CN107051398A - A kind of method for preparing silk-fibroin nanofiber-metal organic frame laminated film - Google Patents
A kind of method for preparing silk-fibroin nanofiber-metal organic frame laminated film Download PDFInfo
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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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- B01J20/00—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
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
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- B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/00—Treatment of water, waste water, or sewage
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- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention discloses a kind of method for preparing silk-fibroin nanofiber-metal organic frame laminated film.By silk-fibroin nano-fiber film vertical immersion in the first ligand solution of metal ion, Ligands solution is added afterwards, so that silk-fibroin nano-fiber film and two kinds of part mixed liquors are reacted into special time at a certain temperature, so that going out Metal-organic frame in silk-fibroin nano-fiber film superficial growth, laminated film is generated；Then laminated film is taken out, cleaned with deionized water, the film is obtained after drying.The problem of present invention solves uneven nucleation in metal organic frame membrane-film preparation process and poor in processability itself, film has the features such as preparing simple, filter efficiency height, load capacity height, uniform particle, good stability and good film continuity, absorption property is more complete, it can realize to a variety of organic and inorganic matter absorption, be widely used.
Description
Technical field
The present invention relates to the new method for preparing high performance composite film, and in particular to one kind prepares silk-fibroin nanofiber
(ESF) method of-metal organic frame (MOFs) laminated film and its answering in water body is organic and inorganic pollution is removed
With.
Background technology
Thin-film material due to its low energy consumption, efficiently, equipment is simple and easy to operate the features such as, meet modern industry to collection
About the demand of type production, has significant progress prospect in fields such as separation, enrichment, catalysis.Industrialized production is realized at present
Film be mostly organic film, it has cost low, the advantages of easy processing, but its heat endurance and chemical stability compared with
Difference, short life, poor selectivity, adsorbance and adsorption efficiency are relatively low, constrain its application in practice.The porous material of crystalline state
Material is because of its good heat endurance, and the pore passage structure of high-specific surface area and long-range order is widely used in high-temperature catalytic in recent years
In terms of reaction, the separation in fine chemistry industry and purification, drinking water purifying, but micropore is confined to its pore structure (most small more
In 1nm), pore structure design underaction.Metal-organic framework materials (MOFs) have attracted the extensive concern of people in recent years, it
Refer to the multiple tooth organic ligand of nitrogen, oxygen by aromatic acid or alkali, pass through coordinate bond and the stereoscopic graticule of inorganic metal center hydridization formation
Network structure crystal, therefore also it is known as Porous coordination polymer.Compared to other traditional material porous materials, MOFs has Gao Bibiao
Area, flexible and programmable pore passage structure, abundant physical and chemical properties and good stability.Extensively should in recent years
It is the Disciplinary Frontiers of international scientific research for gas storage, gas sensing, catalysis and gas separation field.
Although MOFs has broad prospects in separation and enrichment field, on the growth of MOFs localization, film preparation
The starting stage is still in the research in terms of device.Because majority MOFs is synthesized under hydrothermal conditions with ordered structure
Amorphous material, processing characteristics is generally poor, and the adhesion with substrate is weaker, easily occurs to reunite and come off in application process.
The method for manufacturing thin film reported at present includes：Direct in-situ growth method, group assisted in situ growth method, secondary growth method are (brilliant
The method of kind) and MOFs- mixed with polymers base films.Wherein, it is that group assisting growth method needs to carry out substrate to growth mechanism in advance
Modified accordingly, cause preparation process cumbersome.Diauxic growth rule needs previously-introduced crystal seed or by atomic deposition
Method covers nucleating point, it is necessary to more process step or instrument and equipment auxiliary in substrate surface.The preparation of MOFs- thin polymer films
Including binder method and mechanical mixing, the decline of porosity and load capacity is easily caused.Comparatively speaking, in situ synthesis has
Preparation process is simple, easy to operate, the low advantage of hole blocking rate, it is adaptable to the demand of industrial applications.But use in situ raw
The limitation of high performance thin film prepared by regular way is that substrate lacks uniform nucleation site, cause the film equality of generation compared with
Difference, adhesion is weak, and load factor is not high.
In summary, research and development can provide the base material in homogeneous nucleation site for its growth on the basis of growing in the original location
And it is field industrialization urgent problem to be solved to prepare high performance composite film.
