CN109126748B - Composite material PEI-CS-KIT-6 based on inorganic silicon source, preparation method thereof and application thereof in lead removal - Google Patents
Composite material PEI-CS-KIT-6 based on inorganic silicon source, preparation method thereof and application thereof in lead removal Download PDFInfo
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Abstract
The invention relates to a composite material PEI-CS-KIT-6 based on an inorganic silicon source, a preparation method thereof and application thereof in lead removal. The technical scheme is as follows: dissolving P123 in water, adding concentrated HCl, adding N-butanol after water bath overnight, adding sodium silicate after stirring for reaction, pouring the solution into a chitosan solution, dropwise adding glutaraldehyde, transferring into a high-pressure kettle for hydrothermal reaction, dissolving the obtained CS-KIT-6 in dimethyl sulfoxide, adding epichlorohydrin, transferring into a microwave reaction kettle after stirring for microwave reaction, dissolving the obtained ECH-CS-KIT-6 in N, N-dimethylformamide, adding a polyethyleneimine water solution, transferring into the microwave reaction kettle after stirring for microwave reaction, and obtaining PEI-CS-KIT-6. The preparation method is quick and simple, green and pollution-free, and low in cost, and the PEI-CS-KIT-6 adsorbent has a good adsorption effect on Pb (II) and has a large adsorption amount.
Description
Technical Field
The invention is applied to the technical field of effective removal of heavy metal and preparation of green adsorbents, and particularly relates to a PEI-CS-KIT-6 adsorbent which takes mesoporous silica KIT-6 as a matrix and modifies the surface of the PEI-CS-KIT-6 adsorbent with Chitosan (CS) and Polyethyleneimine (PEI), and the PEI-CS-KIT-6 adsorbent can effectively remove Pb (II) from a solution containing heavy metal ions and coexisting metal ions.
Background
With the acceleration of the industrialization process and the continuous development of urban modernization, the quality of the ecological environment is seriously deteriorated. In recent years, heavy metal pollution events are continuously generated, which causes people to heavy metalsConcern over hazards. Lead is a heavy metal element with great harm and has neurotoxicity, so that the lead has no positive physiological function in human bodies, has serious negative influence on the human bodies and only has toxic action on the human bodies. Lead mainly damages the nervous system, hematopoietic system, digestive system, kidney and immune system of human body, lowers the body resistance, and the intelligence damage caused by lead is irreversible. Lead enters human bodies in nature in a food chain mode, and the main source of lead of the human bodies is grains. The lead limit of the grain and the product thereof specified in the NY861-2004 standard of China is 0.4 mg/kg-1And the rapid and accurate determination of the lead content in the grains is beneficial to the effective control of food sanitation and safety. Pb (ii) is considered highly toxic due to its non-biodegradability, being extremely toxic to humans and living beings, and inhalation of pb (ii) increases blood pressure and causes damage to the kidneys, nerves and immune system. Therefore, pb (ii) must be removed from the water body.
Adsorption processes are gaining attention because of their advantages of simplicity, low cost, high efficiency, high flexibility, etc. The adsorption method is a physical and chemical treatment process, and uses porous solid matter as adsorbent to remove some pollutants from water body. In the adsorption process, the key point is to select a proper adsorbent, and the currently commonly used adsorbents for removing heavy metals in water comprise activated carbon taking carbon as a main component, carbon nanotubes and the like, and natural adsorbents comprise clay, zeolite, sepiolite, agricultural and industrial wastes, biological adsorbents, mesoporous materials and the like. In recent years, mesoporous materials have been widely researched and applied in the field of adsorption because of their characteristics of high specific surface area, regular and ordered pore structure, relatively single pore size distribution, and good stability.
The current lead adsorption method mainly comprises the following steps: extraction separation, ion exchange, redox, coagulation, direct precipitation, etc. The most outstanding defects of the methods are that the operation is complicated, the energy consumption is large and secondary pollution is easy to cause when the heavy metal wastewater is treated.
