CN107051398B - Method for preparing silk fibroin nanofiber-metal organic framework composite film - Google Patents
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- 238000000034 method Methods 0.000 title claims abstract description 43
- 108010022355 Fibroins Proteins 0.000 title claims abstract description 23
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
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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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- 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
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
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- Hydrology & Water Resources (AREA)
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- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a method for preparing a silk fibroin nanofiber-metal organic framework composite film. Vertically immersing the fibroin nanofiber membrane in a first ligand solution containing metal ions, and then adding a second ligand solution to react the fibroin nanofiber membrane with a mixed solution of two ligands at a specific temperature for a specific time so as to grow a metal-organic framework on the surface of the fibroin nanofiber membrane and generate a composite membrane; and then taking out the composite film, washing the composite film with deionized water, and drying to obtain the film. The invention solves the problems of nonuniform nucleation and poor processability in the preparation process of the metal organic framework film, the film has the characteristics of simple preparation, high filtration efficiency, high loading capacity, uniform particles, good stability, good film continuity and the like, the adsorption performance is more complete, the adsorption of various organic and inorganic substances can be realized, and the application is wide.
Description
Technical Field
The invention relates to a novel method for preparing a high-performance composite film, in particular to a method for preparing a silk protein nanofiber (ESF) -Metal Organic Framework (MOFs) composite film and application thereof in removing organic and inorganic pollutants in a water body.
Background
The thin film material meets the requirement of modern industry on intensive production due to the characteristics of low energy consumption, high efficiency, simple equipment, convenient operation and the like, and has great development prospect in the fields of separation, enrichment, catalysis and the like. Most of films which are industrially produced at present are organic films, which have the advantages of low cost, easy processing and the like, but the films have poor thermal stability and chemical stability, short service life, poor selectivity and relatively low adsorption capacity and adsorption efficiency, thereby restricting the application of the films in practice. The crystalline porous material is widely used in high-temperature catalytic reaction, separation and purification in fine chemical engineering, drinking water purification and other aspects in recent years due to good thermal stability, high specific surface area and long-range ordered pore channel structure, but the pore structure is mostly limited to micropores (mostly less than 1nm), and the pore structure design is not flexible enough. In recent years, metal-organic framework Materials (MOFs) have attracted much attention, and they are also referred to as porous coordination polymers, because they are stereo-network crystals formed by the hybridization of multidentate organic ligands of nitrogen and oxygen of aromatic acids or bases with inorganic metal centers through coordination bonds. Compared with other traditional porous materials, the MOFs have high specific surface area, flexible and designable pore channel structures, rich physical and chemical properties and good stability. The catalyst is widely applied to the fields of gas storage, gas sensing, catalysis and gas separation in recent years, and is the leading field of international scientific research.
Although MOFs have a broad prospect in the field of separation and enrichment, research on MOFs localized growth, thin film preparation and device formation is still in the beginning. Most MOFs are crystalline substances with regular structures synthesized under the hydrothermal condition, so that the processing performance is generally poor, the bonding force with a substrate is weak, and agglomeration and falling are easy to occur in the application process. The film preparation method reported so far comprises: direct in-situ growth method, group-assisted in-situ growth method, secondary growth method (seed crystal method) and MOFs-polymer mixed base film. The group-assisted growth method requires a substrate to be modified in advance for a growth mechanism, which results in a complicated preparation process. The secondary growth method needs to introduce seed crystals in advance or cover nucleation points on the surface of the substrate by an atomic deposition method, and needs more processing steps or instrument and equipment assistance. The preparation of the MOFs-polymer film comprises a binder method and a mechanical mixing method, and the porosity and the loading capacity are easily reduced. In comparison, the in-situ growth method has the advantages of simple preparation steps, convenience in operation, low hole blocking rate and the like, and is suitable for the requirements of industrial application. However, the limitation of the high performance thin film prepared by the in-situ growth method is that the substrate lacks uniform nucleation sites, resulting in poor uniformity, weak binding force and low loading rate of the generated thin film.
In conclusion, it is known that the research and development of a substrate material capable of providing uniform nucleation sites for the growth of the substrate material and the preparation of a high-performance composite film on the basis of in-situ growth are problems to be solved urgently in industrialization in the field.
