The conductive-nano-fibers porous film material of area load nano-metal particle and its preparationMethodTechnical field
The present invention relates to conductive-nano-fibers materials, belong to technical field of nano material, negative more particularly to a kind of surfaceConductive-nano-fibers porous film material of carried nano-gold metal particles and preparation method thereof.
Background technique
Recently as industrialized continuous propulsion, the organic pollutants such as aromatic compound are increasingly tight to the pollution of water bodyWeight, it not only has high toxicity, and is difficult to degrade in nature, and therefore, the detection and processing of aromatic compound waste water are aobviousIt obtains particularly important.Currently, it is relatively simple to the material function of aromatic compound wastewater recycle and processing, only have detection or urgesChange a kind of function, there has been no the multifunctional material reports of collection detection and catalytic treatment one, therefore, development set pollutant monitoring,Catalyzing integrated multifunctional membrane material is of great significance.
Carbon nano-fiber is a kind of new carbon, have excellent physics, chemistry and electrical property, as high-specific surface area,High intensity, thermal stability, chemical stability and good electric conductivity, moreover, it is also with nano material small sizeThe advantages that effect, bigger serface effect and flexibility and formability have in fields such as electrode, energy storage, UF membrane, catalysisImportant application value.
Precious metal material especially has the nano particle of excellent catalytic performance because of its extra small size and excellent to electricitySub- performance is widely used to pollutant catalytic degradation, antibiotic and sterilizing, physics and chemical sensitisation and based on surface-enhanced RamanThe fields such as substance detection.However nano particle is easy to reunite and be difficult to the characteristics of separating and limits the correlative of nano metal materialPhysicochemical performance and its reusing, the nano particle in addition to suspend in water, which is difficult to recycle, will cause secondary pollution problemsLeading to it is still a huge challenge in water process, and supported precious metal nano-particle can have on suitable carrier materialEffect solves the problems, such as that nano metal particles are easy to reunite, difficult separation and recycling, while having the carrier material and metal of multilevel structureParticle can act synergistically, and promote its performance boost.
As Chinese invention patent application (application publication number: CN104923082A, data of publication of application: 2015-09-23) is openA kind of hydrophilic antibiotic ultrafiltration membrane and preparation method thereof specifically provides a basic filter membrane: dopamine is dissolved in three hydroxylsIn aminomethane buffer solution, it is configured to a dopamine solution；The dopamine solution is coated in the basic filter membraneSurface is to form a poly-dopamine coat in the basic filter membrane surface；An ammonia is formed in poly-dopamine coating layer surfaceBase modifies polyethylene glycol layer；Antibiotic property nanoparticle is set in the amido modified polyethylene glycol layer surface, is obtained described hydrophilicProperty antibacterial ultrafiltration membrane.Nano-metal particle in this kind of method is obtained using in-situ reducing, in the fiber being prepared, is had moreMetallic particles be embedded in fibrous inside.
For another example Chinese invention patent application (application publication number: CN107158962A, data of publication of application: 2017-09-15) is publicThe preparation method for having opened a kind of nano fiber porous film for loading high-activity nano metallic particles, uses receiving for high-specific surface areaCarrier material of the rice fiber film material as supported nano-gold metal particles, is successively soaked in Dopamine hydrochloride aqueous solution, polyethyleneImines aqueous solution is modified, then adsorbs the metallic particles of sodium citrate stabilizer package, and using plasma is handled, mostThe nano fiber porous film of load high-activity nano metallic particles is obtained afterwards.The advantages of the application is high receiving using specific surface areaCarrier material of the rice fiber film material as supported nano-gold metal particles, is prepared and more conducively controls metal grain structure and rulerVery little size, and realize material high activity and the high performance nano fiber porous film of metallic particles, the nano fiber porous film can beThe fields such as filtering, catalysis, antibacterial and surface-enhanced Raman have potential application, the disadvantage is that not considering the electric conductivity of materialEnergy.
Summary of the invention
In order to solve the above technical problems, the purpose of the present invention is to provide a kind of tables for integrating detection and catalytic treatmentThe conductive-nano-fibers porous film material and preparation method thereof of face supported nano-gold metal particles.To achieve the above object, of the inventionA kind of conductive-nano-fibers porous film material of area load nano-metal particle is disclosed, it is by conductive-nano-fibers perforated membraneBe carried on the conductive-nano-fibers porous film surface nano-metal particle form, the conductive-nano-fibers perforated membrane byCarbon fiber three-dimensional network skeleton and the graphene layer composition for being coated on the carbon fiber three-dimensional network skeleton surface, the carbon fiberThree-dimensional network skeleton is by micron carbon fiber base material and the carbon nano-fiber coating group for being carried on micron carbon fiber base material surfaceAt.