The silicon dioxide has the particle size of less than 100nm, hydroxyl on the surface, high melting point and boiling point, strong hardness, high stability, good chemical inertness and thermal stability. The product has wide application range, and is mainly applied to ceramic materials, artificial mullite, rubber modification, bonding agents, coatings, functional fiber additives, drug carriers, cosmetics and the like. In recent years, silica has been applied to industry and agriculture due to its large specific surface area; many scientists have modified silica matrices to produce porous composites. The mesoporous silica (KIT-6) belongs to Ia3d space group cubic phase materials, has a structure form similar to that of MCM-48 and is a three-dimensional cubic ordered mesoporous structure, but has a relatively large pore diameter which is adjustable between 4 nm and 12nm, and is relatively easy to synthesize. This makes KIT-6 a recent research focus. The special three-dimensional cubic pore canal of the MCM-48 composite material is like an open mesoporous template, so that the loading of active species is easy, and the loading matter can be uniformly dispersed in the whole pore canal without forming agglomerated large particles, so that the MCM-48 composite material has excellent structural performance and overcomes the harsh conditions during MCM-48 synthesis. It is also attractive in potential application value in many fields of catalysis, adsorption, separation, light, electricity, magnetism and the like. Compared with a two-dimensional pore channel type mesoporous material based on SBA-15 or MCM-41, the three-dimensional pore channel structure is more beneficial to grafting functionalization treatment, and the circulation of guest molecules in pore channels is stronger. KIT-6 is a novel ideal silicon-based mesoporous material adsorbent which has the advantages of highly ordered structure, uniform and adjustable pore channel, high specific surface area, excellent hydrothermal stability, low cost and recyclability. Therefore, the organic and inorganic group modified KIT-6 is deeply researched, and theoretical and experimental foundations can be provided for the field of water purification.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to reasonably utilize mesoporous silica, select mesoporous silica KIT-6 as a matrix, and carry out chitosan and polyethyleneimine modification on the surface of the mesoporous silica to prepare the adsorbent for adsorbing Pb (II). The operation method of the invention is quick and simple, saves time, has rich resources and has no pollution. The prepared PEI-CS-KIT-6 adsorbent has good adsorption capacity to Pb (II), is widely applicable and has practical applicability.
The invention is realized by the following technical scheme: the composite material PEI-CS-KIT-6 based on the inorganic silicon source is prepared by taking mesoporous silica KIT-6 as a matrix and grafting chitosan CS and polyethyleneimine PEI on the surface of the mesoporous silica KIT-6 according to the mass ratio of CS to PEI (0.05-0.2) to obtain the PEI-PEI composite material PEI.
The preparation method of the composite material PEI-CS-KIT-6 based on the inorganic silicon source comprises the following steps:
1) dissolving appropriate amount of template agent P123 (polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer) in appropriate amount of water, adding concentrated HCl, stirring overnight in water bath at 30-40 deg.C, adding n-butanol, stirring for a certain time, and adding Na2SiO3Reacting the solution for 3-4h to obtain a mixed solution;
2) modified Chitosan (CS): pouring the mixed solution obtained in the step 1) into a chitosan CS solution dissolved by acetic acid, dropwise adding a proper amount of Glutaraldehyde (GA), continuing to react for 22-24h at room temperature, transferring into a high-pressure kettle, performing hydrothermal reaction for 20-22h at 110 ℃, cooling, performing suction filtration, washing to neutrality, drying, and performing Soxhlet extraction with acetone to obtain a product CS-KIT-6;
3) grafted Epichlorohydrin (ECH): dissolving a proper amount of CS-KIT-6 in a proper amount of dimethyl sulfoxide (DMSO), adding a proper amount of Epichlorohydrin (ECH), stirring for 15-20min, transferring into a microwave reaction kettle, performing microwave radiation at a certain temperature and power for a certain time, washing with deionized water to be neutral, and drying to obtain ECH-CS-KIT-6;
4) modified Polyethyleneimine (PEI): dissolving a proper amount of ECH-CS-KIT-6 in a certain amount of N, N-Dimethylformamide (DMF), adding a certain amount of polyethyleneimine water solution, stirring for 15-20min, transferring into a microwave reaction kettle, performing microwave radiation for a certain time at a certain temperature and power, washing with deionized water to be neutral, and drying to obtain the target product PEI-CS-KIT-6.
