CN109097978B - Conductive nanofiber porous membrane material with surface loaded with nano metal particles and preparation method thereof - Google Patents
Conductive nanofiber porous membrane material with surface loaded with nano metal particles and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a conductive nanofiber porous membrane material with surface loaded with nano metal particles and a preparation method thereof, belonging to the technical field of nano materials. The porous membrane material consists of a conductive nanofiber porous membrane and nano metal particles loaded on the surface of the conductive nanofiber porous membrane, the conductive nanofiber porous membrane consists of a carbon fiber three-dimensional network framework and a graphene layer coated on the surface of carbon fibers, and the carbon fiber three-dimensional network framework consists of a micron carbon fiber substrate and a carbon nanofiber coating loaded on the surface of the micron carbon fiber substrate. According to the preparation method, the micron-sized weaved cloth layer and the nanoscale nanofiber layer are combined in a layer-by-layer stacking manner, and the micro-nano carbon fiber three-dimensional network framework and the nanoscale carbon fiber three-dimensional network framework with the gradient structure are formed after carbonization, so that the carbon fiber three-dimensional network framework has the characteristics of excellent conductivity and high sensitivity, and the polydopamine deposited on the surface of the nanofiber is carbonized at high temperature to form the graphene layer which is coated on the surface of the carbon fiber three-dimensional network framework, so that the excellent conductivity of the graphene layer can be better exerted, and the use field of the nanofiber membrane material is widened.
Description
Technical Field
The invention relates to a conductive nanofiber material, belongs to the technical field of nanomaterials, and particularly relates to a conductive nanofiber porous membrane material with surface loaded with nano metal particles and a preparation method thereof.
Background
With the continuous advance of industrialization in recent years, organic pollutants such as aromatic compounds and the like have increasingly serious pollution to water, have high toxicity and are difficult to degrade in nature, so that the detection and treatment of aromatic compound wastewater are particularly important. At present, the material for detecting and treating the aromatic compound wastewater has single function, only has one function of detection or catalysis, and no multifunctional material integrating detection and catalysis treatment is reported, so that the development of the multifunctional membrane material integrating pollutant detection and catalysis is of great significance.
The carbon nanofiber is a novel carbon material, has excellent physical, chemical and electrical properties, such as high specific surface area, high strength, thermal stability, chemical stability and good electrical conductivity, has the advantages of small-size effect, large specific surface area effect and the like of a nano material, is flexible and easy to form, and has important application value in the fields of electrodes, energy storage, membrane separation, catalysis and the like.
Noble metal materials, particularly nanoparticles with excellent catalytic performance, have been widely used in the fields of catalytic degradation of pollutants, antibacterial sterilization, physical and chemical sensing, surface enhanced raman-based substance detection, and the like, due to their ultra-small size and excellent electron donating properties. However, the characteristics of easy agglomeration and difficult separation of nano particles limit the relevant physical and chemical properties and the reusability of the nano metal material, in addition, the problems of secondary pollution and the like caused by difficult recovery of the nano particles suspended in water still cause a huge challenge in water treatment, the problems of easy agglomeration, difficult separation and recovery of the nano metal particles can be effectively solved by loading the noble metal nano particles on a proper carrier material, and meanwhile, the carrier material with a multilevel structure and the metal particles can cooperate to promote the performance of the carrier material.
For example, the Chinese patent application (application publication No. CN104923082A, application publication date: 2015-09-23) discloses a hydrophilic antibacterial ultrafiltration membrane and a preparation method thereof, and specifically provides a basic filtration membrane: dissolving dopamine in a tris buffer solution to prepare a dopamine solution; coating the dopamine solution on the surface of the basic filter membrane to form a polydopamine coating layer on the surface of the basic filter membrane; forming an amino modified polyethylene glycol layer on the surface of the polydopamine coating layer; and arranging antibacterial nano particles on the surface of the amino modified polyethylene glycol layer to obtain the hydrophilic antibacterial ultrafiltration membrane. The nano metal particles in the method are obtained by in-situ reduction, and more metal particles are embedded in the prepared fiber.
For another example, the chinese invention patent application (application publication No. CN107158962A, application publication date: 2017-09-15) discloses a preparation method of a nanofiber porous membrane loaded with high-activity nano metal particles, which comprises the steps of using a nanofiber membrane material with a high specific surface area as a carrier material loaded with nano metal particles, sequentially soaking the carrier material in dopamine hydrochloride aqueous solution and polyethyleneimine aqueous solution for modification, adsorbing metal particles wrapped with a sodium citrate stabilizer, and treating with plasma to obtain the nanofiber porous membrane loaded with high-activity nano metal particles. The preparation method has the advantages that the nano-fiber membrane material with high specific surface area is used as the carrier material for loading the nano-metal particles, the nano-fiber porous membrane which is more beneficial to controlling the structure and the size of the metal particles and realizes high activity of the material and high performance of the metal particles is prepared, the nano-fiber porous membrane can have potential application in the fields of filtration, catalysis, antibiosis, surface enhanced Raman and the like, and the defect that the conductivity of the material is not considered.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a conductive nanofiber porous membrane material with a surface loaded with nano metal particles and integrating detection and catalytic treatment and a preparation method thereof. In order to achieve the purpose, the invention discloses a conductive nanofiber porous membrane material with surface loaded with nano metal particles, which consists of a conductive nanofiber porous membrane and nano metal particles loaded on the surface of the conductive nanofiber porous membrane, wherein the conductive nanofiber porous membrane consists of a carbon fiber three-dimensional network framework and a graphene layer coated on the surface of the carbon fiber three-dimensional network framework, and the carbon fiber three-dimensional network framework consists of a micron carbon fiber substrate and a nano carbon fiber coating loaded on the surface of the micron carbon fiber substrate.
