CN109295615B - Preparation method of durable graphene conductive silk fibroin nanofiber membrane - Google Patents
Preparation method of durable graphene conductive silk fibroin nanofiber membrane Download PDFInfo
- Publication number
- CN109295615B CN109295615B CN201811155837.8A CN201811155837A CN109295615B CN 109295615 B CN109295615 B CN 109295615B CN 201811155837 A CN201811155837 A CN 201811155837A CN 109295615 B CN109295615 B CN 109295615B
- Authority
- CN
- China
- Prior art keywords
- graphene oxide
- silk fibroin
- preparing
- nanofiber membrane
- spinning
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- 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
- D01D1/00—Treatment of filament-forming or like material
- D01D1/02—Preparation of spinning solutions
-
- 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
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
- D06M16/003—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic with enzymes or microorganisms
Abstract
The invention discloses a preparation method of a durable graphene conductive silk fibroin nanofiber membrane. The method of the invention realizes the preparation of the flexible and durable conductive silk fibroin nanofiber membrane, the nanofiber membrane can be used for intelligent wearable clothing fabric, and can also be used in a plurality of fields of flexible electronic devices, medical care, intelligent sports and the like, and the prepared conductive membrane has excellent durability.
Description
Technical Field
The invention belongs to the field of textile chemistry, and particularly relates to a preparation method of a durable graphene conductive silk fibroin nanofiber membrane by an electrostatic spinning method.
Background
Electrospinning is a special fiber manufacturing process, where polymer solutions or melts are jet spun in a strong electric field. Under the action of the electric field, the liquid drop at the needle head changes from a spherical shape to a conical shape (i.e. a Taylor cone) and extends from the tip of the cone to obtain a fiber filament. This way, polymer filaments of nanometer-scale diameter can be produced. The preparation of nanofibrous materials through electrostatic spinning technology is one of the most important academic and technical activities in the field of materials science and technology in the world in recent decades. Electrostatic spinning has become one of the main approaches for effectively preparing nanofiber materials due to the advantages of simple manufacturing device, low spinning cost, various spinnable substances, controllable process and the like. Graphene wearable intelligent textile materials are also the hot spots of current research, wherein conductivity and flexibility are the most important properties, and the most effective method for obtaining flexibility is to prepare a substrate by adopting electrostatic spinning, so that the research on graphene soft conductive electrostatic spinning textile materials is worth paying attention.
The invention discloses a method for preparing a graphene oxide and polyvinyl alcohol composite membrane by electrostatic spinning, which comprises the steps of carrying out electrostatic spinning on a spinning stock solution of graphene oxide and polyvinyl alcohol to obtain a graphene oxide and polyvinyl alcohol composite membrane, and finally treating the graphene oxide and polyvinyl alcohol composite membrane in a mixed solution of acetone, deionized water, hydrochloric acid and a cross-linking agent to obtain a cross-linked graphene oxide and polyvinyl alcohol composite membrane. The invention patent CN 104761737B discloses a method for preparing a collagen/graphene oxide nanofiber composite membrane by an electrostatic spinning method, and the patent mainly utilizes the large specific surface area and excellent mechanical properties of graphene oxide to improve and improve the mechanical properties of a collagen nanofiber membrane. The graphene oxide is added into the electrostatic spinning solution by the two methods, so that the performances such as strength and the like of the electrostatic spinning film are improved, and the conductivity of the electrostatic spinning film is not involved. The invention patent CN 104878590A discloses a preparation method of a graphene conductive nanofiber membrane, which comprises the steps of firstly preparing an electrostatic spinning nanofiber membrane, then carrying out suction filtration on graphene oxide on an electrostatic spinning film, and finally reducing the prepared graphene oxide conductive nanofiber membrane with hydroiodic acid to obtain a conductive film. The invention patent CN 105803672A discloses a preparation method of a conductive nanofiber membrane, which comprises the steps of dissolving polyacrylonitrile and cellulose acetate in a polar organic solvent for electrostatic spinning, firstly preparing a polyacrylonitrile/cellulose acetate composite nanofiber membrane, then carrying out hydrolysis modification on the polyacrylonitrile/cellulose acetate composite nanofiber membrane by using a strong alkaline solution to prepare a polyacrylonitrile/regenerated cellulose composite nanofiber membrane, and finally carrying out silver mirror reaction treatment on the polyacrylonitrile/regenerated cellulose composite nanofiber membrane to obtain the conductive nanofiber membrane. The literature (good Cao, preparation based on graphene oxide flexible conductive fiber material and performance [ D ]. university of south of the Yangtze river, 2017.) discloses a method for preparing a graphene nanofiber membrane by electrostatic spinning with a mixed solution of graphene oxide or reduced graphene oxide and silk fibroin, wherein the graphene in the electrostatic spinning membrane is coated inside the fiber by the silk fibroin, so that the conductivity cannot be tested when the content of the graphene oxide or reduced graphene oxide in the obtained nanofiber membrane is high enough, and the conductivity of the nanofiber membrane can be effectively improved after the GO solution is dipped and reduced again by utilizing the higher specific surface area of the nanofiber. In all of the above three methods, an electrostatic spinning film is prepared, and then a conductive medium is applied to the electrostatic spinning film to obtain a conductive electrostatic spinning film. The invention patent CN 104674362B discloses a preparation method of various fibroin/graphene conductive fiber membranes, which comprises the steps of firstly preparing a graphene oxide and silk fibroin composite membrane, then placing the graphene oxide and silk fibroin composite membrane in a solvent, stirring until the graphene oxide and silk fibroin composite membrane are completely dissolved, carrying out ultrasonic treatment to obtain a spinning solution, placing the spinning solution in a container of electrostatic spinning equipment, carrying out high-pressure electrospinning to obtain composite fibers, and carrying out steam treatment to obtain fibroin/graphene conductive fibers. The method comprises the steps of preparing a film, dissolving the film, performing electrostatic spinning, and performing steam treatment to obtain the conductive film. At present, a preparation method for adding graphene into a silk fibroin spinning solution, obtaining a graphene silk fibroin nanofiber membrane through electrostatic spinning, and obtaining a graphene conductive silk fibroin nanofiber membrane through protease post-treatment is not available.