Disclosure of Invention
In order to solve the problems in the background art, the invention provides a method for preparing a silk fibroin nanofiber (ESF) -Metal Organic Framework (MOFs) composite film and application thereof in removing organic and inorganic pollutants in a water body, wherein the MOFs grows on the protein fiber film to prepare a high-performance composite film and is used for efficiently removing the pollutants in water.
The technical scheme adopted by the invention comprises the following steps:
1) vertically immersing the silk fibroin nanofiber (ESF) film in a first ligand solution containing metal ions, and adding a second ligand solution after 5 minutes to enable the silk fibroin nanofiber film and the mixed solution of the two ligands to react for a specific time at a specific temperature, so that Metal Organic Frameworks (MOFs) grow on the surface of the silk fibroin nanofiber film, and the ESF @ MOFs composite film is generated;
2) and then taking out the ESF @ MOFs composite film, washing the ESF @ MOFs composite film for at least 3 times by using deionized water, and drying to obtain the film.
The silk protein nanofiber film is, but not limited to, protein fiber prepared by electrostatic spinning.
The first ligand solution contains Zn2+The solution of metal ions and the solution of a second ligand adopt the aqueous solution of 2-methylimidazole, the grown Metal Organic Frameworks (MOFs) are ZIF-8, and the prepared ESF @ MOFs composite film is an ESF @ ZIF-8 composite film.
The two ligand solutions have equal volume, and Zn in the first ligand solution2+In the range of 6.0mM to 30.0mM, and the concentration of 2-methylimidazole in the second ligand solution is in the range of 550mM to 2M.
The reaction temperature in the step 1) is 35-60 ℃, and the reaction time is 1-4 hours.
The first ligand solution adopts a solution containing Co2+The metal ion solution and the second ligand solution adopt 2-methylimidazole water solution, the grown Metal Organic Frameworks (MOFs) are ZIF-67, and the prepared ESF @ MOFs composite film is an ESF @ ZIF-67 composite film.
The two ligand solutions have equal volume, and Zn in the first ligand solution2+In the range of 10.4mM to 52.0mM, and the concentration of 2-methylimidazole in the solution of the second ligand is in the range of 550mM to 2M.
The reaction temperature in the step 1) is 60-80 ℃, and the reaction time is 1-4 hours.
The metal-organic frameworks (MOFs) are but not limited to ZIF-8 and ZIF-67, and can be expanded to other MOFs which can be prepared in a water phase.
In the step 2), the drying condition of the ESF @ MOFs composite film is that the temperature is 40-60 ℃ and the time is not less than 12 hours.
The ESF @ MOFs composite film of the present invention is used for treating water pollutants including, but not limited to, heavy metal ions and organic pollutants, such as: as ions, Cr ions, rhodamine B, malachite green, etc.
According to the embodiment of the invention, the dried ESF @ MOFs composite film is mixed with a water sample and kept for a period of time to adsorb pollutants in water, and then the ESF @ MOFs composite film with the pollutants in the water treated is taken out and recycled for measurement, so that a performance result of the film is obtained. Specifically, the appearance, structure and adsorption performance of the film are systematically characterized by an electron microscope, thermogravimetric analysis, X-ray diffraction, ultraviolet-visible spectrophotometer and inductively coupled plasma mass spectrum.
Based on the biomineralization effect, the electrostatic spinning nano-silk protein fiber is adopted as a growth substrate, the surface of the fiber is uniformly covered with a compact MOFs layer, the thickness of a shell layer reaches 200nm (equivalent to the diameter of the fiber), the loading capacity reaches 38%, the loaded ZIF-8 particles are in a microporous structure, and the nano-fibers are in a macroporous structure, so that the heterogeneous porous structure can transfer mass more efficiently, and the filtering efficiency is improved. The novel composite filter membrane with high flux and high adsorption capacity, which can adsorb various organic and inorganic pollutants, is prepared by organically combining the performances of the nano silk protein polymer fiber and the crystalline state porous material.
The ESF @ MOFs composite film prepared by the method has the following advantages:
1. the invention adopts ESF to provide uniform nucleation sites for the growth of MOFs crystals, and solves the problems of nonuniform nucleation in the preparation process of the MOFs film and poor processability of the MOFs. The ESF @ MOFs composite fiber film prepared by the in-situ method solves the technical problems of poor MOFs loading rate and weak adsorption capacity after MOFs loading in the prior art, and is simple to operate and easy to realize industrial production.