Further, the metallic atom in the nano-metal particle and the carbon in the conductive-nano-fibers perforated membrane are formerAlloying forms metallic atom-carbon/nitrogen-atoms solid solution under the high temperature conditions for son or nitrogen-atoms.
Further, the micron carbon fiber base material by woven cloth be carbonized pyrolysis and obtain, the carbon nano-fiber coating byNanofiber carbonization coated on the woven cloth surface is pyrolyzed to obtain.
Further, the woven cloth is cotton, flaxen fiber cellulose fiber woven cloth, viscose fiber woven cloth, polyamide fibreTie up woven cloth, polyester fiber woven cloth, polyurethane fiber woven cloth, aromatic polyamide fibre woven cloth, polyacrylonitrile fibre braidingCloth or one of woven cloth by least two fiber blends.
Preferably, the woven cloth is cotton fiber woven cloth.
Preferably, the woven cloth is flaxen fiber woven cloth.
Preferably, the woven cloth is polyacrylonitrile fibre woven cloth.
Preferably, the woven cloth is viscose fiber woven cloth.
Preferably, the woven cloth is Fypro woven cloth.
Preferably, the woven cloth is polyester fiber woven cloth.
Preferably, the woven cloth is polyurethane fiber woven cloth.
Preferably, the woven cloth is aromatic polyamide fibre woven cloth.
Further, the nanofiber is ethylene-vinyl alcohol copolymer (PVA-co-PE) nanofiber, is to pass throughThe method that melt blending mutually separates is prepared.
Preferably, the diameter of ethylene-vinyl alcohol copolymer (PVA-co-PE) nanofiber is 50nm~300nm.
Further, the graphene layer be deposited on nanofiber surface poly-dopamine carbonization be pyrolyzed to obtain.
Further, the nano-metal particle includes at least one of silver, gold, platinum, copper, iron, palladium elemental metals, instituteThe form of nano-metal particle is stated as one in spherical shape, triangle, cube, cuboid, polyhedron, rodlike and irregular shapeKind.
Preferably, the nano-metal particle is copper metal simple substance.
Preferably, the nano-metal particle is ferrous metal simple substance.
Preferably, the nano-metal particle is palladium metal simple substance.
Preferably, the nano-metal particle is copper-iron alloy.
In order to preferably realize technical purpose of the invention, the present invention also provides a kind of area load nano-metal particlesConductive-nano-fibers porous film material preparation method, it include by nanofiber suspension be coated on woven cloth surface,The porous basement membrane of nanofiber is obtained, obtains poly-dopamine modified lithium in the porous membrane surface deposition poly-dopamine of the nanofiberNano fiber porous film (woven cloth withThe hole of nanofiber coatingIn be deposited with poly-dopamine, the poly-dopamine is in high temperatureUnder the conditions of carbonization be graphene layer, woven cloth carbonization be micron carbon fiber, nanofiber carbonization be carbon nano-fiber, to obtainCarbon fiber three-dimensional network skeleton is coated with the structure of graphene layer), and surface is obtained after carrying out chemical modification to poly-dopamineIt is grafted the nanofiber porous composite film of chemical modified group, it is characterised in that: further include by the surface grafting chemical modificationThe nanofiber porous composite film of group is placed in the nano-metal particle suspension using stabilizer modification and carries out adsorption reaction,The nanofiber porous composite film of supported nano-gold metal particles is obtained, the nanofiber of the supported nano-gold metal particles is porousComposite membrane carries out high temperature cabonization to get the conductive-nano-fibers porous film material of area load nano-metal particle is arrived.
Further, the nanofiber porous composite film of the supported nano-gold metal particles is placed at 600~1000 DEG CInert atmosphere in carry out carbonization treatment 1~5 hour, taken out after cooling down to room temperature, obtain area load metal nano materialThe conductive-nano-fibers porous film material of material.
Preferably, the nanofiber porous composite film of the supported nano-gold metal particles is placed in temperature programming tube furnaceIn, it being carbonized under inert atmosphere protection at 800 DEG C, wherein the woven cloth high temperature cabonization pyrolysis as substrate is micron carbon fiber,The pyrolysis of nanofiber high temperature cabonization is carbon nano-fiber, and micron carbon fiber and carbon nano-fiber form tool by stacked in multi-layersThe carbon fiber three-dimensional network of standby gradient-structure, excellent, the high sensitivity feature of the conductive energy of the carbon fiber three-dimensional network skeleton,Meanwhile the poly-dopamine high temperature cabonization pyrolysis for being deposited on nanofiber surface is graphene layer, it is excellent using the graphene layerElectric conductivity makes final target product also have good electric conductivity.