Disclosure of Invention
The invention aims to solve the technical problem that the current nanofiber membrane prepared by electrostatic spinning of graphene oxide or reduced graphene oxide and silk fibroin mixed solution cannot show conductivity on the surface of the membrane because graphene is coated by silk fibroin, and provides a preparation method of a durable graphene conductive silk fibroin nanofiber membrane.
In order to solve the technical problems, the invention adopts the following technical scheme:
a preparation method of a durable graphene conductive silk fibroin nanofiber membrane comprises the following steps:
(1) preparing graphene oxide: preparing Graphene Oxide (GO) by using graphite as a raw material by an ultrasonic Hummers method, centrifuging to obtain 4000-10000 r/min of graphene oxide precipitate, and freeze-drying to obtain uniformly dispersed graphene oxide;
(2) preparing reduced graphene oxide: preparing the graphene oxide prepared in the step (1) into 0.2-10 g/L aqueous solution by adopting an ultrasonic chemical reduction method, stirring and heating to 80-100 ℃ under an ultrasonic condition, adding 2-20 g/L reducing agent, continuing ultrasonic stirring, keeping the temperature for 10-120 min, filtering, washing with water, and freeze-drying to obtain reduced graphene oxide with uniform fineness;
(3) preparing reduced graphene oxide and silk fibroin electrostatic spinning solution: dispersing 0.5-5 g of reduced graphene oxide in 30 ml of formic acid solution under an ultrasonic condition to obtain a dispersion liquid A, dispersing 10-40 g of silk fibroin in 170 ml of formic acid solution under the ultrasonic condition to obtain a viscous solution B, continuously slowly pouring the dispersion liquid A into the viscous solution B under the ultrasonic condition, and continuously stirring for 10-60 min under the ultrasonic condition at 0-30 ℃ for later use;
(4) electrostatic spinning: spinning the electrostatic spinning solution obtained in the step (3) on an electrostatic spinning machine, and obtaining a reduced graphene oxide silk fibroin nanofiber membrane on a receiving plate after the spinning is finished;
(5) and (3) post-treatment: and (3) drying the reduced graphene oxide silk fibroin nanofiber membrane obtained in the step (4) at 50-80 ℃ for 30-200 min in vacuum, then placing the membrane in 1-10 g/L protease solution, adjusting the pH value to 3-10, treating the membrane at 30-70 ℃ for 10-100 min, and then fully washing and drying the membrane.
In the step (1), the graphene oxide is prepared by using ultrasound, and the monolayer rate of the graphene oxide can be improved by using ultrasound.
In the step (2), the reducing agent is one or more of sodium hydrosulfite, hydrazine hydrate, rongalite, thiourea dioxide and the like, and the preparation process of the reduced graphene oxide uses ultrasound, so that the monolayer rate of the reduced graphene oxide can be improved by the ultrasound, and the aggregation of the reduced graphene oxide is reduced.
The mass concentration of the formic acid solution in the step (3) is 98%.
The purpose of the ultrasonic treatment in the step (3) is to uniformly disperse or dissolve the reduced graphene oxide and the silk fibroin in a formic acid solution with a mass concentration of 98%, slowly add the reduced graphene oxide dispersion liquid into the silk fibroin solution, and uniformly disperse the reduced graphene oxide in the silk fibroin.
And (3) spinning voltage during electrostatic spinning in the step (4) is 8-20 kV, the distance between a pinhole and a receiving plate is 6-15 cm, and the spinning speed is 0.5-4 ml/h.
In the step (4), the reduced graphene oxide and silk fibroin spinning solution can be sprayed onto a receiving plate in a filament shape under the action of high pressure through electrostatic spinning, and a nanofiber film is formed on the receiving plate.
The protease in the step (5) is one or more of neutral protease, acid protease and alkaline protease.
The protease post-treatment in the step (5) aims to corrode and dissolve silk fibroin on the surface of the nanofiber membrane, and the nanofiber membrane for reducing the graphene oxide conducting layer is left, so that the conductivity of the nanofiber membrane is improved.
