CN108816064A - A kind of preparation method of the chitosan nano fiber membrane of growth in situ metal-organic framework material - Google Patents
A kind of preparation method of the chitosan nano fiber membrane of growth in situ metal-organic framework material Download PDFInfo
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- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
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- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
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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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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C—CHEMISTRY; METALLURGY
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Abstract
The invention belongs to the technical field of polymer composite preparation, specifically a kind of preparation methods of the chitosan nano fiber membrane of growth in situ metal-organic framework material.Chitosan is obtained into chitosan nano fiber membrane by electrostatic spinning；It is chelated under acidic environment with the biometallic joint in MOFs material again；Ligand is added after chelating, grows MOFs material in chitin fiber surface in situ, obtains growth in situ MOFs material chitosan nano fiber membrane.The present invention had not only solved the problems, such as that MOFs material and chitosan were compound and has been difficult to bond strength that is evenly dispersed, but also both improving, avoided falling off for MOFs material.The advantages that composite material has preparation process simple, and adsorption efficiency is high, and surface is uniform and stability is good, can be applied to the absorption of a variety of dyestuffs.Meanwhile it also being had potential application in gas filtration, organic solvent separation and water process.
Description
Technical field
The invention belongs to the technical field of polymer composite preparation, specifically a kind of growth in situ metal is organic
The preparation method of the chitosan nano fiber membrane of frame material.
Background technique
Metal organic frame (MOFs) material is a kind of shape and structure for having and only specific molecular being allowed to enter hole
Material.Since the arrangement of organic ligand and metal ion or cluster has apparent directionality, thus different frames can be formed
Frame aperture gap structure.The organic ligand or metal ion of selection are different, and the crystal structure of MOFs material is also different, generallys use transition
Metal ion is as node, such as Zn, Cu, Ni, Co etc., prepared in conjunction with multi-functional organic ligand (Nature,
2015,520:148-150)。
MOFs material is in solid powdery, and mechanical strength is low, it usually needs in conjunction with other materials easily processed into type
Prepare composite material (Advanced Engineering Materials, 2008,10 (12):1151-1155).Wherein, patent
CN 107051398A disclose it is a kind of by MOFs growth in situ on silk-fibroin method, and it is high, negative that filter efficiency has been prepared
The thin-film material that carrying capacity is high, stability is good；Patent CN 107841879A discloses a kind of alginic acid electrospun fibers surface original
The method of position growth MOFs.In addition, by MOFs growth in situ in carboxycellulose (Cellulose, 2012,19 (5):1771-
1779), carboxymethyl cellulose (Nanoscale, 2017,9 (35):It is had been reported on 12850-12854).
Chitosan (Chitosan, CS) is unique in the alkaline polysaccharide and nature obtained by chitin deacetylation
Naturally occurring cationic polymer, have many advantages, such as cheap, nontoxic, biodegradable, good film-forming property, be recognized in recent years
To be the following green material with development potential.But it is only widely used in fields such as organizational project, drug conveyings
(Nanoscale,2017,9(12):4154-4161)。
Although by other natural polymer In-situ reaction existing researches of MOFs and cellulose, alginic acid and silk-fibroin,
The negative electrical charge of the carboxyl institute band on to be by MOFs growth in situ mechanism be natural polymer surface and the positive electricity on metal ion surface
Lotus generates certain electrostatic attraction, and then promotes the initial coordination of macromolecule and metal ion, makes metal ion in fibre
It ties up plain surface and forms nucleus, the introducing of ligand then promotes the growth of crystal.But by MOFs growth in situ on chitosan surface
Composite material is prepared to have not been reported.
Summary of the invention
The object of the present invention is to provide a kind of chitosan nano fiber membranes of growth in situ metal-organic framework material
Preparation method.
To achieve the above object, the invention adopts a technical scheme as：
A kind of preparation method of the chitosan nano fiber membrane of growth in situ metal-organic framework material (MOFs)：Shell is gathered
Sugar obtains chitosan nano fiber membrane by electrostatic spinning；Again by it under acidic environment with the biometallic joint chela in MOFs material
It closes；Ligand is added after chelating, grows MOFs material in chitin fiber surface in situ, obtains growth in situ MOFs material chitosan
Nano fibrous membrane.
