high as 98.9 percent and 99.8 percent.
Example 9
(1) Mixing polyvinyl alcohol (M) w 195000, 10g) are fully dissolved in 50ml of deionized water, an electrostatic spinning solution with the concentration of 20 percent is prepared, the electrostatic spinning speed is controlled to be 0.5ml/h, the diameter of a needle is 1.0mm, the distance between the needle and a receiving plate is 15cm, the voltage is 10kV, the temperature is 25 ℃, the humidity is 30 percent, and an electrostatic nanofiber membrane with the thickness of 1.0mm is prepared for standby. Putting vinyl-beta-cyclodextrin (5g) into 50ml of N, N-Dimethylformamide (DMF) solution at normal temperature, stirring until the vinyl-beta-cyclodextrin is fully dissolved, then putting ammonium persulfate (5g) into the mixed solution, and stirring until the ammonium persulfate is fully dissolved. At normal temperature, 10 sheets of 1.0mm thick nanofiber membrane were placed in the above mixed solution. And then irradiating for 20min by a high-pressure xenon lamp to carry out in-situ crosslinking polymer reaction.
(2) And (2) after the reaction in the step (1) is finished, putting the reaction solid product into deionized water, dialyzing for 72h, and freeze-drying the obtained product at-70 ℃ for 48h to obtain the cyclodextrin-based nano porous composite adsorbing material.
The cyclodextrin-based nano-porous composite adsorbing material has the specific surface area S BET ＝460.89m 2 (ii) in terms of/g. The absorption rate of the sample to methylene blue is as high as 99.9 percent, and the heavy metal ions Sb 3+ And Pb 2+ The adsorption rates of the adsorbent are respectively as high as 98.7% and 99.6%.
Example 10
(1) Mixing polyvinyl alcohol (M) w 195000, 6g) are fully dissolved in 50ml of deionized water, an electrostatic spinning solution with the concentration of 12 percent is prepared, the electrostatic spinning speed is controlled to be 1.0ml/h, the diameter of a needle is 1.0mm, the distance between the needle and a receiving plate is 10cm, the voltage is 10kV, the temperature is 25 ℃, the humidity is 30 percent, and an electrostatic nanofiber membrane with the thickness of 2.0mm is prepared for standby. Putting vinyl-beta-cyclodextrin (5g) into 50ml of N, N-Dimethylformamide (DMF) solution at normal temperature, stirring until the vinyl-beta-cyclodextrin is fully dissolved, then putting ammonium persulfate (5g) into the mixed solution, and stirring until the ammonium persulfate is fully dissolved. 5 pieces of nanofiber membranes with the thickness of 2.0mm are placed in the mixed solution at the normal temperature. And then irradiating for 10min by a high-pressure xenon lamp to carry out in-situ crosslinking polymer reaction.
(2) And (2) after the reaction in the step (1) is finished, putting the reaction solid product into deionized water, dialyzing for 72h, and freeze-drying the obtained product at-70 ℃ for 48h to obtain the cyclodextrin-based nano porous composite adsorbing material.
The cyclodextrin-based nano-porous composite adsorbing material has the specific surface area S BET ＝450.59m 2 (ii) in terms of/g. The absorption rate of the sample to methylene blue is as high as 99.9 percent, and the heavy metal ions Sb 3+ And Pb 2+ The adsorption rates of the adsorbent are respectively as high as 98.9 percent and 99.7 percent.
Example 11
(1) Mixing polyvinyl alcohol (M) w 195000, 7.5g) is fully dissolved in 50ml of deionized water to prepare an electrostatic spinning solution with the concentration of 15 percent, the electrospinning speed is controlled to be 1.5ml/h, the diameter of a needle is 1.0mm, and the needle and a receiving plate are arrangedThe distance between the two layers is 10cm, the voltage is 15kV, the temperature is 25 ℃, the humidity is 35 percent, and the electrostatic nanofiber membrane with the thickness of 5.0mm is prepared for standby. Putting vinyl-beta-cyclodextrin (5g) into 50ml of N, N-Dimethylformamide (DMF) solution at normal temperature, stirring until the vinyl-beta-cyclodextrin is fully dissolved, then putting ammonium persulfate (5g) into the mixed solution, and stirring until the ammonium persulfate is fully dissolved. 5 pieces of nanofiber membrane 5.0mm thick were placed in the above mixed solution at room temperature. And then irradiating for 10min by a high-pressure xenon lamp to carry out in-situ crosslinking polymer reaction.