The invention has the beneficial effects that: according to the invention, the reduced graphene oxide/silk fibroin nanofiber membrane is prepared by performing electrostatic spinning on a mixed formic acid solution of reduced graphene oxide and silk fibroin, the reduced graphene oxide is coated by the silk fibroin and cannot show conductivity on the surface of the membrane, and the silk fibroin on the surface of the membrane is hydrolyzed by treating the graphene/silk fibroin electrostatic spinning nanofiber membrane with a protease solution, so that the graphene on the surface is exposed, a compact conductive layer is formed, and the flexible and durable conductive nanofiber membrane is obtained. The technical scheme of the invention has simple and feasible process, has no special requirements on raw materials, auxiliaries and fabrics, can realize large-scale production by utilizing conventional electrostatic spinning equipment, and has wide application prospect.
Detailed Description
The present invention will be further described with reference to the following examples. It is to be understood that the following examples are illustrative only and are not intended to limit the scope of the invention, which is to be given numerous insubstantial modifications and adaptations by those skilled in the art based on the teachings set forth above.
The preparation method of the durable graphene conductive silk fibroin nanofiber membrane comprises the following steps:
(1) preparing graphene oxide: preparing Graphene Oxide (GO) by using graphite as a raw material by an ultrasonic Hummers method, centrifuging to obtain 4000-10000 r/min of graphene oxide precipitate, and freeze-drying to obtain uniformly dispersed graphene oxide;
(2) preparing reduced graphene oxide: preparing the graphene oxide prepared in the step (1) into 0.2-10 g/L aqueous solution by adopting an ultrasonic chemical reduction method, stirring and heating to 80-100 ℃ under an ultrasonic condition, adding 2-20 g/L reducing agent, continuing ultrasonic stirring, keeping the temperature for 10-120 min, filtering, washing with water, and freeze-drying to obtain reduced graphene oxide with uniform fineness;
(3) preparing reduced graphene oxide and silk fibroin electrostatic spinning solution: dispersing 0.5-5 g of reduced graphene oxide in 30 ml of 98% formic acid solution under an ultrasonic condition to obtain a dispersion liquid A, dispersing 10-40 g of silk fibroin in 170 ml of 98% formic acid solution under the ultrasonic condition to obtain a viscous solution B, slowly pouring the dispersion liquid A into the viscous solution B under the ultrasonic condition, and stirring for 10-60 min under the ultrasonic condition at 0-30 ℃ for later use;
(4) electrostatic spinning: spinning the electrostatic spinning solution obtained in the step (3) on an electrostatic spinning machine, wherein the spinning voltage is 8-20 kV, the distance between a needle hole and a receiving plate is 6-15 cm, the spinning speed is 0.5-4 ml/h, and the reduced graphene oxide silk fibroin nanofiber membrane is obtained on the receiving plate after spinning is finished;
(5) and (3) post-treatment: and (3) drying the reduced graphene oxide silk fibroin nanofiber membrane obtained in the step (4) at 50-80 ℃ for 30-200 min in vacuum, then placing the membrane in 1-10 g/L protease solution, adjusting the pH value to 3-10, treating the membrane at 30-70 ℃ for 10-100 min, and then fully washing and drying the membrane.
Example 1
A preparation method of a durable graphene conductive silk fibroin nanofiber membrane comprises the following steps:
(1) preparing graphene oxide: preparing Graphene Oxide (GO) by using graphite as a raw material by an ultrasonic Hummers method, centrifuging to obtain 4000-10000 r/min of graphene oxide precipitate, and freeze-drying to obtain uniformly dispersed graphene oxide;
(2) preparing reduced graphene oxide: preparing the graphene oxide prepared in the step (1) into a 5g/L aqueous solution by adopting an ultrasonic chemical reduction method, stirring and heating to 90 ℃ under an ultrasonic condition, adding 10g/L reducer sodium hydrosulfite, continuing ultrasonic stirring, keeping the temperature for 40min, filtering, washing with water, and freeze-drying to obtain reduced graphene oxide with uniform fineness;
(3) preparing reduced graphene oxide and silk fibroin electrostatic spinning solution: dispersing 5g of reduced graphene oxide in 30 ml of 98% formic acid solution under an ultrasonic condition to obtain a dispersion liquid A, dispersing 20g of silk fibroin in 170 ml of 98% formic acid solution under the ultrasonic condition to obtain a viscous solution B, slowly pouring the dispersion liquid A into the viscous solution B under the ultrasonic condition, and stirring for 30min at 10 ℃ for later use;
(4) electrostatic spinning: spinning the electrostatic spinning solution obtained in the step (3) on an electrostatic spinning machine, wherein the spinning voltage is 10kV, the distance between a pinhole and a receiving plate is 8cm, the spinning speed is 2 ml/h, and the reduced graphene oxide silk fibroin nanofiber membrane is obtained on the receiving plate after spinning is finished;
(5) and (3) post-treatment: and (3) drying the reduced graphene oxide silk fibroin nanofiber membrane obtained in the step (4) at 60 ℃ for 60min in vacuum, then placing the membrane in 3g/L acidic protease solution, adjusting the pH value to 3, treating the membrane at 70 ℃ for 10min, and then fully washing and drying the membrane.