2. Because stronger acting force exists between the silk protein and the MOFs, the film prepared by the method has the characteristics of good continuity, uniform particles, high loading capacity and good stability.
3. The MOFs particles are in a microporous structure (the pore diameter is generally less than 1nm) and uniformly cover the surface of the nanofiber. The fibers are mainly of a macroporous structure, and the hierarchical porous structure keeps a larger contact area with pollutants to be adsorbed, so that mass transfer of the film is facilitated, and the filtering efficiency can be improved.
4. Integrates the excellent adsorption performance of fibrin and metal organic framework materials, prepares a filter membrane with more complete adsorption performance, and can realize the adsorption of various organic and inorganic pollutants.
Drawings
FIG. 1 is a scanning electron micrograph of an ESF film.
FIG. 2 is a scanning electron micrograph of the product films of example 1 (left image) and example 2 (left image).
FIG. 3 is a scanning electron micrograph of an ESF @ ZIF-8 fiber film prepared by the method of example 1 on a Polyacrylonitrile (PAN) film.
FIG. 4 is an X-ray powder diffraction Pattern (PXRD) for example 1 (left panel) and example 2 (left panel).
FIG. 5 is a diagram showing a device in which an ESF @ ZIF-67 composite fiber membrane is sandwiched between two Polydimethylsiloxane (PDMS) membranes (having a membrane thickness of about 1mm) having through holes of about 3mm in diameter and used as a filtration membrane.
FIG. 6 is a comparison of UV-VIS absorption spectra before and after filtering of water contaminants containing malachite green using the ESF @ ZIF-67 composite fiber membrane of the present invention.
FIG. 7 is a scanning electron micrograph of an ESF @ ZIF-8 fiber film prepared by the method of example 3.
FIG. 8 is a scanning electron micrograph of an ESF @ ZIF-8 fiber film prepared by the method of example 4.
Detailed Description
The invention will be described in further detail with reference to the following drawings and specific embodiments.
In order to make the technical solutions of the present invention better understood, the present invention is further described below with reference to the following examples, but the present invention is not limited to the following examples.
The examples of the invention are as follows:
example 1
ESF @ ZIF-8 composite fiber film prepared by in-situ method
Mixing 1cm2The square ESF membrane of (a) was immersed vertically in 2mL of 18.4mM zinc nitrate hexahydrate solution and after 5 minutes an equal volume of 1.38M 2-methylimidazole solution was added. The standing is to ensure that the nucleation in the system is uniform on the fiber surface, the mixture is quickly and uniformly mixed (about 10s), and then the mixture is placed in a 38 ℃ water bath kettle to react for 2h and then taken out. And (3) washing with deionized water for multiple times, and then putting the washed film in a vacuum drying oven at 40 ℃ for 24 hours to obtain the uniform ESF @ ZIF-8 composite fiber film.
Continuity, crystallinity:
and observing the growth condition of ZIF-8 particles on the fiber surface in the prepared composite fiber film by using a field emission scanning electron microscope. As compared with the smooth ESF (FIG. 1), the primary nanoparticles (. about.20 nm) were uniformly attached to the surface of the ESF fiber in the initial stage of growth (10 minutes) due to the action force between the polypeptide and the nanoparticles on the surface of the protein fiber. ZIF-8 nano particles grow gradually, after two hours, the ZIF-8 nano particles completely cover the surface of the ESF fiber, and the formed ZIF-8 particle phase is interpenetrated and inserted on the surface of the fiber to form a compact ZIF-8 shell layer, so that no defect is generated on the surface of the fiber. The Polyacrylonitrile (PAN) nanofiber-ZIF-8 membrane prepared by the same method has the advantages that only a small amount of ZIF-8 on the surface is distributed on the fiber surface, the distribution is uneven, and the loading capacity is low, as shown in figure 3.
From the XRD pattern (left figure of figure 4), it can be seen that the ESF film is an amorphous polymer without obvious diffraction peak, and the surface growth of ZIF-8 crystal has obvious ZIF-8 diffraction peak, thus proving that the grown ZIF-8 crystal has good crystallinity. As can be seen from the scanning electron microscope result of the left image in FIG. 2, the size of the crystal grains on the surface of the fiber is about 200nm, the size distribution of the crystal grains is uniform, and the continuity is good.
