CN113122938B - 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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- CN113122938B CN113122938B CN202110273930.4A CN202110273930A CN113122938B CN 113122938 B CN113122938 B CN 113122938B CN 202110273930 A CN202110273930 A CN 202110273930A CN 113122938 B CN113122938 B CN 113122938B
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- chitosan
- polyvinyl alcohol
- nanofiber membrane
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- metal salt
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- 229920001661 Chitosan Polymers 0.000 title claims abstract description 169
- 239000004372 Polyvinyl alcohol Substances 0.000 title claims abstract description 167
- 229920002451 polyvinyl alcohol Polymers 0.000 title claims abstract description 167
- 239000012528 membrane Substances 0.000 title claims abstract description 120
- 239000002121 nanofiber Substances 0.000 title claims abstract description 112
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 150000003839 salts Chemical class 0.000 claims abstract description 27
- 229910052751 metal Inorganic materials 0.000 claims abstract description 25
- 239000002184 metal Substances 0.000 claims abstract description 25
- 239000000835 fiber Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 68
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 60
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 48
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 15
- 238000003760 magnetic stirring Methods 0.000 claims description 15
- 229910019142 PO4 Inorganic materials 0.000 claims description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 12
- 239000010452 phosphate Substances 0.000 claims description 12
- 238000005507 spraying Methods 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 239000011888 foil Substances 0.000 claims description 9
- 239000011521 glass Substances 0.000 claims description 9
- 230000002572 peristaltic effect Effects 0.000 claims description 9
- 229920003023 plastic Polymers 0.000 claims description 9
- 239000004033 plastic Substances 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 239000012043 crude product Substances 0.000 claims description 8
- 238000001523 electrospinning Methods 0.000 claims description 8
- JGDITNMASUZKPW-UHFFFAOYSA-K aluminium trichloride hexahydrate Chemical compound O.O.O.O.O.O.Cl[Al](Cl)Cl JGDITNMASUZKPW-UHFFFAOYSA-K 0.000 claims description 6
- 229940009861 aluminum chloride hexahydrate Drugs 0.000 claims description 6
- 229940044631 ferric chloride hexahydrate Drugs 0.000 claims description 6
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 6
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 150000004676 glycans Chemical class 0.000 claims description 2
- 229920001282 polysaccharide Polymers 0.000 claims description 2
- 239000005017 polysaccharide Substances 0.000 claims description 2
- -1 polytetrafluoroethylene Polymers 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 17
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 16
- 239000011574 phosphorus Substances 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 14
- 239000002105 nanoparticle Substances 0.000 abstract description 4
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 238000011068 loading method Methods 0.000 abstract description 2
- 239000000499 gel Substances 0.000 description 26
- 238000002329 infrared spectrum Methods 0.000 description 21
- 239000013207 UiO-66 Substances 0.000 description 19
- 239000000463 material Substances 0.000 description 19
- 238000001179 sorption measurement Methods 0.000 description 17
- 239000013177 MIL-101 Substances 0.000 description 16
- 239000013179 MIL-101(Fe) Substances 0.000 description 15
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 10
- 150000003754 zirconium Chemical class 0.000 description 10
- 239000003463 adsorbent Substances 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 150000002505 iron Chemical class 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000000703 high-speed centrifugation Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 241000195493 Cryptophyta Species 0.000 description 1
- 229920000858 Cyclodextrin Polymers 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- 229910007746 Zr—O Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000010041 electrostatic spinning Methods 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 230000003090 exacerbative effect Effects 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052816 inorganic phosphate Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
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- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
- B01J20/28038—Membranes or mats made from fibers or filaments
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
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- D01F1/00—General methods for the manufacture of artificial filaments or the like
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- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