The content of the invention
In order to solve problem present in background technology, silk-fibroin nanofiber is prepared the invention provides one kind
(ESF) method of-metal organic frame (MOFs) laminated film and its answering in water body is organic and inorganic pollution is removed
With, MOFs is grown on azelon film and prepares high performance composite film, and for the efficient removal of water pollutant.
The technical solution adopted by the present invention comprises the following steps：
1) silk-fibroin nanofiber (ESF) film normal is immersed in the first ligand solution of metal ion, 5 minutes
Ligands solution is added afterwards so that silk-fibroin nano-fiber film and two kinds of part mixed liquors are reacted special at a certain temperature
Fix time so that go out Metal-organic frame (MOFs) in silk-fibroin nano-fiber film superficial growth, generation ESF@MOFs are answered
Close film；
2) and then by ESF MOFs laminated films take out, cleaned with deionized water at least 3 times, obtain described thin after drying
Film.
Silk-fibroin nano-fiber film used be but be not limited to electrostatic spinning preparation azelon.
The first described ligand solution uses and includes Zn2+The solution of metal ion, Ligands solution uses 2- methyl miaows
The aqueous solution of azoles, the Metal-organic frame (MOFs) of growth is ZIF-8, and the ESF@MOFs laminated films being made are ESF@
ZIF-8 laminated films.
Described two ligand solutions are isometric, Zn in the first ligand solution2+Concentration range be 6.0mM-30.0mM, the
The concentration range of 2-methylimidazole is 550mM-2M in two ligand solutions.
The step 1) in reaction temperature be 35-60 degrees Celsius, the reaction time be 1-4 hours.
The first described ligand solution uses and includes Co2+The solution of metal ion, Ligands solution uses 2- methyl miaows
The aqueous solution of azoles, the Metal-organic frame (MOFs) of growth is ZIF-67, and the ESF@MOFs laminated films being made are ESF@
ZIF-67 laminated films.
Described two ligand solutions are isometric, Zn in the first ligand solution2+Concentration range be 10.4mM -52.0mM, the
The concentration range of 2-methylimidazole is 550mM-2M in two ligand solutions.
The step 1) in reaction temperature be 60-80 degrees Celsius, the reaction time be 1-4 hours.
Described Metal-organic frame (MOFs) is but is not limited to ZIF-8 and ZIF-67, can be extended to it is other can be
The MOFs prepared in aqueous phase.
The step 2) in ESF@MOFs laminated films drying condition be 40-60 degrees Celsius of temperature, the time is no less than 12 small
When.
The water pollutant that the ESF@MOFs laminated films of the present invention are used to handle includes but is not limited to heavy metal ion and had
Organic pollutants, such as：As ions, Cr ions, rhodamine B, malachite green etc..
ESF@MOFs laminated films after above-mentioned drying are mixed and kept for a period of time by embodiments of the invention with water sample
It to adsorb water pollutant, then will be measured, obtain after the ESF MOFs laminated films taking-up recovery for having handled water pollutant
Obtain the results of property of film.Particular by electron microscope, thermogravimetric analysis, X-ray diffraction, ultraviolet-visible spectrophotometer
And inductivity coupled plasma mass spectrometry carries out the sign of system to the pattern of film, structure and absorption property.
Based on biomineralization effect, the present invention uses electrostatic spinning nano wire protein fiber as growth substrate, in fiber
The fine and close MOFs layers of surface uniform fold, shell thickness reaches 200nm (suitable with fibre diameter), and load capacity reaches
38%, the ZIF-8 particles being supported are microcellular structure, and between nanofiber are macroporous structure, this heterogeneous pore structure
Mass transfer that can be more efficient, improves filter efficiency.By by the performance of nano wire protein polymer fiber and crystalline state porous material
Organically be combined together, prepared the high flux that can adsorb a variety of organic and inorganic pollutions, high adsorption capacity it is new
Composite filter membrane.
ESF@MOFs laminated films prepared by the inventive method have advantages below：
1st, the present invention uses ESF to provide uniform nucleation site for the growth of MOFs crystal, solves MOFs film systems
Nucleation is uneven during standby and the problem of MOFs poor in processability itself.The ESF@MOFs prepared by in-situ method are combined
Fiber membrane solves the problem of adsorption capacity is weak after the technical problem of MOFs load factors difference in the prior art and MOFs loads, and
And it is simple to operate, it is easy to accomplish industrialized production.