Further, the surface charge and nanometer of the nanofiber porous composite film of the surface grafting chemical modification groupThe positive negativity of the surface charge of metal particle suspension is on the contrary, realize the stable bond of the two by coulomb active force.
Preferably, the specific preparation process of the nanofiber suspension is as follows:
Take ethylene-vinyl alcohol copolymer nanofiber dispersion in the mixed solvent of ethyl alcohol and deionized water that mass ratio is 1:1In, it stirs evenly to form the ethylene-vinyl alcohol copolymer nanofiber suspension that mass percent concentration is 0.5~5.0%, it is closeEnvelope saves.
Preferably, the specific preparation process of the porous basement membrane of the nanofiber is as follows:
The ethylene-vinyl alcohol copolymer nanofiber suspension of above-mentioned preparation is coated on woven cloth by the way of sprayingOne or two surface on, coating thickness be 1~100 μm, coating density be 3~20g/m2, it is dried in vacuo under room temperature, that is, makesIt is standby to obtain the porous basement membrane of nanofiber that aperture is 50~1000nm,.
Preferably, the specific preparation process of the nano fiber porous film of the poly-dopamine modified lithium is as follows:
Dopamine hydrochloride aqueous solution is prepared first, and detailed process is that configuration concentration is the trihydroxy methyl amino of 0.1mol/LMethane (Tris-HCl) buffer solution, and use sodium hydroxide adjustment buffer solution pH be 8.5, weigh Dopamine hydrochloride dissolveInto Tris-HCl buffer solution, the Dopamine hydrochloride aqueous solution that concentration is 2~20g/L is obtained；
Surface impurity is removed secondly, the porous basement membrane of the nanofiber of above-mentioned preparation is first soaked in ethyl alcohol, then is setIn the Dopamine hydrochloride aqueous solution prepared, under oxygen atmosphere, controlled at 37 DEG C, oscillating reactions at least 12h, take out,It is cleaned using deionized water, air drying is the nano fiber porous film that poly-dopamine modified lithium is prepared.
Further, as follows to the specific preparation process of poly-dopamine progress chemical modification:
The nano fiber porous film of poly-dopamine modified lithium is placed in chemical modifier aqueous solution, reaction obtains surface graftingThe nanofiber porous composite film of chemical modification group, the chemical modifier include polyamines base, more imido grpups, more carboxylicsThe compound of at least one of base, polyhydroxy, polyphenol hydroxyl, more sulfydryls group.
Preferably, the nano fiber porous film of poly-dopamine modified lithium is placed in the chemical modifier water that concentration is 2~20g/LIn solution, controlled at 45 DEG C, react 1~5h, take out after completion of the reaction, adopt and be washed with deionized, under room temperature drying beThe nanofiber porous composite film of surface grafting chemical modification group is obtained, the chemical modification group of the surface grafting is conducive toThe fixation nano-metal particle of effect.
Preferably, the chemical modifier is polyethyleneimine or iminodiacetic acid.
Preferably, the specific preparation process of the nanofiber porous composite film of the supported nano-gold metal particles is as follows: willThe nanofiber porous composite film of the surface grafting chemical modification group is placed in the nano-metal particle modified using stabilizerAdsorption reaction is carried out in suspension, the reaction time is 1~60min, it takes out, is cleaned using deionized water after completion of the reaction, room temperatureThe nanofiber porous composite film of supported nano-gold metal particles is prepared in lower vacuum drying.
Further, the stabilizer is sodium borohydride, sodium hydroxide, polyethylene pyrrole alkanone, sodium alginate or Vitamin CAt least one of acid.
Preferably, the stabilizer is sodium borohydride.
Preferably, the stabilizer is sodium hydroxide.
Preferably, the stabilizer is polyethylene pyrrole alkanone.
Preferably, the stabilizer is sodium alginate.
Preferably, the stabilizer is ascorbic acid.
The beneficial effects are mainly reflected as follows following aspects:
1. preparation method of the invention combines micron-sized woven cloth with the nanofiber coating on its surface, after carbonizationMicro-, nano-scale carbon fibre three-dimensional network skeleton with gradient-structure can not only be formed, and by three-dimensional network skeleton surfaceThe poly-dopamine high temperature cabonization pyrolysis of deposition is graphene layer, and then forms three-dimensional conductive network, improves the conduction of materialPerformance；
2. the present invention forms metallic atom-carbon/nitrogen-atoms solid solution by high temperature cabonization means on the surface of the material, realizeEffective combination of carbon nanofiber networks framework material and precious metal material.
