CN113122938A - Preparation method and application of MOFs-containing chitosan/polyvinyl alcohol nanofiber membrane - Google Patents
Preparation method and application of MOFs-containing chitosan/polyvinyl alcohol nanofiber membrane Download PDFInfo
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Abstract
The preparation method of the MOFs-containing chitosan/polyvinyl alcohol nanofiber membrane comprises the following steps: a: preparing a chitosan/polyvinyl alcohol gel solution containing metal salt; b: preparing a chitosan/polyvinyl alcohol nanofiber membrane containing metal salt; c: preparing the chitosan/polyvinyl alcohol nanofiber membrane containing the MOFs. According to the MOFs-containing chitosan/polyvinyl alcohol nanofiber membrane disclosed by the invention, MOFs nanoparticles are loaded on the surface of the fiber membrane through an in-situ growth method, so that the loading efficiency and the phosphorus removal effect are greatly improved, and the preparation process is simple and easy to operate.
Description
Technical Field
The invention relates to a preparation method and application of a chitosan/polyvinyl alcohol nanofiber membrane containing MOFs, belonging to the technical field of chemistry.
Background
Phosphate is a major nutrient necessary for the proper functioning of many organisms in the ecosystem. However, excessive phosphate enters the aquatic system, resulting in eutrophication of the water body, promotion of growth of harmful algae, and reduction of dissolved oxygen in the water. Recent studies have shown that the total phosphorus content in lakes and rivers with higher water content increases significantly, thereby exacerbating water quality deterioration and disrupting the overall ecological balance. Common phosphorus removal methods mainly comprise biological methods, chemical precipitation, reverse osmosis, adsorption methods and the like. Among them, the adsorption method is widely used because of its high efficiency, low cost, simple operation, and strong applicability. The Chinese patent with the application number of 201910373627.4, namely 'a phosphorus removal bimetallic organic framework material, a preparation method and application thereof', discloses a Fe-Zr bimetallic organic framework material which has the characteristics of high porosity, low density, large specific surface area and the like, has a better phosphate removal effect than common adsorbent materials, but is powdery, has high recovery difficulty and is not beneficial to practical application. Chinese patent No. 202010544275.7, polyester fiber film for adsorbing heavy metals and preparation method thereof, discloses a pyridine group-containing nano polyester fiber film, which can form coordination with most of transition metals and rare earth metals, thereby adsorbing harmful heavy metals in ecological water environment. However, the preparation process involves high-temperature reaction, so that the experimental safety problem is easily caused, and the material is easy to cause secondary pollution. Chinese patent No. 201810527170.3, entitled "method for preparing quaternized polyvinyl alcohol/chitosan electrospun solid electrolyte membrane", discloses a quaternized polyvinyl alcohol nano-spinning fibrous membrane, which has good mechanical properties and stability through crosslinking technology, but has limited functional group content, and thus the technology cannot achieve ideal practical effects. Chinese patent No. 201910650544.5, entitled "method for preparing composite membrane with heavy metal and organic pollutant adsorption" discloses an adsorbent of high molecular polymer cyclodextrin/chitosan fibrous membrane composite polyamine and hydrophilic polymer, which greatly improves the adsorption effect through loaded nano titanium dioxide and a functional layer, regulates and controls the structure, but the actual loading capacity is poor, so that the cost is increased, and the synthesis process is complicated. A phosphorus-removing bimetallic organic metal frame material, a preparation method and application thereof disclosed in chinese patent No. 201910373627.4, which adopts MOFs material with Fe and Zr as metal center. Although the obtained powder has excellent phosphate adsorption performance, the self-adsorbing material is powdery, is difficult to recover and is difficult to recycle, so the powder basically has no direct use value, and at present, the powder can not be directly used or loaded on any carrier for application in practical application, and the adsorption quantity of the powder state can not be reflected in terminal use, so the adsorption quantity of the powder state can not represent the actual adsorption quantity in the final practical use state, and the used MOFs material is expensive, and the preparation process is easy to cause secondary pollution. Therefore, a novel adsorbent which has a good dephosphorization effect, does not cause secondary pollution, is simple and safe to operate and can be recycled is needed.
Disclosure of Invention
The invention aims to overcome the problems in the prior phosphorus removal adsorbent and provides a preparation method and application of a chitosan/polyvinyl alcohol nanofiber membrane containing MOFs.
In order to realize the purpose of the invention, the following technical scheme is adopted: the preparation method of the MOFs-containing chitosan/polyvinyl alcohol nanofiber membrane comprises the following steps:
a: preparing a chitosan/polyvinyl alcohol gel solution containing metal salt;
b: preparing a chitosan/polyvinyl alcohol nanofiber membrane containing metal salt;
c: preparing the chitosan/polyvinyl alcohol nanofiber membrane containing the MOFs.