It is further that chitosan nano fiber membrane and metal salt are added in organic solvent, and adds in system
Enter concentrated acid solution；0.5h-3.5h then is stirred under conditions of rate is 100r/min-300r/min, is then allowed to stand 1h-3h；
It is used organic solvent washing 3-5 times after staticly settling, is added in aqueous slkali, is added after ligand stirs evenly through organic after washing
Solvent washing, the dry chitosan nano fiber membrane that surface growth MOFs can be obtained.
The metal salt refers to using major element, transition elements or lanthanide series as in the water soluble salt of metal cation
One or more；Its dosage is 1-10 times of chitin fiber film quality, and the ligand refers to oxygen-containing or nitrogen have containing carboxyl
One or more of machine anion ligand, or be used in conjunction with nitrogen-containing heterocycle organic neutral ligands, ligand additional amount is poly- for shell
1-20 times of sugared fiber film quality,
It is preferred that the dosage of metal salt is 3-5 times of chitin fiber film quality, preferably ligand additional amount is chitin fiber
2-10 times of film quality.
It is preferred that the metal salt is zinc nitrate, cobalt chloride, copper acetate, chromic nitrate, zirconium chloride or nickel chloride；The ligand
For 2-methylimidazole, trimesic acid, terephthalic acid (TPA), 2- amino terephthalic acid (TPA) or terephthalic acid (TPA).
Above-mentioned metal salt can be by existing preparation with dosage relation when ligand formation MOFs material between the two simultaneously
Method carries out, and deploys.
The organic solvent refers to anhydrous methanol and/or dehydrated alcohol；The volume matter of organic solvent and chitin fiber film
(mL/g) is measured than being 200-1000：1, preferably 300-700：1；It is described wash the organic solvent that uses for anhydrous methanol and/or
Dehydrated alcohol；
The aqueous slkali is the ammonia spirit that concentration is 0.05mol/L-0.3mol/L；Ammonia spirit and chitin fiber film
Volume mass (mL/g) than be 100-2000：1, preferably 500-1000:1.
System stirs 0.5h-5h under conditions of revolving speed is 100-300r/min after the addition ligand, then with organic
Solvent washs 3-5 all over rear drying, and drying condition is 30 DEG C -50 DEG C, 5min-30min.
The chitosan nano fiber is to be less than 200nm by the diameter that electrostatic spinning mode obtains using chitosan as raw material
Fiber.Wherein, electrostatic spinning modeFor example, wet spinning, dry spinning etc.
The chitosan nano fiber be by chitosan be raw material by electrostatic spinning in a manner of prepare, by chitosan
Addition water after mixing, which is respectively added slowly into concentrated acid solution, with polyethylene glycol oxide obtains uniformly sticky chitosan solution to be spun,
Electrostatic spinning is carried out after being then ultrasonically treated, chitin fiber is obtained after removing；Wherein, (quality is dense for the final concentration of acid solution
Degree) it is 1%-10%, chitosan accounts for the 0.5%-5% of acid solution quality, and polyethylene glycol oxide accounts for the 0.1%- of acid solution quality
10%.
The final concentration (mass concentration) of preferred acid solution is 3%-5%, and chitosan accounts for the 1%-3% of acid solution quality,
Polyethylene glycol oxide accounts for the 0.1%-1% of acid solution quality.
After solution ultrasound, solution is extracted with syringe and carries out electrostatic spinning, using tinfoil as receiver board, spinning condition
For：Positive pressure is 2.0KV-13.0KV, and negative pressure is -5.0KV--10.0KV, and injecting speed is 0.02mm/min-0.15mm/min, is put down
Shifting speed is 100mm/min-500mm/min, and the revolving speed for receiving roller is 5r/min-30r/min.
The preparation of the chitosan nano fiber membrane of growth in situ MOFs of the invention has the following advantages that：
(1) in acid condition, the amino on strand has preferable chelation to the metal ion in MOFs, into
And suitable, uniform nucleation site is provided for MOFs crystal, system is adjusted to alkalinity when then introducing ligand, makes metal ion
MOFs is obtained with ligand reaction, and then is uniformly grown in chitosan nano fiber membrane surface.It is more difficult that this efficiently solves MOFs
The problem of chitosan surface in situ is grown, and avoids caused MOFs bad dispersibility when MOFs and chitosan blend, bears
Load rate is low and the technical problem of the two binding strength difference.