Further, in the preparation method of the inorganic silicon source-based composite material PEI-CS-KIT-6, in the step 1), according to the mass ratio, P123, water, n-butanol and Na2SiO3＝1:(25-35):1:(2.5-3.5)。
Further, in the preparation method of the composite material PEI-CS-KIT-6 based on the inorganic silicon source, in the step 2), the dosage of glutaraldehyde is according to the mass ratio，Na2SiO3Glutaraldehyde (11-12) and (15-20); the dosage of the chitosan CS is, by mass ratio, Na2SiO3Chitosan CS (11-12) and (1-3).
Further, in the preparation method of the inorganic silicon source-based composite material PEI-CS-KIT-6, in step 3), epichlorohydrin and dimethyl sulfoxide are added in a volume ratio of 1: 1.
Further, in the preparation method of the composite material PEI-CS-KIT-6 based on the inorganic silicon source, in the step 3), the microwave reaction conditions are as follows: temperature: 50-90 ℃, power: 200 and 500W, and performing microwave radiation for 5-20 min.
Further, in the preparation method of the composite material PEI-CS-KIT-6 based on the inorganic silicon source, in the step 4), the concentration of the polyethyleneimine aqueous solution is 0.02 g/mL-1The dosage of the polyethyleneimine is ECH-CS-KIT-6: PEI ═ 1 (0.1-0.4) according to the mass ratio.
Further, in the preparation method of the composite material PEI-CS-KIT-6 based on the inorganic silicon source, in the step 4), the microwave reaction conditions are as follows: temperature: 70-115 ℃, power: 200 and 500W, and performing microwave radiation for 5-15 min.
The composite material PEI-CS-KIT-6 based on the inorganic silicon source is applied to adsorbing Pb (II) as an adsorbent. The method comprises the following steps: adjusting the pH value to 1-6 in a solution containing Pb (II), adding the composite material PEI-CS-KIT-6 based on the inorganic silicon source according to the solid-to-liquid ratio of 1mg:0.2-5mL, and shaking for 24 hours at 303K.
The invention has the beneficial effects that:
1) containing a large amount of-NH on polyethyleneimine2Can generate chelation with Pb (II), so that the KIT-6 is modified by using chitosan and polyethyleneimine to form the composite material PEI-CS-KIT-6, and the defects of the KIT-6 are overcome.
2) The invention has rich raw materials. The silicon dioxide has the particle size of less than 100nm, hydroxyl on the surface, high melting point and boiling point, strong hardness, high stability, good chemical inertness and thermal stability. The silica of the present invention is widely available.
3) The synthetic method is simple. The method firstly synthesizes CS-KIT-6, and the PEI-CS-KIT-6 adsorbent is prepared by further modifying the surface of CS-KIT-6 with PEI, so that the adsorbent has a good removing effect on heavy metal ions Pb (II).
4) The PEI-CS-KIT-6 adsorbent prepared by the invention has good adsorption effect, and the adsorption rate of Pb (II) can reach more than 90% under the condition that the pH value is more than 4.
5) The invention is energy-saving and environment-friendly. The invention uses microwave synthesis method, which is more beneficial to shortening the synthesis time than the conventional heating. And the solvents used in the method are non-toxic and do not pollute the environment.
6) The adsorbent has good adsorption effect on heavy metals Pb (II) in sewage under certain acidity, and 0.01 mol.L is adopted-1HNO3The adsorbed pb (ii) may be eluted. The saturated adsorption amount of the PEI-CS-KIT-6 adsorbent prepared by the invention to Pb (II) is 132.83mg g at pH 6-1。
7) The adsorbent PEI-CS-KIT-6 prepared by the invention can effectively adsorb Pb (II), and the method is simple, energy-saving, environment-friendly, high in adsorption rate and practical in practicability.
