CN111575917A - High-specific-surface-area honeycomb-like structure nanofiber material and preparation method thereof - Google Patents

High-specific-surface-area honeycomb-like structure nanofiber material and preparation method thereof Download PDF

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CN111575917A
CN111575917A CN202010446712.1A CN202010446712A CN111575917A CN 111575917 A CN111575917 A CN 111575917A CN 202010446712 A CN202010446712 A CN 202010446712A CN 111575917 A CN111575917 A CN 111575917A
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honeycomb
surface area
specific surface
nano
high specific
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CN111575917B (en
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王先锋
张宇菲
丁彬
俞建勇
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Donghua University
National Dong Hwa University
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Donghua University
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
    • D01D5/0076—Electro-spinning characterised by the electro-spinning apparatus characterised by the collecting device, e.g. drum, wheel, endless belt, plate or grid
    • D01D5/0084—Coating by electro-spinning, i.e. the electro-spun fibres are not removed from the collecting device but remain integral with it, e.g. coating of prostheses
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0015—Electro-spinning characterised by the initial state of the material
    • D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
    • D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
    • D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H13/00—Other non-woven fabrics
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/02—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of forming fleeces or layers, e.g. reorientation of yarns or filaments
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00—Physical properties
    • D10B2401/02—Moisture-responsive characteristics
    • D10B2401/022—Moisture-responsive characteristics hydrophylic

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Nonwoven Fabrics (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)

Abstract

The invention relates to a nano-fiber material with a high specific surface area and a honeycomb-like structure and a preparation method thereof, wherein the preparation method comprises the following steps: performing electrostatic spinning on the polymer solution dispersed with the nanoscale metal-organic framework, and taking an insulating material subjected to charge elimination as a receiving base material to prepare the honeycomb-like structure nanofiber material with the high specific surface area; the finally prepared material has a certain thickness and is microscopically in a three-dimensional honeycomb communicated pore channel structure, the pore channel is a conical through pore channel, the pore diameter of the large end of the pore channel is 20-100 mu m, the pore diameter of the small end of the pore channel is 5-25 mu m, the single fiber is in a bead-like shape, is rough and porous, and the specific surface area is more than 600m2(ii) in terms of/g. The invention can prepare the three-dimensional honeycomb-shaped connector in one step without a templateThe prepared nano-fiber material with the honeycomb-like structure is provided with the conical through hole channel, so that water vapor is quickly and directionally transmitted in the thickness direction, and the oriented fibers communicated in the hole wall effectively promote the horizontal diffusion of water, so that the nano-fiber material has a wide application prospect in the fields of water guide and dehumidification.

Description

High-specific-surface-area honeycomb-like structure nanofiber material and preparation method thereof
Technical Field
The invention belongs to the technical field of nanofiber materials, and relates to a high-specific-surface-area honeycomb-like structure nanofiber material and a preparation method thereof.
Background
Most of fiber materials prepared by the traditional electrostatic spinning technology are two-dimensional fiber membranes, and fibers in the two-dimensional fiber membranes are randomly oriented and stacked. The nanofiber material with the three-dimensional honeycomb communicated pore channel structure is constructed by utilizing the electrostatic spinning technology, so that the resistance in water vapor transmission can be effectively reduced, the water transmission capacity of the material is expected to be greatly improved, the water capacity is expected to be improved, and the nanofiber material has wide application prospects in the fields of water diversion and dehumidification.
The document [ Patterned, high lattice and conductive nanofiber PANI/PVDF lattice sensors based on electrochemical and in situ polymerization, Nanoscale,2016,8, 2944-.
The literature [ Honeycom-like polysulphone/polyurethane nanofiber filter for the removal of organic/inorganic specific Materials from streams, Journal of Hazardous Materials,2018,347,325-333] reports the use of a Honeycomb template as receiving substrate and the collection of polysulfone/polyurethane electrospun fibrous Materials with a Honeycomb-like through-hole structure (pore size 5mm) on its surface.
In the literature [ Patterning electronic nanoparticles via imaging hydrogel formation cell orientation in microfluidic device, Small,2017,13,1-7], the fiber material with a circular through hole structure can be obtained by utilizing the shielding effect of a circular array baffle plate on an electric field.
The technology adopts a specially designed collecting device to prepare the fiber material with the through hole structure, but the small size (aperture) is difficult to obtain due to the limitation of the size of the hole of the collecting device<100 μm) via structures and obtained by electrospinning of single or multiple polymersThe specific surface area of the fiber material with the through hole structure is extremely low (less than 20 m)2/g) does not impart excellent unidirectional moisture-conducting and moisture-absorbing quick-drying properties to the material.
Disclosure of Invention
The invention aims to solve the problems in the prior art, provides a high-specific-surface-area honeycomb-like structure nanofiber material with excellent unidirectional moisture-conducting and moisture-absorbing quick-drying performances and a preparation method thereof, and particularly provides an electrostatic spinning technology which is suitable for wide polymer raw material range, specific functional metal-organic framework range and can be used for preparing a small-size through hole structure with regular pore diameter and uniform distribution in one step without a template.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a nano-fiber material with a high specific surface area honeycomb-like structure comprises the steps of carrying out electrostatic spinning on a polymer solution dispersed with a nano-metal-organic framework, and taking an insulating material subjected to charge elimination as a receiving base material to prepare the nano-fiber material with the high specific surface area honeycomb-like structure;
generally, it is more suitable to use a nano-sized metal-organic framework mixed with a polymer for electrospinning because electrospun fibers are mostly nanofibers; if micron-sized particles are added, the phenomenon of needle blockage is easy to occur in the spinning process, and the metal-organic framework is not easy to be ejected by an electrostatic spinning technology and is not easy to be compounded with the nano-fibers; therefore, the nano-sized metal-organic framework is more suitable for preparing the honeycomb-like structure nanofiber material by utilizing the electrostatic spinning technology; in addition, the size of the metal-organic framework can be regulated and controlled in the synthesis process, and a person skilled in the art can regulate and control the nanoscale metal-organic framework with corresponding size according to requirements;
the polymer solution dispersed with the nanoscale metal-organic framework has the viscosity ranging from 1 to 500mPa · S and the conductivity ranging from 100 to 10000 muS/cm; the electrostatic spinning is that a low-viscosity solution is extruded under a high-voltage electrostatic field, and jet flow is sprayed and dispersed;
the technological parameters of electrostatic spinning comprise: the voltage is 10-40 kV, the filling speed is 0.5-4 mL/h, the distance between a spinning head and a receiving base material is 6-20 cm, and the relative humidity of the environment is 30-60%;
the insulating material is non-woven fabric or electrostatic spinning fiber membrane, which is obviously different from a honeycomb template in the prior art, and the honeycomb template is not needed in the invention, and only common non-woven fabric or electrostatic spinning fiber membrane is needed to be used as a receiving substrate;
the method for eliminating charges comprises the following steps: and (3) placing the insulating material in a charge eliminating solvent for a period of time, and then drying, wherein the solvent is used as a conductor to eliminate static electricity of the base material, and removing residual charges on the surface of the base material, so that the formed honeycomb-like structure is obvious.