(2) chitosan nano fiber that uses of the present invention is compared with chitosan, has biggish specific surface area and porous
Structure can effectively facilitate chelation between its surface amino groups and metal ion, and its aperture structure can be made by changing
Standby technique is adjusted, and MOFs particle has mesoporous or microcellular structure, can also be according to different purposes to different pore size
MOFs is screened, and this adjustable graded porous structure is conducive to MOFs- Chitosan Composites in absorption or filtering
Using, and service efficiency can be improved.
(3) method therefor of the present invention is simple and easy, is easy to be mass produced.
Detailed description of the invention
Fig. 1 is the chitin fiber film preparation flow chart of growth in situ MOFs provided in an embodiment of the present invention.
Fig. 2 is the SEM figure of chitosan nano fiber membrane prepared by the embodiment of the present invention 1.
Fig. 3 is the pictorial diagram of ZIF-8@chitin fiber film prepared by the embodiment of the present invention 1.
Fig. 4 is the SEM figure of ZIF-8@chitin fiber film prepared by the embodiment of the present invention 1.
Fig. 5 is the absorbance curve of ZIF-8@chitin fiber film prepared by the embodiment of the present invention 1.
Fig. 6 is the variation of rhodamine b solution colour after ZIF-8@chitin fiber film absorption prepared by the embodiment of the present invention 1
It is (left：0.1% rhodamine b solution, it is right：Rhodamine b solution after composite membrane absorption for 24 hours).
Fig. 7 is the absorbance curve of ZIF-67@chitin fiber film prepared by the embodiment of the present invention 2.
Specific embodiment
The feasibility of this method is further described below by way of specific implementation example, but is not intended that the invention be limited to
These examples.
The present invention does not have carboxyl using chitosan nano fiber membrane as raw material in chitosan molecule structure, although chitosan
Amino in molecule can also generate certain chelation to metal ion in acid condition, but need after introducing ligand
It can be just that metal ion and ligand form MOFs crystal under alkaline condition；And then for MOFs is supported on shell using in situ synthesis
Glycan fiber film surface is prepared for a kind of chitin fiber membrane material of even porous.It is not influencing chitin fiber property
Under the premise of, so that MOFs material and chitin fiber film is realized firm combination, solves MOFs and be easy aggregation in the polymer
Problem.In addition, MOFs is supported on chitosan nano fiber membrane and forms adjustable porous structure with biggish specific surface area,
It is expected to as in absorption or the fields such as filtering material application separation and gas storage.
The present invention had not only solved the problems, such as that MOFs material and chitosan were compound and has been difficult to knot that is evenly dispersed, but also both improving
Intensity is closed, falling off for MOFs material is avoided.The composite material has preparation process simple, and adsorption efficiency is high, surface uniformly and
The advantages that stability is good can be applied to the absorption of a variety of dyestuffs.Meanwhile at gas filtration, organic solvent separation and water
It is also had potential application in reason.