2nd, due to there is stronger active force between silk-fibroin and MOFs particles, film made from this method has continuity
Well, the characteristics of particle is uniform, load capacity is high, stability is good.
3rd, because MOFs particles are microcellular structure (general aperture<1nm) and it is uniformly covered on nanofiber surface.Fiber
Between predominantly macroporous structure, this graded porous structure keeps, having larger contact area between contaminated thing to be adsorbed, having
Beneficial to the mass transfer of film, the efficiency of filtering can be lifted.
4th, fibrin and the excellent absorption property of metal-organic framework material are incorporated, absorption property is prepared more complete
Filter membrane, can realize to a variety of organic and inorganic pollution absorption.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of ESF films.
Fig. 2 is the scanning electron microscope (SEM) photograph of embodiment 1 (left figure) and embodiment 2 (left figure) product film.
Fig. 3 is sweeping for the ESF@ZIF-8 fiber membranes that fine (PAN) film of polypropylene uses that method is prepared in embodiment 1
Retouch electron microscope.
Fig. 4 is the X-ray powder diffraction figure (PXRD) of embodiment 1 (left figure) and embodiment 2 (left figure).
Fig. 5 is that ESF@ZIF-67 composite fiber thin films are carried into the polydimethylsiloxanes that diameter is about 3mm through holes with two panels
It is used as the installation drawing of filter membrane after alkane (PDMS) film (film thickness is about 1mm) clamping.
Fig. 6 is using before and after water pollutant of the ESF ZIF-67 composite fiber thin films filtering containing malachite green in the present invention
Ultraviolet-visible absorption spectroscopy comparison diagram.
Fig. 7 is the scanning electron microscope (SEM) photograph of the ESF@ZIF-8 fiber membranes prepared by method in embodiment 3.
Fig. 8 is the scanning electron microscope (SEM) photograph of the ESF@ZIF-8 fiber membranes prepared by method in embodiment 4.
Embodiment
The present invention is described in further details below in conjunction with the accompanying drawings and the specific embodiments.
In order to provide a better understanding of the technical solution of the present invention by those skilled in the art, with reference to embodiment to this hair
It is bright to be described further, but the present invention is not limited to following examples.
Embodiments of the invention are as follows：
Embodiment 1
In-situ method prepares ESF@ZIF-8 composite fiber thin films
By 1cm2Square ESF films vertical immersion in 2mL 18.4mM zinc nitrate hexahydrate solution, after 5 minutes add etc. body
Long-pending 1.38M 2-methylimidazole solution.The purpose of standing is to ensure that nucleation is uniform in fiber surface in body series, quick mixing
Uniformly it is placed in 38 DEG C of water-bath, is taken out after reaction 2h after (about 10s).It is true at 40 DEG C after being cleaned multiple times using deionized water
24h in empty drying box, that is, be made uniform ESF@ZIF-8 composite fiber thin films.
Continuity, crystallinity：
The growing state of fiber surface ZIF-8 particles in the composite fiber thin film prepared with field emission microscopy observation.
As a result show, compared to smooth ESF (Fig. 1), due to there is active force between the polypeptide and nano-particle on azelon surface, growth
At initial stage (10 minutes), primary nano-particle (~20nm) is to be uniformly adhered to ESF fiber surfaces.ZIF-8 nano-particles are gradually
Growth, after two hours, ESF fiber surfaces are completely covered ZIF-8 nano-particles, and the ZIF-8 particles of formation are mutually interspersed in fibre
Dimension table face forms the ZIF-8 shells of densification, and fiber surface does not have defect generation.And the polypropylene for using same procedure to prepare is fine
(PAN) then surface only has a small amount of ZIF-8 and is distributed in fiber surface, and skewness, load capacity nanofiber-ZIF-8 films
It is low, as shown in Figure 3.
It can be seen that ESF films are amorphous polymer from XRD (Fig. 4 left figure), without obvious diffraction maximum, and surface
It grown the diffraction maximum for having obvious ZIF-8 after ZIF-8 crystal, it was demonstrated that the ZIF-8 crystal of growth has good crystallinity.