Further, the method comprises the following steps of; the step A, the step B and the step C are specifically as follows:
a: under the condition of magnetic stirring, dissolving chitosan in an acetic acid solution, adding a metal salt which is zirconium tetrachloride or ferric chloride hexahydrate or aluminum chloride hexahydrate after the chitosan is dissolved, then pouring the metal salt into a round-bottom flask, then pouring the dissolved polyvinyl alcohol into the round-bottom flask, continuing magnetic stirring in a water bath kettle, and finally obtaining a uniformly mixed chitosan/polyvinyl alcohol gel solution containing the metal salt;
b: transferring the chitosan/polyvinyl alcohol gel solution containing the metal salt into a plastic capillary tube through a peristaltic pump, applying a voltage of 20 kV through a high-voltage generator, enabling the distance from a needle point to a target to be 20 cm, spraying the chitosan/polyvinyl alcohol gel solution out, and collecting fibers on a glass plate covered with an aluminum foil; obtaining a chitosan/polyvinyl alcohol nanofiber membrane containing metal salt through electrospinning, and drying in a vacuum oven;
c: putting the obtained chitosan/polyvinyl alcohol nanofiber membrane containing the metal salt into an N, N-Dimethylformamide (DMF) solution in which terephthalic acid is dissolved, pouring the solution into a reaction kettle with a polytetrafluoroethylene lining, and performing high-temperature treatment in an oven;
and after cooling, taking out the obtained MOFs-loaded chitosan/polyvinyl alcohol nanofiber membrane, washing the crude product for multiple times by using methanol, performing high-speed centrifugation by using a centrifuge, and performing vacuum drying in an oven to obtain the MOFs-loaded chitosan/polyvinyl alcohol nanofiber membrane.
Further, the method comprises the following steps of; in the step A, the mass ratio of chitosan, acetic acid, water, metal salt and polyvinyl alcohol is as follows: and (3) chitosan: acetic acid: water: metal salt: polyvinyl alcohol = 1: (0.05-0.1): (50-100): (0.2-5): (1-5); the magnetic stirring speed is 200r/min, the magnetic stirring is carried out for 4 hours, and the water bath temperature is 70oC。
Further, the method comprises the following steps of; in the step B, the spraying speed of the chitosan/polyvinyl alcohol gel solution is 0.2-1 mL/h; trueThe air drying temperature is 40-60 deg.CoC, drying for 12-24 h.
Further, the method comprises the following steps of; the mass ratio of the chitosan/polyvinyl alcohol nanofiber membrane containing the metal salt, the terephthalic acid and the N, N-dimethylformamide in the step C is as follows: polysaccharide/polyvinyl alcohol nanofiber membranes: terephthalic acid: n, N-dimethylformamide = 1: (0.5-2): (50-70); the heating temperature in the reaction kettle is 110-oC, heating for 20-48 h; the rotating speed of the centrifuge is 80000 r/min; the mass ratio of the MOFs-containing chitosan/polyvinyl alcohol nanofiber membrane to methanol is 1: (20-80); the drying temperature in the oven is 60-80 DEG CoC, drying for 12-24 h.
The application of the MOFs-containing chitosan/polyvinyl alcohol nanofiber membrane is applied to removal of phosphate.
The invention has the positive and beneficial technical effects that: after the technical scheme is adopted, the invention has the following beneficial effects: (1) according to the MOFs-containing chitosan/polyvinyl alcohol nanofiber membrane, MOFs nanoparticles are loaded on the surface of the fiber membrane through an in-situ growth method, so that the loading efficiency and the phosphorus removal effect are greatly improved; (2) the MOFs-containing chitosan/polyvinyl alcohol nanofiber membrane is added with the bio-based high molecular polymer chitosan, so that the MOFs-containing chitosan/polyvinyl alcohol nanofiber membrane is low in cost, wide in source, free of secondary pollution and biodegradable, and the product can be directly used for removing phosphorus; (3) the MOFs-containing chitosan/polyvinyl alcohol nanofiber membrane of the invention has a large number of functional groups on rich chitosan molecules, so that phosphate can be effectively removed; (4) the MOFs-containing chitosan/polyvinyl alcohol nanofiber membrane has cyclic regeneration capacity, can be repeatedly used, and keeps a high phosphorus removal effect; (5) the preparation process of the MOFs-containing chitosan/polyvinyl alcohol nanofiber membrane is simple and easy to operate.
Drawings
FIG. 1 is an infrared spectrum of the chitosan/polyvinyl alcohol nanofiber membrane containing UIO-66 synthesized in example 1.
FIG. 2 is an infrared spectrum of the MIL-101(Fe) -containing chitosan/polyvinyl alcohol nanofiber membrane synthesized in example 2.
FIG. 3 is an infrared spectrum of the MIL-101(Fe) -containing chitosan/polyvinyl alcohol nanofiber membrane synthesized in example 3.
FIG. 4 is an infrared spectrum of the MIL-101(Al) -containing chitosan/polyvinyl alcohol nanofiber membrane synthesized in example 4.