Embodiment 1
In situ synthesis prepares ZIF-8@chitosan nano fiber membrane
1) preparation of chitosan nano fiber：Chitosan and polyethylene glycol oxide are respectively added slowly in glacial acetic acid to mix
Close liquid, wherein glacial acetic acid solution final concentration (mass concentration) is 3% in mixed liquor, and chitosan accounts for the 1% of acid solution quality, is gathered
Ethylene oxide accounts for the 0.1% of acid solution quality；Magnetic stirring apparatus is opened after addition, revolving speed 500r/min consolidates after stirring 30min
Body is completely dissolved；Solution after ultrasound 10min, is carried out quiet under the intensity of 300W with the syringe of 5mL extraction solution after dissolution
Electrospun, using tinfoil as receiver board, spinning condition is：Positive pressure is 2.0KV, and negative pressure is -10.0KV, and injecting speed is
0.02mm/min, translational velocity 100mm/min, the revolving speed for receiving roller is 5r/min；After spinning, tinfoil is removed,
It is cut into the fritter of 2cm × 2cm, chitin fiber film is removed (referring to fig. 2) from tinfoil；
2) preparation of Zn- chitosan nano fiber membrane：Chitosan nano fiber membrane and zinc nitrate is taken to be added in methanol, so
1g glacial acetic acid is added dropwise afterwards.Wherein, the dosage of zinc nitrate is 3 times of chitin fiber film quality, i.e. 0.15g；Methanol and chitosan
The volume mass (mL/g) of tunica fibrosa is than being 300：1.System stirs 0.5h under 100r/min speed, after standing 1h, uses methanol
Washing 3 times, the Zn that removal fiber surface does not chelate2+Ion obtains Zn- chitosan nano fiber membrane；
3) Zn- chitosan nano fiber membrane is added to ammonium hydroxide (ammonia concn 0.05mol/L, with chitin fiber film
Volume mass (mL/g) than be 500：1) in, 2-methylimidazole is then added, and (2-methylimidazole 0.1g, dosage are that chitosan is fine
2 times for tieing up film quality), which stirs 0.5h at 100r/min；Then after washing 3 times with methanol, air blast is dry at 30 DEG C
The chitosan nano fiber membrane of surface growth ZIF-8 can be obtained in dry 5min.By test, ZIF-8@chitosan nano fiber
The load capacity of ZIF-8 is higher (8.3%) in film.Find out from SEM figure, the crystal structure that ZIF-8 is formed in chitin fiber
Rule and be uniformly dispersed.(ginseng is seen figures 3 and 4).
Verifying 1
ZIF-8@chitin fiber composite membrane is used for the absorption of rhodamine b
Weigh the 0.05g ZIF-8@chitin fiber composite membrane prepared in example 1,0.05g chitosan nano fiber membrane with
And 1mg ZIF-8, it is respectively placed in 0.1% rhodamine b- ethanol solution, seals.It is to be adsorbed for 24 hours after, take supernatant respectively
200 μ L are added in cuvette, test its absorbance value (Fig. 5) at 554nm using ultraviolet-visible spectrophotometer method,
And then the concentration of rhodamine b after absorption is calculated, Fig. 6 is the color change of absorption front and back rhodamine b solution.By testing,
After chitosan nano fiber membrane, the absorption of ZIF-8 and ZIF-8@chitin fiber film, the concentration of rhodamine b solution is from 0.1%
0.08%, 0.004% and 0.008% is dropped to respectively, and dyestuff removal rate is respectively 20%, 96%, 92%, i.e., gives birth in situ
Chitosan nano fiber membrane significantly improves the adsorption capacity to rhodamine b after long MOFs.
Embodiment 2
In situ synthesis prepares ZIF-67@chitosan nano fiber membrane
1) preparation of chitosan nano fiber：Chitosan and polyethylene glycol oxide are respectively added slowly in glacial acetic acid to mix
Close liquid, wherein glacial acetic acid solution final concentration (mass concentration) is 5% in mixed liquor, and chitosan accounts for the 3% of acid solution quality, is gathered
Ethylene oxide accounts for the 1% of acid solution quality.Magnetic stirring apparatus is opened after mixing, revolving speed 700r/min stirs solid after 30min
It is completely dissolved；Solution after ultrasound 30min, is extracted solution with the syringe of 5mL and carry out electrostatic under the intensity of 1500W after dissolution
Spinning, using tinfoil as receiver board, spinning condition is：Positive pressure is 5.0KV, and negative pressure is -6.0KV, and injecting speed is 0.15mm/
Min, translational velocity 500mm/min, the revolving speed for receiving roller is 30r/min；After spinning, tinfoil is removed, is cut into 2cm
The fritter of × 2cm removes chitin fiber film from tinfoil；
2) preparation of Co- chitosan nano fiber membrane：Chitosan nano fiber membrane 0.5g is taken to be added to cobalt chloride anhydrous
In ethyl alcohol, 0.05g glacial acetic acid is then added dropwise.Wherein, the dosage of cobalt chloride is 10 times of chitin fiber film quality, dehydrated alcohol
With chitin fiber membrane volume quality (mL/g) ratio 700：1.System stirs 3h under 300r/min speed, after standing 3h, with nothing
Water-ethanol washs 5 times, the Co that removal fiber film surface does not chelate2+Ion obtains Co- chitosan nano fiber membrane；
3) Co- chitosan nano fiber membrane is added to ammonium hydroxide (ammonia concn 0.3mol/L, with chitin fiber film
Volume mass (mL/g) is than being 1000：1) in, 2-methylimidazole is then added, and (2-methylimidazole dosage is 0.5g, poly- for shell
10 times of sugared fiber film quality), which stirs 5h at 300r/min；Then after washing 5 times with dehydrated alcohol, at 50 DEG C
The ZIF-67@chitosan nano fiber membrane that ZIF-67 load capacity is 5.9% can be obtained in forced air drying 30min.