Load capacity:
the loading of ZIF-8 particles on the ESF fiber surface was determined by thermogravimetric analysis (TGA) by weighing ESF, ESF @ ZIF-8, ZIF-8, respectively, at a mass of about 3mg in N2Calcining in atmosphere at a temperature rise rate of 10 deg.C for min－1The change in mass of the film from 50 ℃ to 600 ℃ was recorded.
The loading of the examples was calculated from the final residue of the pure ESF film, the ZIF-8 crystal and the ESF @ ZIF-8 composite film. The ESF fiber had a residue at 400 ℃ of about 45%, the ZIF-8 had a residue at 600 ℃ of about 85%, and the ESF @ ZIF-8 film had a residue of about 60%. Calculated, when the reaction time is 2 hours, the amount of the ZIF-8 loaded by the ESF is about 38% (the load amount of the ZIF-fiber composite film with higher continuity prepared by the existing PAN fiber film modified by the atomic deposition method is about 8%).
Verification 1
Application of ESF @ ZIF-8 composite fiber film to As in aqueous solutionVIon adsorption
2.6mg of ESF @ ZIF-8 (loaded with 1mg of ZIF-8) composite fiber film prepared in example 1 was weighed, and 1mg of ESF and 1mg of ZIF-8 were placed in 10mL of 55. mu.g mL of each composite fiber film－1As of (A)VIn the aqueous solution, respectively taking supernatant after 24 hours, and measuring the residual As in the supernatant by adopting an inductively coupled plasma mass spectrometry (ICP-OES) methodVContent of ions, As remaining in solutionVThe ion content is 5 mug mL respectively－1,55μg mL－1And 5. mu.g mL－1. ESF fiber pair AsVThe ion adsorption has no adsorption capacity, and the adsorption capacity of the ZIF-8 particles loaded on the fiber is equal to that of ZIF-8 crystal particles with the same mass to AsVThe adsorption capacity of the ions is equivalent, which shows that the MOF-polymer film prepared by the in-situ method has no barrier effect on the pore structure of the MOF and has no barrier effect on As in waterVThe removal efficiency of ions is as high as 91%.
The result shows that the microporous structure of the ZIF-8 crystal on the surface of the fiber is completely reserved, the heavy metal ions in the solution can be uniformly adsorbed, and the composite fiber film can be used for heavy metal As in waterVAnd (4) removing ions.
Authentication 2
ESF @ ZIF-8 composite fiber film for adsorbing rhodamine B in aqueous solution
1.6mg of the ESF @ ZIF-8 conjugate fiber film (1), the ESF film (2) and 1mg of the ZIF-8 (3) prepared in example 1 were weighed and placed in a volume of 1mL of 0.04g L－1In rhodamine B solution. And after 24 hours of adsorption, respectively taking 200 mu L of supernatant, adding the supernatant into a quartz cuvette, and measuring the content of the residual rhodamine B in the solution according to the characteristic absorption peak of the rhodamine B at 554nm by adopting an ultraviolet-visible spectrophotometer method. (1) The residual content of rhodamine B in the compounds (2) and (3) is 6.4 mug mL respectively－1，16μgmL－1，18μg mL－1The removal efficiency was 86%, 60%, 55%, respectively. Compared with an ESF film without the ZIF-8 crystal, the surface of the fiber can obviously enhance the capacity of adsorbing rhodamine B in water after the ZIF-8 crystal grows on the surface of the fiber.
The composite fiber film can play a synergistic role in adsorbing specific pollutants.
Example 2
ESF @ ZIF-67 composite film prepared by in-situ method
Mixing 1cm2The square ESF membrane was vertically immersed in a 32.4mM cobalt nitrate hexahydrate solution, allowed to stand for 5 minutes, then an equal volume of 1.38M 2-methylimidazole solution was added thereto, rapidly mixed uniformly (about 10 seconds) and placed in a water bath at 80 ℃ for reaction for 2 hours, and then taken out. And washing with deionized water for three times, and keeping the washed solution in a vacuum drying oven at 40 ℃ for 24 hours to obtain the uniform ESF @ ZIF-67 composite fiber film.