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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 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. A phosphorus removal bimetallic organic frame material, a preparation method and an application thereof disclosed in a chinese patent with application number 201910373627.4, 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 in material, has a high recovery difficulty, and is not beneficial to practical application. Chinese patent No. 202010544275.7, a polyester fiber membrane for adsorbing heavy metals and a preparation method thereof, discloses a pyridine group-containing nano polyester fiber membrane which can form coordination with most of transition metals and rare earth metals so as to adsorb 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. In a Chinese patent 'preparation method of a quaternized polyvinyl alcohol/chitosan electrostatic spinning solid electrolyte film', the application number of which is 201810527170.3, a nano spinning fiber film of quaternized polyvinyl alcohol is disclosed, and the material has good mechanical properties and stability through a crosslinking technology, but the content of functional groups of the material is limited, so that the technology cannot achieve ideal actual effects. Chinese patent 'a preparation method of a composite membrane with heavy metal and organic pollutant absorption' with application number 201910650544.5 discloses an adsorbent of high-molecular polymer cyclodextrin/chitosan fiber membrane composite polyamine and hydrophilic polymer, through loaded nano titanium dioxide and a functional layer, the adsorption effect is greatly improved, the structure is regulated, but the actual load capacity is poor, the cost is increased, and the synthesis process is complicated. A phosphorus-removing bimetallic organometallic framework material, a preparation method and application thereof disclosed in a Chinese patent with the application number of 201910373627.4, and an MOFs material adopting Fe and Zr as metal centers. 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 MOFs-containing chitosan/polyvinyl alcohol nanofiber membrane.
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 acetic acid solution, after dissolving, adding metal salt which is zirconium tetrachloride or ferric chloride hexahydrate or aluminum chloride hexahydrate, 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 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, wherein the distance from a needle point to a target is 20 cm, spraying out the chitosan/polyvinyl alcohol gel solution, 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 with methanol for multiple times, centrifuging at a high speed by using a centrifuge, and performing vacuum drying in an oven to obtain the MOFs-containing 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 70 o C。
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; vacuum drying temperature is 40-60 deg.C o C, drying for 12-24h.
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 110-150 DEG C o C, heating for 20-48h; the rotating speed of the centrifuge is 80000r/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 C o C, drying for 12-24h.
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 IR spectrum of the MIL-101 (Fe) -containing chitosan/PVA 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 IR spectrum of 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 was also poured into a round bottom flask (the mass ratio of chitosan, acetic acid, water, zirconium tetrachloride, polyvinyl alcohol was 1.05. 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 20h;
putting the chitosan/polyvinyl alcohol nanofiber membrane containing the zirconium salt into an N, N-Dimethylformamide (DMF) solution dissolved with terephthalic acid (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 1.8). 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 to carry out high-speed centrifugation, the rotation 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).
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. The dissolved polyvinyl alcohol was then also poured into a round bottom flask (mass ratio of chitosan, acetic acid, water, ferric chloride hexahydrate, polyvinyl alcohol 1.08. 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 18h;
putting the obtained chitosan/polyvinyl alcohol nanofiber membrane containing the iron 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 iron salt to the terephthalic acid to the N, N-Dimethylformamide (DMF) is 1. After cooling, the obtained MIL-101 (Fe) -loaded chitosan/polyvinyl alcohol nanofiber membrane is taken out, the crude product is washed for multiple times (high-speed centrifugation is carried out by adopting a centrifuge, the rotating speed of the centrifuge is 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.
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. The dissolved polyvinyl alcohol was then also poured into a round bottom flask (mass ratio of chitosan, acetic acid, water, ferric chloride hexahydrate, polyvinyl alcohol 1. Finally, a chitosan/polyvinyl alcohol gel solution containing iron 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 electric spinning to obtain a chitosan/polyvinyl alcohol nanofiber membrane containing ferric salt, and carrying out overnight drying in a vacuum oven at the vacuum drying temperature of 60 ℃ for 24 hours;
putting the obtained chitosan/polyvinyl alcohol nanofiber membrane containing the iron 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 iron salt to the terephthalic acid to the N, N-Dimethylformamide (DMF) is 1. After cooling, the obtained MIL-101 (Fe) -loaded chitosan/polyvinyl alcohol nanofiber membrane is taken out, the crude product is washed for multiple times (high-speed centrifugation is carried out by adopting a centrifuge, the rotating speed of the centrifuge is 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).