FIG. 5 is an infrared spectrum of the chitosan/polyvinyl alcohol nanofiber membrane containing UIO-66 synthesized in example 5.
FIG. 6 is an infrared spectrum of the MIL-101(Al) -containing chitosan/polyvinyl alcohol nanofiber membrane synthesized in example 6.
Fig. 7 is an infrared spectrum of the chitosan/polyvinyl alcohol nanofiber membrane synthesized in comparative example 1.
FIG. 8 is a graph showing the adsorption amounts of phosphate to the chitosan/polyvinyl alcohol nanofiber membranes synthesized in examples 1 to 6 and comparative example 1.
Detailed Description
In order to make the content of the present invention more easily and clearly understood, the technical solution of the present invention is further described in detail by the following specific embodiments in combination with the attached drawings.
Example 1:
the chitosan was dissolved in acetic acid solution under magnetic stirring, after which a certain amount of zirconium tetrachloride was added thereto and then poured into a round-bottom flask. Then, the dissolved polyvinyl alcohol is also poured into a round-bottom flask (the mass ratio of the chitosan to the acetic acid to the water to the zirconium tetrachloride to the polyvinyl alcohol is 1: 0.05: 50: 3: 4), and magnetic stirring is continued in a water bath kettle (the magnetic stirring speed is 200 r/min) for 4 hours, and the water bath temperature is 70 ℃. Finally, uniformly mixed chitosan/polyvinyl alcohol gel solution containing zirconium salt is obtained;
the chitosan/polyvinyl alcohol gel solution containing the zirconium salt is transferred into a plastic capillary (the inner diameter is 1.2 mm) through a peristaltic pump, a voltage of 20 kV is applied through a high-voltage generator, the distance from a needle point to a target is 20 cm, the chitosan/polyvinyl alcohol gel solution is sprayed out at a certain speed, the spraying speed of the solution is 0.4 mL/h, and the fibers are collected on a glass plate covered with an aluminum foil. Carrying out electrospinning to obtain a chitosan/polyvinyl alcohol nanofiber membrane containing zirconium salt, and drying in a vacuum oven overnight at the vacuum drying temperature of 50 ℃ for 20 h;
putting the obtained chitosan/polyvinyl alcohol nanofiber membrane containing the zirconium salt into an N, N-Dimethylformamide (DMF) solution in which terephthalic acid is dissolved (the mass ratio of the chitosan/polyvinyl alcohol nanofiber membrane containing the zirconium salt to the terephthalic acid to the N, N-Dimethylformamide (DMF) is 1: 0.8: 60), pouring the solution into a reaction kettle with a polytetrafluoroethylene lining, and carrying out high-temperature overnight treatment in an oven at the heating temperature of 130 ℃ for 40 hours. After cooling, the obtained UIO-66-loaded chitosan/polyvinyl alcohol nanofiber membrane is taken out, the crude product is washed for multiple times (a centrifuge is adopted for high-speed centrifugation, the rotating speed of the centrifuge is 80000 r/min) by methanol (the mass ratio of the UIO-66-containing chitosan/polyvinyl alcohol nanofiber membrane to the methanol is 1: 60), and vacuum drying is carried out in an oven (the temperature is 70 ℃ and the time is 18 h), so that the UIO-66-containing chitosan/polyvinyl alcohol nanofiber membrane is obtained.
As a result:
FIG. 1 is an infrared spectrum of the chitosan/polyvinyl alcohol nanofiber membrane containing UIO-66 synthesized in this example. As seen from FIG. 1, in the infrared spectrum of the chitosan/polyvinyl alcohol nanofiber membrane containing UIO-66, there were characteristic peaks at about 3431, 1581 and 1387 cm-1, which are respectively the C-N stretching vibration peak, the C-O bond of terephthalic acid and the C-C bond vibration stretching peak, indicating the successful synthesis of the chitosan/polyvinyl alcohol nanofiber membrane containing UIO-66.