Drawings
FIG. 1 is a schematic diagram of the synthesis of PEI-CS-KIT-6.
FIG. 2a is an X-ray diffraction pattern of PEI-CS-KIT-6 prepared at the same temperature and at different times in example 2.
FIG. 2b is an X-ray diffraction pattern of PEI-CS-KIT-6 prepared at the same time and at different temperatures in example 2.
FIG. 2c is an X-ray diffraction pattern of PEI-CS-KIT-6 prepared at the same time and at different temperatures in example 2.
FIG. 2d is an X-ray diffraction pattern of PEI-CS-KIT-6 prepared at the same temperature and at different times in example 2.
FIG. 3a is a graph showing the adsorption performance of PEI-CS-KIT-6 prepared at the same temperature at different times for Pb (II) at different acidity in example 2.
FIG. 3b is a graph showing the adsorption performance of PEI-CS-KIT-6 prepared at the same time and at different temperatures in example 2 on Pb (II) at different acidity.
FIG. 3c is a graph showing the adsorption performance of PEI-CS-KIT-6 prepared at the same time and at different temperatures in example 2 on Pb (II) at different acidity.
FIG. 3d is a graph showing the adsorption performance of PEI-CS-KIT-6 prepared at the same temperature at different times for Pb (II) according to example 2.
FIG. 4 is an X-ray diffraction pattern of PEI-CS-KIT-6 prepared with different amounts of PEI from example 2.
FIG. 5 is a graph showing the adsorption performance of PEI-CS-KIT-6 prepared in example 2 at different amounts of PEI, on Pb (II) at different acidity.
FIG. 6 is an adsorption isotherm of the PEI-CS-KIT-6 adsorbent prepared in example 1 for adsorption of Pb (II).
Detailed Description
Example 1 composite Material PEI-CS-KIT-6 based on inorganic silicon Source
(I) preparation method
The mesoporous silica KIT-6 is used as a matrix, CS and PEI are modified on the surface of the mesoporous silica KIT-6 to obtain the PEI-CS-KIT-6 composite material, and as shown in figure 1, the synthetic route comprises the following steps:
1) weighing 4g P123 and dissolving in 120g deionized water, adding 20mL concentrated HCl, stirring at 35 deg.C overnight to dissolve, adding 4g n-butanol dropwise the next day, stirring for 1 hr, and adding 11.73g Na at 35 deg.C dropwise2SiO3·9H2Na of O2SiO3Reacting the solution for 3 to 4 hours;
2) modified Chitosan (CS): pouring the solution into 2g of Chitosan (CS) solution dissolved by 50-70mL of acetic acid, dropwise adding 15mL of Glutaraldehyde (GA), continuing to react for 24h at room temperature, transferring into a high-pressure kettle, carrying out hydrothermal reaction for 20h at 100 ℃, cooling, carrying out suction filtration, washing to neutrality, drying, and carrying out Soxhlet extraction with acetone to obtain a product CS-KIT-6;
3) grafted Epichlorohydrin (ECH): dissolving 1g of CS-KIT-6 in 25mL of dimethyl sulfoxide (DMSO), adding 25mL of Epichlorohydrin (ECH), stirring for 15min, transferring into a microwave reaction kettle, carrying out microwave reaction at the temperature of 50 ℃ for 20min at 500W, washing with deionized water to be neutral, and drying to obtain ECH-CS-KIT-6;
4) modified Polyethyleneimine (PEI): dissolving 1g ECH-CS-KIT-6 in 25mL of N, N-dimethyl formamideAmide (DMF), 10mL of 0.02 g/mL-1Stirring a Polyethyleneimine (PEI) water solution for 15min, transferring into a microwave reaction kettle, carrying out microwave reaction for 15min at the temperature of 115 ℃ under 500W, washing to be neutral by deionized water, and drying to obtain a final product PEI-CS-KIT-6.