It can see from the ESEM result of Fig. 2 left figures, the grain size of fiber surface is about 200nm, and grain size distribution is uniform,
Continuity is good.
Load capacity：
ZIF-8 particles in the load capacity of ESF fiber surfaces are determined by thermogravimetry (TGA), and quality is weighed respectively
About 3mg ESF, ESF@ZIF-8, ZIF-8, in N2Calcined under atmosphere, programming rate is 10 DEG C of min- 1, record from 50 DEG C of heatings
The mass change of film between to 600 DEG C.
The load capacity of embodiment is that ZIF-8 crystal and ESF@ZIF-8 laminated films are most by calculating simple ESF films
Whole level of residue is obtained.Level of residue of the ESF fibers at 400 DEG C is about that 45%, ZIF-8 is about 85% in 600 DEG C of level of residue,
And the level of residue of ESF@ZIF-8 films is about 60%.It is computed, when the reaction time is 2h, ESF loads ZIF-8 amount is about
38% (the higher ZIF- fiber composite films of PAN fiber film preparation continuity after existing general use atom deposition method modification
Load capacity be 8% or so).
Checking 1
ESF@ZIF-8 composite fiber thin films are used for As in the aqueous solutionVIonic adsorption
Weigh 2.6mg ESF@ZIF-8 (the load 1mg ZIF-8) composite fiber thin film, 1mg prepared in embodiment 1
ESF, 1mg ZIF-8 are respectively placed in the μ g mL of 10mL 55- 1AsVIn the aqueous solution, supernatant is taken after 24h respectively, using inductance coupling
Plasma mass (ICP-OES) method of conjunction determines residue As in supernatantVThe As remained in the content of ion, solutionVIon contains
Amount is respectively 5 μ g mL- 1,55μg mL- 1With 5 μ g mL- 1.ESF fibers are to AsVIonic adsorption does not have adsorption capacity, and on fiber
The adsorption capacity of the ZIF-8 particles of load is with equal quality ZIF-8 crystal grains to AsVThe adsorption capacity of ion is suitable, table
The without hindrance effect of pore structure of MOF- thin polymer films prepared by bright use in-situ method to MOF, and to As in waterVIon is gone
Except efficiency high is up to 91%.
The result shows, the microcellular structure of fiber surface ZIF-8 crystal retains complete, can be uniformly in adsorbent solution
Heavy metal ion, the composite fiber thin film can be used in heavy metal As in waterVIon remaval.
Checking 2
ESF@ZIF-8 composite fiber thin films are used for rhodamine B in the aqueous solution and adsorbed
Weigh the 1.6mg ESF@ZIF-8 composite fiber thin films (1) prepared in embodiment 1, ESF films (2) and 1mg
ZIF-8 (3) is placed in 1mL 0.04g L- 1Rhodamine B solution in.After 24h to be adsorbed, the μ L of supernatant 200 are taken respectively, are added
Quartz colorimetric utensil, using ultraviolet-visible spectrophotometer method, is surveyed according to the characteristic absorption peak of its rhodamine B at 554nm
Determine remaining rhodamine B content in solution.(1), the remaining content of rhodamine B is respectively 6.4 μ g mL in (2), (3)- 1, 16 μ g
mL- 1, 18 μ g mL- 1, removal efficiency difference 86%, 60%, 55%.Compared to the ESF films for not growing ZIF-8 crystal, fiber
Its ability for adsorbing rhodamine B in water can be remarkably reinforced after superficial growth ZIF-8 crystal.
The composite fiber thin film can play synergy when adsorbing specific pollutants.
Embodiment 2
In-situ method prepares ESF@ZIF-67 laminated films
By 1cm2Square ESF films vertical immersion in 32.4mM cabaltous nitrate hexahydrate solution, added after standing 5 minutes etc.
The 1.38M of volume 2-methylimidazole solution, is quickly well mixed (about 10s) and is placed in 80 DEG C of water-bath, taken after reaction 2h
Go out.Cleaned with deionized water and keep 24h after three times in 40 DEG C of vacuum drying chambers, that is, uniform ESF ZIF-67 are made and are combined
Fiber membrane.