3. high temperature cabonization technique of the invention can not only remove the impurity such as the surface stabilizer of metallic particles, and activateParticle surface, facilitates the promotion of catalytic performance；In addition, the carrier of metallic particles is three containing carbon fiber and graphene layerConductive network is tieed up, is conducive to metallic particles to the electrochemical sensing of target molecule, and then has reached the collaboration function of catalysis and detectionEnergy.
4. the present invention is using the nanofiber coating and micrometer fibers woven cloth of high-specific surface area high porosity as carrierMaterial improves the specific surface area for being supported on the metal nanoparticle of fiber surface, while improving the contact with target substanceArea effectively raises reactivity；
5. the present invention is used as carrier for nanofiber coating and braiding cloth base material are compound, by the rock-steady structure of woven cloth,Improve the strength and stability of entire material；In addition, porous film material substrate of the invention is flexible fibrous material, processabilityIt is good, it is able to satisfy the use condition of various complexity.
6. nanofiber of the invention is prepared using melt spinning method, suspension is using green solvents systems such as water or ethyl alcoholStandby, nano-metal particle also uses conventional hydrothermal reaction preparation, furthermore the surface cleaning of the metallic particles loaded is used etc.The method of gas ions surface treatment, whole preparation process green non-pollution are easy to industrialization promotion.
Detailed description of the invention
Fig. 1 is between the carbon nano-fiber coating and micron carbon fiber base material of conductive-nano-fibers porous film material of the present inventionStructural schematic diagram；
Fig. 2 is the structural schematic diagram of carbon nano-fiber；
Fig. 3 is the structural schematic diagram of micron carbon fiber；
Wherein each part numbers are as follows in FIG. 1 to FIG. 3:
Carbon nano-fiber coating 1, micron carbon fiber base material 2, nano-metal particle 3, graphene layer 4.
Specific embodiment
The invention discloses a kind of conductive-nano-fibers porous film materials of area load nano-metal particle, it is by conductionNano fiber porous film and the nano-metal particle composition for being carried on the conductive-nano-fibers porous film surface, the conduction are receivedRice fiber multihole film is by carbon fiber three-dimensional network skeleton and is coated on the graphene layer on the carbon fiber three-dimensional network skeleton surfaceComposition, the carbon fiber three-dimensional network skeleton by micron carbon fiber base material be carried on receiving for micron carbon fiber base material surfaceRice carbon fiber coating layer composition.As shown in Figure 1, the micron carbon fiber base material 2 is to be pyrolyzed by woven cloth high temperature cabonization and obtained, compilingOne or two surface coated with nano fibrous suspension of woven fabric obtains nanofiber coating after dry, and Fig. 1 of the invention is preferredNanofiber coating, the nanofiber coating high temperature cabonization are obtained in a surface coated with nano fibrous suspension of woven clothPyrolysis obtains carbon nano-fiber coating 1, in conjunction with Fig. 2 it is found that the nanofiber surface in carbon nano-fiber coating 1 successively loads and hasGraphene layer 4 and nano-metal particle 3, the graphene layer 4 are the poly-dopamine pyrocarbon by being deposited on nanofiber surfaceChange pyrolysis to obtain, similarly, in conjunction with Fig. 3 it is found that also successively load has graphene on the micrometer fibers surface of micron carbon fiber base material 2Layer 4 and nano-metal particle 3, similarly, the graphene layer 4 are the poly-dopamine high temperature cabonization by being deposited on micrometer fibers surfacePyrolysis obtains, and therefore, after high temperature cabonization is capable of forming micro-, nano-scale carbon fibre three-dimensional network skeleton with gradient-structure, andAnd the poly-dopamine high temperature cabonization that three-dimensional network skeleton surface deposits is pyrolyzed as graphene layer, and then form three-dimensional conductive netNetwork, improves the electric conductivity of material, while the metallic atom-carbon/nitrogen-atoms solid solution formed on the surface of the material, realizes carbonEffective combination of Nanofiber Network framework material and precious metal material is conducive to metallic particles and passes to the electrochemistry of target moleculeSense, and then reach the synergistic function of catalysis and detection.
In order to better explain the present invention, below in conjunction with specific preparation method the present invention is furture elucidated it is main inHold, but the contents of the present invention are not limited solely to the preparation method of following embodiment.