Verifying 2
ZIF-67@chitin fiber film is used for the absorption of malachite green
Weigh the 0.05g ZIF-67@chitin fiber film prepared in example 2,0.05g chitosan nano fiber membrane and
1mg ZIF-8 is respectively placed in 1% malachite green aqueous solution, sealing.Be slowly stirred, it is to be adsorbed for 24 hours after, take supernatant respectively
200 μ L of liquid is added in cuvette, tests its absorbance value (figure at 616.9nm using ultraviolet-visible spectrophotometer method
7), so be calculated absorption after malachite green concentration.By test, after the absorption of ZIF-67@chitin fiber film, malachite
The concentration of green solution drops to 0.12% from 1%, and removal efficiency 88%, second adsorption is then completely removed.Due to malachite
Green is toxic triphenylmethane chemicals, has the shortcomings that high toxicity, high residue, and ZIF-67@chitin fiber film is inhaled
The effect of attached this kind of dyestuff is preferable, and therefore, ZIF-67@chitin fiber film has biggish application prospect in water treatment field.
Embodiment 3
In situ synthesis prepares HKUST-1@chitosan nano fiber membrane
1) preparation of chitosan nano fiber：Chitosan and polyethylene glycol oxide are respectively added slowly in glacial acetic acid to mix
Close solution, wherein glacial acetic acid final concentration (mass concentration) is 4.5% in mixed solution, and chitosan accounts for acid solution quality
1.5%, polyethylene glycol oxide accounts for the 0.7% of acid solution quality.Magnetic stirring apparatus, revolving speed 500r/min, stirring are opened after mixing
Solid is completely dissolved after 30min；By solution under the intensity of 700W after ultrasound 30min, solution is extracted with the syringe of 5mL and is carried out
Electrostatic spinning, using tinfoil as receiver board, spinning condition is：Positive pressure is 3.0KV, and negative pressure is -9.0KV, and injecting speed is
0.10mm/min, translational velocity 400mm/min, the revolving speed for receiving roller is 10r/min；After spinning, tinfoil is removed,
It is cut into the fritter of 2cm × 2cm, chitin fiber film is removed from tinfoil；
2) preparation of Cu- chitosan nano fiber membrane：Chitosan nano fiber membrane 0.4g is taken to be added to Salicylaldoxime
In dehydrated alcohol, 1g glacial acetic acid is then added dropwise.Wherein, the dosage of Salicylaldoxime is 8 times of chitin fiber film quality, anhydrous
Ethyl alcohol and chitin fiber membrane volume quality (mL/g) are than being 500：1.System stirs 2.5h under 500r/min speed, stands 2h
Afterwards, it is washed 5 times with methanol, the Cu that removal fiber surface does not chelate2+Ion obtains Cu- chitosan nano fiber membrane；
3) Cu- chitosan nano fiber membrane is added to ammonium hydroxide (ammonia concn 0.11mol/L, with chitin fiber
Membrane volume quality (mL/g) is than being 700：1) in, trimesic acid is then added, and (trimesic acid dosage is 0.2g, and dosage is poly- for shell
4 times of sugared fiber film quality)；System stirs 2h at 200r/min；Then after washing 5 times with methanol, air blast is dry at 40 DEG C
The HKUST-1@chitosan nano fiber membrane that load capacity is 6.2% can be obtained in dry 10min.
The HKUST-1@chitosan nano fiber membrane of above-mentioned acquisition adsorbs tonyred (initial concentration 2%), passes through
The removal efficiency of tonyred is 74% after the absorption of HKUST-1@chitosan nano fiber membrane, can then be gone completely through second adsorption
It removes.