Continuity, crystallinity：
The growing state of the composite fiber thin film surface ZIF-67 particles prepared with field emission microscopy observation, due to
There is active force between the polypeptide and nano-particle on azelon surface, early growth period, primary nano-particle (~100nm) is uniform
Be attached to ESF fiber surfaces.Nano-particle is grown into, after two hours, from the field emission scanning electron microscope result of Fig. 2 right figure
It can be seen that, the grain size of fiber surface is about 200nm, and grain size distribution is uniform, and continuity is good, and surface is not covered with not
Defect is produced caused by completely.
It can be seen that ESF films are amorphous polymer from XRD (Fig. 4 right figure), without obvious diffraction maximum, and surface
It grown the diffraction maximum for having obvious ZIF-67 after ZIF-67 crystal, it was demonstrated that the ZIF-67 crystal of growth has good crystallization
Degree.
Load capacity：
Load capacity of the ZIF-67 particles on wire protein fiber surface is determined by thermogravimetry (TGA), weighs matter
Amount is about 3mg film, in N2Calcined under atmosphere, programming rate is 10 DEG C of min- 1, record from 50 DEG C be warming up to 600 DEG C between film
Mass change.
Load capacity is the final residue by calculating ESF films, ZIF-67 crystal and ESF@ZIF-67 composite fiber thin films
Measure.ESF fibers are about that 22%, ZIF-67 is about 59% in 600 DEG C of level of residue in 600 DEG C of level of residue, and ESF@
The level of residue of ZIF-67 composite fiber thin films is about 37%.It is computed, after loading two hours, ESF loads ZIF-67 amount
About 39%.
Checking 1
ESF@ZIF-67 composite fiber thin films are used for Cr in the aqueous solutionVIIonic adsorption
Weigh 2.6mg ESF@ZIF-67 (the load 1mg ZIF-67) film, ESF, 1mg ZIF- prepared in embodiment 2
67 are respectively placed in the μ g mL of 10mL 8- 1CrVIIn the aqueous solution, Cr in water is measured using ICP-OES methods respectively after 24hVIIon it is residual
Allowance, measures Cr in waterVIResidual quantity be respectively：0.2μg mL- 1,8μg mL- 1, 0.2 μ g mL- 1, ESF fibers are right in itself
CrVIIon is without suction-operated, and the microcellular structure of the ZIF-67 particles loaded on fiber is intact, with equal quality ZIF-
67 crystal grains are to Cr in waterVIThe adsorbance of ion is suitable.
The composite fiber thin film of preparation is to Cr in waterVIThe removal efficiency of ion is up to 98%, can effectively go in water removal
Heavy metal CrVIIon.
Checking 2
ESF@ZIF-67 composite fiber thin films are adsorbed for aqueous solution Malachite Green
The ESF@ZIF-67 (load 1mg ZIF-67) prepared in 2.6mg embodiments 2 are weighed, respectively by 2.6mg
ZIF-67@ESF composite fiber thin films, 1mg ESF films, 1mg ZIF-67 are placed in 1mL 2.4kg L- 1Malachite green solution
In, stand after 24h, take the μ L of supernatant 200 to add in quartz colorimetric utensil, its supernatant is measured using ultraviolet specrophotometer and existed
Absorption peak strength at 240nm, it is respectively 99%, 10%, 99% to calculate its adsorption efficiency.Simple ZIF-67 crystal is contrasted to exist
The amount of malachite green is adsorbed in water, it was demonstrated that the pore structure of ESF fiber surfaces retains complete, adsorbance reaches that ZIF-67 crystal is inhaled
The theoretical upper limit of attached malachite green, the composite fiber thin film can efficiently adsorb the malachite green in water, for having in water body
The purification of organic pollutants.
Checking 3
ESF@ZIF-67 composite fiber thin films are filtered for the malachite green aqueous solution
By the ESF@ZIF-67 films prepared using 2 kinds of methods of embodiment and the gathering with a diameter of 3mm through holes with two panels
Dimethyl siloxane (PDMS) film fixes (Fig. 5), and the film is fixed in self-control filter, syringe is used with 5mL
h- 1Flow filtration 1mL 50mg mL-1Malachite green solution, takes the μ L of filtrate 200 to add in quartz colorimetric utensil, using ultraviolet
The characteristic absorption peak of malachite green of the solution at 618nm after the measurement filtering of visible absorption spectra figure, filtrate Malachite Green
Content is about 0.4mg mL-1, the efficiency high of the film single filtration malachite green is calculated up to 98% (Fig. 6), second of filtering
In solution 99% malachite green can be removed, very there is prospect in terms of the malachite green in actual filtration sewage.