Embodiment 1
Present embodiment discloses a kind of conductive-nano-fibers porous film materials of area load nano-metal particle, including such asLower preparation step:
(1) prepare nanofiber suspension: by 10g, diameter is the ethylene-vinyl alcohol copolymer Nanowire of 100~200nmDimension is scattered in the in the mixed solvent that the mass ratio of 1000g ethyl alcohol and deionized water is 1:1, stirs evenly to form nanofiber and contain admittedlyThe ethylene-vinyl alcohol copolymer nanofiber suspension that (mass percent concentration) is 1wt% is measured, is sealed.
(2) prepare the porous basement membrane of nanofiber: the ethylene-vinyl alcohol copolymer for step (1) being obtained by the way of sprayingNanofiber suspension is coated on a surface of cotton fiber woven cloth, and coating thickness is 20 μm, and coating density is 10g/m2,It is dried in vacuo under room temperature, it is 200~600nm by cotton fiber woven cloth and the nanofiber for being attached to its surface that aperture, which is prepared,The coat composed porous basement membrane of nanofiber.
(3) configure Dopamine hydrochloride aqueous solution: configuration concentration is the trishydroxymethylaminomethane (Tris- of 0.1mol/LHCl) buffer solution, and use the pH of sodium hydroxide adjustment buffer solution for 8.5, it weighs Dopamine hydrochloride and is dissolved into Tris-HClIn buffer solution, the Dopamine hydrochloride aqueous solution that concentration is 2g/L is obtained.
(4) prepare the nano fiber porous film of poly-dopamine modified lithium: the porous basement membrane of nanofiber prepared by step (2) soaksIt steeps and removes surface impurity in ethyl alcohol, then put it into the configured Dopamine hydrochloride aqueous solution of step (3), in oxygen atmosphereUnder, it controlled at 37 DEG C, oscillating reactions 12h, takes out and is cleaned with deionized water, poly-dopamine is prepared in air dryingModified nano fiber porous film.
(5) it prepares the nanofiber porous composite film of surface grafting amino group: poly-dopamine prepared by step (4) is changedProperty nano fiber porous film be placed in concentration be 10g/L aq. polyethyleneimine in, controlled at 45 DEG C, react 3h,It takes out and is cleaned with deionized water after completion of the reaction, the nanofiber that surface grafting amino group can be obtained in air drying is porousComposite membrane.
(6) the nanofiber porous composite film of loading nano silvery particle is prepared: surface grafting amino prepared by step (5)The nanofiber porous composite film of group is placed in the suspension of the nano-Ag particles of sodium borohydride modification and adsorbs 60min, reactsAfter take out and cleaned with deionized water, under room temperature vacuum drying can be obtained loading nano silvery particle nanofiber it is porousComposite membrane.
(7) the conductive-nano-fibers porous film material of area load nano-Ag particles is prepared: load prepared by step (6)The nanofiber porous composite film of nano-Ag particles is placed in temperature programming tube furnace, is carbonized 2 at 800 DEG C under inert atmosphere protectionHour, it is taken out after cooling down to room temperature, obtains the conductive-nano-fibers porous film material of area load nano-Ag particles.
Embodiment 2
Present embodiment discloses a kind of conductive-nano-fibers porous film materials of area load nano-metal particle, including such asLower preparation step:
(1) prepare nanofiber suspension: by 10g, diameter is the ethylene-vinyl alcohol nanofiber dispersion of 100~200nmThe in the mixed solvent for being 1:1 in 1000g ethyl alcohol and the mass ratio of deionized water, stirs evenly, and forms nanofiber solid content (matterMeasure percent concentration) be 1wt% ethylene-vinyl alcohol copolymer nanofiber suspension, be sealed.
(2) prepare the porous basement membrane of nanofiber: the ethylene-vinyl alcohol copolymer for step (1) being obtained by the way of sprayingNanofiber suspension is coated on two surfaces of polyacrylonitrile woven cloth, and coating thickness is 10 μm, and coating density is 5g/m2, it is dried in vacuo under room temperature, it is 50~300nm by polyacrylonitrile woven cloth and the nanometer for being attached to its surface that aperture, which is prepared,The porous basement membrane of nanofiber of fiber coat composition.
(3) configure Dopamine hydrochloride aqueous solution: configuration concentration is the trishydroxymethylaminomethane (Tris- of 0.1mol/LHCl) buffer solution, and use the pH of sodium hydroxide adjustment buffer solution for 8.5, it weighs Dopamine hydrochloride and is dissolved into Tris-HClIn buffer solution, the aqueous solution of the Dopamine hydrochloride of 2g/L is obtained.
(4) prepare the nano fiber porous film of poly-dopamine modified lithium: the porous basement membrane of nanofiber prepared by step (2) soaksIt steeps and removes surface impurity in ethyl alcohol, then put it into the configured Dopamine hydrochloride aqueous solution of step (3), in oxygen atmosphereUnder, controlled at 37 DEG C, oscillating reactions 12h, takes out and cleaned with deionized water, air drying can be obtained poly-dopamine and changeThe nano fiber porous film of property.