Example 2 application of composite PEI-CS-KIT-6 based on inorganic silicon source in adsorption of Pb (II)
(one) the adsorption effect of PEI-CS-KIT-6 adsorbents prepared at different time and different temperature on Pb (II)
1. PEI-CS-KIT-6 adsorbent prepared at different time and different temperature
1) Preparation of CS-KIT-6: same as in steps 1) and 2) of example 1.
2) Grafted Epichlorohydrin (ECH): weighing 1g of CS-KIT-6, dissolving in 25mL of DMSO, adding 25mL of LECH, stirring for 15min, transferring into a microwave reaction kettle, respectively radiating at 50 ℃, 70 ℃ and 90 ℃ for 5min, 10min and 20min at a power of 500W, washing the product with deionized water to neutrality, and drying to obtain T1/t1-ECH-CS-KIT-6；
3) Modified Polyethyleneimine (PEI): weighing 1g T1/t1-ECH-CS-KIT-6 was dissolved in 25mL of DMF, and 10mL of 0.02 g/mL was added-1Stirring PEI aqueous solution for 15min, transferring into a microwave reaction kettle, radiating at 70 deg.C, 90 deg.C and 115 deg.C for 5min, 10min and 15min respectively at 500W, washing the product with deionized water to neutrality, drying to obtain PEI-CS-KIT-6 adsorbent prepared at different time and temperature, and respectively using T1/t1-CS/KIT-6-T2/t2-0.2g PEI.
As can be seen from FIGS. 2a to 2d, under the reaction conditions of different temperatures and different times, the composite PEI-CS-KIT-6 based on inorganic silicon source has an obvious diffraction peak at 2 theta ≈ 0.9 degrees, which indicates that the composite still has a long-range ordered mesoporous structure.
2. Adsorption effect on Pb (II)
The method comprises the following steps: 10mg of the PEI-CS-KIT-6 adsorbent prepared in the above way and having different irradiation time and temperature is added into the solution with the solid-liquid ratio of 1mg:1mL, and the solution is added into the solution with the pH value of 1, 2, 3,4. 5, 6 (Pb (II) ═ 20ppm) at 303K and 180r min-1Then, shaking for 24h, filtering, taking the filtrate and the stock solution to measure the concentration, and calculating the adsorption rate, wherein the results are shown in fig. 3 a-3 d.
As can be seen from FIGS. 3a to 3d, PEI-CS-KIT-6 adsorbents with different irradiation times and different irradiation temperatures have better adsorption effects on Pb (II). The adsorption rate of PEI-CS-KIT-6 adsorbent to Pb (II) in Pb (II) solution (Pb (II) 20ppm) with different acidity reaches the maximum at pH 6. The adsorption rate of 50/20-CS/KIT-6-115/15-0.2g PEI was at a maximum of 95.81% at pH 6. Therefore, in the step of grafting Epichlorohydrin (ECH), the microwave reaction condition is that the power is 500W, the temperature is 50 ℃, and the radiation is 20 min. In the step of modifying the Polyethyleneimine (PEI), the microwave reaction condition is that the power is 500W, the temperature is 115 ℃, and the radiation is 15 min.
(II) adsorption effect of PEI-CS-KIT-6 adsorbent prepared by different amounts of polyethyleneimine on Pb (II)
1. Preparation of PEI-CS-KIT-6 adsorbent prepared by using different amounts of polyethyleneimine
1) Preparation of CS-KIT-6: same as in step 1) and step 2) of example 1.
2) Grafted Epichlorohydrin (ECH): weighing 1g of CS-KIT-6, dissolving in 25mL of DMSO, adding 25mL of LECH, stirring for 15min, transferring into a microwave reaction kettle, radiating at 50 ℃ for 20min at the power of 500W, washing the product to be neutral by deionized water, and drying to obtain 50/20-ECH-CS-KIT-6;
3) modified Polyethyleneimine (PEI): weighing 1g 50/20-ECH-CS-KIT-6, dissolving in 25mL DMF, adding 5mL, 10mL, 15mL, 20mL 0.02 g/mL-1And stirring the PEI aqueous solution for 15min, transferring the PEI aqueous solution into a microwave reaction kettle, radiating the PEI aqueous solution for 15min at the temperature of 115 ℃ at 500W, washing the product to be neutral by using deionized water, and drying to obtain PEI-CS-KIT-6 adsorbents, wherein the PEI-CS-KIT-6 adsorbents are prepared according to different amounts of polyethyleneimine according to the mass ratio of ECH-CS-KIT-6 to PEI-1: 0.1, 1:0.2, 1:0.3 and 1:0.4, and are respectively marked as 50/20-CS-KIT-6-115/15-mPEI.