Continuity, crystallinity:
the growth condition of ZIF-67 particles on the surface of the prepared composite fiber film is observed by using a field emission scanning electron microscope, and primary nanoparticles (100 nm) are uniformly attached to the surface of an ESF fiber in the initial growth stage due to the acting force between the polypeptide and the nanoparticles on the surface of the protein fiber. After two hours, the nano particles grow gradually, and as can be seen from the result of the field emission scanning electron microscope in the right image of fig. 2, the grain size of the fiber surface is about 200nm, the grain size distribution is uniform, the continuity is good, and no defect is generated due to incomplete surface coverage.
From the XRD pattern (right pattern of FIG. 4), it can be seen that the ESF film is an amorphous polymer without obvious diffraction peak, and the surface growth of the ZIF-67 crystal has obvious diffraction peak of ZIF-67, thus proving that the grown ZIF-67 crystal has good crystallinity.
Load capacity:
the loading of ZIF-67 particles on the surface of the silk fibroin fibers was measured by thermogravimetric analysis (TGA), and a film having a mass of about 3mg was weighed out in N2Calcining in atmosphere at a temperature rise rate of 10 deg.C for min－1The change in mass of the film from 50 ℃ to 600 ℃ was recorded.
The load capacity is obtained by calculating the final residue quantity of the ESF film, the ZIF-67 crystal and the ESF @ ZIF-67 composite fiber film. The residue content of the ESF fiber at 600 ℃ is about 22%, the residue content of the ZIF-67 at 600 ℃ is about 59%, and the residue content of the ESF @ ZIF-67 composite fiber film is about 37%. Calculated two hours after loading, the amount of ESF loaded with ZIF-67 was about 39%.
Verification 1
Application of ESF @ ZIF-67 composite fiber film to Cr in aqueous solutionVIIon adsorption
2.6mg of the ESF @ ZIF-67 (loaded with 1mg of ZIF-67) membrane prepared in example 2 was weighed, and the ESF and 1mg of ZIF-67 were placed in 10mL of 8. mu.g mL of each membrane－1CrVIRespectively measuring Cr in water by adopting an ICP-OES method after 24 hours in the aqueous solutionVIThe residual quantity of ions is measured to obtain Cr in waterVIThe residual amounts of (A) are: 0.2. mu.g mL－1,8μg mL－1，0.2μg mL－1ESF fibers per se to CrVIThe ions have no adsorption effect, the microporous structure of the ZIF-67 particles loaded on the fibers is well preserved, and the ZIF-67 crystal particles have the same mass as that of the ZIF-67 crystal particles and can be used for treating Cr in waterVIThe adsorption amount of the ions is equivalent.
Prepared composite fiber film for Cr in waterVIThe removal efficiency of the ions reaches 98 percent, and the heavy metal Cr in the water can be effectively removedVIIons.
Authentication 2
ESF @ ZIF-67 composite fiber film for adsorbing malachite green in aqueous solution
2.6mg of ESF @ ZIF-67 (loaded with 1mg of ZIF-67) 2.6mg ZIF-67 @ ESF composite fiber film, 1mg ESF film and 1mg ZIF-67 are respectively placed in 1mL of 2.4kg L－1After standing for 24 hours, taking 200 mu L of supernatant liquid, adding the supernatant liquid into a quartz cuvette, and measuring the absorption peak intensity of the supernatant liquid at 240nm by using an ultraviolet spectrophotometer to calculate that the adsorption efficiencies are 99%, 10% and 99% respectively. Compared with the amount of adsorbing the malachite green in water by a pure ZIF-67 crystal, the composite fiber film proves that the pore structure on the surface of the ESF fiber is completely reserved, the adsorption amount reaches the theoretical upper limit of adsorbing the malachite green by the ZIF-67 crystal, and the composite fiber film can efficiently adsorb the malachite green in water and is used for purifying organic pollutants in water.