The material with excellent one-way moisture conducting and moisture absorbing and quick drying performances can be prepared by the method of the invention because:
according to the invention, the metal-organic framework is added into the spinning solution, the metal-organic framework can be taken out by the polymer in the spinning process, so that single fibers are in a string-like rough porous structure, the self-assembly of the porous fibers can obtain the honeycomb-like structure nanofiber material with ultrahigh specific surface area and high porosity, the structural characteristics of ultrahigh specific surface area and high porosity can improve the capillary effect of the material, the contact area of the material and air is greatly increased, the moisture absorption and moisture conduction performance, the moisture diffusion speed and the drying speed of the material are enhanced, the material is endowed with excellent one-way moisture conduction and moisture absorption quick-drying performance, and meanwhile, the introduction of the metal-organic framework enables the surface of the nanofiber to contain a large number of hydrophilic active sites, and the one-way moisture conduction and moisture absorption quick-drying performance of the material can also be improved.
In addition, the introduction of the metal-organic framework changes the properties of the electrostatic spinning solution body, the conductivity of the spinning solution is increased, so that the surface charge density is increased in the jet drafting process, the electrostatic repulsion among fibers deposited on a base material is increased, the branching of fiber bundles is induced, and the rapid self-assembly of the fiber bundles is promoted to form a honeycomb-like structure.
The forming mechanism of the honeycomb-like structure nanofiber material is shown in fig. 4, and is specifically as follows:
the high voltage electrostatic field charges and deforms the spinning dope to form a hanging conical drop at the end of the spinneret. When the repulsion force of the surface of the liquid drop exceeds the surface tension, the polymer micro jet flow is formed by spraying and atomizing on the surface of the liquid drop at a high speed, the nano metal-organic framework is taken out along with the polymer at the same time, and the jet flow is stretched at a high speed by the electric field force within a short distance, volatilized by the solvent and finally deposited on a receiving substrate. In the electrostatic spinning process, under a high-voltage electric field, as perfusion advances, spinning solution is extruded into fibers, and the extruded fibers are electrostatically charged at a rate exceeding the rate of electrostatic dissipation, so that electrostatic charge is accumulated on the fibers to form charged fiber bundles. The forming of the honeycomb-like stacking structure depends on the competition effect of the surface tension and the electrostatic repulsion of the charged fiber bundles, and the forming process relates to dynamic processes of charged jet stretching deformation, aggregation bundling, fiber bundle branching stacking and the like. The insulating material is subjected to charge elimination treatment, the charged fibers are just deposited on the base material at random, the wet fibers which are not volatilized by a solvent can be partially fused to form fiber clusters, when the subsequent charged fibers are deposited and contact with the partially overlapped fiber clusters, the surface tension can promote partial fibers near the contact points to be merged into the fiber clusters, the parts far away from the contact points are outwards bent due to the increase of electrostatic repulsion, meanwhile, the nanofiber clusters can also be reversely bent, and finally, a branch-shaped structure is formed (the 120-degree triangular branch-shaped structure is most stable). On the basis, the deposited nano fibers are stacked layer by layer in the spinning process to form a honeycomb-like structure consisting of a plurality of branch fiber clusters.
The reason why the viscosity of the polymer solution in which the nano-sized metal-organic framework is dispersed is controlled to be 1 to 500 mPas and the conductivity is controlled to be 100 to 10000. mu.S/cm is as follows: the bulk properties (viscosity, conductivity) of the spinning dope are the necessary conditions for the formation of charged fiber bundles; if the spinning solution is high in viscosity and low in conductivity, the spinning solution still belongs to the electrostatic spinning category within the spinnability, but compared with a low-viscosity solution, the high-viscosity solution is more difficult to jet out of liquid drops under the action of the same electric field force because the intermolecular friction force is higher, namely the liquid drops are not easy to split and are not easy to branch into fine fibers; the spinning solution with lower conductivity is difficult to generate the surface charge accumulation phenomenon of the fiber bundle under a high-voltage electric field, the density of the surface charge of the fiber is reduced, the electrostatic repulsion force among fibers deposited on a base material is reduced, the fiber bundle is not easy to branch, the rapid self-assembly forming of the charged fiber bundle under the electrostatic field is prevented, and a honeycomb-like network structure is not easy to generate.
The reason why the invention controls the voltage of 10 to 40kV, the filling speed of 0.5 to 4mL/h, the distance between the spinning head and the receiving substrate of 6 to 20cm and the relative humidity of the environment of 30 to 60 percent is that: whether a honeycomb-like structure can be formed is determined, the liquid drops cannot be split to form fine fibers due to too low voltage, the electric field intensity under low voltage is low, the surface charge density of the fibers is reduced, the electrostatic repulsion among fiber bundles deposited on a base material is reduced, the branching effect among the fibers is weakened, and the aperture of the honeycomb-like structure is reduced and even tends to be unpatterned; the perfusion speed influences the shape of a Taylor cone (a suspended conical liquid drop formed at the tail end of a capillary by the charged liquid), the perfusion speed is too low or too high, the Taylor cone is unstable or jumps, the instability of jet flow is increased, and the morphological structure of the fiber cannot be patterned; the change of the spinning distance (namely the distance between a spinning nozzle and a receiving substrate) changes the electric field intensity, further influences the charge density of the charged fiber bundle, and finally influences the size of the aperture of the honeycomb (also determines the obvious degree of the honeycomb structure), for example, the increase of the spinning distance reduces the electric field intensity, the charge density of the fibers is reduced, the electrostatic repulsion among the fibers is reduced, the branching effect among the fibers is weakened, and the aperture of the honeycomb-like structure is reduced and even tends to be unpatterned; humidity can make corona discharge reduce to make the difficult dissipation of electric charge at this within range, leads to fibre charge density to increase to make the fibre static repulsion that deposits on the substrate increase, take place the induced similar honeycomb structure self-assembly formation of competition with surface tension, if humidity is too high, the corona discharge reinforcing makes the charge dissipation, and fibre charge density reduces, makes the fibre static repulsion that deposits on the substrate reduce, and static repulsion is too little then can't provide self-assembly.
The reason why the present invention controls the receiving substrate to be an insulating material subjected to a charge-eliminating treatment is that: when positively charged fibers are emitted to the negative receiver, the fiber deposition pattern is controlled by the intensity of the charges carried by the fibers and the electrostatic repulsion and surface tension between the deposited fibers, the wet fibers are fused when in contact by the surface tension, and the fused fibers are pulled apart by the electrostatic repulsion. The high charge strength receiver fibers repel newly received similarly charged fibers and drive them to conductive points on a nearby receiver substrate for easier charge dissipation. The nanofibers captured by the fiber clusters are stacked upward by electrostatic repulsion, causing the fiber clusters to grow in height into the walls of a three-dimensional honeycomb-like structure. Therefore, the insulation material subjected to charge elimination treatment plays a key role as a receiving substrate, the charge intensity of the charged fiber bundles initially deposited on the substrate is not obviously changed, and a strong electrostatic repulsion force is kept between the charged fiber bundles and the subsequently deposited charged fibers, so that the patterned topological structure is favorably formed. When the substrate receives the first layer of fiber film, the charges of the deposited fibers still exist in the fibers to form charged fiber bundles, and the competition effect of surface tension and electrostatic repulsion exists between the fibers with the same charges which are deposited subsequently. The substrate selected by the invention is an insulating material, so that the charges on the deposited charged fibers can not be conducted away, and the action of electrostatic repulsion with the subsequently deposited fibers is reserved. If the base material is not treated, the carried charges are accumulated on the surface of the material and cannot be leaked out to generate a charge accumulation phenomenon, the charges on the fibers deposited at the beginning are partially neutralized, so that the competition effect of the surface tension of the charged fibers and the electrostatic repulsion is influenced, and finally formed fibers are distributed in random orientation, namely, the conductive base material is not easy to form the nano fibers with the honeycomb-like structure, and the insulating material is not treated and is not easy to form the nano fibers with the honeycomb-like structure.