Embodiment 4
In situ synthesis prepares MIL-101 (Cr)@chitosan nano fiber membrane
1) preparation of chitosan nano fiber：Chitosan and polyethylene glycol oxide are respectively added slowly in glacial acetic acid to mix
Closing solution, wherein glacial acetic acid solution final concentration (mass concentration) is 4% in mixed liquor, and chitosan accounts for the 2% of acid solution quality,
Polyethylene glycol oxide accounts for the 0.5% of acid solution quality.Magnetic stirring apparatus is opened, revolving speed 400r/min, solid is complete after stirring 30min
Fully dissolved；By solution under the intensity of 700W after ultrasound 30min, solution is extracted with the syringe of 5mL and carries out electrostatic spinning, is used
Tinfoil is as receiver board, spinning condition：Positive pressure is 10.0KV, and negative pressure is -8.0KV, and injecting speed is 0.08mm/min, translation
Speed is 400mm/min, and the revolving speed for receiving roller is 25r/min；After spinning, tinfoil is removed, is cut into 2cm × 2cm's
Fritter removes chitin fiber film from tinfoil；
2) preparation of Cr- chitosan nano fiber membrane：Chitosan nano fiber membrane and chromic nitrate 0.25g is taken to be added to methanol
In, 1g glacial acetic acid is then added dropwise.Wherein, the dosage of chromic nitrate is 5 times of chitin fiber film quality, methanol and chitin fiber
Membrane volume quality (mL/g) is than being 600：1.System stirs 1.5h under 200r/min speed, after standing 1h, washs 3 with methanol
Cr secondary, that removal fiber film surface does not chelate2+Ion obtains Cr- chitosan nano fiber membrane；
3) Cr- chitosan nano fiber membrane is added to ammonium hydroxide (ammonia concn 0.05mol/L, with chitin fiber film
Volume mass (mL/g) is than being 1000：1) in, terephthalic acid (TPA) (terephthalic acid (TPA) 0.4g) then is added, dosage is poly- for shell
8 times of sugared fiber film quality, which stirs 1.5h at 100r/min；Then after washing 5 times with methanol, the air blast at 30 DEG C
Dry 10min, can be obtained the chitosan nano fiber membrane of surface growth MIL-101 (Cr).
MIL-101 (Cr) the@chitosan nano fiber membrane for being 8.9% by the load capacity of above-mentioned acquisition is (first to methylene blue
Beginning concentration 1%) it is adsorbed, the removal efficiency of methylene blue is after the absorption of MIL-101 (Cr)@chitosan nano fiber membrane
90.1%.
Embodiment 5
In situ synthesis prepares UiO-66-NH2@chitosan nano fiber membrane
1) preparation of chitosan nano fiber：Chitosan and polyethylene glycol oxide are respectively added slowly in glacial acetic acid to mix
Close solution, wherein glacial acetic acid solution final concentration (mass concentration) is 3.5% in mixed solution, and chitosan accounts for acid solution quality
1.5%, polyethylene glycol oxide accounts for the 0.9% of acid solution quality.Open magnetic stirring apparatus, revolving speed 700r/min, after stirring 30min
Solid is completely dissolved；By solution under the intensity of 700W after ultrasound 30min, solution is extracted with the syringe of 5mL and carries out Static Spinning
Silk, using tinfoil as receiver board, spinning condition is：Positive pressure is 10.0KV, and negative pressure is -8.0KV, and injecting speed is 0.08mm/
Min, translational velocity 400mm/min, the revolving speed for receiving roller is 15r/min；After spinning, tinfoil is removed, is cut into 2cm
The fritter of × 2cm removes chitin fiber film from tinfoil；
2) preparation of Zr- chitosan nano fiber membrane：Chitosan nano fiber membrane and zirconium chloride 0.3g is taken to be added to first
In alcohol, 1g glacial acetic acid is then added dropwise.Wherein, the dosage of zirconium chloride is 6 times of chitin fiber film quality, methanol and chitosan
Tunica fibrosa volume mass (mL/g) is than being 550：1.3h is stirred under 300r/min speed, after standing 3h, washs 5 with dehydrated alcohol
Zr secondary, that removal fiber film surface does not chelate4+Ion obtains Zr- chitosan nano fiber membrane；
3) Zr- chitosan nano fiber membrane is added to ammonium hydroxide (ammonia concn 0.3mol/L, with chitin fiber membrane body
Product quality (mL/g) is than being 900：1) in, 2- amino terephthalic acid (TPA) 0.35g is then added, dosage is chitin fiber film quality
7 times of amount, which stirs 3h at 300r/min；Then after washing 5 times with dehydrated alcohol, the forced air drying at 50 DEG C
Surface growth UiO-66-NH can be obtained in 30min2Chitosan nano fiber membrane (load capacity 7.8%).By verifying,
UiO-66-NH2Chitosan nano fiber membrane is 82% to the removal efficiency of methylene orange (initial concentration 1.5%), second adsorption
It can then completely remove.