Embodiment 3
In-situ method prepares ESF@ZIF-8 composite fiber thin films
By 1cm2Square ESF films vertical immersion added in 2mL 10mM zinc nitrate hexahydrate solution, after 5 minutes it is isometric
690mM 2-methylimidazole solution.The purpose of standing is to ensure that nucleation is uniform in fiber surface in body series, and quick mixing is equal
It is placed in 38 DEG C of water-bath, is taken out after reaction 2h after even (about 10s).After being cleaned multiple times using deionized water, in 40 DEG C of vacuum
24h in drying box, that is, be made uniform ESF@ZIF-8 composite fiber thin films.
Continuity, crystallinity：
The growing state of fiber surface ZIF-8 particles in the composite fiber thin film prepared with field emission microscopy observation.
As a result (Fig. 7) is shown, compared to smooth ESF (Fig. 1) and Fig. 2 (left side) Suo Shi, the ZIF-8 crystal of wire protein fiber area load
It is less.And from unlike the result that higher zinc ion concentration in embodiment 1 is reacted, the flower-shaped ZIF-8 of a large amount of intermediate products are adsorbed
There is also more flower-shaped ZIF-8 intermediate products in film surface, and interfibrous gap, cause fiber surface covering endless
Entirely, therefore under the concentration, although be prepared for the ESF@ZIF-8 fiber composite films with higher load amount.But due to more
The generation of intermediate product so that the continuity of the film declines.Therefore, the film obtained under the concentration is not optimal production bar
Part.
Embodiment 4
In-situ method prepares ESF@ZIF-8 composite fiber thin films
By 1cm2Square ESF films vertical immersion added in 2mL 20mM zinc nitrate hexahydrate solution, after 5 minutes it is isometric
2M 2-methylimidazole solution.The purpose of standing is to ensure that nucleation is uniform in fiber surface in body series, quick well mixed
It is placed in 38 DEG C of water-bath, is taken out after reaction 2h after (about 10s).It is dry in 40 DEG C of vacuum after being cleaned multiple times using deionized water
24h in dry case, that is, be made uniform ESF@ZIF-8 composite fiber thin films.
Continuity, crystallinity：
The growing state of fiber surface ZIF-8 particles in the composite fiber thin film prepared with field emission microscopy observation.
As a result (Fig. 8) is shown, compared to smooth ESF (Fig. 1) and Fig. 2 (left side), although fiber surface has the ZIF-8 layers generation of densification, but
It is due to that reactant concentration is higher, a large amount of micron ZIF-8 is formed in solution and generates and is supported on the surface of fiber membrane, cause fibre
The continuity in dimension table face is not high, it is difficult to control the surface topography of fiber membrane, due between ZIF-8 crystal and fiber membrane
Weaker active force, also causes ZIF-8 crystal coming off in use, causes secondary pollution.
Load capacity：
ZIF-8 particles in the load capacity of ESF fiber surfaces are determined by thermogravimetry (TGA), and quality is weighed respectively
About 3mg ESF, ESF@ZIF-8, ZIF-8, in N2Calcined under atmosphere, programming rate is 10 DEG C of min- 1, record from 50 DEG C of heatings
The mass change of film between to 600 DEG C.
The load capacity of embodiment is that ZIF-8 crystal and ESF@ZIF-8 laminated films are most by calculating simple ESF films
Whole level of residue is obtained.Level of residue of the ESF fibers at 400 DEG C is about that 45%, ZIF-8 is about 85% in 600 DEG C of level of residue,
And the level of residue of ESF@ZIF-8 films is about 66%.It is computed, when the reaction time is 2h, ESF loads ZIF-8 amount is about
50%.Compared to relatively low reaction density in embodiment 1, the load capacity of film rises, but because the shell thickness of fiber is certain, therefore
The increase of load capacity causes mainly due to the micron ZIF-8 attachments generated in solution, has certain negative shadow to the continuity of film
Ring.