(5) it prepares the nanofiber porous composite film of surface grafting amino group: poly-dopamine prepared by step (4) is changedProperty nano fiber porous film be placed in concentration be 5g/L aq. polyethyleneimine in, controlled at 45 DEG C, react 2h, insteadIt takes out after answering and is cleaned with deionized water, the ethylene-vinyl alcohol nanofiber of surface grafting amino can be obtained in air dryingPorous composite film.
(6) the nanofiber porous composite film of area load nanogold particle is prepared: surface grafting prepared by step (5)The nanofiber porous composite film of amino group is placed in the suspension of the nanogold particle of polyethylene pyrrole alkanone modification and adsorbs60min, take out simultaneously cleaned with deionized water, under room temperature vacuum drying can be obtained supported nano-gold particle nanofiber it is porousComposite membrane.
(7) the conductive-nano-fibers porous film material of area load nanogold particle is prepared: load prepared by step (6)The nanofiber porous composite film of nanogold particle is placed in temperature programming tube furnace, and carbonization 4 is small under 600 DEG C of inert atmosphere protectionsWhen, it takes out after cooling down to room temperature, obtains the highly conductive nano fiber porous film material of area load nanogold particle.
Embodiment 3
(1) prepare nanofiber suspension: by 10g, diameter is the ethylene-vinyl alcohol nanofiber dispersion of 150~300nmThe in the mixed solvent for being 1:1 in 1000g ethyl alcohol and the mass ratio of deionized water, stirring form nanofiber solid content (quality hundredPoint specific concentration) be 1wt% ethylene-vinyl alcohol copolymer nanofiber suspension, be sealed.
(2) prepare the porous basement membrane of nanofiber: the ethylene-vinyl alcohol copolymer for step (1) being obtained by the way of sprayingNanofiber suspension is coated on a surface of polyacrylonitrile woven cloth, and coating thickness is 30 μm, and coating density is 20g/m2,It is dried in vacuo under room temperature, it is 500~800nm by polyacrylonitrile woven cloth and the Nanowire for being attached to its surface that aperture, which is prepared,Tie up the porous basement membrane of coat composed nanofiber.
(3) configure Dopamine hydrochloride aqueous solution: configuration concentration is the trishydroxymethylaminomethane (Tris- of 0.1mol/LHCl) buffer solution, and use the pH of sodium hydroxide adjustment buffer solution for 8.5, it weighs Dopamine hydrochloride and is dissolved into Tris-HClIn buffer solution, the aqueous solution of the Dopamine hydrochloride of 5g/L is obtained.
(4) prepare the nano fiber porous film of poly-dopamine modified lithium: the porous basement membrane of nanofiber prepared by step (2) soaksIt steeps and removes surface impurity in ethyl alcohol, then put it into the configured Dopamine hydrochloride aqueous solution of step (3), in oxygen atmosphereUnder, controlled at 37 DEG C, oscillating reactions 12h, takes out and cleaned with deionized water, air drying can be obtained poly-dopamine and changeThe nano fiber porous film of property.
(5) it prepares the nanofiber porous composite film of surface grafting carboxylic group: poly-dopamine prepared by step (4) is changedProperty nano fiber porous film be placed in concentration be 10g/L iminodiacetic acid (salt) aqueous acid in, controlled at 45 DEG C, reaction2h takes out after completion of the reaction and is cleaned with deionized water, and the nanofiber of surface grafting carboxylic group can be obtained in air dryingPorous composite film.
(6) the nanofiber porous composite film of preparation load nano copper particle: by the Nanowire of surface grafting carboxylic groupDimension porous composite film, which is placed in the suspension of polyvinyl pyrrolidon modified nano copper particle, adsorbs 60min, after completion of the reactionTake out simultaneously cleaned with deionized water, under room temperature vacuum drying can be obtained load nano copper particle nanofiber it is porous compoundFilm.
(7) it prepares the conductive-nano-fibers porous film material of area load nano copper particle: nano copper particle will be loadedNanofiber porous composite film is placed in temperature programming tube furnace, is carbonized 2 hours under inert atmosphere protection at 800 DEG C, is cooled down coldBut to taking out after room temperature, the conductive-nano-fibers porous film material of area load nano copper particle is obtained.