Authentication 3
ESF @ ZIF-67 composite fiber film for filtering malachite green aqueous solution
The ESF @ ZIF-67 film prepared by the method of example 2 was fixed with two Polydimethylsiloxane (PDMS) films having through-holes of 3mm in diameter (FIG. 5), and the films were fixed in a home-made filtration apparatus using a syringe at 5mLh－1Flow rate of 1mL of 50mg mL-1Adding 200 μ L of filtrate into quartz cuvette, measuring characteristic absorption peak of malachite green at 618nm with ultraviolet visible absorption spectrogram, and measuring content of malachite green in filtrate to be about 0.4mg mL-1The efficiency of the membrane for filtering the malachite green once is calculated to be as high as 98 percent (figure 6), the membrane for filtering the malachite green for the second time can remove 99 percent of the malachite green in the solution, and the membrane has a very good prospect in the aspect of actually filtering the malachite green in the sewage.
Example 3
ESF @ ZIF-8 composite fiber film prepared by in-situ method
Mixing 1cm2The square ESF membrane of (a) was immersed vertically in 2mL of a 10mM zinc nitrate hexahydrate solution and after 5 minutes an equal volume of 690mM 2-methylimidazole solution was added. The standing is to ensure that the nucleation in the system is uniform on the fiber surface, the mixture is quickly and uniformly mixed (about 10s), and then the mixture is placed in a 38 ℃ water bath kettle to react for 2h and then taken out. And (3) washing with deionized water for multiple times, and then putting the washed film in a vacuum drying oven at 40 ℃ for 24 hours to obtain the uniform ESF @ ZIF-8 composite fiber film.
Continuity, crystallinity:
and observing the growth condition of ZIF-8 particles on the fiber surface in the prepared composite fiber film by using a field emission scanning electron microscope. The results show (FIG. 7) that the surface of the fibroin fibers was loaded with fewer ZIF-8 crystals than the smooth ESF (FIG. 1) and that shown in FIG. 2 (left). And unlike the results of the higher zinc ion concentration reaction in example 1, a large amount of intermediate flower-like ZIF-8 was adsorbed on the surface of the film, and there were also more flower-like ZIF-8 intermediate in the gaps between fibers, resulting in incomplete coverage of the fiber surface, so at this concentration, although an ESF @ ZIF-8 fiber composite film having a higher loading was prepared. However, the film continuity is reduced due to the generation of more intermediate products. Therefore, the resulting film at this concentration is not an optimal production condition.
Example 4
ESF @ ZIF-8 composite fiber film prepared by in-situ method
Mixing 1cm2The square ESF membrane of (a) was immersed vertically in 2mL of a 20mM zinc nitrate hexahydrate solution and after 5 minutes an equal volume of 2M 2-methylimidazole solution was added. The standing is to ensure that the nucleation in the system is uniform on the fiber surface, the mixture is quickly and uniformly mixed (about 10s), and then the mixture is placed in a 38 ℃ water bath kettle to react for 2h and then taken out. And (3) washing with deionized water for multiple times, and then putting the washed film in a vacuum drying oven at 40 ℃ for 24 hours to obtain the uniform ESF @ ZIF-8 composite fiber film.
Continuity, crystallinity:
and observing the growth condition of ZIF-8 particles on the fiber surface in the prepared composite fiber film by using a field emission scanning electron microscope. The results show (FIG. 8), compared with the smooth ESF (FIG. 1) and FIG. 2 (left), although the fiber surface has a dense ZIF-8 layer, due to the high concentration of reactants, a large amount of micron ZIF-8 is formed in the solution and loaded on the surface of the fiber film, so that the continuity of the fiber surface is not high, the surface morphology structure of the fiber film is difficult to control, and the ZIF-8 crystals fall off during the use due to the weak acting force between the ZIF-8 crystals and the fiber film, so that secondary pollution is caused.
Load capacity:
the loading of ZIF-8 particles on the ESF fiber surface was determined by thermogravimetric analysis (TGA) by weighing ESF, ESF @ ZIF-8, ZIF-8, respectively, at a mass of about 3mg in N2Calcining in atmosphere at a temperature rise rate of 10 deg.C for min－1The change in mass of the film from 50 ℃ to 600 ℃ was recorded.
The loading of the examples was calculated from the final residue of the pure ESF film, the ZIF-8 crystal and the ESF @ ZIF-8 composite film. The residue content of the ESF fiber at 400 ℃ is about 45%, that of the ZIF-8 at 600 ℃ is about 85%, and that of the ESF @ ZIF-8 film is about 66%. The amount of ESF loaded with ZIF-8 was calculated to be about 50% at a reaction time of 2 h. The loading of the film was increased compared to the lower reaction concentration in example 1, but the increase in loading was mainly due to the adhesion of the micron ZIF-8 formed in the solution, which had a negative effect on the continuity of the film, since the shell thickness of the fiber was constant.