Embodiment 6
In situ synthesis prepares MOFs-74 (Ni)@chitosan nano fiber membrane
1) preparation of chitosan nano fiber：Chitosan and polyethylene glycol oxide are respectively added slowly in glacial acetic acid to mix
Close liquid, wherein glacial acetic acid solution final concentration (mass concentration) is 10% in mixed liquor, and chitosan accounts for the 5% of acid solution quality, is gathered
Ethylene oxide accounts for the 10% of acid solution quality.Magnetic stirring apparatus is opened, revolving speed 550r/min, solid is complete after stirring 30min
Dissolution；By solution under the intensity of 700W after ultrasound 30min, solution is extracted with the syringe of 5mL and carries out electrostatic spinning, using tin
Paper is as receiver board, spinning condition：Positive pressure is 13.0KV, and negative pressure is -10.0KV, and injecting speed is 0.15mm/min, translation
Speed is 500mm/min, and the revolving speed for receiving roller is 5r/min；After spinning, tinfoil is removed, is cut into the small of 2cm × 2cm
Block removes chitin fiber film from tinfoil；
2) MOFs-74 (Ni)-chitosan nano fiber membrane preparation：Chitosan nano fiber membrane is taken to add with nickel chloride 0.5g
Enter into dehydrated alcohol, 1g glacial acetic acid is then added dropwise.Wherein, the dosage of nickel chloride is 10 times of chitin fiber film quality, nothing
Water-ethanol and chitin fiber membrane volume quality (mL/g) are than being 1000：1.System stirs 0.5h under 100r/min speed, quiet
It after setting 1h, is washed 3 times with methanol, the Ni that removal fiber surface does not chelate2+Ion obtains Ni- chitosan nano fiber membrane；
3) Ni- chitosan nano fiber membrane is added to ammonium hydroxide (ammonia concn 0.05mol/L, with chitin fiber film
Volume mass (mL/g) is than being 2000：1) in, terephthalic acid (TPA) 1g is then added, dosage is the 20 of chitin fiber film quality
Times, which stirs 1h at 100r/min；Then after washing 3 times with methanol, forced air drying 5min, be can be obtained at 30 DEG C
Surface grows the chitosan nano fiber membrane (load capacity 2.9%) of MOFs-74 (Ni).
Above-mentioned gained MOFs-74 (Ni)@chitosan nano fiber membrane inhales rhodamine b (initial concentration 1.2%)
Attached, the removal efficiency after film adsorbs is 32.4%.
In summary example, the present invention is based on the nano fibrous membranes that electrostatic spinning obtains chitosan, using in situ synthesis
It is successfully prepared MOFs@chitosan nano fiber membrane, example, which demonstrates the film, has preferably the dyestuff in water or organic solvent
Suction-operated, adsorption capacity is suitable with MOFs material, and removal rate reaches as high as 92%.Therefore, the film is in dye wastewater treatment
In have broad application prospects.
Claims (9)
1. a kind of preparation method of the chitosan nano fiber membrane of growth in situ metal-organic framework material (MOFs), feature
It is：Chitosan is obtained into chitosan nano fiber membrane by electrostatic spinning；Again by it under acidic environment with the gold in MOFs material
Belong to node chelating；Ligand is added after chelating, grows MOFs material in chitin fiber surface in situ, obtains growth in situ MOFs material
Expect chitosan nano fiber membrane.