(2) And (2) after the reaction in the step (1) is finished, putting the reaction solid product into deionized water, dialyzing for 72h, and freeze-drying the obtained product at-70 ℃ for 48h to obtain the cyclodextrin-based nano porous composite adsorbing material.
The cyclodextrin-based nano-porous composite adsorbing material has the specific surface area S BET ＝451.93m 2 (ii) in terms of/g. The absorption rate of the sample to methylene blue is as high as 99.9 percent, and the heavy metal ions Sb 3+ And Pb 2+ The adsorption rates of the adsorbent are respectively as high as 99.5 percent and 99.8 percent.
Example 12
(1) Mixing polyvinyl alcohol (M) w 195000, 10g) are fully dissolved in 50ml of deionized water, an electrostatic spinning solution with the concentration of 20 percent is prepared, the electrostatic spinning speed is controlled to be 1.5ml/h, the diameter of a needle is 1.0mm, the distance between the needle and a receiving plate is 15cm, the voltage is 15kV, the temperature is 25 ℃, the humidity is 35 percent, and an electrostatic nanofiber membrane with the thickness of 5.0mm is prepared for standby. Putting vinyl-beta-cyclodextrin (5g) into 50ml of N, N-Dimethylformamide (DMF) solution at normal temperature, stirring until the vinyl-beta-cyclodextrin is fully dissolved, then putting ammonium persulfate (5g) into the mixed solution, and stirring until the ammonium persulfate is fully dissolved. At normal temperature, 10 sheets of 5.0mm thick nanofiber membrane were placed in the above mixed solution. And then irradiating for 20min by a high-pressure xenon lamp to carry out in-situ crosslinking polymer reaction.
(2) And (2) after the reaction in the step (1) is finished, putting the reaction solid product into deionized water, dialyzing for 72h, and freeze-drying the obtained product at-70 ℃ for 48h to obtain the cyclodextrin-based nano porous composite adsorbing material.
Synthesized as described aboveCyclodextrin-based nano-porous composite adsorbing material with specific surface area S BET ＝446.63m 2 (ii) in terms of/g. The absorption rate of the sample to methylene blue is as high as 99.9 percent, and the heavy metal ions Sb 3+ And Pb 2+ The adsorption rates of the adsorbent are respectively as high as 99.3 percent and 99.9 percent.
Firstly, preparing high molecular polymer nano fiber membranes with different microstructures, then placing a plurality of layers of nano fiber membranes into a cyclodextrin derivative mixed solution with carbon-carbon double bonds, carrying out in-situ cross-linking polymerization reaction, and carrying out layer-by-layer compounding to prepare a nano porous composite material with a three-dimensional porous structure and controllable structural performance 3+ ) Lead ion (Pb) 2+ ) The high-efficiency removal of the heavy metal ions Sb3+ and Pb2+ is more than 98 percent respectively.
Claims (10)
1. A preparation method of a cyclodextrin-based nano-porous composite adsorption material comprises the following steps:
s1, fully dissolving a certain amount of high molecular polymer in a certain volume of solvent, preparing high molecular polymer electrostatic spinning solution, regulating and controlling electrostatic spinning conditions, and preparing the electrostatic nanofiber membrane with controllable microstructure;
s2, placing the cyclodextrin derivative containing the carbon-carbon double bond into N, N-Dimethylformamide (DMF) solution at normal temperature, stirring until the cyclodextrin derivative is fully dissolved, then placing a certain amount of catalyst into the mixed solution, stirring until the catalyst is fully dissolved, placing a certain amount of nanofiber membranes into the cyclodextrin derivative mixed solution containing the carbon-carbon double bond, and then irradiating for 5-20 min by a high-pressure xenon lamp to carry out in-situ cross-linked polymer reaction;
and S3, after the reaction in the step S2 is finished, putting the reaction solid product into deionized water, dialyzing for 24-72 hours, and freeze-drying the obtained product at-70 to-30 ℃ for 24-48 hours to obtain the cyclodextrin-based nano porous composite adsorbing material.
2. The method according to claim 1, wherein in step S1, the high molecular weight polymer is cellulose and/or polyvinyl alcohol (PVA).