Example 2:
the chitosan was dissolved in acetic acid solution under magnetic stirring, after which a certain amount of ferric chloride hexahydrate was added and then poured into a round bottom flask. Then pouring the dissolved polyvinyl alcohol into a round-bottom flask (the mass ratio of the chitosan to the acetic acid to the water to the ferric chloride hexahydrate to the polyvinyl alcohol is 1: 0.08: 80: 1: 5), and continuing to stir by magnetic force in a water bath (the rotating speed of the magnetic stirring is 200 r/min) for 4 hours, wherein the temperature of the water bath is 70 ℃. Finally, uniformly mixed chitosan/polyvinyl alcohol gel solution containing ferric salt is obtained;
the chitosan/polyvinyl alcohol gel solution containing the iron salt is transferred into a plastic capillary (the inner diameter is 1.2 mm) through a peristaltic pump, a voltage of 20 kV is applied through a high-voltage generator, the distance from a needle point to a target is 20 cm, the chitosan/polyvinyl alcohol gel solution is sprayed out at a certain speed, the spraying speed of the solution is 0.2 mL/h, and the fibers are collected on a glass plate covered with an aluminum foil. Carrying out electrospinning to obtain a chitosan/polyvinyl alcohol nanofiber membrane containing ferric salt, and drying in a vacuum oven overnight at 40 ℃ for 18 h;
putting the obtained ferric salt-containing chitosan/polyvinyl alcohol nanofiber membrane into an N, N-Dimethylformamide (DMF) solution in which terephthalic acid is dissolved (the mass ratio of the ferric salt-containing chitosan/polyvinyl alcohol nanofiber membrane to the terephthalic acid to the N, N-Dimethylformamide (DMF) is 1: 0.1: 70), pouring the solution into a polytetrafluoroethylene-lined reaction kettle, and carrying out high-temperature overnight treatment in an oven at the heating temperature of 110 ℃ for 48 hours. And after cooling, taking out the obtained MIL-101(Fe) -loaded chitosan/polyvinyl alcohol nanofiber membrane, washing the crude product for multiple times (high-speed centrifugation is carried out by adopting a centrifuge at the rotating speed of 80000 r/min) by using methanol (the mass ratio of the MIL-101(Fe) -containing chitosan/polyvinyl alcohol nanofiber membrane to the methanol is 1: 40), and carrying out vacuum drying in an oven (the temperature is 80 ℃ and the time is 12 hours), thereby obtaining the MIL-101(Fe) -containing chitosan/polyvinyl alcohol nanofiber membrane.
As a result:
FIG. 2 is an infrared spectrum of the synthesized MIL-101(Fe) -containing chitosan/PVA nanofiber membrane of this example. As seen from FIG. 2, in the infrared spectrum of the chitosan/polyvinyl alcohol nanofiber membrane containing MIL-101(Fe), there were characteristic peaks at about 3432, 1641 and 1485 cm-1, which are C-N stretching vibration peak, C-O bond of terephthalic acid and C-C bond vibration stretching peak, respectively, indicating the successful synthesis of the chitosan/polyvinyl alcohol nanofiber membrane containing MIL-101 (Fe).
Example 3
The chitosan was dissolved in acetic acid solution under magnetic stirring, after which a certain amount of ferric chloride hexahydrate was added and then poured into a round bottom flask. Then pouring the dissolved polyvinyl alcohol into a round-bottom flask (the mass ratio of the chitosan to the acetic acid to the water to the ferric chloride hexahydrate to the polyvinyl alcohol is 1: 0.1: 100: 5: 1), and continuing to stir by magnetic force in a water bath (the rotating speed of the magnetic stirring is 200 r/min) for 4 hours, wherein the temperature of the water bath is 70 ℃. Finally, uniformly mixed chitosan/polyvinyl alcohol gel solution containing ferric salt is obtained;
the chitosan/polyvinyl alcohol gel solution containing the iron salt is transferred into a plastic capillary (the inner diameter is 1.2 mm) through a peristaltic pump, a voltage of 20 kV is applied through a high-voltage generator, the distance from a needle point to a target is 20 cm, the chitosan/polyvinyl alcohol gel solution is sprayed out at a certain speed, the spraying speed of the solution is 0.8 mL/h, and the fibers are collected on a glass plate covered with an aluminum foil. Carrying out electrospinning to obtain a chitosan/polyvinyl alcohol nanofiber membrane containing ferric salt, and drying in a vacuum oven overnight at the vacuum drying temperature of 60 ℃ for 24 h;
putting the obtained ferric salt-containing chitosan/polyvinyl alcohol nanofiber membrane into an N, N-Dimethylformamide (DMF) solution in which terephthalic acid is dissolved (the mass ratio of the ferric salt-containing chitosan/polyvinyl alcohol nanofiber membrane to the terephthalic acid to the N, N-Dimethylformamide (DMF) is 1: 0.5: 50), pouring the solution into a polytetrafluoroethylene-lined reaction kettle, and carrying out high-temperature overnight treatment in an oven at the heating temperature of 150 ℃ for 20 hours. And after cooling, taking out the obtained MIL-101(Fe) -loaded chitosan/polyvinyl alcohol nanofiber membrane, washing the crude product for multiple times (high-speed centrifugation is carried out by adopting a centrifuge at the rotating speed of 80000 r/min) by using methanol (the mass ratio of the MIL-101(Fe) -containing chitosan/polyvinyl alcohol nanofiber membrane to the methanol is 1: 20), and carrying out vacuum drying in an oven (the temperature is 60 ℃ and the time is 15 hours), thereby obtaining the MIL-101(Fe) -containing chitosan/polyvinyl alcohol nanofiber membrane.