Further, the metal atoms in the nano metal particles and the carbon atoms or nitrogen atoms in the conductive nanofiber porous membrane are alloyed under high temperature conditions to form a metal atom-carbon/nitrogen atom solid solution.
Furthermore, the micron carbon fiber base material is obtained by carbonizing and pyrolyzing woven cloth, and the nano carbon fiber coating is obtained by carbonizing and pyrolyzing nano fibers coated on the surface of the woven cloth.
Further, the woven fabric is one of cotton, a fibrilia fiber woven fabric, a viscose fiber woven fabric, a polyamide fiber woven fabric, a polyester fiber woven fabric, a polyurethane fiber woven fabric, a polyaramide fiber woven fabric, a polyacrylonitrile fiber woven fabric, or a woven fabric blended by at least two kinds of fibers.
Preferably, the woven cloth is a cotton fiber woven cloth.
Preferably, the woven cloth is a fibrilia woven cloth.
Preferably, the woven cloth is polyacrylonitrile fiber woven cloth.
Preferably, the woven cloth is viscose fiber woven cloth.
Preferably, the woven cloth is a polyamide fiber woven cloth.
Preferably, the woven cloth is a polyester fiber woven cloth.
Preferably, the woven cloth is a polyurethane fiber woven cloth.
Preferably, the woven cloth is polyaramide fiber woven cloth.
Further, the nanofiber is an ethylene vinyl alcohol copolymer (PVA-co-PE) nanofiber which is prepared by a method of melt blending and phase separation.
Preferably, the diameter of the ethylene vinyl alcohol copolymer (PVA-co-PE) nano fiber is 50nm to 300 nm.
Further, the graphene layer is obtained by carbonizing and pyrolyzing polydopamine deposited on the surface of the nanofiber.
Further, the nano metal particles comprise at least one of silver, gold, platinum, copper, iron and palladium elementary metals, and the form of the nano metal particles is one of spherical, triangular, cubic, cuboid, polyhedral, rod-shaped and irregular.
Preferably, the nano metal particles are elementary copper metal.
Preferably, the nano metal particles are iron metal simple substances.
Preferably, the nano metal particles are palladium metal simple substances.
Preferably, the nano metal particles are copper-iron alloy.
In order to better realize the technical purpose of the invention, the invention also provides a preparation method of the conductive nanofiber porous membrane material with the surface loaded with the nano metal particles, which comprises the steps of coating the nanofiber suspension on the surface of woven cloth to obtain a nanofiber porous basement membrane, and depositing polydopamine on the surface of the nanofiber porous basement membrane to obtain the polydopamine modified nanofiber porous membrane (woven cloth and woven clothPores of nanofiber coatingIn the composite material, polydopamine is deposited, and the polydopamine is carbonized into graphene layers under the high-temperature condition, and woven cloth is carbonized into micron carbon fibersThe nano-fiber is carbonized into the nano-carbon fiber, so that a structure that a graphene layer is coated outside a carbon fiber three-dimensional network framework is obtained), and the nano-fiber porous composite membrane with the surface grafted with the chemical modification group is obtained after the poly-dopamine is chemically modified, and the nano-fiber porous composite membrane is characterized in that: the preparation method further comprises the steps of placing the nanofiber porous composite membrane with the surface grafted with the chemical modification group in a nano metal particle suspension modified by a stabilizer for adsorption reaction to obtain a nanofiber porous composite membrane loaded with the nano metal particles, and carrying out high-temperature carbonization on the nanofiber porous composite membrane loaded with the nano metal particles to obtain the conductive nanofiber porous membrane material with the surface loaded with the nano metal particles.
And further, placing the nanofiber porous composite membrane loaded with the nano metal particles in an inert atmosphere at 600-1000 ℃ for carbonization for 1-5 hours, cooling to room temperature, and taking out to obtain the conductive nanofiber porous membrane material loaded with the metal nano material on the surface.
Preferably, the nanofiber porous composite membrane loaded with the nano metal particles is placed in a temperature programming tube furnace and carbonized under the protection of inert atmosphere at 800 ℃, wherein woven cloth serving as a base material is carbonized and pyrolyzed at high temperature to form micron carbon fibers, the nanofiber is carbonized and pyrolyzed at high temperature to form nano carbon fibers, and the micron carbon fibers and the nano carbon fibers are stacked layer by layer to form a carbon fiber three-dimensional network with a gradient structure.
Further, the surface charge of the nanofiber porous composite membrane with the surface grafted with the chemical modification group is opposite to the positive and negative of the surface charge of the nano metal particle suspension, and the stable combination of the surface charge and the surface charge of the nano metal particle suspension is realized through coulomb force.
Preferably, the specific preparation process of the nanofiber suspension is as follows:
dispersing the ethylene vinyl alcohol copolymer nanofiber in a mixed solvent of ethanol and deionized water in a mass ratio of 1:1, uniformly stirring to form an ethylene vinyl alcohol copolymer nanofiber suspension with the mass percentage concentration of 0.5-5.0%, and sealing for storage.