The result is shown in fig. 4, after modification by different amounts of PEI, the composite material has an obvious diffraction peak at 2 θ ≈ 0.9 °, which indicates that the material still has a long-range ordered mesoporous structure.
2. Adsorption effect on Pb (II)
The method comprises the following steps: 10mg of 50/20-CS/KIT-6-115/15-mPEI adsorbent prepared as described above was added to a lead (Pb (II) ═ 20ppm) solution having pH values of 1, 2, 3, 4, 5 and 6, respectively, at a solid-to-liquid ratio of 1mg:1mL, and the mixture was heated at 303K and 180 r.min-1Then, shaking for 24h, filtering, taking the filtrate and the stock solution to measure the concentration, and calculating the adsorption rate, wherein the result is shown in fig. 5.
As can be seen from fig. 5, the adsorption rate gradually increased with increasing pH, and at pH > 4, the adsorption rate reached 90% or more and reached the maximum at pH 6. It can be seen that pH 6 is the optimum adsorption condition. The adsorption rate of 50/20-CS/KIT-6-115/15-0.2g PEI was at a maximum of 95.81% at pH 6. Therefore, it is preferable that ECH-CS-KIT-6: PEI is 1:0.2 in a mass ratio.
(III) influence of Pb (II) solutions with different initial concentrations on Pb (II) adsorption
The method comprises the following steps: respectively prepared at a concentration of 10mg g-1，20mg·g-1，30mg·g-1，40mg·g-1，50mg·g-1，70mg·g-1，90mg·g-1，100mg·g-1，200mg·g-1，400mg·g-1，600mg·g-1Adjusting the pH of the Pb (II) solution to 6, adding 50/20-CS/KIT-6-115/15-0.2g of PEI adsorbent prepared in example 2 according to the solid-to-liquid ratio of 1mg:1mL, and rotating at the temperature of 303K and the rotating speed of 180 r.min-1And then, shaking and adsorbing for 24 hours. The results are shown in FIG. 6.
FIG. 6 is a saturated adsorption isotherm of PEI-CS-KIT-6 for adsorbing Pb (II), the adsorbent is used for oscillating and adsorbing Pb (II) solutions with different concentrations at a solid-to-liquid ratio of 1mg:1mL under the condition that the acidity is pH 6, and oscillating for 24 hours at 303K to ensure that the maximum adsorption quantity of Pb (II) can reach 132.83mg g-1。
Claims (9)
1. The preparation method of the composite material PEI-CS-KIT-6 based on the inorganic silicon source is characterized in that the composite material PEI-CS-KIT-6 based on the inorganic silicon source is prepared by taking mesoporous silica KIT-6 as a matrix and grafting chitosan CS and polyethyleneimine PEI on the surface of the mesoporous silica KIT-6, wherein the preparation method comprises the following steps of:
1) dissolving appropriate amount of template agent P123 in appropriate amount of water, adding concentrated HCl, stirring overnight in water bath at 30-40 deg.C, adding n-butanol, stirring for a certain time, and adding Na2SiO3Reacting the solution for 3-4h to obtain a mixed solution;
2) modified chitosan CS: pouring the mixed solution obtained in the step 1) into a chitosan CS solution dissolved by acetic acid, dropwise adding a proper amount of glutaraldehyde GA, continuing to react for 22-24h at room temperature, transferring into a high-pressure kettle, performing hydrothermal reaction for 20-22h at 110 ℃, cooling, performing suction filtration, washing to be neutral, drying, and performing Soxhlet extraction by using acetone to obtain a product CS-KIT-6;
3) grafting epichlorohydrin ECH: dissolving a proper amount of CS-KIT-6 in a proper amount of dimethyl sulfoxide DMSO, adding a proper amount of epichlorohydrin ECH, stirring for 15-20min, transferring into a microwave reaction kettle, performing microwave radiation at a certain temperature and power for a certain time, washing with deionized water to be neutral, and drying to obtain ECH-CS-KIT-6;
4) modified polyethyleneimine PEI: dissolving a proper amount of ECH-CS-KIT-6 in a certain amount of N, N-dimethylformamide DMF, adding a certain amount of polyethyleneimine water solution, stirring for 15-20min, transferring into a microwave reaction kettle, performing microwave radiation for a certain time at a certain temperature and power, washing with deionized water to be neutral, and drying to obtain the target product PEI-CS-KIT-6.