As a result:
FIG. 3 is an infrared spectrum of the synthesized MIL-101(Fe) -containing chitosan/PVA nanofiber membrane of this example. As seen from FIG. 3, in the infrared spectrum of the chitosan/polyvinyl alcohol nanofiber membrane containing MIL-101(Fe), there were characteristic peaks at about 3442, 1625 and 1483 cm-1, which are C-N stretching vibration peak, C-O bond of terephthalic acid and C-C bond vibration stretching peak, respectively, indicating the successful synthesis of the chitosan/polyvinyl alcohol nanofiber membrane containing MIL-101 (Fe).
Example 4
The chitosan was dissolved in acetic acid solution under magnetic stirring, after which a certain amount of aluminum chloride hexahydrate was added and then poured into a round bottom flask. Then pouring the dissolved polyvinyl alcohol into a round-bottom flask (the mass ratio of the chitosan to the acetic acid to the water to the aluminum chloride hexahydrate to the polyvinyl alcohol is 1: 0.07: 70: 0.5: 3), and continuing to stir by magnetic force in a water bath (the rotating speed of the magnetic stirring is 200 r/min) for 4 hours, wherein the temperature of the water bath is 70 ℃. Finally, the chitosan/polyvinyl alcohol gel solution containing aluminum salt is obtained;
the chitosan/polyvinyl alcohol gel solution containing the aluminum salt is transferred into a plastic capillary (the inner diameter is 1.2 mm) through a peristaltic pump, a voltage of 20 kV is applied through a high-voltage generator, the distance from a needle point to a target is 20 cm, the chitosan/polyvinyl alcohol gel solution is sprayed out at a certain speed, the spraying speed of the solution is 0.5 mL/h, and the fibers are collected on a glass plate covered with an aluminum foil. Carrying out electrospinning to obtain a chitosan/polyvinyl alcohol nanofiber membrane containing aluminum salt, and drying in a vacuum oven overnight at the vacuum drying temperature of 50 ℃ for 12 h;
putting the obtained chitosan/polyvinyl alcohol nanofiber membrane containing the aluminum salt into an N, N-Dimethylformamide (DMF) solution in which terephthalic acid is dissolved (the mass ratio of the chitosan/polyvinyl alcohol nanofiber membrane containing the aluminum salt to the terephthalic acid to the N, N-Dimethylformamide (DMF) is 1: 0.8: 60), pouring the solution into a reaction kettle with a polytetrafluoroethylene lining, and carrying out high-temperature overnight treatment in an oven at the heating temperature of 110 ℃ for 48 hours. And after cooling, taking out the obtained MIL-101(Al) -loaded chitosan/polyvinyl alcohol nanofiber membrane, washing the crude product for multiple times (high-speed centrifugation is carried out by adopting a centrifuge at the rotating speed of 80000 r/min) by using methanol (the mass ratio of the MIL-101(Al) -containing chitosan/polyvinyl alcohol nanofiber membrane to the methanol is 1: 80), and carrying out vacuum drying in an oven (the temperature is 80 ℃ and the time is 24 hours), thereby obtaining the MIL-101(Al) -containing chitosan/polyvinyl alcohol nanofiber membrane.
As a result:
FIG. 4 is an infrared spectrum of the synthesized MIL-101(Al) -containing chitosan/polyvinyl alcohol nanofiber membrane of this example. As seen from FIG. 4, in the infrared spectrum of the chitosan/polyvinyl alcohol nanofiber membrane containing MIL-101(Al), there were characteristic peaks at about 3421, 1734 and 1492 cm-1, which are respectively the C-N stretching vibration peak, the C-O bond of terephthalic acid and the C-C bond vibration stretching peak, indicating the successful synthesis of the chitosan/polyvinyl alcohol nanofiber membrane containing MIL-101 (Al).