3. The method of claim 1, wherein in step S2, the cyclodextrin derivative is one of vinyl- α -cyclodextrin, vinyl- β -cyclodextrin, and vinyl- γ -cyclodextrin.
4. The method according to claim 1, wherein in step S2, the catalyst is one of ammonium persulfate and Azobisisobutyronitrile (AIBN).
5. The method according to any one of claims 1 to 4, wherein the polymer electrospinning solution is prepared at a concentration of 10% to 25% by mass in step S1. The electrospinning speed is 0.3-1.5 ml/h.
6. The preparation method according to claim 5, wherein in the step S2, the feeding mass ratio of the catalyst to the cyclodextrin derivative is 1-3:1, and the number of the nanofiber membranes is 1-10.
7. The method according to claim 6, wherein in step S1, the nanofiber membrane has a thickness of 0.5-5 mm.
8. The method according to claim 6 or 7, wherein in the step S1, the electrospinning conditions are such that the diameter of the needle is 1.0mm and the distance between the needle and the receiving plate is 10-20 cm. The voltage is 15kV, the temperature is 20-30 ℃, and the humidity is 25-35%.
9. A cyclodextrin-based nanoporous composite adsorbent material, obtainable by the method of any one of claims 1 to 8.
10. The cyclodextrin-based nanoporous composite adsorbent material according to claim 9, wherein the cyclodextrin-based nanoporous composite adsorbent material is applied to dye Methylene Blue (MB) and heavy metal antimony ions (Sb) in dyeing and finishing wastewater 3+ ) Lead ion (Pb) 2+ ) Efficient removal of the active species.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102872836A (en) * | 2012-09-11 | 2013-01-16 | 安徽理工大学 | Cyclodextrin immobilized macromolecular polymer and preparation method and application thereof |
| CN106757767A (en) * | 2016-12-29 | 2017-05-31 | 嘉兴德扬生物科技有限公司 | A kind of preparation and application of high intensity beta cyclodextrin/cellulose acetate composite nano-fiber membrane |
| CN109351210A (en) * | 2018-09-27 | 2019-02-19 | 南昌大学 | It is a kind of for simultaneously go water removal in the nano fibrous membrane of micro heavy ion and organic pollutant preparation method |
| CN111286869A (en) * | 2018-12-10 | 2020-06-16 | 天津农学院 | Photo-crosslinking polyvinyl alcohol derivative composite nanofiber and preparation method thereof |
| CN112934198A (en) * | 2021-01-29 | 2021-06-11 | 浙江理工大学 | Cyclodextrin porous adsorption material and preparation method and application thereof |
| CN113773459A (en) * | 2021-09-03 | 2021-12-10 | 福建农林大学 | Preparation method of beta-cyclodextrin modified polystyrene resin with high grafting amount |
-
2022
- 2022-05-20 CN CN202210209861.5A patent/CN114849660A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102872836A (en) * | 2012-09-11 | 2013-01-16 | 安徽理工大学 | Cyclodextrin immobilized macromolecular polymer and preparation method and application thereof |
| CN106757767A (en) * | 2016-12-29 | 2017-05-31 | 嘉兴德扬生物科技有限公司 | A kind of preparation and application of high intensity beta cyclodextrin/cellulose acetate composite nano-fiber membrane |
| CN109351210A (en) * | 2018-09-27 | 2019-02-19 | 南昌大学 | It is a kind of for simultaneously go water removal in the nano fibrous membrane of micro heavy ion and organic pollutant preparation method |
| CN111286869A (en) * | 2018-12-10 | 2020-06-16 | 天津农学院 | Photo-crosslinking polyvinyl alcohol derivative composite nanofiber and preparation method thereof |
| CN112934198A (en) * | 2021-01-29 | 2021-06-11 | 浙江理工大学 | Cyclodextrin porous adsorption material and preparation method and application thereof |
| CN113773459A (en) * | 2021-09-03 | 2021-12-10 | 福建农林大学 | Preparation method of beta-cyclodextrin modified polystyrene resin with high grafting amount |
Non-Patent Citations (2)
| Title |
|---|
| XIANG WANG ET AL: "Bendable poly(vinylidene fluoride)/polydopamine/β-cyclodextrin composite electrospun membranes for highly efficient and bidirectional adsorption of cation and anion dyes from aqueous media" * |
| 李伟 等: "β-环糊精修饰聚乙烯醇纳米纤维的制备及其吸附性质研究" * |
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