Preferably, the specific preparation process of the nanofiber porous base membrane is as follows:
coating the prepared ethylene vinyl alcohol copolymer nanofiber suspension on one or two surfaces of woven cloth in a spraying mode, wherein the coating thickness is 1-100 mu m, and the coating density is 3-20 g/m2And vacuum drying at normal temperature to obtain the nanofiber porous base membrane with the pore diameter of 50-1000 nm.
Preferably, the specific preparation process of the polydopamine modified nanofiber porous membrane is as follows:
preparing a dopamine hydrochloride aqueous solution, specifically, preparing a Tris (hydroxymethyl) aminomethane (Tris-HCl) buffer solution with the concentration of 0.1mol/L, adjusting the pH of the buffer solution to 8.5 by adopting sodium hydroxide, weighing dopamine hydrochloride, and dissolving the dopamine hydrochloride into the Tris-HCl buffer solution to obtain the dopamine hydrochloride aqueous solution with the concentration of 2-20 g/L;
and secondly, soaking the prepared nanofiber porous base membrane in ethanol to remove surface impurities, then placing the nanofiber porous base membrane in a prepared dopamine hydrochloride aqueous solution, controlling the temperature to be 37 ℃ in an oxygen environment, carrying out oscillation reaction for at least 12 hours, taking out, cleaning with deionized water, and drying at normal temperature to obtain the poly-dopamine modified nanofiber porous membrane.
Further, the specific preparation process for chemically modifying polydopamine is as follows:
the method comprises the following steps of placing a polydopamine modified nanofiber porous membrane in a chemical modifier aqueous solution, and reacting to obtain a nanofiber porous composite membrane with a surface grafted with a chemical modification group, wherein the chemical modifier comprises a compound containing at least one group of polyamine, polyimine, polycarboxyl, polyhydroxy, polyphenol hydroxyl and multi-sulfhydryl.
Preferably, the polydopamine modified nanofiber porous membrane is placed in a chemical modifier aqueous solution with the concentration of 2-20 g/L, the temperature is controlled to be 45 ℃, the reaction is carried out for 1-5 hours, the reaction product is taken out after the reaction is finished, deionized water is adopted for washing, and the drying at normal temperature is carried out, so that the nanofiber porous composite membrane with the surface grafted with the chemical modification groups is obtained, and the surface grafted chemical modification groups are favorable for effectively fixing the nano metal particles.
Preferably, the chemical modifier is polyethyleneimine or iminodiacetic acid.
Preferably, the specific preparation process of the nanofiber porous composite membrane loaded with the nano metal particles is as follows: and placing the nanofiber porous composite membrane with the surface grafted with the chemical modification group into a nano metal particle suspension modified by a stabilizer for adsorption reaction for 1-60 min, taking out after the reaction is finished, cleaning by using deionized water, and drying in vacuum at normal temperature to obtain the nanofiber porous composite membrane loaded with the nano metal particles.
Further, the stabilizer is at least one of sodium borohydride, sodium hydroxide, polyvinylpyrrolidone, sodium alginate or ascorbic acid.
Preferably, the stabilizer is sodium borohydride.
Preferably, the stabilizer is sodium hydroxide.
Preferably, the stabilizer is polyvinylpyrrolidone.
Preferably, the stabilizing agent is sodium alginate.
Preferably, the stabilizer is ascorbic acid.
The beneficial effects of the invention are mainly embodied in the following aspects:
1. according to the preparation method, the micron-sized woven cloth is combined with the nanofiber coating on the surface of the micron-sized woven cloth, so that a micro-nano carbon fiber three-dimensional network framework with a gradient structure can be formed after carbonization, and polydopamine deposited on the surface of the three-dimensional network framework is carbonized and pyrolyzed into a graphene layer at high temperature, so that a three-dimensional conductive network is formed, and the conductivity of the material is improved;
2. according to the invention, a metal atom-carbon/nitrogen atom solid solution is formed on the surface of the material by a high-temperature carbonization method, so that the effective combination of the carbon nanofiber network framework material and the noble metal material is realized.
3. The high-temperature carbonization process can remove impurities such as surface stabilizer of metal particles, activate the surfaces of the particles and contribute to the improvement of catalytic performance; in addition, the carrier of the metal particles is a three-dimensional conductive network containing carbon fibers and a graphene layer, so that the electrochemical sensing of the metal particles on target molecules is facilitated, and the synergistic functions of catalysis and detection are further achieved.
4. According to the invention, the nano-fiber coating with high specific surface area and high porosity and the micro-fiber woven cloth are used as carrier materials, so that the specific surface area of the metal nano-particles loaded on the fiber surface is increased, the contact area with a target substance is increased, and the reaction activity is effectively improved;
5. according to the invention, the nanofiber coating and the woven cloth substrate are compounded to be used as a carrier, and the strength and stability of the whole material are improved through the stable structure of the woven cloth; in addition, the porous membrane material base material is a flexible fiber material, has good processability and can meet various complicated use conditions.
6. The nano-fiber is prepared by a melt spinning method, the suspension is prepared by green solvents such as water or ethanol, the nano-metal particles are also prepared by conventional hydrothermal reaction, and the surface of the loaded metal particles is cleaned by a plasma surface treatment method, so that the whole preparation process is green and pollution-free, and the industrial popularization is easy.