Example 5
The chitosan was dissolved in acetic acid solution under magnetic stirring, after which a certain amount of zirconium tetrachloride was added thereto and then poured into a round-bottom flask. Then pouring the dissolved polyvinyl alcohol into a round-bottom flask (the mass ratio of the chitosan to the acetic acid to the water to the zirconium tetrachloride to the polyvinyl alcohol is 1: 0.1: 80: 2: 3), continuing to stir by magnetic force in a water bath (the rotating speed of the magnetic stirring is 200 r/min), and stirring by magnetic force for 4 hours, wherein the temperature of the water bath is 70 ℃. Finally, uniformly mixed chitosan/polyvinyl alcohol gel solution containing zirconium salt is obtained;
transferring the chitosan/polyvinyl alcohol gel solution containing the zirconium salt into a plastic capillary (the inner diameter is 1.2 mm) through a peristaltic pump, applying a voltage of 20 kV through a high-voltage generator, enabling the distance from a needle point to a target to be 20 cm, ejecting the chitosan/polyvinyl alcohol gel solution at a certain speed, enabling the solution ejection speed to be 1 mL/h, and collecting fibers on a glass plate covered with an aluminum foil. Carrying out electrospinning to obtain a chitosan/polyvinyl alcohol nanofiber membrane containing zirconium salt, and drying in a vacuum oven overnight at the vacuum drying temperature of 60 ℃ for 18 h;
putting the obtained chitosan/polyvinyl alcohol nanofiber membrane containing the zirconium salt into an N, N-Dimethylformamide (DMF) solution in which terephthalic acid is dissolved (the mass ratio of the chitosan/polyvinyl alcohol nanofiber membrane containing the zirconium salt to the terephthalic acid to the N, N-Dimethylformamide (DMF) is 1: 2: 70), pouring the solution into a reaction kettle with a polytetrafluoroethylene lining, and carrying out high-temperature overnight treatment in an oven at the heating temperature of 150 ℃ for 20 hours. After cooling, the obtained UIO-66-loaded chitosan/polyvinyl alcohol nanofiber membrane is taken out, the crude product is washed for multiple times (a centrifuge is adopted for high-speed centrifugation, the rotating speed of the centrifuge is 80000 r/min) by methanol (the mass ratio of the UIO-66-containing chitosan/polyvinyl alcohol nanofiber membrane to the methanol is 1: 50), and vacuum drying is carried out in an oven (the temperature is 60 ℃ and the time is 12 hours), so that the UIO-66-containing chitosan/polyvinyl alcohol nanofiber membrane is obtained.
As a result:
FIG. 5 is an infrared spectrum of the chitosan/polyvinyl alcohol nanofiber membrane containing UIO-66 synthesized in this example. As seen from FIG. 5, in the infrared spectrum of the chitosan/polyvinyl alcohol nanofiber membrane containing UIO-66, there were characteristic peaks at about 3402, 1666 and 1482 cm-1, which are C-N stretching vibration peak, C-O bond of terephthalic acid and C-C bond vibration stretching peak, respectively, indicating the successful synthesis of the chitosan/polyvinyl alcohol nanofiber membrane containing UIO-66.
Example 6
The chitosan was dissolved in acetic acid solution under magnetic stirring, after which a certain amount of aluminum chloride hexahydrate was added and then poured into a round bottom flask. Then pouring the dissolved polyvinyl alcohol into a round-bottom flask (the mass ratio of the chitosan to the acetic acid to the water to the aluminum chloride hexahydrate to the polyvinyl alcohol is 1: 0.08: 60: 2: 4), and continuing to stir by magnetic force in a water bath (the rotating speed of the magnetic stirring is 200 r/min) for 4 hours, wherein the temperature of the water bath is 70 ℃. Finally, the chitosan/polyvinyl alcohol gel solution containing aluminum salt is obtained;
the chitosan/polyvinyl alcohol gel solution containing the aluminum salt is transferred into a plastic capillary (the inner diameter is 1.2 mm) through a peristaltic pump, a voltage of 20 kV is applied through a high-voltage generator, the distance from a needle point to a target is 20 cm, the chitosan/polyvinyl alcohol gel solution is sprayed out at a certain speed, the spraying speed of the solution is 0.6 mL/h, and the fibers are collected on a glass plate covered with an aluminum foil. Carrying out electrospinning to obtain a chitosan/polyvinyl alcohol nanofiber membrane containing aluminum salt, and drying in a vacuum oven overnight at 40 ℃ for 20 h;
putting the obtained chitosan/polyvinyl alcohol nanofiber membrane containing the aluminum salt into an N, N-Dimethylformamide (DMF) solution in which terephthalic acid is dissolved (the mass ratio of the chitosan/polyvinyl alcohol nanofiber membrane containing the aluminum salt to the terephthalic acid to the N, N-Dimethylformamide (DMF) is 1: 1: 60), pouring the solution into a reaction kettle with a polytetrafluoroethylene lining, and carrying out high-temperature overnight treatment in an oven at the heating temperature of 110 ℃ for 30 hours. And after cooling, taking out the obtained MIL-101(Al) -loaded chitosan/polyvinyl alcohol nanofiber membrane, washing the crude product for multiple times (high-speed centrifugation is carried out by adopting a centrifuge at the rotating speed of 80000 r/min) by using methanol (the mass ratio of the MIL-101(Al) -containing chitosan/polyvinyl alcohol nanofiber membrane to the methanol is 1: 70), and carrying out vacuum drying in an oven (the temperature is 60 ℃ and the time is 18 hours), thereby obtaining the MIL-101(Al) -containing chitosan/polyvinyl alcohol nanofiber membrane.
As a result:
FIG. 6 is an infrared spectrum of the synthesized MIL-101(Al) -containing chitosan/PVA nanofiber membrane of this example. As seen from FIG. 6, in the infrared spectrum of the chitosan/polyvinyl alcohol nanofiber membrane containing MIL-101(Al), there were characteristic peaks at about 3431, 1653 and 1488 cm-1, which are C-N stretching vibration peak, C-O bond of terephthalic acid and C-C bond vibration stretching peak, respectively, indicating the successful synthesis of the chitosan/polyvinyl alcohol nanofiber membrane containing MIL-101 (Al).