To sum up embodiment, biomineralization effect of the inventive method based on MOFs materials, utilize electrostatic spinning silk-fibroin fibre
Tie up and provide uniform nucleation site for its growth, be successfully prepared two kinds of silk-fibroin nanofiber-metal organic frames and be combined
Film (ESF@ZIF-8, ESF@ZIF-67).Two kinds of composite fiber thin films of embodiment, are realized to many kinds of metal ions in water
(AsV, CrVI) and organic pollution (malachite green, rhodamine B) absorption, adsorption capacity is suitable with MOFs powders.
Further malachite green solution is filtered using filter, single filtration efficiency reaches 98%.It can be seen that
There is body to protrude significant technique effect for invention, can be applied to the absorption of contents of many kinds of heavy metal ion and organic pollution, it is expected to
The thin-film device preparation method of general MOFs a kind of is provided and extensive use is found in terms of water pollution removal.
Claims (10)
1. a kind of method for preparing silk-fibroin nanofiber-metal organic frame laminated film, it is characterised in that including following step
Suddenly：
1) silk-fibroin nanofiber (ESF) film normal is immersed in the first ligand solution of metal ion, added after 5 minutes
Enter Ligands solution so that when silk-fibroin nano-fiber film and two kinds of part mixed liquors are reacted into specific at a certain temperature
Between so that go out Metal-organic frame (MOFs) in silk-fibroin nano-fiber film superficial growth, generate ESF@MOFs THIN COMPOSITEs
Film；
2) and then by ESF MOFs laminated films take out, cleaned with deionized water at least 3 times, the film is obtained after drying.
2. a kind of method for preparing silk-fibroin nanofiber-metal organic frame laminated film according to claim 1,
It is characterized in that：Silk-fibroin nano-fiber film used be but be not limited to electrostatic spinning preparation azelon.
3. a kind of method for preparing silk-fibroin nanofiber-metal organic frame laminated film according to claim 1,
It is characterized in that：The first described ligand solution uses and includes Zn2+The solution of metal ion, Ligands solution uses 2- first
The aqueous solution of base imidazoles, the Metal-organic frame (MOFs) of growth is ZIF-8, and the ESF@MOFs laminated films being made are
ESF@ZIF-8 laminated films.
4. a kind of method for preparing silk-fibroin nanofiber-metal organic frame laminated film according to claim 3,
It is characterized in that：Described two ligand solutions are isometric, Zn in the first ligand solution2+Concentration range be 6.0mM-30.0mM,
The concentration range of 2-methylimidazole is 550mM-2M in Ligands solution.
5. a kind of method for preparing silk-fibroin nanofiber-metal organic frame laminated film according to claim 3,
It is characterized in that：The step 1) in reaction temperature be 35-60 degrees Celsius, the reaction time be 1-4 hours.
6. a kind of method for preparing silk-fibroin nanofiber-metal organic frame laminated film according to claim 1,
It is characterized in that：The first described ligand solution uses and includes Co2+The solution of metal ion, Ligands solution uses 2- first
The aqueous solution of base imidazoles, the Metal-organic frame (MOFs) of growth is ZIF-67, and the ESF@MOFs laminated films being made are
ESF@ZIF-67 laminated films.
7. a kind of method for preparing silk-fibroin nanofiber-metal organic frame laminated film according to claim 6,
It is characterized in that：Described two ligand solutions are isometric, Zn in the first ligand solution2+Concentration range for 10.4mM-
The concentration range of 2-methylimidazole is 550mM-2M in 52.0mM, Ligands solution.
8. a kind of method for preparing silk-fibroin nanofiber-metal organic frame laminated film according to claim 6,
It is characterized in that：The step 1) in reaction temperature be 60-80 degrees Celsius, the reaction time be 1-4 hours.
9. according to a kind of any described silk-fibroin nanofiber-metal organic frame laminated films that prepare of claim 1-8
Method, it is characterised in that：Described Metal-organic frame (MOFs) is but is not limited to ZIF-8 and ZIF-67.
10. silk-fibroin nanofiber-metal organic frame laminated film is prepared according to any described one kind of claim 1-8
Method, it is characterised in that：The step 2) in ESF@MOFs laminated films drying condition be 40-60 degrees Celsius of temperature, the time
No less than 12 hours.
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