As a preferred technical scheme:
in the preparation method of the honeycomb-like structure nanofiber material with high specific surface area, the metal-organic framework is MIL-101(Cr) or MIL-101(Cr) -NH2、MIL-100(Fe)、HKUST-1、CAU-1(Al)、CAU-23(Al)、UiO-66、UiO-66-NH2KAUST-8, MOF-801, MOF-804, MOF-841, DUT-67(Zr), DUT-51(Zr), DUT-53(Zr), MOF-74(Mg), and MOF-74(Ni). The preparation of the nano-fiber material with the high specific surface area and the honeycomb-like structure has no limitation on the types of metal-organic frameworks, and the metal-organic frameworks with hygroscopicity and water stability are selected according to the application field.
In the preparation method of the nano-fiber material with the high specific surface area and the honeycomb-like structure, the polymer is more than one of polyacrylonitrile, polyurethane, cellulose acetate, polyvinyl alcohol, polylactic acid, polysulfone, polyethylene oxide, polycaprolactone, polyamide 6, polyamide 66, polyimide, polyether sulfone, polyethylene terephthalate, polystyrene sulfonic acid sodium salt, polyacrylate resin, polyethylene glycol, polyvinylpyrrolidone, thermoplastic polyurethane elastomer, chitosan, cellulose derivative and ion exchange resin.
In the preparation method of the honeycomb-like structure nanofiber material with the high specific surface area, the solvent in the polymer solution is more than one of N, N-dimethylformamide, N-dimethylacetamide, trichloromethane, tetrahydrofuran, N-methylpyrrolidone, chloroform, methanol, ethanol, isopropanol, deionized water, acetone, dichloromethane, formic acid, acetic acid, dimethyl sulfoxide, diethyl ether, toluene, trichloroacetic acid and trifluoroacetic acid.
The preparation method of the honeycomb-like structure nanofiber material with high specific surface area comprises the following steps of: adding a metal-organic framework into a solvent, performing ultrasonic dispersion for 1-4 hours, adding a polymer, and continuously stirring for 2-24 hours at room temperature or 50-90 ℃ by using a magnetic stirring device, wherein the room temperature is 23-26 ℃.
According to the preparation method of the honeycomb-like structure nanofiber material with the high specific surface area, in the polymer solution dispersed with the nanoscale metal-organic framework, the mass content of the polymer is 3-15%, and the mass content of the metal-organic framework is 10-30%.
According to the preparation method of the honeycomb-like structure nanofiber material with the high specific surface area, the technological parameters of electrostatic spinning further comprise: the ambient temperature is 23-26 ℃.
According to the preparation method of the honeycomb-like structure nanofiber material with the high specific surface area, the charge eliminating solvent is deionized water and/or isopropanol; the period of time is 1-3 min.
The invention also provides the high-specific-surface-area honeycomb-like structure nanofiber material prepared by the preparation method of the high-specific-surface-area honeycomb-like structure nanofiber material, which has a certain thickness and is microscopically in a three-dimensional honeycomb communicated pore channel structure, wherein the pore channel is a conical straight-through pore channel, the large end of the pore channel is far away from the base material, the small end of the pore channel is close to the base material, the pore diameter of the large end of the pore channel is 20-100 mu m, the pore diameter of the small end of the pore channel is 5-25 mu m, and single fibers are beaded and coarse and porous.
As a preferred technical scheme:
the high specific surface area honeycomb-like structure nano-fiber material has the thickness of more than 0.8mm and the specific surface area of more than 600m2The porosity is more than 75 percent, the one-way moisture permeability index is more than 1300 percent, and the moisture permeability is more than 10kg/m2And d, the moisture permeability is used for representing the quick-drying performance of the product, and the larger the moisture permeability is, the better the quick-drying performance of the product is.
Has the advantages that:
(1) different from the traditional method for preparing the three-dimensional ordered fiber stacking structure based on the patterned receiving template method, the method utilizes electrostatic aggregation to form the charged fiber bundle in the electrostatic spinning process, the charged fiber bundle induces the honeycomb-like stacking structure to be self-assembled and formed on the surface of the insulating receiving base material under the competitive action of surface tension and electrostatic repulsion, the controllable preparation of the nano fiber material with the honeycomb-like structure with high specific surface area is realized, and the controllability of the fiber diameter, the pore diameter and the thickness is strong; according to the invention, a template is not needed, the high-specific-surface-area nanofiber material with a three-dimensional honeycomb-shaped communicated pore channel structure can be prepared in one step, and the material has a regular and uniformly distributed small-size through hole structure (the pore diameter of the large end of the pore channel is 20-100 mu m, and the pore diameter of the small end of the pore channel is 5-25 mu m) and rough and porous beaded single fibers, so that the material has a wide application prospect in the fields of water diversion and dehumidification;
(2) different from the traditional preparation technology of the electrostatic spinning pure polymer nanofiber membrane and the polymer/metal-organic framework composite nanofiber membrane, the invention adopts the extremely low polymer mass concentration and the extremely high metal-organic framework mass concentration, namely, the polymer/metal-organic framework mixed solution with low viscosity and high conductivity is used for electrostatic spinning, the metal-organic framework further induces the accumulation of the surface charges of the fibers, and is beneficial to the rapid self-assembly of the charged fiber bundles in an electrostatic field to form a honeycomb-like structure, namely, the introduction of the metal-organic framework increases the surface charge density of the fibers in the jet flow drafting process, so that the branched nanofibers are more easily formed, the formation of the honeycomb-like structure nanofiber material is promoted, the invention is suitable for polymer and metal-organic framework raw materials with wide range of types;
(3) the specific surface area of the traditional honeycomb-like structure nanofiber material is extremely low (lower than 20 m)2The application is limited, the single fiber structure of the material is obviously changed by introducing the metal-organic framework, the material is in a beaded rough porous structure, the specific surface area and the porosity of the material are obviously improved by a honeycomb-like network structure consisting of porous single fibers, and the moisture absorption and quick drying performance of the material are obviously improved by the honeycomb-like structure with ultrahigh specific surface area;
(4) the invention firstly utilizes the electrostatic spinning technology and the charge eliminating treatment method to prepare the polymer/metal-organic framework composite nanofiber material with the honeycomb-like structure in one step, the thickness of the material can exceed 0.8mm, the limitation of preparing a two-dimensional nanofiber membrane by the traditional electrostatic spinning technology is broken through, and the controllable construction of the nanofiber material with the three-dimensional honeycomb-like communicated pore structure is realized.
Drawings
FIG. 1 is a scanning electron microscope picture of a conventional electrospun polymer nanofiber material;
FIG. 2 is a scanning electron microscope photograph of a conventional electrospun polymer/metal-organic framework composite nanofiber material;
FIG. 3 is a scanning electron microscope photograph of an electrospun honeycomb-like structure polymer/metal-organic framework composite nanofiber material, the left image being a photomicrograph at a larger magnification and the right image being a photomicrograph at a smaller magnification;
fig. 4 is a diagram of a forming mechanism of an electrospun honeycomb-like structure polymer/metal-organic framework composite nanofiber material.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
The polymers in examples 1-9 are selected from polyacrylonitrile (molecular weight 20W), polyvinyl alcohol (molecular weight 19.5W), cellulose acetate (acetyl 39.8 wt%, hydroxyl 3.5 wt%), polyurethane (molecular weight 20W), polylactic acid (molecular weight 80W), polysulfone (molecular weight 30W), polycaprolactone (molecular weight 20W); the solvent is selected from N, N-dimethylformamide, deionized water, acetone, dimethyl sulfoxide, N-dimethylacetamide, chloroform and chloroform, and is all produced by Shanghai crystal pure reagent company Limited.