Drawings
FIG. 1 is a schematic structural diagram of a carbon nanofiber coating and a carbon nanofiber substrate of the conductive nanofiber porous membrane material of the present invention;
FIG. 2 is a schematic structural diagram of a filamentous nanocarbon;
FIG. 3 is a schematic structural view of a carbon microfiber;
wherein the parts in figures 1 to 3 are numbered as follows:
the carbon nanofiber coating comprises a carbon nanofiber coating 1, a micron carbon fiber substrate 2, nano metal particles 3 and a graphene layer 4.
Detailed Description
The invention discloses a conductive nanofiber porous membrane material with surface loaded with nano metal particles, which consists of a conductive nanofiber porous membrane and nano metal particles loaded on the surface of the conductive nanofiber porous membrane, wherein the conductive nanofiber porous membrane consists of a carbon fiber three-dimensional network framework and a graphene layer coated on the surface of the carbon fiber three-dimensional network framework, and the carbon fiber three-dimensional network framework consists of a micron carbon fiber substrate and a nano carbon fiber coating loaded on the surface of the micron carbon fiber substrate. As shown in fig. 1, the microfiber substrate 2 is obtained by high temperature carbonization and pyrolysis of woven fabric, one or both surfaces of the woven fabric are coated with nanofiber suspension, and dried to obtain a nanofiber coating, in fig. 1 of the present invention, it is preferable that one surface of the woven fabric is coated with nanofiber suspension to obtain a nanofiber coating, the nanofiber coating is subjected to high temperature carbonization and pyrolysis to obtain the nanofiber coating 1, as can be seen from fig. 2, a graphene layer 4 and nano metal particles 3 are sequentially loaded on the nanofiber surface of the nanofiber coating 1, the graphene layer 4 is obtained by high temperature carbonization and pyrolysis of polydopamine deposited on the nanofiber surface, and similarly, as can be seen from fig. 3, a graphene layer 4 and nano metal particles 3 are sequentially loaded on the microfiber surface of the microfiber substrate 2, and similarly, the graphene layer 4 is obtained by high temperature carbonization and pyrolysis of polydopamine deposited on the microfiber surface, therefore, after high-temperature carbonization, a micro-nano carbon fiber three-dimensional network framework with a gradient structure can be formed, polydopamine deposited on the surface of the three-dimensional network framework is carbonized and pyrolyzed into a graphene layer at high temperature, a three-dimensional conductive network is further formed, the conductivity of the material is improved, and meanwhile, a metal atom-carbon/nitrogen atom solid solution is formed on the surface of the material, so that the effective combination of the carbon nanofiber network framework material and a noble metal material is realized, the electrochemical sensing of metal particles on target molecules is facilitated, and the synergistic function of catalysis and detection is further achieved.
In order to better explain the invention, the following further illustrate the main content of the invention in connection with specific preparation methods, but the content of the invention is not limited to the preparation methods of the following examples.
Example 1
The embodiment discloses a conductive nanofiber porous membrane material with surface loaded with nano metal particles, which comprises the following preparation steps:
(1) preparing a nanofiber suspension: dispersing 10g of ethylene vinyl alcohol copolymer nano-fibers with the diameter of 100-200 nm in 1000g of mixed solvent of ethanol and deionized water in a mass ratio of 1:1, uniformly stirring to form ethylene vinyl alcohol copolymer nano-fiber suspension with the solid content (mass percentage concentration) of the nano-fibers of 1 wt%, and sealing and storing.
(2) Preparing a nanofiber porous base membrane: coating the ethylene vinyl alcohol copolymer nanofiber suspension obtained in the step (1) on one surface of the cotton fiber woven cloth in a spraying mode, wherein the coating thickness is 20 mu m, and the coating density is 10g/m2And (3) drying in vacuum at normal temperature to prepare the nano fiber porous base membrane with the aperture of 200-600 nm and composed of the cotton fiber woven cloth and the nano fiber coating attached to the surface of the cotton fiber woven cloth.
(3) Preparing dopamine hydrochloride aqueous solution: preparing a Tris (hydroxymethyl) aminomethane (Tris-HCl) buffer solution with the concentration of 0.1mol/L, adjusting the pH value of the buffer solution to 8.5 by adopting sodium hydroxide, weighing dopamine hydrochloride, and dissolving the dopamine hydrochloride into the Tris-HCl buffer solution to obtain a dopamine hydrochloride aqueous solution with the concentration of 2 g/L.
(4) Preparing a polydopamine modified nanofiber porous membrane: and (3) soaking the nanofiber porous base membrane prepared in the step (2) in ethanol to remove surface impurities, then placing the membrane into the dopamine hydrochloride aqueous solution prepared in the step (3), controlling the temperature to be 37 ℃ in an oxygen environment, carrying out oscillation reaction for 12 hours, taking out the membrane, washing the membrane with deionized water, and drying the membrane at normal temperature to obtain the poly-dopamine modified nanofiber porous membrane.
(5) Preparing a nanofiber porous composite membrane with the surface grafted with amino groups: and (3) placing the polydopamine modified nanofiber porous membrane prepared in the step (4) in a polyethyleneimine water solution with the concentration of 10g/L, controlling the temperature to be 45 ℃, reacting for 3 hours, taking out after the reaction is finished, cleaning with deionized water, and drying at normal temperature to obtain the nanofiber porous composite membrane with the surface grafted with amino groups.