In conclusion, the method provided by the invention is based on the biomineralization effect of MOFs materials, utilizes the electrostatic spinning silk protein fibers to provide uniform nucleation sites for the growth of the MOFs materials, and successfully prepares two silk protein nanofiber-metal organic framework composite films (ESF @ ZIF-8 and ESF @ ZIF-67). The two composite fiber films of the embodiment realize the effect on various metal ions (As) in waterV，CrVI) And organic pollutants (malachite green, rhodamine B), and the adsorption capacity is equivalent to that of MOFs powder.
The malachite green solution is further filtered by using a filtering device, and the single filtering efficiency reaches 98 percent. The preparation method has the advantages of obvious technical effect, can be applied to adsorption of various heavy metal ions and organic pollutants, is expected to provide a general MOFs thin film device preparation method, and is widely applied to the aspects of water pollution removal and the like.
Claims (9)
1. A method for preparing a silk protein nanofiber-metal organic framework composite film is characterized by comprising the following steps:
1) vertically immersing the silk fibroin nanofiber (ESF) film in a first ligand solution containing metal ions, and adding a second ligand solution after 5 minutes to enable the silk fibroin nanofiber film and the mixed solution of the two ligands to react for a specific time at a specific temperature, so that Metal Organic Frameworks (MOFs) grow on the surface of the silk fibroin nanofiber film, and the ESF @ MOFs composite film is generated;
the silk protein nanofiber membrane is protein fiber prepared by electrostatic spinning;
2) and then taking out the ESF @ MOFs composite film, washing the ESF @ MOFs composite film for at least 3 times by using deionized water, and drying to obtain the film.
2. The method for preparing the silk fibroin nanofiber-metal organic framework composite film according to claim 1, wherein: the first ligand solution contains Zn2+The solution of metal ions and the solution of a second ligand adopt the aqueous solution of 2-methylimidazole, the grown Metal Organic Frameworks (MOFs) are ZIF-8, and the prepared ESF @ MOFs composite film is an ESF @ ZIF-8 composite film.
3. The method for preparing the silk fibroin nanofiber-metal organic framework composite film according to claim 2, wherein: the two ligand solutions have equal volume, and Zn in the first ligand solution2+In the range of 6.0mM to 30.0mM, and the concentration of 2-methylimidazole in the second ligand solution is in the range of 550mM to 2M.
4. The method for preparing the silk fibroin nanofiber-metal organic framework composite film according to claim 2, wherein: the reaction temperature in the step 1) is 35-60 ℃, and the reaction time is 1-4 hours.
5. The method for preparing the silk fibroin nanofiber-metal organic framework composite film according to claim 1, wherein: the first ligand solution adopts a solution containing Co2+The ESF @ MOFs composite film is prepared by adopting a solution of metal ions and a solution of a second ligand, namely a 2-methylimidazole aqueous solution, and adopting ZIF-67 as a grown metal-organic framework (MOFs)Is an ESF @ ZIF-67 composite film.
6. The method for preparing the silk fibroin nanofiber-metal organic framework composite film according to claim 5, wherein: the two ligand solutions have equal volume, and Zn in the first ligand solution2+In the range of 10.4mM to 52.0mM, and the concentration of 2-methylimidazole in the solution of the second ligand is in the range of 550mM to 2M.
7. The method for preparing the silk fibroin nanofiber-metal organic framework composite film according to claim 5, wherein: the reaction temperature in the step 1) is 60-80 ℃, and the reaction time is 1-4 hours.
8. The method for preparing a silk fibroin nanofiber-metal organic framework composite film according to any one of claims 1 to 7, wherein: the metal-organic frameworks (MOFs) are but not limited to ZIF-8 and ZIF-67.
9. The method for preparing a silk fibroin nanofiber-metal organic framework composite film according to any one of claims 1 to 7, wherein: in the step 2), the drying condition of the ESF @ MOFs composite film is that the temperature is 40-60 ℃ and the time is not less than 12 hours.
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