Example 2
A preparation method of a durable graphene conductive silk fibroin nanofiber membrane comprises the following steps:
(1) preparing graphene oxide: preparing Graphene Oxide (GO) by using graphite as a raw material by an ultrasonic Hummers method, centrifuging to obtain 4000-10000 r/min of graphene oxide precipitate, and freeze-drying to obtain uniformly dispersed graphene oxide;
(2) preparing reduced graphene oxide: preparing the graphene oxide prepared in the step (1) into 0.2g/L aqueous solution by adopting an ultrasonic chemical reduction method, stirring and heating to 80 ℃ under an ultrasonic condition, adding 2g/L reducing agent rongalite, continuing ultrasonic stirring, keeping the temperature for 10min, filtering, washing with water, and freeze-drying to obtain reduced graphene oxide with uniform fineness;
(3) preparing reduced graphene oxide and silk fibroin electrostatic spinning solution: dispersing 0.5 g of reduced graphene oxide in 30 ml of 98% formic acid solution under an ultrasonic condition to obtain a dispersion liquid A, dispersing 10g of silk fibroin in 170 ml of 98% formic acid solution under the ultrasonic condition to obtain a viscous solution B, slowly pouring the dispersion liquid A into the viscous solution B under the ultrasonic condition, and stirring for 10min under the ultrasonic condition at 30 ℃ for later use;
(4) electrostatic spinning: spinning the electrostatic spinning solution obtained in the step (3) on an electrostatic spinning machine, wherein the spinning voltage is 8kV, the distance between a pinhole and a receiving plate is 6cm, the spinning speed is 0.5 ml/h, and after the spinning is finished, the reduced graphene oxide silk fibroin nanofiber membrane is obtained on the receiving plate;
(5) and (3) post-treatment: and (3) drying the reduced graphene oxide silk fibroin nanofiber membrane obtained in the step (4) at 50 ℃ for 30min in vacuum, then placing the membrane in a neutral protease solution of 1g/L, adjusting the pH value to 7, treating the membrane at 30 ℃ for 100min, and then fully washing and drying the membrane.
Example 3
A preparation method of a durable graphene conductive silk fibroin nanofiber membrane comprises the following steps:
(1) preparing graphene oxide: preparing Graphene Oxide (GO) by using graphite as a raw material by an ultrasonic Hummers method, centrifuging to obtain 4000-10000 r/min of graphene oxide precipitate, and freeze-drying to obtain uniformly dispersed graphene oxide;
(2) preparing reduced graphene oxide: preparing the graphene oxide prepared in the step (1) into 10g/L aqueous solution by adopting an ultrasonic chemical reduction method, stirring and heating to 100 ℃ under an ultrasonic condition, adding 20g/L reducing agent hydrazine hydrate, continuing ultrasonic stirring, keeping the temperature for 120min, filtering, washing with water, and freeze-drying to obtain reduced graphene oxide with uniform fineness;
(3) preparing reduced graphene oxide and silk fibroin electrostatic spinning solution: dispersing 5g of reduced graphene oxide in 30 ml of 98% formic acid solution under an ultrasonic condition to obtain a dispersion liquid A, dispersing 40 g of silk fibroin in 170 ml of 98% formic acid solution under the ultrasonic condition to obtain a viscous solution B, slowly pouring the dispersion liquid A into the viscous solution B under the ultrasonic condition, and stirring for 60min under the ultrasonic condition at 0 ℃ for later use;
(4) electrostatic spinning: spinning the electrostatic spinning solution obtained in the step (3) on an electrostatic spinning machine, wherein the spinning voltage is 20kV, the distance between a pinhole and a receiving plate is 15cm, the spinning speed is 4 ml/h, and the reduced graphene oxide silk fibroin nanofiber membrane is obtained on the receiving plate after the spinning is finished;
(5) and (3) post-treatment: and (3) drying the reduced graphene oxide silk fibroin nanofiber membrane obtained in the step (4) at 80 ℃ for 200min in vacuum, then placing the membrane in 10g/L alkaline protease solution, adjusting the pH value to 10, treating the membrane at 60 ℃ for 10min, and then fully washing and drying the membrane.