Example 1
A preparation method of a honeycomb-like structure nanofiber material with a high specific surface area comprises the following specific steps:
(1) adding MIL-101(Cr) into N, N-dimethylformamide, ultrasonically dispersing for 3 hours, then adding polyacrylonitrile into the dispersion liquid, and continuously stirring for 12 hours at room temperature by using a magnetic stirring device to obtain uniform and stable mixed liquid, wherein the mass percent of the polyacrylonitrile in the mixed liquid is 5%, the mass percent of the MIL-101(Cr) in the mixed liquid is 20%, the viscosity of the mixed liquid is 30mPa & S, and the conductivity of the mixed liquid is 146.4 muS/cm;
(2) placing the non-woven fabric in deionized water for 3min, drying, using the deionized water as a conductor to eliminate static electricity, removing residual charges on the surface of the non-woven fabric, and using the non-woven fabric subjected to charge elimination as a receiving base material;
(3) and (3) performing electrostatic spinning on the prepared mixed solution, wherein the voltage is 12kV, the filling speed is 1mL/h, the distance between a spinning nozzle and a receiving base material is 15cm, the ambient temperature is 24 +/-1 ℃, and the ambient relative humidity is 46 +/-3%, so as to obtain the nano-fiber material with the honeycomb-like structure.
The finally prepared honeycomb-like structure nanofiber material with the high specific surface area is shown in fig. 3, has a certain thickness, is microscopically in a three-dimensional honeycomb communicated pore channel structure, the pore channel is a conical straight-through pore channel, the large end of the pore channel is far away from the base material, the small end of the pore channel is close to the base material, the pore diameter of the large end of the pore channel is 55 +/-5 microns, the pore diameter of the small end of the pore channel is 15 +/-5 microns, and single fibers are in a beaded shape and are rough and porous; the thickness of the nano-fiber material with the high specific surface area honeycomb-like structure is 1mm, and the specific surface area is 820m2The porosity is 85 percent, the one-way moisture permeability index is 1402 percent, and the moisture permeability is 11.6kg/m2And d, the moisture absorption and quick drying effects are good.
Comparative example 1
A preparation method of a nanofiber material comprises the following specific steps:
(1) adding MIL-101(Cr) into N, N-dimethylformamide, ultrasonically dispersing for 3 hours, then adding polyacrylonitrile into the dispersion liquid, and continuously stirring for 12 hours at room temperature by using a magnetic stirring device to obtain a uniform and stable mixed liquid, wherein the mass percent of the polyacrylonitrile in the mixed liquid is 12%, the mass percent of the MIL-101(Cr) in the mixed liquid is 8%, the viscosity of the mixed liquid is 900mPa & S, and the conductivity is 85.4 muS/cm;
(2) taking an aluminum foil as a receiving substrate;
(3) and (3) performing electrostatic spinning on the prepared mixed solution, wherein the voltage is 12kV, the filling speed is 1mL/h, the distance between a spinning nozzle and a receiving base material is 15cm, the ambient temperature is 24 +/-1 ℃, and the ambient relative humidity is 46 +/-3%, so as to obtain the nanofiber material.
As shown in figure 2, the finally prepared nanofiber material is a two-dimensional fiber film on the macro scale, the thickness of the fiber film is only micron-sized (100 mu m), the fibers on the micro scale are randomly oriented and stacked, single fibers are rough and porous, MIL-101(Cr) is uniformly distributed on the single fibers, and the common two-dimensional structure limits the fiber material to be uniform in distributionThe moisture permeability is 3.4kg/m in the application of water guide and dehumidification field2And d, having no one-way moisture-conducting performance.
Comparing example 1 with comparative example 1, it can be seen that the mixed solution of example 1 has a low polyacrylonitrile content (resulting in a low viscosity of the mixed solution), a high MIL-101(Cr) content (resulting in a high conductivity of the mixed solution), and the receiving substrate is an insulating material after charge removal treatment, which together result in the formation of a honeycomb-like structure, so that the finally prepared nanofiber material has a certain thickness, and microscopic conical through channels stacked in a fiber network, the single fibers are extremely fine and coarse and porous, the MOF is distributed on the single fibers in a beaded manner, the conical through channels enable water vapor to be rapidly oriented and transmitted in the thickness direction, and the oriented fibers communicated in the channel walls effectively promote the horizontal diffusion of water, thereby having a broad application prospect in the fields of water diversion and dehumidification.
Comparative example 2
A preparation method of a nanofiber material is basically the same as that of comparative example 1, except that MIL-101(Cr) is not contained in a mixed solution, polyacrylonitrile accounts for 12% of the solution by mass, the viscosity of the mixed solution is 500mPa · S, and the conductivity is 58.8 muS/cm.
Comparing the comparative example 1 with the comparative example 2, it can be seen that the mixed solution of the comparative example 2 does not contain a metal-organic framework, the conductivity of the solution is obviously reduced, the receiving base material is conductive base material aluminum foil, a non-honeycomb-like structure is formed, the finally prepared nanofiber material is shown in fig. 1, macroscopically, the nanofiber membrane is a two-dimensional fiber membrane, the thickness is only micron-sized (80 μm), microscopically, the fibers are randomly oriented and stacked, the surface of a single fiber is smooth, the common two-dimensional structure limits the application of the nanofiber material in the fields of water guiding and dehumidification, and the moisture permeability is 3.3kg/m2And d, having no one-way moisture-conducting performance.
Comparative example 3
A preparation method of a nanofiber material comprises the following specific steps:
(1) adding MIL-101(Cr) into N, N-dimethylformamide, ultrasonically dispersing for 3 hours, then adding polyacrylonitrile into the dispersion liquid, and continuously stirring for 12 hours at room temperature by using a magnetic stirring device to obtain a uniform and stable mixed liquid, wherein the mass percent of the polyacrylonitrile in the mixed liquid is 12%, the mass percent of the MIL-101(Cr) in the mixed liquid is 8%, the viscosity of the mixed liquid is 900mPa & S, and the conductivity is 85.4 muS/cm;
(2) placing the non-woven fabric in deionized water for 3min, drying, using the deionized water as a conductor to eliminate static electricity, removing residual charges on the surface of the non-woven fabric, and using the non-woven fabric subjected to charge elimination as a receiving base material;
(3) and (3) performing electrostatic spinning on the prepared mixed solution, wherein the voltage is 12kV, the filling speed is 1mL/h, the distance between a spinning nozzle and a receiving base material is 15cm, the ambient temperature is 24 +/-1 ℃, and the ambient relative humidity is 46 +/-3%, so as to obtain the nanofiber material.
The finally prepared nanofiber material is a two-dimensional fiber film on the macroscopic scale, the thickness of the nanofiber film is only micron-sized (100 mu m), the fibers on the microscopic scale are randomly oriented and stacked, single fibers are rough and porous, MIL-101(Cr) is uniformly distributed on the single fibers, the application of the nanofiber material in the water guide and dehumidification fields is limited by the common two-dimensional structure, and the moisture permeability is 3.4kg/m2And d, having no one-way moisture-conducting performance.