Example 7
Dephosphorization application of MOFs-containing chitosan/polyvinyl alcohol nanofiber membrane
1g of the MOFs-containing chitosan/polyvinyl alcohol nanofiber membrane adsorbent prepared in examples 1 to 6 (the solid content of the adsorbent is 10% due to hydrogel pellets, and the mass content of the actually added adsorbent is 0.1 g) is added into each 150 mL conical flask respectively. Then, 100 mL of an aqueous potassium dihydrogen phosphate solution having a concentration of 50, 70, 90, 110, 130, or 150 ppm was added thereto, and the pH was maintained at 7. After closing the stopper, the amount of each adsorbent adsorbed at each concentration was measured after shaking the flask sufficiently at 25 ℃ for 24 hours, and the results are shown in FIG. 8.
As can be seen from FIG. 8, the MOFs-containing chitosan/polyvinyl alcohol nanofiber membranes synthesized in examples 1-6 all have a certain phosphorus removal capability. Wherein, the chitosan/polyvinyl alcohol nanofiber membrane containing UIO-66 synthesized in the example 5 has the highest dephosphorization effect under the same conditions.
Comparative example 1
The chitosan was dissolved in acetic acid solution under magnetic stirring, and after dissolution, poured into a round bottom flask. Then pouring the dissolved polyvinyl alcohol into a round-bottom flask (the mass ratio of the chitosan to the acetic acid to the water to the polyvinyl alcohol is 1: 0.1: 80: 3), and continuing to stir by magnetic force in a water bath kettle (the rotating speed of the magnetic force stirring is 200 r/min) for 4 hours, wherein the temperature of the water bath is 70 ℃. Finally, chitosan/polyvinyl alcohol gel solution which is mixed evenly is obtained;
transferring the chitosan/polyvinyl alcohol gel solution into a plastic capillary (the inner diameter is 1.2 mm) through a peristaltic pump, applying a voltage of 20 kV through a high-voltage generator, enabling the distance from a needle point to a target to be 20 cm, ejecting the chitosan/polyvinyl alcohol gel solution at a certain speed, enabling the ejection speed of the solution to be 0.5 mL/h, and collecting fibers on a glass plate covered with an aluminum foil. Carrying out overnight drying on the chitosan/polyvinyl alcohol nanofiber membrane obtained by electrospinning in a vacuum oven at the vacuum drying temperature of 60 ℃ for 24 hours;
as a result:
FIG. 7 is an infrared spectrum of the chitosan/polyvinyl alcohol nanofiber membrane synthesized in this comparative example. As seen from FIG. 7, in the infrared spectrum of the chitosan/polyvinyl alcohol nanofiber membrane, there were characteristic peaks at about 3442 and 1385 cm-1, which are C-N stretching vibration peak and C-C bond stretching vibration peak, respectively, indicating the successful synthesis of the chitosan/polyvinyl alcohol nanofiber membrane.
The adsorbent in example 7 was changed from "the MOFs-containing chitosan/polyvinyl alcohol nanofiber membrane synthesized in examples 1-6" to the chitosan/polyvinyl alcohol nanofiber membrane synthesized in the comparative example, and the rest was the same as example 7, so as to obtain the effect graph of removing phosphorus from the chitosan/polyvinyl alcohol nanofiber membrane synthesized in the comparative example, as shown in fig. 8. As can be seen from fig. 8, although the chitosan/polyvinyl alcohol nanofiber membrane without supporting MOFs nanoparticles has a certain phosphorus removal effect due to a large amount of hydroxyl and amino functional groups, the chitosan/polyvinyl alcohol nanofiber membrane has a certain difference in phosphorus removal capability compared to the chitosan/polyvinyl alcohol nanofiber membrane containing MOFs. Of the materials prepared in examples 1-6, it is clear that the material of example 1, i.e., the chitosan/polyvinyl alcohol nanofiber membrane containing UIO-66, provides the best phosphate removal due to the specific adsorption of inorganic phosphate by Zr in UIO-66 relative to MIL-101(Fe) and MIL-101(Al) and that Zr-O is much stronger than other metal-O bonds. While also the UIO-66 loaded nanofiber membrane, the material of example 5 was less effective in adsorbing due to the smaller amount of UIO-66 loaded therein. While in the remaining examples, the adsorption performance depends on the amount of the MOFs on the load. In general, under the same experimental conditions, the phosphorus removal effect of UIO-66 is better than that of MIL-101(Al) and MIL-101(Fe), and the adsorption performance of MIL-101(Al) and MIL-101(Fe) to phosphate is not greatly different. The differences in adsorption performance exhibited by the final examples 1-6 are mainly due to the differences in the supported MOFs content on the material during the preparation process. This again demonstrates that the addition of MOFs nanoparticles plays an important role in phosphorus removal in the MOFs-containing chitosan/polyvinyl alcohol nanofiber membranes synthesized in examples 1-6.