(6) Preparing a nanofiber porous composite membrane loaded with nano silver particles: and (3) placing the nanofiber porous composite membrane with the surface grafted with the amino group prepared in the step (5) into a suspension of nano-silver particles modified by sodium borohydride for adsorption for 60min, taking out after the reaction is finished, cleaning with deionized water, and drying in vacuum at normal temperature to obtain the nanofiber porous composite membrane loaded with the nano-silver particles.
(7) Preparing a conductive nanofiber porous membrane material with the surface loaded with nano silver particles: and (3) placing the nanofiber porous composite membrane loaded with the nano silver particles prepared in the step (6) in a temperature programming tube furnace, carbonizing for 2 hours at 800 ℃ under the protection of inert atmosphere, cooling to room temperature, and taking out to obtain the conductive nanofiber porous membrane material loaded with the nano silver particles on the surface.
Example 2
The embodiment discloses a conductive nanofiber porous membrane material with surface loaded with nano metal particles, which comprises the following preparation steps:
(1) preparing a nanofiber suspension: dispersing 10g of ethylene vinyl alcohol nano-fibers with the diameter of 100-200 nm in 1000g of mixed solvent of ethanol and deionized water in a mass ratio of 1:1, uniformly stirring to form ethylene vinyl alcohol copolymer nano-fiber suspension with the solid content (mass percentage concentration) of the nano-fibers of 1 wt%, and sealing and storing.
(2) Preparing a nanofiber porous base membrane: coating the ethylene vinyl alcohol copolymer nanofiber suspension obtained in the step (1) on two surfaces of polyacrylonitrile woven cloth in a spraying mode, wherein the coating thickness is 10 mu m, and the coating density is 5g/m2And vacuum drying at normal temperature to prepare the nano-fiber porous base membrane with the aperture of 50-300 nm and composed of polyacrylonitrile woven cloth and a nano-fiber coating attached to the surface of the polyacrylonitrile woven cloth.
(3) Preparing dopamine hydrochloride aqueous solution: preparing a Tris (hydroxymethyl) aminomethane (Tris-HCl) buffer solution with the concentration of 0.1mol/L, adjusting the pH of the buffer solution to 8.5 by adopting sodium hydroxide, weighing dopamine hydrochloride, and dissolving the dopamine hydrochloride into the Tris-HCl buffer solution to obtain 2g/L dopamine hydrochloride aqueous solution.
(4) Preparing a polydopamine modified nanofiber porous membrane: and (3) soaking the nanofiber porous base membrane prepared in the step (2) in ethanol to remove surface impurities, then placing the membrane into the dopamine hydrochloride aqueous solution prepared in the step (3), controlling the temperature to be 37 ℃ in an oxygen environment, carrying out oscillation reaction for 12 hours, taking out the membrane, washing the membrane with deionized water, and drying the membrane at normal temperature to obtain the poly-dopamine modified nanofiber porous membrane.
(5) Preparing a nanofiber porous composite membrane with the surface grafted with amino groups: and (3) placing the polydopamine modified nanofiber porous membrane prepared in the step (4) in a polyethyleneimine water solution with the concentration of 5g/L, controlling the temperature to be 45 ℃, reacting for 2 hours, taking out after the reaction is finished, cleaning with deionized water, and drying at normal temperature to obtain the ethylene vinyl alcohol nanofiber porous composite membrane with the surface grafted with amino groups.
(6) Preparing a nano-fiber porous composite membrane with nano-gold particles loaded on the surface: and (3) placing the nanofiber porous composite membrane with the surface grafted with the amino group prepared in the step (5) into a suspension of polyvinylpyrrolidone modified gold nanoparticles for adsorption for 60min, taking out and washing with deionized water, and drying in vacuum at normal temperature to obtain the nanofiber porous composite membrane loaded with the gold nanoparticles.
(7) Preparing a conductive nanofiber porous membrane material with the surface loaded with the nanogold particles: and (4) placing the nano-gold particle loaded nano-fiber porous composite membrane prepared in the step (6) in a temperature programmed tube furnace, carbonizing for 4 hours at 600 ℃ under the protection of inert atmosphere, cooling to room temperature, and taking out to obtain the nano-gold particle loaded high-conductivity nano-fiber porous membrane material.
Example 3
(1) Preparing a nanofiber suspension: dispersing 10g of ethylene vinyl alcohol nano-fibers with the diameter of 150-300 nm in 1000g of mixed solvent of ethanol and deionized water in a mass ratio of 1:1, stirring to form ethylene vinyl alcohol copolymer nano-fiber suspension with the nano-fiber solid content (mass percentage concentration) of 1 wt%, and sealing for storage.
(2) Preparing a nanofiber porous base membrane: coating the ethylene vinyl alcohol copolymer nanofiber suspension obtained in the step (1) on one surface of polyacrylonitrile woven cloth in a spraying mode, wherein the coating thickness is 30 microns,the coating density was 20g/m2And vacuum drying at normal temperature to prepare the nano-fiber porous base membrane with the aperture of 500-800 nm and composed of polyacrylonitrile woven cloth and a nano-fiber coating attached to the surface of the polyacrylonitrile woven cloth.