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 the dissolved polyvinyl alcohol was also poured into a round bottom flask (the mass ratio of chitosan, acetic acid, water, aluminum chloride hexahydrate, polyvinyl alcohol was 1. 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 12h;
putting the 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. After cooling, the obtained MIL-101 (Al) -loaded chitosan/polyvinyl alcohol nanofiber membrane was taken out, the crude product was washed with methanol (mass ratio of MIL-101 (Al) -containing chitosan/polyvinyl alcohol nanofiber membrane to methanol was 1: 80) multiple times (high speed centrifugation using a centrifuge at 80000 r/min), and vacuum-dried in an oven (temperature of 80 ℃ for 24 hours), thereby obtaining 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 the dissolved polyvinyl alcohol was also poured into a round bottom flask (the mass ratio of chitosan, acetic acid, water, zirconium tetrachloride, polyvinyl alcohol was 1.1. 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 solution spraying speed is 1 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 60 ℃ for 18h;
putting the chitosan/polyvinyl alcohol nanofiber membrane containing the zirconium salt into an N, N-Dimethylformamide (DMF) solution dissolved with terephthalic acid (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. After cooling, the obtained UIO-66-loaded chitosan/polyvinyl alcohol nanofiber membrane is taken out, the crude product is washed for multiple times (high-speed centrifugation is carried out by adopting a centrifuge, the rotating speed of the centrifuge is 80000 r/min) by using methanol (the mass ratio of the UIO-66-containing chitosan/polyvinyl alcohol nanofiber membrane to the methanol is 1), 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 the dissolved polyvinyl alcohol was also poured into a round bottom flask (the mass ratio of chitosan, acetic acid, water, aluminum chloride hexahydrate, polyvinyl alcohol was 1.08. 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 20h;
putting the 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. After cooling, the obtained MIL-101 (Al) -loaded chitosan/polyvinyl alcohol nanofiber membrane is taken out, the crude product is washed for multiple times (high-speed centrifugation is carried out by adopting a centrifuge, the rotating speed of the centrifuge is 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).
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 flask was shaken sufficiently at a temperature of 25 ℃ for 24 hours, and then the adsorption amount of each adsorbent at each concentration was measured, 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 the dissolved polyvinyl alcohol was also poured into a round bottom flask (the mass ratio of chitosan, acetic acid, water, polyvinyl alcohol was 1.1. 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, spraying the chitosan/polyvinyl alcohol gel solution at a certain speed, enabling the spraying 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 are characteristic peaks at about 3442 and 1385 cm-1, which are C-N stretching vibration peak and C-C bond stretching 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 (4)
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 a chitosan/polyvinyl alcohol nanofiber membrane containing MOFs;
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; 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 70 o C；
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 with methanol for multiple times, centrifuging at a high speed by using a centrifuge, and performing vacuum drying in an oven to obtain the MOFs-containing chitosan/polyvinyl alcohol nanofiber membrane.
2. The method for preparing the MOFs-containing chitosan/polyvinyl alcohol nanofiber membrane according to claim 1, 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.C o C, drying for 12-24h.
3. The method of preparing MOFs-containing chitosan/polyvinyl alcohol nanofiber membrane according to claim 1, wherein: 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 110-150 DEG C o C, heating for 20-48h; the rotating speed of the centrifuge is 80000r/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 C o C, drying for 12-24h.
4. Use of a chitosan/polyvinyl alcohol nanofibrous membrane containing MOFs, with a chitosan/polyvinyl alcohol nanofibrous membrane containing MOFs according to any of claims 1 to 3, characterised in that: the method is applied to the removal of phosphate.
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