Example 4
A preparation method of a durable graphene conductive silk fibroin nanofiber membrane comprises the following steps:
(1) preparing graphene oxide: preparing Graphene Oxide (GO) by using graphite as a raw material by an ultrasonic Hummers method, centrifuging to obtain 4000-10000 r/min of graphene oxide precipitate, and freeze-drying to obtain uniformly dispersed graphene oxide;
(2) preparing reduced graphene oxide: preparing the graphene oxide prepared in the step (1) into 4g/L aqueous solution by adopting an ultrasonic chemical reduction method, stirring and heating to 90 ℃ under an ultrasonic condition, adding 5g/L reducing agent (2 g/L thiourea dioxide and 3g/L sodium hydrosulfite), continuously stirring ultrasonically, keeping the temperature for 60min, filtering, washing with water, and freeze-drying to obtain reduced graphene oxide with uniform fineness;
(3) preparing reduced graphene oxide and silk fibroin electrostatic spinning solution: dispersing 2g of reduced graphene oxide in 30 ml of 98% formic acid solution under an ultrasonic condition to obtain a dispersion liquid A, dispersing 20g of silk fibroin in 170 ml of 98% formic acid solution under the ultrasonic condition to obtain a viscous solution B, continuously slowly pouring the dispersion liquid A into the viscous solution B under the ultrasonic condition, and continuously stirring at 10 ℃ for 40min for later use;
(4) electrostatic spinning: spinning the electrostatic spinning solution obtained in the step (3) on an electrostatic spinning machine, wherein the spinning voltage is 10kV, the distance between a pinhole and a receiving plate is 8cm, the spinning speed is 1 ml/h, and the reduced graphene oxide silk fibroin nanofiber membrane is obtained on the receiving plate after the spinning is finished;
(5) and (3) post-treatment: and (3) drying the reduced graphene oxide silk fibroin nanofiber membrane obtained in the step (4) at 70 ℃ for 100min in vacuum, then placing the membrane in 1g/L alkaline protease solution, adjusting the pH value to 10, treating the membrane at 40 ℃ for 100min, and then fully washing and drying the membrane.
Example 5
A preparation method of a durable graphene conductive silk fibroin nanofiber membrane comprises the following steps:
(1) preparing graphene oxide: preparing Graphene Oxide (GO) by using graphite as a raw material by an ultrasonic Hummers method, centrifuging to obtain 4000-10000 r/min of graphene oxide precipitate, and freeze-drying to obtain uniformly dispersed graphene oxide;
(2) preparing reduced graphene oxide: preparing the graphene oxide prepared in the step (1) into a 3g/L aqueous solution by adopting an ultrasonic chemical reduction method, stirring and heating to 80 ℃ under an ultrasonic condition, adding 10g/L reducing agent (5 g/L sodium hydrosulfite and 5g/L hydrazine hydrate), continuing ultrasonic stirring, keeping the temperature for 10min, filtering, washing with water, and freeze-drying to obtain reduced graphene oxide with uniform fineness;
(3) preparing reduced graphene oxide and silk fibroin electrostatic spinning solution: dispersing 4g of reduced graphene oxide in 30 ml of 98% formic acid solution under an ultrasonic condition to obtain a dispersion liquid A, dispersing 30 g of silk fibroin in 170 ml of 98% formic acid solution under the ultrasonic condition to obtain a viscous solution B, continuously slowly pouring the dispersion liquid A into the viscous solution B under the ultrasonic condition, and continuously stirring for 10min under the ultrasonic condition at 0 ℃ for later use;
(4) electrostatic spinning: spinning the electrostatic spinning solution obtained in the step (3) on an electrostatic spinning machine, wherein the spinning voltage is 12kV, the distance between a pinhole and a receiving plate is 12cm, the spinning speed is 1.6 ml/h, and after the spinning is finished, a reduced graphene oxide silk fibroin nanofiber membrane is obtained on the receiving plate;
(5) and (3) post-treatment: and (3) drying the reduced graphene oxide silk fibroin nanofiber membrane obtained in the step (4) at 50 ℃ for 200min in vacuum, then placing the membrane in 3g/L acidic protease solution, adjusting the pH value to 5, treating the membrane at 50 ℃ for 30min, and then fully washing and drying the membrane.
Example 6
A preparation method of a durable graphene conductive silk fibroin nanofiber membrane is characterized by comprising the following steps:
(1) preparing graphene oxide: preparing Graphene Oxide (GO) by using graphite as a raw material by an ultrasonic Hummers method, centrifuging to obtain 4000-10000 r/min of graphene oxide precipitate, and freeze-drying to obtain uniformly dispersed graphene oxide;
(2) preparing reduced graphene oxide: preparing the graphene oxide prepared in the step (1) into a 2g/L aqueous solution by adopting an ultrasonic chemical reduction method, stirring and heating to 100 ℃ under an ultrasonic condition, adding 4g/L reducer sodium hydrosulfite, continuing ultrasonic stirring, keeping the temperature for 10min, filtering, washing with water, and freeze-drying to obtain reduced graphene oxide with uniform fineness;
(3) preparing reduced graphene oxide and silk fibroin electrostatic spinning solution: dispersing 2.5 g of reduced graphene oxide in 30 ml of 98% formic acid solution under an ultrasonic condition to obtain a dispersion liquid A, dispersing 18 g of silk fibroin in 170 ml of 98% formic acid solution under the ultrasonic condition to obtain a viscous solution B, slowly pouring the dispersion liquid A into the viscous solution B under the ultrasonic condition, and stirring for 60min under the ultrasonic condition at 20 ℃ for later use;
(4) electrostatic spinning: spinning the electrostatic spinning solution obtained in the step (3) on an electrostatic spinning machine, wherein the spinning voltage is 16kV, the distance between a pinhole and a receiving plate is 10cm, the spinning speed is 3 ml/h, and the reduced graphene oxide silk fibroin nanofiber membrane is obtained on the receiving plate after spinning is finished;
(5) and (3) post-treatment: and (3) drying the reduced graphene oxide silk fibroin nanofiber membrane obtained in the step (4) at 50 ℃ for 200min in vacuum, then placing the membrane in a neutral protease solution of 1g/L, adjusting the pH value to 7.5, treating the membrane at 30 ℃ for 100min, and then fully washing and drying the membrane.