Comparing example 1 with comparative example 3, it can be seen that when the viscosity of the mixed solution is high (exceeding the viscosity range of 1-500 mPa · S) and the conductivity is low (exceeding the conductivity range of 100-10000 μ S/cm), a honeycomb-like structure is difficult to form, because the surface charge repulsion of the liquid drop formed by the high-viscosity mixed solution at the end of the spinneret is difficult to exceed the surface tension thereof, the liquid drop is difficult to be jetted out to form a tiny fluid, the spray-like divergence of the jet flow is difficult to realize, the fiber is difficult to be branched, the polymer content is high, the viscosity is high, and the obtained fiber is also thick; the mixed liquid with lower conductivity is difficult to generate the surface charge accumulation phenomenon of the fiber bundle under a high-voltage electric field, the charge density is reduced, the electrostatic repulsion between fibers deposited on a base material is reduced, the fiber bundle is not easy to branch, and the rapid self-assembly molding of the charged fiber bundle under the electrostatic field is hindered.
Comparative example 4
A preparation method of a nanofiber material comprises the following specific steps:
(1) adding MIL-101(Cr) into N, N-dimethylformamide, ultrasonically dispersing for 3 hours, then adding polyacrylonitrile into the dispersion liquid, and continuously stirring for 12 hours at room temperature by using a magnetic stirring device to obtain uniform and stable mixed liquid, wherein the mass percent of the polyacrylonitrile in the mixed liquid is 5%, the mass percent of the MIL-101(Cr) in the mixed liquid is 20%, the viscosity of the mixed liquid is 30mPa & S, and the conductivity of the mixed liquid is 146.4 muS/cm;
(2) taking an aluminum foil as a receiving substrate;
(3) and (3) performing electrostatic spinning on the prepared mixed solution, wherein the voltage is 12kV, the filling speed is 1mL/h, the distance between a spinning nozzle and a receiving base material is 15cm, the ambient temperature is 24 +/-1 ℃, and the ambient relative humidity is 46 +/-3%, so as to obtain the nanofiber material.
The finally prepared nanofiber material is a two-dimensional fiber film on the macroscopic level, the thickness is only micron-sized (130 mu m), fibers on the microscopic level are randomly oriented and stacked, single fibers are beaded and coarse and porous, the application of the nanofiber material in the fields of water guiding and dehumidification is limited by the common two-dimensional structure, and the moisture permeability is 3.6kg/m2And d, having no one-way moisture-conducting performance.
Comparing example 1 with comparative example 4, it can be seen that when the receiving substrate is a conductive material, it is difficult to form a honeycomb-like structure, because the aluminum foil as a conductive substrate will cause the charges on the initially deposited charged fibers to be conducted away, and sufficient electrostatic repulsion cannot be generated between the subsequently deposited charged fibers, so that the fiber bundles are difficult to be branched, i.e. the self-assembly of the honeycomb structure is difficult to occur.
Comparative example 5
A preparation method of a nanofiber material comprises the following specific steps:
(1) adding MIL-101(Cr) into N, N-dimethylformamide, ultrasonically dispersing for 3 hours, then adding polyacrylonitrile into the dispersion liquid, and continuously stirring for 12 hours at room temperature by using a magnetic stirring device to obtain uniform and stable mixed liquid, wherein the mass percent of the polyacrylonitrile in the mixed liquid is 5%, the mass percent of the MIL-101(Cr) in the mixed liquid is 20%, the viscosity of the mixed liquid is 30mPa & S, and the conductivity of the mixed liquid is 146.4 muS/cm;
(2) placing the non-woven fabric in deionized water for 3min, drying, using the deionized water as a conductor to eliminate static electricity, removing residual charges on the surface of the non-woven fabric, and using the non-woven fabric subjected to charge elimination as a receiving base material;
(3) and (3) performing electrostatic spinning on the prepared mixed solution, wherein the voltage is 8kV, the filling speed is 5mL/h, the distance between a spinning nozzle and a receiving base material is 23cm, the environmental temperature is 24 +/-1 ℃, and the environmental relative humidity is 65 +/-3%, so as to obtain the nanofiber material.
The finally prepared nanofiber material is a two-dimensional fiber membrane on the macroscopic level, the thickness is only micron-sized (150 mu m), fibers on the microscopic level are randomly oriented and stacked, single fibers are beaded and coarse and porous, the application of the nanofiber material in the fields of water guiding and dehumidification is limited by the common two-dimensional structure, and the moisture permeability is 3.1kg/m2And d, having no one-way moisture-conducting performance.
Comparing example 1 with comparative example 5, it can be seen that when the electrostatic spinning process parameters exceed the set range (voltage 10-40 kV, filling speed 0.5-4 mL/h, spinneret distance 6-20 cm from receiving substrate, environment relative humidity 30-60%), it is difficult to form honeycomb-like structure, because the variation of electrostatic spinning process parameters changes the electric field intensity, and further affects the surface charge density of the charged fiber bundle, thereby affecting the electrostatic repulsion between fibers deposited on the substrate, and finally affecting the size of honeycomb aperture (also determining the apparent degree of honeycomb structure). The liquid drops can not be split to form thin fibers due to too low voltage, the electric field intensity under low voltage is low, the surface charge density of the fibers is reduced, the electrostatic repulsion among the fiber bundles deposited on the base material is reduced, the branching effect among the fibers is weakened, and the aperture of the honeycomb-like structure is reduced and even tends to be unpatterned; similarly, the increase of the spinning distance reduces the electric field intensity, reduces the charge density of the fibers, reduces the electrostatic repulsion among the fibers deposited on the base material, weakens the branching effect among the fibers, and leads to the reduction of the aperture of the honeycomb-like structure and even tends to no patterning; the humidity is too high, the corona discharge is enhanced to dissipate the charges, the surface charge density of the fibers is reduced, and therefore the electrostatic repulsion among the fibers is reduced, and the fibers are difficult to compete with the surface tension to induce the self-assembly of the honeycomb-like structure.
Comparative example 6
A preparation method of a nanofiber material is basically the same as that in example 1, except that mixed solution does not contain MIL-101(Cr), polyacrylonitrile accounts for 5% by mass of the solution, the solution viscosity is 26mPa · S, the conductivity is 48.8 muS/cm, the voltage is 25kV, the perfusion speed is 0.2mL/h, and the ambient relative humidity is 23 +/-3%.
Comparing example 1 with comparative example 6, it can be seen that the mixed solution of comparative example 6 does not contain metal-organic framework, the conductivity of the solution is obviously reduced, but the electric field intensity is increased due to the increase of voltage, the electric charge is not easy to dissipate due to the reduction of corona discharge caused by the reduction of relative humidity, the surface charge density of the fiber can still be increased, so that the electrostatic repulsion between the fibers deposited on the base material is increased, and the self-assembly formation of the honeycomb-like structure is induced by the competition effect with the surface tension. That is, if the spinning solution without the metal-organic framework is to form the nano-fiber material with the honeycomb-like structure, voltage needs to be increased and the environmental humidity needs to be strictly controlled, the spinning equipment needs to be placed in a closed space, and a temperature and humidity control device is installed in the closed space, so that a large amount of energy is consumed when the environmental humidity is reduced to an extremely low level; meanwhile, due to the change of voltage and humidity, the perfusion speed also needs to be correspondingly reduced, and the extremely low perfusion speed obviously reduces the yield of the electrospun fibers. Therefore, the honeycomb-like structure prepared by using the pure polymer has complex operation and strict requirements on spinning conditions, and the fine regulation and control of the structure are difficult to realize. In addition, in terms of structure and performance, the nanofiber material prepared in comparative example 6 has a honeycomb-like structure, but single-fiber non-porous fibers and a specific surface area of only 6m2The moisture absorption and quick drying performance can not reach the index of example 1.