Embodiment 4
(1) prepare nanofiber suspension: by 10g, diameter is the ethylene-vinyl alcohol nanofiber dispersion of 200~300nmThe in the mixed solvent for being 1:1 in 1000g ethyl alcohol and the mass ratio of deionized water, stirs evenly, and forms nanofiber solid content (matterMeasure percent concentration) be 1wt% ethylene-vinyl alcohol copolymer nanofiber suspension, be sealed.
(2) prepare the porous basement membrane of nanofiber: the ethylene-vinyl alcohol copolymer for step (1) being obtained by the way of sprayingNanofiber suspension is coated on the surface of polyacrylonitrile woven cloth, and coating thickness is 10 μm, and coating density is 8g/m2, room temperatureLower vacuum drying, it is 700~1000nm by polyacrylonitrile woven cloth and the nanofiber for being attached to its surface that aperture, which is prepared,The coat composed porous basement membrane of nanofiber.
(3) configure Dopamine hydrochloride aqueous solution: configuration concentration is the trishydroxymethylaminomethane (Tris- of 0.1mol/LHCl) buffer solution, and use the pH of sodium hydroxide adjustment buffer solution for 8.5, it weighs Dopamine hydrochloride and is dissolved into Tris-HClIn buffer solution, the aqueous solution of the Dopamine hydrochloride of 2g/L is obtained.
(4) prepare the nano fiber porous film of poly-dopamine modified lithium: the porous basement membrane of nanofiber prepared by step (2) soaksIt steeps and removes surface impurity in ethyl alcohol, then put it into the configured Dopamine hydrochloride aqueous solution of step (3), in oxygen atmosphereUnder, it controlled at 37 DEG C, oscillating reactions 12h, takes out and is cleaned with deionized water, poly-dopamine is prepared in air dryingModified nano fiber porous film.
(5) it prepares the nanofiber porous composite film of surface grafting amino group: poly-dopamine prepared by step (4) is changedProperty nano fiber porous film be placed in concentration be 5g/L polyethyleneimine aqueous solution in, controlled at 45 DEG C, react 2h,It takes out and is cleaned with deionized water after completion of the reaction, the nanofiber that surface grafting amino group can be obtained in air drying is porousComposite membrane.
(6) the nanofiber porous composite film of preparation load nano-platinum particle: surface grafting amino prepared by step (5)The nanofiber porous composite film of group is placed in the suspension of the Platinum Nanoparticles metal particles of sodium borohydride modification and adsorbs 60min, insteadAfter answering take out and cleaned with deionized water, under room temperature vacuum drying can be obtained load nano-platinum particle nanofiber it is moreHole composite membrane.
(7) the conductive-nano-fibers porous film material of area load nano-platinum particle is prepared: load prepared by step (6)The nanofiber porous composite film of nano-platinum particle is placed in temperature programming tube furnace, is carbonized 2 at 800 DEG C under inert atmosphere protectionHour, it is taken out after cooling down to room temperature, obtains the conductive-nano-fibers porous film material of area load nano-platinum particle.
Embodiment 5
(1) prepare nanofiber suspension: by 10g, ethylene-vinyl alcohol nanofiber dispersion that diameter is 50~200nm inThe in the mixed solvent that 1000g ethyl alcohol and the mass ratio of deionized water are 1:1, stirs evenly, and forms nanofiber solid content (qualityPercent concentration) be 1wt% ethylene-vinyl alcohol copolymer nanofiber suspension, be sealed.
(2) prepare the porous basement membrane of nanofiber: the ethylene-vinyl alcohol copolymer for step (1) being obtained by the way of sprayingNanofiber suspension is coated on the surface of cotton fiber woven cloth, and coating thickness is 20 μm, and coating density is 10g/m2, room temperatureIt is porous that the nanofiber being made of cotton fiber woven cloth with the nanofiber coating for being attached to its surface is prepared in vacuum dryingFilm.
(3) configure Dopamine hydrochloride aqueous solution: configuration concentration is the trishydroxymethylaminomethane (Tris- of 0.1mol/LHCl) buffer solution, and use the pH of sodium hydroxide adjustment buffer solution for 8.5, it weighs Dopamine hydrochloride and is dissolved into Tris-HClIn buffer solution, the aqueous solution of the Dopamine hydrochloride of 2g/L is obtained.
(4) prepare the nano fiber porous film of poly-dopamine modified lithium: the porous basement membrane of nanofiber prepared by step (2) soaksIt steeps and removes surface impurity in ethyl alcohol, then put it into the aqueous solution of step (3) configured Dopamine hydrochloride, in oxygen atmosphereUnder, controlled at 37 DEG C, oscillating reactions 12h, takes out and cleaned with deionized water, air drying can be obtained poly-dopamine and changeThe nano fiber porous film of property.