(3) Preparing dopamine hydrochloride aqueous solution: preparing a Tris (hydroxymethyl) aminomethane (Tris-HCl) buffer solution with the concentration of 0.1mol/L, adjusting the pH of the buffer solution to 8.5 by adopting sodium hydroxide, weighing dopamine hydrochloride, and dissolving the dopamine hydrochloride into the Tris-HCl buffer solution to obtain 5g/L dopamine hydrochloride aqueous solution.
(4) Preparing a polydopamine modified nanofiber porous membrane: and (3) soaking the nanofiber porous base membrane prepared in the step (2) in ethanol to remove surface impurities, then placing the membrane into the dopamine hydrochloride aqueous solution prepared in the step (3), controlling the temperature to be 37 ℃ in an oxygen environment, carrying out oscillation reaction for 12 hours, taking out the membrane, washing the membrane with deionized water, and drying the membrane at normal temperature to obtain the poly-dopamine modified nanofiber porous membrane.
(5) Preparing a nanofiber porous composite membrane with a surface grafted with carboxyl groups: and (3) placing the polydopamine modified nanofiber porous membrane prepared in the step (4) in an iminodiacetic acid aqueous solution with the concentration of 10g/L, controlling the temperature to be 45 ℃, reacting for 2 hours, taking out after the reaction is finished, cleaning with deionized water, and drying at normal temperature to obtain the nanofiber porous composite membrane with the surface grafted with carboxyl groups.
(6) Preparing a nano-fiber porous composite membrane loaded with nano-copper particles: and placing the nanofiber porous composite membrane with the surface grafted with carboxyl groups into a suspension of polyvinylpyrrolidone modified nano-copper particles for adsorption for 60min, taking out after the reaction is finished, cleaning with deionized water, and drying in vacuum at normal temperature to obtain the nanofiber porous composite membrane loaded with the nano-copper particles.
(7) Preparing a conductive nanofiber porous membrane material with the surface loaded with nano copper particles: and (3) placing the nano-fiber porous composite membrane loaded with the nano-copper particles in a temperature programming tube furnace, carbonizing for 2 hours at 800 ℃ under the protection of inert atmosphere, cooling to room temperature, and taking out to obtain the conductive nano-fiber porous membrane material loaded with the nano-copper particles on the surface.
Example 4
(1) Preparing a nanofiber suspension: dispersing 10g of ethylene vinyl alcohol nano-fibers with the diameter of 200-300 nm in 1000g of mixed solvent of ethanol and deionized water in a mass ratio of 1:1, uniformly stirring to form ethylene vinyl alcohol copolymer nano-fiber suspension with the solid content (mass percentage concentration) of the nano-fibers of 1 wt%, and sealing and storing.
(2) Preparing a nanofiber porous base membrane: coating the ethylene vinyl alcohol copolymer nanofiber suspension obtained in the step (1) on the surface of polyacrylonitrile woven cloth in a spraying mode, wherein the coating thickness is 10 mu m, and the coating density is 8g/m2And vacuum drying at normal temperature to prepare the nano-fiber porous base membrane with the aperture of 700-1000 nm and composed of polyacrylonitrile woven cloth and a nano-fiber coating attached to the surface of the polyacrylonitrile woven cloth.
(3) Preparing dopamine hydrochloride aqueous solution: preparing a Tris (hydroxymethyl) aminomethane (Tris-HCl) buffer solution with the concentration of 0.1mol/L, adjusting the pH of the buffer solution to 8.5 by adopting sodium hydroxide, weighing dopamine hydrochloride, and dissolving the dopamine hydrochloride into the Tris-HCl buffer solution to obtain 2g/L dopamine hydrochloride aqueous solution.
(4) Preparing a polydopamine modified nanofiber porous membrane: and (3) soaking the nanofiber porous base membrane prepared in the step (2) in ethanol to remove surface impurities, then placing the membrane into the dopamine hydrochloride aqueous solution prepared in the step (3), controlling the temperature to be 37 ℃ in an oxygen environment, carrying out oscillation reaction for 12 hours, taking out the membrane, washing the membrane with deionized water, and drying the membrane at normal temperature to obtain the poly-dopamine modified nanofiber porous membrane.
(5) Preparing a nanofiber porous composite membrane with the surface grafted with amino groups: and (3) placing the polydopamine modified nanofiber porous membrane prepared in the step (4) in a polyethyleneimine water solution with the concentration of 5g/L, controlling the temperature to be 45 ℃, reacting for 2 hours, taking out after the reaction is finished, cleaning with deionized water, and drying at normal temperature to obtain the nanofiber porous composite membrane with the surface grafted with amino groups.
(6) Preparing a nano-fiber porous composite membrane loaded with nano-platinum particles: and (3) placing the nanofiber porous composite membrane with the surface grafted with the amino group prepared in the step (5) into a suspension of nano platinum particles modified by sodium borohydride for adsorption for 60min, taking out the membrane after the reaction is finished, cleaning the membrane by using deionized water, and drying the membrane in vacuum at normal temperature to obtain the nanofiber porous composite membrane loaded with the nano platinum particles.
(7) Preparing a conductive nanofiber porous membrane material with the surface loaded with nano platinum particles: and (3) placing the nanofiber porous composite membrane loaded with the nano platinum particles prepared in the step (6) in a temperature programming tube furnace, carbonizing for 2 hours at 800 ℃ under the protection of inert atmosphere, cooling to room temperature, and taking out to obtain the conductive nanofiber porous membrane material loaded with the nano platinum particles on the surface.