Example 2
A preparation method of a honeycomb-like structure nanofiber material with a high specific surface area comprises the following specific steps:
(1) MIL-101(Cr) -NH is firstly mixed2Adding the mixture into N, N-dimethylformamide, performing ultrasonic dispersion for 4h, adding polyacrylonitrile into the dispersion liquid, and continuously stirring for 14h at room temperature by using a magnetic stirring device to obtain uniform and stable mixed liquid, wherein the mass percent of the polyacrylonitrile in the mixed liquid is 8%, and the MIL-101(Cr) -NH is2The mixed solution accounts for 24 percent of the mass percentage, and the viscosity of the mixed solution is53 mPas, the conductivity is 256.4 mu S/cm;
(2) placing the non-woven fabric in isopropanol, drying for 1min, wherein the isopropanol can be used as a conductor to eliminate static electricity, removing residual charges on the surface of the non-woven fabric, and using the non-woven fabric subjected to charge elimination treatment as a receiving base material;
(3) and (3) performing electrostatic spinning on the prepared mixed solution, wherein the voltage is 20kV, the filling speed is 1.2mL/h, the distance between a spinning nozzle and a receiving base material is 15cm, the ambient temperature is 24 +/-1 ℃, and the ambient relative humidity is 46 +/-3%, so as to obtain the honeycomb-like structure nanofiber material.
The finally prepared nano fiber material with the high specific surface area honeycomb-like structure has a certain thickness, is microscopically in a three-dimensional honeycomb communicated pore channel structure, the pore channel is a conical through pore channel, the large end of the pore channel is far away from the base material, the small end of the pore channel is close to the base material, the pore diameter of the large end of the pore channel is 75 +/-5 mu m, the pore diameter of the small end of the pore channel is 20 +/-5 mu m, and single fibers are in a bead-like shape and are rough and; the thickness of the nano-fiber material with the high specific surface area honeycomb-like structure is 1.5mm, and the specific surface area is 780m2Per g, porosity of 68%, one-way moisture conductivity index of 1556%, and moisture permeability of 12.1kg/m2And d, the moisture absorption and quick drying effects are good.
Example 3
A preparation method of a honeycomb-like structure nanofiber material with a high specific surface area comprises the following specific steps:
(1) MIL-101(Cr) -NH is firstly mixed2Adding the mixture into deionized water, performing ultrasonic dispersion for 3h, adding polyvinyl alcohol into the dispersion, and continuously stirring the mixture for 12h at room temperature by using a magnetic stirring device to obtain uniform and stable mixed solution, wherein the polyvinyl alcohol accounts for 6% of the mixed solution by mass, and MIL-101(Cr) -NH2The mixed solution accounts for 24 percent of the mass percent, the viscosity of the mixed solution is 43 mPa.s, and the conductivity is 5079 mu S/cm;
(2) placing the electrostatic spinning fiber membrane in deionized water for 2min, drying, using the deionized water as a conductor to eliminate static electricity, removing residual charges on the surface of the electrostatic spinning fiber membrane, and using the electrostatic spinning fiber membrane subjected to charge elimination treatment as a receiving base material;
(3) and (3) performing electrostatic spinning on the prepared mixed solution, wherein the voltage is 18kV, the filling speed is 1mL/h, the distance between a spinning nozzle and a receiving base material is 15cm, the ambient temperature is 24 +/-1 ℃, and the ambient relative humidity is 46 +/-3%, so as to obtain the nano-fiber material with the honeycomb-like structure.
The finally prepared nano fiber material with the high specific surface area honeycomb-like structure has a certain thickness, is microscopically in a three-dimensional honeycomb communicated pore channel structure, the pore channel is a conical through pore channel, the large end of the pore channel is far away from the base material, the small end of the pore channel is close to the base material, the pore diameter of the large end of the pore channel is 45 +/-5 mu m, the pore diameter of the small end of the pore channel is 10 +/-5 mu m, and single fibers are in a bead-string shape and are rough and; the thickness of the nano-fiber material with the high specific surface area honeycomb-like structure is 1.3mm, and the specific surface area is 800m2The porosity is 84 percent, the one-way moisture permeability index is 1487 percent, and the moisture permeability is 11.3kg/m2And d, the moisture absorption and quick drying effects are good.
Example 4
A preparation method of a honeycomb-like structure nanofiber material with a high specific surface area comprises the following specific steps:
(1) firstly, adding MIL-100(Fe) into a mixed solvent of acetone and dimethyl sulfoxide, wherein the mass ratio of the mixed solvent is 3:2, ultrasonically dispersing for 2h, then adding cellulose acetate into the dispersion, and continuously stirring for 14h by using a magnetic stirring device at room temperature to obtain a uniform and stable mixed solution, wherein the cellulose acetate accounts for 8% by mass of the mixed solution, the MIL-100(Fe) accounts for 24% by mass of the mixed solution, the viscosity of the mixed solution is 85mPa & S, and the conductivity is 4540 muS/cm;
(2) placing the electrostatic spinning fiber membrane in isopropanol for 1min, drying, wherein the isopropanol can be used as a conductor to eliminate static electricity, removing residual charges on the surface of the electrostatic spinning fiber membrane, and using the electrostatic spinning fiber membrane subjected to charge elimination treatment as a receiving base material;
(3) and (3) performing electrostatic spinning on the prepared mixed solution, wherein the voltage is 25kV, the filling speed is 1.5mL/h, the distance between a spinning nozzle and a receiving base material is 15cm, the ambient temperature is 24 +/-1 ℃, and the ambient relative humidity is 46 +/-3%, so as to obtain the honeycomb-like structure nanofiber material.
The finally prepared nano fiber material with the high specific surface area and the honeycomb-like structure has a certain thickness and is microscopically in a three-dimensional honeycomb communicated pore channel structureThe single fiber is a conical straight-through pore canal, the large end of the pore canal is far away from the base material, the small end of the pore canal is close to the base material, the pore diameter of the large end of the pore canal is 95 +/-5 mu m, the pore diameter of the small end of the pore canal is 25 +/-5 mu m, and the single fiber is beaded, rough and porous; the thickness of the nano-fiber material with the high specific surface area honeycomb-like structure is 2mm, and the specific surface area is 710m2Perg, porosity of 80%, unidirectional wet permeability index of 1573%, and moisture permeability of 11.5kg/m2And d, the moisture absorption and quick drying effects are good.
Example 5
A preparation method of a honeycomb-like structure nanofiber material with a high specific surface area comprises the following specific steps:
(1) firstly, adding HKUST-1 into N, N-dimethylformamide, ultrasonically dispersing for 3h, then adding polyacrylonitrile into the dispersion liquid, and continuously stirring for 12h by using a magnetic stirring device at room temperature to obtain a uniform and stable mixed liquid, wherein the mass percent of the polyacrylonitrile in the mixed liquid is 6%, the mass percent of the HKUST-1 in the mixed liquid is 24%, the viscosity of the mixed liquid is 37 mPas, and the conductivity of the mixed liquid is 163.2 muS/cm;
(2) placing the non-woven fabric in a mixed solvent of deionized water and isopropanol, wherein the mass ratio of the mixed solvent is 1:1, soaking for 2min, and then drying, wherein the mixed solvent of the deionized water and the isopropanol can be used as a conductor to eliminate static electricity, remove residual charges on the surface of the non-woven fabric, and use the non-woven fabric subjected to charge elimination treatment as a receiving base material;
(3) and (3) performing electrostatic spinning on the prepared mixed solution, wherein the voltage is 18kV, the filling speed is 0.8mL/h, the distance between a spinning nozzle and a receiving base material is 20cm, the ambient temperature is 24 +/-1 ℃, and the ambient relative humidity is 46 +/-3%, so as to obtain the honeycomb-like structure nanofiber material.