(5) it prepares the nanofiber porous composite film of surface grafting amino group: poly-dopamine prepared by step (4) is changedProperty nano fiber porous film material be placed in concentration be 10g/L aq. polyethyleneimine in, controlled at 45 DEG C, reaction3h takes out after completion of the reaction and is cleaned with deionized water, and the nanofiber of surface grafting amino group can be obtained in air dryingPorous composite film.
(6) the nanofiber porous composite film of supported nano-gold Argent grain is prepared: by the nanometer of surface grafting amino groupFiber multihole composite membrane is placed in the nano silver of sodium borohydride modification and the mixing suspension of nanogold particle and adsorbs 60min, insteadIt takes out after answering and is cleaned with deionized water, the nanometer of supported nano-gold silver hybrid particles can be obtained in vacuum drying under room temperatureFiber multihole composite membrane.
(7) the conductive-nano-fibers porous film material of area load nanometer gold silver particle is prepared: by the negative of step (6) preparationThe nanofiber porous composite film of carried nano-gold silver hybrid particles is placed in temperature programming tube furnace, and inert atmosphere is protected at 700 DEG CShield is lower to be carbonized 3 hours, takes out after cooling down to room temperature, obtains the conductive-nano-fibers of area load nanometer gold silver hybrid particlesPorous film material.
Embodiment 6
(1) prepare nanofiber suspension: by 10g, diameter be 100~200nm ethylene-vinyl alcohol nanofiber dispersion inThe in the mixed solvent that 1000g ethyl alcohol and the mass ratio of deionized water are 1:1, stirring form nanofiber solid content (quality percentageSpecific concentration) be 1wt% ethylene-vinyl alcohol copolymer nanofiber suspension, be sealed.
(2) prepare the porous basement membrane of nanofiber: the ethylene-vinyl alcohol copolymer for step (1) being obtained by the way of sprayingNanofiber suspension is coated on a surface of polyacrylonitrile woven cloth, and coating thickness is 30 μm, and coating density is 15g/m2,It is dried in vacuo under room temperature, it is 400~500nm by polyacrylonitrile woven cloth and the Nanowire for being attached to its surface that aperture, which is prepared,Tie up the porous basement membrane of coat composed nanofiber.
(3) configure Dopamine hydrochloride aqueous solution: configuration concentration is the trishydroxymethylaminomethane (Tris- of 0.1mol/LHCl) buffer solution, and use the pH of sodium hydroxide adjustment buffer solution for 8.5, it weighs Dopamine hydrochloride and is dissolved into Tris-HClIn buffer solution, the aqueous solution of the Dopamine hydrochloride of 2g/L is obtained.
(4) prepare the nano fiber porous film of poly-dopamine modified lithium: the porous basement membrane of nanofiber prepared by step (2) soaksIt steeps and removes surface impurity in ethyl alcohol, then put it into the aqueous solution for having configured Dopamine hydrochloride, under oxygen atmosphere, control temperatureIt is 37 DEG C, oscillating reactions 12h, takes out and cleaned with deionized water, the Nanowire of poly-dopamine modified lithium can be obtained in air dryingTie up perforated membrane.
(5) it prepares the nanofiber porous composite film of surface grafting amino group: poly-dopamine prepared by step (4) is changedProperty nano fiber porous film be placed in concentration be 10g/L aq. polyethyleneimine in, controlled at 45 DEG C, react 2h,It takes out and is cleaned with deionized water after completion of the reaction, the nanofiber that surface grafting amino can be obtained in air drying is porous compoundFilm.
(6) the nanofiber porous composite film of supported nano-gold copper particle is prepared: surface grafting ammonia prepared by step (5)The nanofiber porous composite film of base group is placed in the mixing suspension of polyvinyl pyrrolidon modified nanogold copper particle60min is adsorbed, take out after completion of the reaction and is cleaned with deionized water, supported nano-gold copper can be obtained in vacuum drying under room temperatureThe nanofiber porous composite film of grain.
(7) the conductive-nano-fibers porous film material of area load nano-metal particle is prepared: by supported nano-gold copperThe nanofiber porous composite film of grain is placed in temperature programming tube furnace, is carbonized 5 hours under 600 DEG C of inert atmosphere protections, is cooled downIt is taken out after being cooled to room temperature, obtains the conductive-nano-fibers porous film material of area load nanogold copper particle.
Above embodiments are only best citing, rather than a limitation of the embodiments of the present invention.Except above-described embodimentOutside, there are also other embodiments by the present invention.All technical solutions formed using equivalent substitution or equivalent transformation, all fall within the present inventionIt is required that protection scope.