Example 5
(1) Preparing a nanofiber suspension: dispersing 10g of ethylene vinyl alcohol nano-fibers with the diameter of 50-200 nm in 1000g of mixed solvent of ethanol and deionized water in a mass ratio of 1:1, uniformly stirring to form ethylene vinyl alcohol copolymer nano-fiber suspension with the solid content (mass percentage concentration) of the nano-fibers of 1 wt%, and sealing and storing.
(2) Preparing a nanofiber porous base membrane: coating the ethylene vinyl alcohol copolymer nanofiber suspension obtained in the step (1) on the surface of the cotton fiber woven cloth in a spraying mode, wherein the coating thickness is 20 mu m, and the coating density is 10g/m2And drying at normal temperature in vacuum to prepare the nano fiber porous membrane consisting of the cotton fiber woven cloth and the nano fiber coating attached to the surface of the cotton fiber woven cloth.
(3) Preparing dopamine hydrochloride aqueous solution: preparing a Tris (hydroxymethyl) aminomethane (Tris-HCl) buffer solution with the concentration of 0.1mol/L, adjusting the pH of the buffer solution to 8.5 by adopting sodium hydroxide, weighing dopamine hydrochloride, and dissolving the dopamine hydrochloride into the Tris-HCl buffer solution to obtain 2g/L dopamine hydrochloride aqueous solution.
(4) Preparing a polydopamine modified nanofiber porous membrane: and (3) soaking the nanofiber porous base membrane prepared in the step (2) in ethanol to remove surface impurities, then placing the membrane into the dopamine hydrochloride aqueous solution prepared in the step (3), controlling the temperature to be 37 ℃ in an oxygen environment, carrying out oscillation reaction for 12 hours, taking out the membrane, washing the membrane with deionized water, and drying the membrane at normal temperature to obtain the poly-dopamine modified nanofiber porous membrane.
(5) Preparing a nanofiber porous composite membrane with the surface grafted with amino groups: and (3) placing the polydopamine modified nano-fiber porous membrane material prepared in the step (4) into a 10g/L polyethyleneimine water solution, controlling the temperature at 45 ℃, reacting for 3 hours, taking out after the reaction is finished, cleaning with deionized water, and drying at normal temperature to obtain the nano-fiber porous composite membrane with the surface grafted with amino groups.
(6) Preparing a nano-fiber porous composite membrane loaded with nano gold and silver particles: and placing the nanofiber porous composite membrane with the surface grafted with the amino group into a mixed suspension of nano-silver and nano-gold particles modified by sodium borohydride for adsorption for 60min, taking out after the reaction is finished, cleaning with deionized water, and drying in vacuum at normal temperature to obtain the nanofiber porous composite membrane loaded with the nano-gold and silver mixed particles.
(7) Preparing a conductive nanofiber porous membrane material with the surface loaded with nano gold and silver particles: and (3) placing the nanofiber porous composite membrane loaded with the nano gold and silver mixed particles prepared in the step (6) into a temperature programming tubular furnace, carbonizing for 3 hours at 700 ℃ under the protection of inert atmosphere, cooling to room temperature, and taking out to obtain the conductive nanofiber porous membrane material loaded with the nano gold and silver mixed particles on the surface.
Example 6
(1) Preparing a nanofiber suspension: dispersing 10g of ethylene vinyl alcohol nano-fibers with the diameter of 100-200 nm in 1000g of mixed solvent of ethanol and deionized water in a mass ratio of 1:1, stirring to form ethylene vinyl alcohol copolymer nano-fiber suspension with the nano-fiber solid content (mass percentage concentration) of 1 wt%, and sealing for storage.
(2) Preparing a nanofiber porous base membrane: coating the ethylene vinyl alcohol copolymer nanofiber suspension obtained in the step (1) on one surface of polyacrylonitrile woven cloth in a spraying mode, wherein the coating thickness is 30 mu m, and the coating density is 15g/m2And vacuum drying at normal temperature to prepare the nano-fiber porous base membrane with the aperture of 400-500 nm and composed of polyacrylonitrile woven cloth and a nano-fiber coating attached to the surface of the polyacrylonitrile woven cloth.
(3) Preparing dopamine hydrochloride aqueous solution: preparing a Tris (hydroxymethyl) aminomethane (Tris-HCl) buffer solution with the concentration of 0.1mol/L, adjusting the pH of the buffer solution to 8.5 by adopting sodium hydroxide, weighing dopamine hydrochloride, and dissolving the dopamine hydrochloride into the Tris-HCl buffer solution to obtain 2g/L dopamine hydrochloride aqueous solution.
(4) Preparing a polydopamine modified nanofiber porous membrane: and (3) soaking the nanofiber porous base membrane prepared in the step (2) in ethanol to remove surface impurities, then putting the nanofiber porous base membrane into a prepared dopamine hydrochloride aqueous solution, controlling the temperature to be 37 ℃ in an oxygen environment, carrying out oscillation reaction for 12 hours, taking out the membrane, washing the membrane with deionized water, and drying the membrane at normal temperature to obtain the poly-dopamine modified nanofiber porous membrane.
(5) Preparing a nanofiber porous composite membrane with the surface grafted with amino groups: and (3) placing the polydopamine modified nanofiber porous membrane prepared in the step (4) in a polyethyleneimine water solution with the concentration of 10g/L, controlling the temperature to be 45 ℃, reacting for 2 hours, taking out after the reaction is finished, cleaning with deionized water, and drying at normal temperature to obtain the nanofiber porous composite membrane with the surface grafted with amino groups.