In order to compare the practical application value of the product of the invention, the phosphorus removal adsorption performance of the material prepared by the patent is compared with the existing related materials (from literature and commercial products) which can be directly applied to phosphorus removal. The specific comparison result of the adsorption performance is shown in table 1, and it is obvious that the material prepared by the method has excellent adsorption performance relative to other materials, and the analysis is due to two aspects, namely, the amplification effect after double superposition generated by the electrostatic action of the functional group of the chitosan and the phosphate and the specific adsorption of the loaded MOFs material and the phosphate, and the effect of 'one plus one is greater than two' is realized.
The above embodiments are described in further detail to solve the technical problems, technical solutions and advantages of the present invention, and it should be understood that the above embodiments are only examples of the present invention and are not intended to limit the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. The preparation method of the MOFs-containing chitosan/polyvinyl alcohol nanofiber membrane is characterized by comprising the following steps of:
a: preparing a chitosan/polyvinyl alcohol gel solution containing metal salt;
b: preparing a chitosan/polyvinyl alcohol nanofiber membrane containing metal salt;
c: preparing the chitosan/polyvinyl alcohol nanofiber membrane containing the MOFs.
2. The method of preparing MOFs-containing chitosan/polyvinyl alcohol nanofiber membrane according to claim 1, wherein: the step A, the step B and the step C are specifically as follows:
a: under the condition of magnetic stirring, dissolving chitosan in an acetic acid solution, adding a metal salt which is zirconium tetrachloride or ferric chloride hexahydrate or aluminum chloride hexahydrate after the chitosan is dissolved, then pouring the metal salt into a round-bottom flask, then pouring the dissolved polyvinyl alcohol into the round-bottom flask, continuing magnetic stirring in a water bath kettle, and finally obtaining a uniformly mixed chitosan/polyvinyl alcohol gel solution containing the metal salt;
b: transferring the chitosan/polyvinyl alcohol gel solution containing the metal salt into a plastic capillary tube through a peristaltic pump, applying a voltage of 20 kV through a high-voltage generator, enabling the distance from a needle point to a target to be 20 cm, spraying the chitosan/polyvinyl alcohol gel solution out, and collecting fibers on a glass plate covered with an aluminum foil; obtaining a chitosan/polyvinyl alcohol nanofiber membrane containing metal salt through electrospinning, and drying in a vacuum oven;
c: putting the obtained chitosan/polyvinyl alcohol nanofiber membrane containing the metal salt into an N, N-Dimethylformamide (DMF) solution in which terephthalic acid is dissolved, pouring the solution into a reaction kettle with a polytetrafluoroethylene lining, and performing high-temperature treatment in an oven;
and after cooling, taking out the obtained MOFs-loaded chitosan/polyvinyl alcohol nanofiber membrane, washing the crude product for multiple times by using methanol, performing high-speed centrifugation by using a centrifuge, and performing vacuum drying in an oven to obtain the MOFs-loaded chitosan/polyvinyl alcohol nanofiber membrane.
3. The method for preparing the MOFs-containing chitosan/polyvinyl alcohol nanofiber membrane according to claim 2, wherein: in the step A, the mass ratio of chitosan, acetic acid, water, metal salt and polyvinyl alcohol is as follows: and (3) chitosan: acetic acid: water: metal salt: polyvinyl alcohol = 1: (0.05-0.1): (50-100): (0.2-5): (1-5); the magnetic stirring speed is 200r/min, the magnetic stirring is carried out for 4 hours, and the water bath temperature is 70oC。
4. The method for preparing the MOFs-containing chitosan/polyvinyl alcohol nanofiber membrane according to claim 2, wherein: in the step B, the spraying speed of the chitosan/polyvinyl alcohol gel solution is 0.2-1 mL/h; vacuum drying temperature is 40-60 deg.CoC, drying for 12-24 h.
5. The method for preparing the MOFs-containing chitosan/polyvinyl alcohol nanofiber membrane according to claim 2, wherein: step C, chitosan/polyvinyl alcohol nanofiber membrane and pair containing metal saltThe mass ratio of the phthalic acid to the N, N-dimethylformamide is as follows: polysaccharide/polyvinyl alcohol nanofiber membranes: terephthalic acid: n, N-dimethylformamide = 1: (0.5-2): (50-70); the heating temperature in the reaction kettle is 110-oC, heating for 20-48 h; the rotating speed of the centrifuge is 80000 r/min; the mass ratio of the MOFs-containing chitosan/polyvinyl alcohol nanofiber membrane to methanol is 1: (20-80); the drying temperature in the oven is 60-80 DEG CoC, drying for 12-24 h.
6. Use of a MOFs containing chitosan/polyvinyl alcohol nanofibrous membrane, characterized in that: the method is applied to the removal of phosphate.
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