2. The method for preparing the inorganic silicon source-based composite material PEI-CS-KIT-6 according to claim 1, wherein the method comprises the following steps: in the step 1), according to the mass ratio, P123, water, n-butanol and Na2SiO3=1:（25-35）:1:（2.5-3.5）。
3. The method for preparing the inorganic silicon source-based composite material PEI-CS-KIT-6 according to claim 1, wherein the method comprises the following steps: in the step 2), the dosage of the glutaraldehyde is Na according to the mass ratio2SiO3Glutaraldehyde = (11-12): 15-20); the dosage of the chitosan CS is, by mass ratio, Na2SiO3Chitosan CS = (11-12): (1-3).
4. The method for preparing the inorganic silicon source-based composite material PEI-CS-KIT-6 according to claim 1, wherein the method comprises the following steps: in the step 3), according to the volume ratio, epichlorohydrin to dimethyl sulfoxide =1: 1.
5. The method for preparing the inorganic silicon source-based composite material PEI-CS-KIT-6 according to claim 1, wherein the method comprises the following steps: in the step 3), the microwave reaction conditions are as follows: temperature: 50-90 ℃, power: 200 and 500W, and performing microwave radiation for 5-20 min.
6. The method for preparing the inorganic silicon source-based composite material PEI-CS-KIT-6 according to claim 1, wherein the method comprises the following steps: in step 4), the concentration of the aqueous polyethyleneimine solution was 0.02g ∙ mL-1The dosage of the polyethyleneimine is ECH-CS-KIT-6: PEI =1 (0.1-0.4) according to the mass ratio.
7. The method for preparing the inorganic silicon source-based composite material PEI-CS-KIT-6 according to claim 1, wherein the method comprises the following steps: in the step 4), the microwave reaction conditions are as follows: temperature: 70-115 ℃, power: 200 and 500W, and performing microwave radiation for 5-15 min.
8. Use of the inorganic silicon source based composite PEI-CS-KIT-6 prepared according to the method of claim 1 as adsorbent for adsorption of pb (ii).
9. Use according to claim 8, characterized in that the method is as follows: adjusting the pH to 1-6 in a solution containing Pb (II), adding the inorganic silicon source-based composite material PEI-CS-KIT-6 prepared according to the method of claim 1 in a solid-to-liquid ratio of 1mg:0.2-5mL, and shaking at 303K for 24 h.
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| CN112076734A (en) * | 2020-08-25 | 2020-12-15 | 辽宁大学 | Preparation method of salicylaldoxime/polydopamine/three-dimensional mesoporous silica composite material and application of salicylaldoxime/polydopamine/three-dimensional mesoporous silica composite material in gallium recovery |
| CN113713780A (en) * | 2021-09-15 | 2021-11-30 | 辽宁大学 | 3D chitosan/silicon dioxide composite material, preparation method thereof and application thereof in adsorption separation of rhenium |
| CN113753903B (en) * | 2021-09-24 | 2023-01-17 | 江苏大学 | Preparation method of high-density site circular nanosheet and application of nanosheet in adsorbing blood lead |
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