The finally prepared nano fiber material with the high specific surface area honeycomb-like structure has a certain thickness, is microscopically in a three-dimensional honeycomb communicated pore channel structure, the pore channel is a conical through pore channel, the large end of the pore channel is far away from the base material, the small end of the pore channel is close to the base material, the pore diameter of the large end of the pore channel is 25 +/-5 mu m, the pore diameter of the small end of the pore channel is 6 +/-5 mu m, and single fibers are in a bead-string shape and are rough and; the thickness of the nano-fiber material with the high specific surface area honeycomb-like structure is 0.9mm, and the specific surface area is 910m2(ii)/g, porosity of 78%, unidirectional moisture permeability index of1314 percent and the moisture permeability is 10.5kg/m2And d, the moisture absorption and quick drying effects are good.
Example 6
A preparation method of a honeycomb-like structure nanofiber material with a high specific surface area comprises the following specific steps:
(1) adding MIL-101(Cr) into N, N-dimethylacetamide, ultrasonically dispersing for 2h, then adding polyurethane into the dispersion, and continuously stirring for 12h by using a magnetic stirring device at room temperature to obtain uniform and stable mixed liquid, wherein the mass percent of the polyurethane in the mixed liquid is 3%, the mass percent of the MIL-101(Cr) in the mixed liquid is 15%, the viscosity of the mixed liquid is 148mPa & S, and the conductivity is 150.5 muS/cm;
(2) placing the electrostatic spinning fiber membrane into a mixed solvent of deionized water and isopropanol, wherein the mass ratio of the mixed solvent is 2:1, soaking for 2min, and then drying, wherein the mixed solvent of the deionized water and the isopropanol can be used as a conductor to eliminate static electricity, removing residual charges on the surface of the electrostatic spinning fiber membrane, and using the electrostatic spinning fiber membrane subjected to charge elimination treatment as a receiving base material;
(3) and (3) performing electrostatic spinning on the prepared mixed solution, wherein the voltage is 25kV, the filling speed is 0.6mL/h, the distance between a spinning nozzle and a receiving base material is 18cm, the ambient temperature is 24 +/-1 ℃, and the ambient relative humidity is 33 +/-3%, so as to obtain the honeycomb-like structure nanofiber material.
The finally prepared nano fiber material with the high specific surface area honeycomb-like structure has a certain thickness, is microscopically in a three-dimensional honeycomb communicated pore channel structure, the pore channel is a conical through pore channel, the large end of the pore channel is far away from the base material, the small end of the pore channel is close to the base material, the pore diameter of the large end of the pore channel is 95 +/-5 mu m, the pore diameter of the small end of the pore channel is 24 +/-5 mu m, and single fibers are in a bead-string shape and are rough and; the thickness of the nano-fiber material with the high specific surface area honeycomb-like structure is 1mm, and the specific surface area is as high as 850m2Per g, porosity of 85%, one-way moisture permeability index of 1358%, and moisture permeability of 14.5kg/m2And d, the moisture absorption and quick drying effects are good.
Example 7
A preparation method of a honeycomb-like structure nanofiber material with a high specific surface area comprises the following specific steps:
(1) firstly, adding CAU-1(Al) into a mixed solvent of N, N-dimethylformamide and trichloromethane, wherein the mass ratio of the N, N-dimethylformamide to the trichloromethane is 1:1, ultrasonically dispersing for 4 hours, then adding polylactic acid into the dispersion, and continuously stirring for 12 hours at room temperature by using a magnetic stirring device to obtain a uniform and stable mixed solution, wherein the polylactic acid accounts for 4% by mass of the mixed solution, the CAU-1(Al) accounts for 24% by mass of the mixed solution, the viscosity of the mixed solution is 236mPa & S, and the conductivity is 443 muS/cm;
(2) placing the non-woven fabric in a mixed solvent of deionized water and isopropanol, wherein the mass ratio of the mixed solvent is 1:2, soaking for 2min, and then drying, wherein the mixed solvent of the deionized water and the isopropanol can be used as a conductor to eliminate static electricity, remove residual charges on the surface of the non-woven fabric, and use the non-woven fabric subjected to charge elimination treatment as a receiving base material;
(3) and (3) performing electrostatic spinning on the prepared mixed solution, wherein the voltage is 40kV, the filling speed is 0.6mL/h, the distance between a spinning nozzle and a receiving base material is 20cm, the ambient temperature is 25 +/-1 ℃, and the ambient relative humidity is 37 +/-3%, so as to obtain the honeycomb-like structure nanofiber material.
The finally prepared nano fiber material with the high specific surface area honeycomb-like structure has a certain thickness, is microscopically in a three-dimensional honeycomb communicated pore channel structure, the pore channel is a conical through pore channel, the large end of the pore channel is far away from the base material, the small end of the pore channel is close to the base material, the pore diameter of the large end of the pore channel is 85 +/-5 mu m, the pore diameter of the small end of the pore channel is 20 +/-5 mu m, and single fibers are in a bead-string shape and are rough and; the thickness of the nano-fiber material with the high specific surface area honeycomb-like structure is 1.5mm, and the specific surface area is 750m2The porosity is 87 percent, the one-way moisture conductivity index is 1554 percent, and the moisture permeability is 13.6kg/m2And d, the moisture absorption and quick drying effects are good.
Example 8
A preparation method of a honeycomb-like structure nanofiber material with a high specific surface area comprises the following specific steps:
(1) firstly, adding HKUST-1 into a mixed solvent of dimethyl sulfoxide and N, N-dimethylacetamide, wherein the mass ratio of the dimethyl sulfoxide to the N, N-dimethylacetamide is 1:1, carrying out ultrasonic dispersion for 4 hours, then adding polysulfone and polyurethane with the mass ratio of 1:1 into the dispersion, and continuously stirring for 16 hours at room temperature by using a magnetic stirring device to obtain a uniform and stable mixed solution, wherein the polymer accounts for 5% by mass of the mixed solution, the HKUST-1 accounts for 30% by mass of the mixed solution, the viscosity of the mixed solution is 240mPa & S, and the conductivity is 130.2 muS/cm;
(2) placing the electrostatic spinning fiber membrane in deionized water for 1min, drying, using the deionized water as a conductor to eliminate static electricity, removing residual charges on the surface of the electrostatic spinning fiber membrane, and using the electrostatic spinning fiber membrane subjected to charge elimination treatment as a receiving base material;
(3) and (3) performing electrostatic spinning on the prepared mixed solution, wherein the voltage is 40kV, the filling speed is 2mL/h, the distance between a spinning nozzle and a receiving base material is 20cm, the ambient temperature is 25 +/-1 ℃, and the ambient relative humidity is 57 +/-3%, so as to obtain the nano-fiber material with the honeycomb-like structure.