Example 7
A preparation method of a durable graphene conductive silk fibroin nanofiber membrane comprises the following steps:
(1) preparing graphene oxide: preparing Graphene Oxide (GO) by using graphite as a raw material by an ultrasonic Hummers method, centrifuging to obtain 4000-10000 r/min of graphene oxide precipitate, and freeze-drying to obtain uniformly dispersed graphene oxide;
(2) preparing reduced graphene oxide: preparing the graphene oxide prepared in the step (1) into 0.2g/L aqueous solution by adopting an ultrasonic chemical reduction method, stirring and heating to 80 ℃ under an ultrasonic condition, adding 2g/L reducing agent hydrazine hydrate, continuing ultrasonic stirring, keeping the temperature for 10min, filtering, washing with water, and freeze-drying to obtain reduced graphene oxide with uniform fineness;
(3) preparing reduced graphene oxide and silk fibroin electrostatic spinning solution: dispersing 5g of reduced graphene oxide in 30 ml of 98% formic acid solution under an ultrasonic condition to obtain a dispersion liquid A, dispersing 20g of silk fibroin in 170 ml of 98% formic acid solution under the ultrasonic condition to obtain a viscous solution B, continuously slowly pouring the dispersion liquid A into the viscous solution B under the ultrasonic condition, and continuously stirring for 10min under the ultrasonic condition at 0 ℃ for later use;
(4) electrostatic spinning: spinning the electrostatic spinning solution obtained in the step (3) on an electrostatic spinning machine, wherein the spinning voltage is 20kV, the distance between a pinhole and a receiving plate is 8cm, the spinning speed is 1 ml/h, and the reduced graphene oxide silk fibroin nanofiber membrane is obtained on the receiving plate after the spinning is finished;
(5) and (3) post-treatment: and (3) drying the reduced graphene oxide silk fibroin nanofiber membrane obtained in the step (4) at 50 ℃ for 200min in vacuum, then placing the membrane in 5g/L protease solution, adjusting the pH value to 10, treating the membrane at 50 ℃ for 30min, and then fully washing and drying the membrane.
Example 8
A preparation method of a durable graphene conductive silk fibroin nanofiber membrane comprises the following steps:
(1) preparing graphene oxide: preparing Graphene Oxide (GO) by using graphite as a raw material by an ultrasonic Hummers method, centrifuging to obtain 4000-10000 r/min of graphene oxide precipitate, and freeze-drying to obtain uniformly dispersed graphene oxide;
(2) preparing reduced graphene oxide: preparing the graphene oxide prepared in the step (1) into a 3g/L aqueous solution by adopting an ultrasonic chemical reduction method, stirring and heating to 85 ℃ under an ultrasonic condition, adding 6g/L reducing agent rongalite, continuing ultrasonic stirring, keeping the temperature for 100min, filtering, washing with water, and freeze-drying to obtain reduced graphene oxide with uniform fineness;
(3) preparing reduced graphene oxide and silk fibroin electrostatic spinning solution: dispersing 3g of reduced graphene oxide in 30 ml of 98% formic acid solution under an ultrasonic condition to obtain a dispersion liquid A, dispersing 25 g of silk fibroin in 170 ml of 98% formic acid solution under the ultrasonic condition to obtain a viscous solution B, slowly pouring the dispersion liquid A into the viscous solution B under the ultrasonic condition, and stirring for 10min under the ultrasonic condition at 30 ℃ for later use;
(4) electrostatic spinning: spinning the electrostatic spinning solution obtained in the step (3) on an electrostatic spinning machine, wherein the spinning voltage is 10kV, the distance between a pinhole and a receiving plate is 13cm, the spinning speed is 0.5 ml/h, and after the spinning is finished, a reduced graphene oxide silk fibroin nanofiber membrane is obtained on the receiving plate;
(5) and (3) post-treatment: and (3) drying the reduced graphene oxide silk fibroin nanofiber membrane obtained in the step (4) at 70 ℃ for 80min in vacuum, then placing the membrane in 6g/L alkaline protease solution, adjusting the pH value to 9, treating the membrane at 55 ℃ for 50min, and then fully washing and drying the membrane.
Effects of the invention
After the treatment of examples 1-8, the following tests were performed on the nanofiber membranes, and the test results are shown in table 1.
1) Measurement of washing fastness
The test is carried out according to GB/T3921-2008 'color fastness to soaping' of textiles.
2) Conductivity test
The surface resistance of the nanofiber membrane was measured on a SZT-2A four-probe tester (Suzhou Co-Ltd.).