2. the preparation of the chitosan nano fiber membrane of growth in situ metal-organic framework material (MOFs) according to claim 1
Method, it is characterized in that：Chitosan nano fiber membrane and metal salt are added in organic solvent, and addition concentrated acid is molten in system
Liquid；0.5h-3.5h then is stirred under conditions of rate is 100r/min-300r/min, is then allowed to stand 1h-3h；It staticly settles
It uses organic solvent washing 3-5 times afterwards, is added in aqueous slkali after washing, adds after ligand stirs evenly and washed through organic solvent
It washs, the dry chitosan nano fiber membrane that surface growth MOFs can be obtained.
3. the chitosan nano fiber membrane of growth in situ metal-organic framework material (MOFs) as described in claim 1 or 2
Preparation method, it is characterized in that：The metal salt refers to using major element, transition elements or lanthanide series as the water of metal cation
One or more of dissolubility salt；Its dosage is 1-10 times of chitin fiber film quality：
The ligand refers to one or more of oxygen-containing or nitrogen organic anionic ligands containing carboxyl, or organic with nitrogen-containing heterocycle
Neutral ligand is used in conjunction with, and ligand additional amount is 1-20 times of chitin fiber film quality.
4. the preparation of the chitosan nano fiber membrane of growth in situ metal-organic framework material (MOFs) according to claim 3
Method, it is characterized in that：The metal salt is zinc nitrate, cobalt chloride, copper acetate, chromic nitrate, zirconium chloride or nickel chloride；It is described to match
Body is 2-methylimidazole, trimesic acid, terephthalic acid (TPA), 2- amino terephthalic acid (TPA) or terephthalic acid (TPA).
5. the preparation of the chitosan nano fiber membrane of growth in situ metal-organic framework material (MOFs) as described in claim 2
Method, it is characterized in that：The organic solvent refers to anhydrous methanol and/or dehydrated alcohol, organic solvent and chitin fiber film
Volume mass ratio is 200-1000：1；The aqueous slkali is the ammonia spirit that concentration is 0.05mol/L-0.3mol/L；Ammonium hydroxide is molten
The volume mass ratio of liquid and chitin fiber film is 100-2000：1.
6. the chitosan nano fiber membrane of growth in situ metal-organic framework material (MOFs) as described in claim 1 or 2
Preparation method, it is characterized in that：System stirs 0.5h-5h under conditions of revolving speed is 100-300r/min after the addition ligand,
Then with organic solvent washing 3-5 all over rear drying, drying condition is 30 DEG C -50 DEG C, 5min-30min.
7. the chitosan nano fiber membrane of growth in situ metal-organic framework material (MOFs) as described in claim 1 or 2
Preparation method, it is characterized in that：The chitosan nano fiber be obtained using chitosan as raw material by electrostatic spinning mode it is straight
Diameter is less than the fiber of 200nm.
8. the preparation of the chitosan nano fiber membrane of growth in situ metal-organic framework material (MOFs) according to claim 7
Method, it is characterized in that：The chitosan nano fiber be by chitosan be raw material by electrostatic spinning in a manner of prepare, will
Chitosan and polyethylene glycol oxide, which are respectively added slowly into concentrated acid solution water is added after mixing, to be obtained uniformly sticky chitosan and waits for
Solution is spun, carries out electrostatic spinning after being then ultrasonically treated, chitin fiber is obtained after removing；Wherein, the final concentration of acid solution
For 1%-10%, chitosan accounts for the 0.5%-5% of acid solution quality, and polyethylene glycol oxide accounts for the 0.1%-10% of acid solution quality.
9. the preparation of the chitosan nano fiber membrane of growth in situ metal-organic framework material (MOFs) according to claim 8
Method, it is characterized in that：After solution ultrasound, solution is extracted with syringe and carries out electrostatic spinning, using tinfoil as receiver board, spin
Strand part is：Positive pressure is 2.0KV-13.0KV, and negative pressure is -5.0KV--10.0KV, and injecting speed is 0.02mm/min-0.15mm/
Min, translational velocity 100mm/min-500mm/min, the revolving speed for receiving roller is 5r/min-30r/min.
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