The finally prepared nano fiber material with the high specific surface area honeycomb-like structure has a certain thickness, is microscopically in a three-dimensional honeycomb communicated pore channel structure, the pore channel is a conical through pore channel, the large end of the pore channel is far away from the base material, the small end of the pore channel is close to the base material, the pore diameter of the large end of the pore channel is 85 +/-5 mu m, the pore diameter of the small end of the pore channel is 20 +/-5 mu m, and single fibers are in a bead-string shape and are rough and; the thickness of the nano-fiber material with the high specific surface area honeycomb-like structure is 1mm, and the specific surface area is 900m2The porosity is 80 percent, the one-way moisture permeability index is 1421 percent, and the moisture permeability is 14.3kg/m2And d, the moisture absorption and quick drying effects are good.
Example 9
A preparation method of a honeycomb-like structure nanofiber material with a high specific surface area comprises the following specific steps:
(1) adding MIL-100(Fe) into a mixed solvent of chloroform and N, N-dimethylformamide, wherein the mass ratio of chloroform to N, N-dimethylformamide is 4:1, performing ultrasonic dispersion for 3 hours, then adding polycaprolactone into the dispersion liquid, and continuously stirring for 12 hours at room temperature by using a magnetic stirring device to obtain a uniform and stable mixed liquid, wherein the mass percentage of polycaprolactone in the mixed liquid is 5%, the mass percentage of MIL-100(Fe) in the mixed liquid is 25%, the viscosity of the mixed liquid is 48mPa & S, and the conductivity is 1966 muS/cm;
(2) placing the non-woven fabric in isopropanol, drying for 2min, wherein the isopropanol can be used as a conductor to eliminate static electricity, removing residual charges on the surface of the non-woven fabric, and using the non-woven fabric subjected to charge elimination as a receiving base material;
(3) and (3) performing electrostatic spinning on the prepared mixed solution, wherein the voltage is 40kV, the filling speed is 3mL/h, the distance between a spinning nozzle and a receiving base material is 20cm, the ambient temperature is 25 +/-1 ℃, and the ambient relative humidity is 57 +/-3%, so as to obtain the nano-fiber material with the honeycomb-like structure.
The finally prepared nano fiber material with the high specific surface area honeycomb-like structure has a certain thickness, is microscopically in a three-dimensional honeycomb communicated pore channel structure, the pore channel is a conical through pore channel, the large end of the pore channel is far away from the base material, the small end of the pore channel is close to the base material, the pore diameter of the large end of the pore channel is 95 +/-5 mu m, the pore diameter of the small end of the pore channel is 20 +/-5 mu m, and single fibers are in a bead-string shape and are rough and; the thickness of the nano-fiber material with the high specific surface area honeycomb-like structure is 2mm, and the specific surface area is 740m2Per g, porosity of 83%, unidirectional moisture permeability index of 1693%, and moisture permeability of 12.8kg/m2And d, the moisture absorption and quick drying effects are good.

Claims (10)

1. The preparation method of the nano-fiber material with the high specific surface area honeycomb-like structure is characterized in that polymer solution dispersed with a nano-scale metal-organic framework is subjected to electrostatic spinning, and an insulating material subjected to charge elimination treatment is used as a receiving base material to prepare the nano-fiber material with the high specific surface area honeycomb-like structure;
the polymer solution dispersed with the nanoscale metal-organic framework has the viscosity ranging from 1 to 500mPa · S and the conductivity ranging from 100 to 10000 muS/cm;
the technological parameters of electrostatic spinning comprise: the voltage is 10-40 kV, the filling speed is 0.5-4 mL/h, the distance between a spinning head and a receiving base material is 6-20 cm, and the relative humidity of the environment is 30-60%;
the insulating material is non-woven fabric or electrostatic spinning fiber membrane;
the method for eliminating charges comprises the following steps: and (3) placing the insulating material in a charge eliminating solvent for a period of time and then drying.
2. A shank as set forth in claim 1The preparation method of the nano-fiber material with the specific surface area and the honeycomb-like structure is characterized in that the metal-organic framework is MIL-101(Cr) or MIL-101(Cr) -NH2、MIL-100(Fe)、HKUST-1、CAU-1(Al)、CAU-23(Al)、UiO-66、UiO-66-NH2KAUST-8, MOF-801, MOF-804, MOF-841, DUT-67(Zr), DUT-51(Zr), DUT-53(Zr), MOF-74(Mg), and MOF-74 (Ni).
3. The method for preparing the nano-fiber material with the high specific surface area and the honeycomb-like structure according to claim 2, wherein the polymer is one or more of polyacrylonitrile, polyurethane, cellulose acetate, polyvinyl alcohol, polylactic acid, polysulfone, polyethylene oxide, polycaprolactone, polyamide 6, polyamide 66, polyimide, polyethersulfone, polyethylene terephthalate, polystyrene sulfonic acid sodium salt, polyacrylate resin, polyethylene glycol, polyvinylpyrrolidone, thermoplastic polyurethane elastomer, chitosan, cellulose derivative and ion exchange resin.
4. The method for preparing a nano-fiber material with a high specific surface area and a honeycomb-like structure according to claim 3, wherein the solvent in the polymer solution is one or more of N, N-dimethylformamide, N-dimethylacetamide, chloroform, tetrahydrofuran, N-methylpyrrolidone, chloroform, methanol, ethanol, isopropanol, deionized water, acetone, dichloromethane, formic acid, acetic acid, dimethyl sulfoxide, diethyl ether, toluene, trichloroacetic acid and trifluoroacetic acid.
5. The method for preparing the nano fiber material with the high specific surface area honeycomb-like structure according to claim 4, wherein the polymer solution dispersed with the nano metal-organic framework is prepared by the following steps: adding a metal-organic framework into a solvent, performing ultrasonic dispersion for 1-4 hours, adding a polymer, and continuously stirring for 2-24 hours at room temperature or 50-90 ℃ by using a magnetic stirring device.
6. The method for preparing the nano-fiber material with the high specific surface area and the honeycomb-like structure as claimed in claim 4, wherein the polymer solution dispersed with the nano-scale metal-organic framework comprises 3-15% by mass of the polymer and 10-30% by mass of the metal-organic framework.
7. The method for preparing a nano fiber material with a high specific surface area and a honeycomb-like structure according to claim 1, wherein the electrostatic spinning process parameters further comprise: the ambient temperature is 23-26 ℃.
8. The method for preparing the nano fiber material with the high specific surface area and the honeycomb-like structure according to claim 1, wherein the charge eliminating solvent is deionized water and/or isopropanol; the period of time is 1-3 min.
9. The high specific surface area honeycomb-like structure nanofiber material prepared by the preparation method of the high specific surface area honeycomb-like structure nanofiber material according to any one of claims 1 to 8, wherein the high specific surface area honeycomb-like structure nanofiber material has a certain thickness and is microscopically in a three-dimensional honeycomb-like communicated pore channel structure, the pore channels are tapered through pore channels, the large ends of the pore channels are far away from the base material, the small ends of the pore channels are close to the base material, the pore diameter of the large ends of the pore channels is 20-100 μm, the pore diameter of the small ends of the pore channels is 5-25 μm, and single fibers are in a bead-.
10. The high specific surface area honeycomb-like structure nanofiber material as claimed in claim 9, wherein the high specific surface area honeycomb-like structure nanofiber material has a thickness of more than 0.8mm and a specific surface area of more than 600m2The porosity is more than 75 percent, the one-way moisture permeability index is more than 1300 percent, and the moisture permeability is more than 10kg/m2/d。
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