Table 1 test results of nanofiber membranes of examples
As can be seen from table 1, the technical solution provided by the present invention can provide the nanofiber membrane with excellent conductivity and excellent conductivity washing fastness, and the conductivity is almost unchanged after 50 times of washing. Compared with the literature (good Cao, based on the preparation of graphene oxide flexible conductive fiber materials and performance [ D ]. university of south of the Yangtze river, 2017.), the nanofiber membrane prepared by the method only needs to use graphene once in the preparation process, and the literature needs to use graphene or graphene oxide once in the spinning and post-treatment processes respectively; the surface resistance value of the nanofiber membrane obtained by the method is lower than 100 omega/cm and far lower than the lowest 3.5 komega/cm of the document, so the nanofiber membrane has better conductivity; furthermore, the third chapter of the above document already mentions that the surface resistance of the conductive silk obtained by coating graphene on the silk surface by a method of post-treating impregnated graphene oxide increases with the increase of the number of washing times, i.e. the conductivity decreases, and thus it can be seen from table 1 that the nanofiber membrane of the present invention has better conductive washing resistance. Therefore, the silk fibroin nanofiber membrane prepared by the method is excellent in conductivity and conductive durability.
The foregoing shows and describes the general principles and features of the present invention, together with the advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (6)
1. A preparation method of a durable graphene conductive silk fibroin nanofiber membrane is characterized by comprising the following steps: the method comprises the following steps:
(1) preparing graphene oxide: preparing graphene oxide by using graphite as a raw material by an ultrasonic Hummers method, centrifuging under the condition of 4000-10000 r/min, and reserving a graphene oxide precipitate, and freeze-drying to obtain uniformly dispersed graphene oxide;
(2) preparing reduced graphene oxide: preparing the graphene oxide prepared in the step (1) into 0.2-10 g/L aqueous solution by adopting an ultrasonic chemical reduction method, stirring and heating to 80-100 ℃ under an ultrasonic condition, adding 2-20 g/L reducing agent, continuing ultrasonic stirring, keeping the temperature for 10-120 min, filtering, washing with water, and freeze-drying to obtain reduced graphene oxide with uniform fineness;
(3) preparing reduced graphene oxide and silk fibroin electrostatic spinning solution: dispersing 0.5-5 g of reduced graphene oxide in 30 ml of formic acid solution under an ultrasonic condition to obtain a dispersion liquid A, dispersing 10-40 g of silk fibroin in 170 ml of formic acid solution under the ultrasonic condition to obtain a viscous solution B, slowly pouring the dispersion liquid A into the viscous solution B under the ultrasonic condition, and stirring for 10-60 min at 0-30 ℃ for later use;
(4) electrostatic spinning: spinning the electrostatic spinning solution obtained in the step (3) on an electrostatic spinning machine, and obtaining a reduced graphene oxide silk fibroin nanofiber membrane on a receiving plate after spinning is finished;
(5) and (3) post-treatment: and (3) drying the reduced graphene oxide silk fibroin nanofiber membrane obtained in the step (4) at 50-80 ℃ for 30-200 min in vacuum, then placing the membrane in 1-10 g/L protease solution, adjusting the pH value to 3-10, treating at 30-70 ℃ for 10-100 min, and then fully washing and drying.
2. The method for preparing the durable graphene conductive silk fibroin nanofiber membrane as claimed in claim 1, wherein: the graphene oxide in the step (1) is prepared by using ultrasound.
3. The method for preparing the durable graphene conductive silk fibroin nanofiber membrane as claimed in claim 1, wherein: the reducing agent in the step (2) is one or more of sodium hydrosulfite, hydrazine hydrate, rongalite and thiourea dioxide, and the preparation process of the reduced graphene oxide uses ultrasound.
4. The method for preparing the durable graphene conductive silk fibroin nanofiber membrane as claimed in claim 1, wherein: the mass concentration of the formic acid solution in the step (3) is 98%.
5. The method for preparing the durable graphene conductive silk fibroin nanofiber membrane as claimed in claim 1, wherein: and (3) spinning voltage during electrostatic spinning in the step (4) is 8-20 kV, the distance between a pinhole and a receiving plate is 6-15 cm, and the spinning speed is 0.5-4 ml/h.