(6) Preparing a nano-fiber porous composite membrane loaded with nano-gold copper particles: and (3) placing the nanofiber porous composite membrane with the surface grafted with the amino groups prepared in the step (5) into a mixed suspension of the gold-nanoparticle modified by polyvinylpyrrolidone for adsorption for 60min, taking out after the reaction is finished, cleaning with deionized water, and drying in vacuum at normal temperature to obtain the nanofiber porous composite membrane loaded with the gold-nanoparticle.
(7) Preparing a conductive nanofiber porous membrane material with the surface loaded with nano metal particles: and (3) placing the nanofiber porous composite membrane loaded with the nano gold copper particles in a temperature programming tube furnace, carbonizing for 5 hours at 600 ℃ under the protection of inert atmosphere, cooling to room temperature, and taking out to obtain the conductive nanofiber porous membrane material loaded with the nano gold copper particles on the surface.
The above examples are merely preferred examples and are not intended to limit the embodiments of the present invention. In addition to the above embodiments, the present invention has other embodiments. All technical solutions formed by adopting equivalent substitutions or equivalent transformations fall within the protection scope of the claims of the present invention.
Claims (7)
1. A surface load nanometer metal particle's electrically conductive nanofiber porous membrane material which characterized in that: the conductive nanofiber porous membrane consists of a conductive nanofiber porous membrane and nano metal particles loaded on the surface of the conductive nanofiber porous membrane, wherein the conductive nanofiber porous membrane consists of a carbon fiber three-dimensional network framework and a graphene layer coated on the surface of the carbon fiber three-dimensional network framework, and the carbon fiber three-dimensional network framework consists of a micron carbon fiber substrate and a carbon nanofiber coating loaded on the surface of the micron carbon fiber substrate; the micron carbon fiber base material is obtained by carbonizing and pyrolyzing woven cloth, and the nano carbon fiber coating is obtained by carbonizing and pyrolyzing nano fibers coated on the surface of the woven cloth;
the metal atoms in the nano metal particles and the carbon atoms or the nitrogen atoms in the conductive nanofiber porous membrane are alloyed under the high-temperature condition to form a metal atom-carbon/nitrogen atom solid solution; the nano metal particles comprise at least one of silver, gold, platinum, copper, iron and palladium elementary metals, and the nano metal particles are in any one of a spherical shape, a polyhedral shape, a rod shape and an irregular shape.
2. The conductive nanofiber porous membrane material with the surface loaded with the nano metal particles as claimed in claim 1, wherein: the graphene layer is obtained by carbonizing and pyrolyzing polydopamine deposited on the surface of the nanofiber.
3. A method for preparing the conductive nano-fiber porous membrane material with the surface loaded with nano-metal particles as in claim 1, which comprises the steps of coating a nano-fiber suspension on the surface of woven cloth to obtain a nano-fiber porous basement membrane, depositing polydopamine on the surface of the nano-fiber porous base membrane to obtain a polydopamine-modified nano-fiber porous membrane, chemically modifying the polydopamine to obtain a nano-fiber porous composite membrane with a surface grafted with a chemically modified group, placing the nano-fiber porous composite membrane with the surface grafted with the chemically modified group in a nano-metal particle suspension modified by a stabilizing agent for adsorption reaction to obtain a nano-fiber porous composite membrane loaded with nano-metal particles, and carbonizing the nano-fiber porous composite membrane loaded with the nano-metal particles at high temperature to obtain the conductive nano-fiber porous membrane material with the surface loaded with the nano-metal particles.
4. The method for preparing the conductive nanofiber porous membrane material with the surface loaded with the nano metal particles as claimed in claim 3, is characterized in that: and (3) placing the nanofiber porous composite membrane loaded with the nano metal particles in an inert atmosphere at 600-1000 ℃ for carbonization for 1-5 hours, cooling to room temperature, and taking out to obtain the conductive nanofiber porous membrane material loaded with the metal nano material on the surface.
5. The method for preparing the conductive nanofiber porous membrane material with the surface loaded with the nano metal particles as claimed in claim 3 or 4, is characterized in that: the surface charge of the nanofiber porous composite membrane with the surface grafted with the chemical modification group is opposite to the surface charge of the nano metal particle suspension in positive and negative.
6. The method for preparing the conductive nanofiber porous membrane material with the surface loaded with the nano metal particles as claimed in claim 3 or 4, is characterized in that: the specific process for chemically modifying polydopamine is as follows: the method comprises the following steps of placing a polydopamine modified nanofiber porous membrane in a chemical modifier aqueous solution, and reacting to obtain a nanofiber porous composite membrane with a surface grafted with a chemical modification group, wherein the chemical modifier comprises a compound containing at least one group of polyamine, polyimine, polycarboxyl and polyphenol hydroxyl.
7. The method for preparing the conductive nanofiber porous membrane material with the surface loaded with the nano metal particles as claimed in claim 3 or 4, is characterized in that: the stabilizing agent is sodium alginate.
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| CN113398901B (en) * | 2021-05-28 | 2022-11-08 | 广西大学 | Biomass-based thermosensitive bionic hydrogel adsorption material and preparation method and application thereof |
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