6. The method for preparing the durable graphene conductive silk fibroin nanofiber membrane as claimed in claim 1, wherein: the protease in the step (5) is one or more of neutral protease, acid protease and alkaline protease.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811155837.8A CN109295615B (en) | 2018-09-30 | 2018-09-30 | Preparation method of durable graphene conductive silk fibroin nanofiber membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811155837.8A CN109295615B (en) | 2018-09-30 | 2018-09-30 | Preparation method of durable graphene conductive silk fibroin nanofiber membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109295615A CN109295615A (en) | 2019-02-01 |
| CN109295615B true CN109295615B (en) | 2020-03-17 |
Family
ID=65161306
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811155837.8A Active CN109295615B (en) | 2018-09-30 | 2018-09-30 | Preparation method of durable graphene conductive silk fibroin nanofiber membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109295615B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113463377A (en) * | 2021-07-20 | 2021-10-01 | 浙江理工大学 | Manufacturing method of flexible bionic electronic skin material |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101297366B1 (en) * | 2011-09-07 | 2013-08-14 | 경북대학교 산학협력단 | Preparation method of silk composition for electrospinning with improved production rate |
| JP2014012907A (en) * | 2012-07-04 | 2014-01-23 | Taiyo Kagaku Co Ltd | Binder containing food product or food additive |
| CN104674362A (en) * | 2015-03-11 | 2015-06-03 | 湖州吉昌丝绸有限公司 | Preparation method of fibroin/graphene conductive fiber |
| CN105926075A (en) * | 2016-05-13 | 2016-09-07 | 东莞市联洲知识产权运营管理有限公司 | Graphene modified silk fiber preparing method |
| KR101691039B1 (en) * | 2015-05-27 | 2016-12-29 | 국방과학연구소 | 3-dimenstinal nanofiber membrane and Method of manufacturing the same using liquid collector |
| CN106400312A (en) * | 2016-09-07 | 2017-02-15 | 东华大学 | Method for preparing conductive composite nanofiber nervous tissue engineering scaffold based on graphene |
| CN106913910A (en) * | 2017-04-28 | 2017-07-04 | 武汉理工大学 | A kind of preparation method of fibroin albumen/Graphene composite nano-fiber support material |
-
2018
- 2018-09-30 CN CN201811155837.8A patent/CN109295615B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101297366B1 (en) * | 2011-09-07 | 2013-08-14 | 경북대학교 산학협력단 | Preparation method of silk composition for electrospinning with improved production rate |
| JP2014012907A (en) * | 2012-07-04 | 2014-01-23 | Taiyo Kagaku Co Ltd | Binder containing food product or food additive |
| CN104674362A (en) * | 2015-03-11 | 2015-06-03 | 湖州吉昌丝绸有限公司 | Preparation method of fibroin/graphene conductive fiber |
| KR101691039B1 (en) * | 2015-05-27 | 2016-12-29 | 국방과학연구소 | 3-dimenstinal nanofiber membrane and Method of manufacturing the same using liquid collector |
| CN105926075A (en) * | 2016-05-13 | 2016-09-07 | 东莞市联洲知识产权运营管理有限公司 | Graphene modified silk fiber preparing method |
| CN106400312A (en) * | 2016-09-07 | 2017-02-15 | 东华大学 | Method for preparing conductive composite nanofiber nervous tissue engineering scaffold based on graphene |
| CN106913910A (en) * | 2017-04-28 | 2017-07-04 | 武汉理工大学 | A kind of preparation method of fibroin albumen/Graphene composite nano-fiber support material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109295615A (en) | 2019-02-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107059251B (en) | The preparation method of one-way wet-guide nanofiber multilayer complex films with wetting gradient | |
| WO2020221286A1 (en) | β-FEOOH/POLYACRYLONITRILE COMPOSITE NANOFIBER MEMBRANE, PREPARATION METHOD THEREFOR AND USE THEREOF | |
| Zhuang et al. | Solution blowing of submicron-scale cellulose fibers | |
| Wang et al. | Electrospun ultra-fine silk fibroin fibers from aqueous solutions | |
| WO2018108011A1 (en) | Method of manufacturing flexible transparent electrically conductive thin film, and product thereof | |
| CN109537163B (en) | Chitosan/sodium alginate/polyvinyl alcohol polyelectrolyte nanofiber composite membrane and preparation method thereof | |
| CN110379642B (en) | Stretchable nanofiber, application thereof, stretchable capacitor electrode comprising stretchable nanofiber and preparation method | |
| CN103173892A (en) | Preparation method of nano bamboo fiber composite material | |
| CN108611704B (en) | Nano carbon fiber and preparation method thereof | |
| CN105734724A (en) | Novel method for preparing carbon nanofibers through electrospinning | |
| CN109295615B (en) | Preparation method of durable graphene conductive silk fibroin nanofiber membrane | |
| CN110607582A (en) | Method for preparing continuous PAN piezoelectric yarn by electrostatic spinning | |
| CN114717704B (en) | Antibacterial and antistatic polyurethane composite yarn and preparation method and integrated device thereof | |
| CN103726233A (en) | Preparation method and application of polyisophthaloyl metaphenylene diamine-polyacrylonitrile composite nanofiber film | |
| CN109208104A (en) | A kind of preparation method of conductive cellulose fiber | |
| CN113622089B (en) | Polyimide/cerium dioxide composite nanofiber membrane and preparation method thereof | |
| CN108277556A (en) | A kind of superhigh-flexibility graphene fiber and preparation method thereof prepared by dry spinning | |
| CN111719212B (en) | Preparation method of flexible graphene conductive yarn capable of being woven | |
| CN105970483A (en) | Electrostatic spinning directional nanofiber membrane and preparation method and application thereof | |
| KR20190071149A (en) | Method of coating for nanofiber using reduction of metalic salts and method for manufacturing transparent electrode | |
| CN111850760A (en) | Method for preparing high-orientation-degree silk fibroin nanofiber yarn by using waste silk | |
| Cheng et al. | Effect of surface active agent on bubble-electrospun polyacrylonitrile nanofibers | |
| CN110863349A (en) | Preparation method of centrifugal spinning nanofiber body material | |
| CN109234916A (en) | A kind of preparation method with cross-linked structure asphalt-based nano fabric nonwoven cloth | |
| CN110656391B (en) | Composite conductive fabric and manufacturing method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |