CN107603240A - Cellulose based on graphene/nano silver wire/silk magnetic porous composite material - Google Patents
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Abstract
The invention discloses a kind of cellulose based on graphene/nano silver wire/silk magnetic porous composite material and preparation method thereof, using modified cellulose and silk-fibroin as carrier, load nano ferriferrous oxide granule, and obtain cellulose/silk magnetic porous composite material by crosslinking, liquid nitrogen, freeze-drying process, then in the surface layer self assembly nano silver wire and graphene oxide of cellulose/silk magnetic porous composite material, finally graphene oxide is reduced to obtain the cellulose based on graphene/nano silver wire/silk magnetic porous composite material.This invention ensures that the Stability Analysis of Structures and mechanical strength of cellulose/silk porous material, and the dispersing uniformity of graphene and nano silver wire in cellulose/silk matrix, there is potential application value in fields such as photoelectric material, sorbing material, medical material, biomaterials.
Description
Technical field
The present invention relates to a kind of cellulose based on graphene/nano silver wire/silk magnetic porous composite material, category are compound
Material Field.
Background technology
For a long time, cellulose is always weaving, the key industry raw material of papermaking, with its recyclability, biodegradable
Property and cost advantage are increasingly subject to the attention of people, in medicine control, release tech, immobilization technology, biology sensor, membrane material
Material, performance chemicalses and additive etc. show good development prospect.Reduction and oil, natural gas due to arable land etc.
The increasingly depleted of fossil resource, the yield of synthetic fibers will be restricted more and more.And a kind of green of cellulose conduct,
Environmentally friendly, reproducible resource, obtain a unprecedented opportunity to develop.
Silk is described as fiber queen, and its is soft, abundant, smooth, plentiful, possesses gloss soft as pearl,
Weaving, apparel industry are widely used.Silk is made up of silk gum and fibroin, and wherein silk gum is located at the outer layer of silk, content
Between 20%-30%, fibroin is located at the internal layer of silk, and content is between 70%-80%.Fibroin positioned at silk internal layer is one
Kind natural macromolecular material, by serine（serine）, glycine（Glycine）, alanine（alanine）Deng 18 kinds of amino
Acid composition, molecular weight is about 2300kDa, is made up of heavy chain, light chain and P25, and wherein the molecular weight of heavy chain H chains is 350kDa, gently
Chain L chain molecular weights are 26kDa, and P25 molecular weight is 30kDa, and the ratio of three is 6:6:1.Fibroin share 11 noncrystalline domains and
12 crystal regions, by disulfide bond between heavy chain H chains and light chain L chains, form H-L complexs.
The crystal habit of fibroin is broadly divided into two kinds of the type of fibroin I and II type of fibroin.The type of fibroin I is a kind of knot of meta-stable
Structure, conformation are crank shape or zigzag, are a kind of intermediatenesses between alpha-helix and beta sheet, and structure cell belongs to orthorhombic
System.Handled through damp and hot, sour, polar solvent etc., the type of fibroin I is easy to change to the type of fibroin II.The type of fibroin II is antiparallel β-folding
Stack structure, belong to orthorhombic system, peptide chain arranged regular, hydrogen bond and intermolecular gravitation make adjacent chain is intersegmental to be tightly combined, tension
It is strong to stretch ability, and is insoluble in water, it is strong to the resistance of acid, alkali, salt, enzyme and heat.In addition, recent years are found that one kind is new again
Fibroin crystal habit, i.e. the type of fibroin III, its crystal structure is similar with polyglycine II, belongs to hexagonal crystal system.
Silk obtained regenerated silk fibroin after degumming, dissolving, purification have nontoxic, non-stimulated, biological degradability,
Biocompatibility, good engineering properties, are easily processed into various forms, as silk protein films, gel, fiber, three-dimensional rack,
Sponge etc., it is a kind of important natural function material, available for fields such as biology, medical science, photoelectric materials, is carried as medicament slow release
Body, tissue engineering bracket, operation suture thread, artificial skin, artificial tendon, cell culture vector, wound dressing, electrically conducting transparent are thin
Film, sorbing material etc.（Silk, 2017,03:6-12；Biomedical engineering magazine, 2015,06:1364-1368；Sericulture section
Learn, 2016,02:341-345）.
2004, Univ Manchester UK physicist An Deliehaimu and Constantine's Nuo Woxiao loves, utilize
The method for tearing adhesive tape, successfully isolates the graphene of individual layer atomic arrangement from graphite, therefore two people also obtain 2010
The Nobel Prize in physics in year（Science,2004,306( 5696):666-669）.Graphene is by carbon atom with sp2Hydridization rail
Road forms hexangle type honeycomb lattice, and its construction unit is carbon hexatomic ring, and it is a kind of two-dimentional material of only single layer of carbon atom thickness
Material.Graphene is the basic system unit for forming carbon-based material.It can be wrapped to form zero dimension Fullerenes, be rolled into one-dimensional
Carbon nanotube, layer upon layer is into three-dimensional graphite.From graphene find that day, graphene just into
For the focus and focus of research, in ultracapacitor, transparency electrode, desalinization, light emitting diode, sensor, hydrogen storage, the sun
The fields such as energy battery, catalyst carrier, composite, biologic bracket material, bio-imaging, drug delivery, weaving, printing and dyeing have extensively
General application（Novel charcoal material, 2014,05:329-356, Chinese invention patent 201410565512.2）.
Graphene composite material is research direction important in graphene application field（Chemical Engineer, 2015,01:34-
38+46）.Existing graphene composite material is by graphene oxide and another material mostly（Inorganic material, polymeric material
Material etc.）Uniformly it is mixed in solvent, finished product is then obtained by the methods of spin processes, vacuum filtration, spin coating.But due to graphene
The problem of certain be present in the π-π stackings effect easily aggregation of itself, its dispersiveness in a solvent（Chemical progress, 2016,05:
647-656）, the preparation of follow-up composite and the final performance of product can be influenceed.
The nano silver wire of one-dimentional structure has high-specific surface area, heat conduction, conduction, printing opacity, ductility, mechanical strength and flexibility
Etc. performance, there is potential application value in fields such as flexible conductive film, solar cell, touch-screen, display screen, sensors
（Chinese material is in progress, 2016 (07): 545-551）.Current most graphene/silver nanowire composite materials are thin with two dimension
Based on membrane material, it is used for electrode material（Preparation, sign and its application [J] physics in nesa coating of graphene
Chemical journal, 2016,32 (10):2399-2410；The preparation of reduced graphene oxide serving-nano silver wire flexible compound electrode with
Performance study [J] lights journal, 2015,36 (05):545-551；Graphene/nano silver wire compound transparent electricity conductive film photoelectricity
Performance and stability study [J] artificial lens journals, 2015,44 (12):3788-3792+3798；Chinese invention patent
201380035160.3 utilize mixed electrode of nano silver wire and graphene and preparation method thereof）.
The content of the invention
In view of the above problems, the present invention provides a kind of cellulose/silk based on graphene/nano silver wire is magnetic porous multiple
Condensation material and preparation method thereof.
The technical scheme is that：
（1）1-100g/L dopamine Tris-HCl buffer solutions are prepared, cellulose is immersed in by regulation pH value at room temperature to 8.5
24h in above-mentioned buffer solution, bath raio 1:50, after deionized water is cleaned repeatedly, obtain poly-dopamine modified lithium cellulose.（2）By silk egg
It is dissolved in vain in deionized water, is configured to the 1g/L-100g/L aqueous solution, by the three of 1g/L-100g/L under conditions of 50-80 DEG C
Valency molysite aqueous solution is slowly dropped into silk protein aqueous solution, is stirred, wherein the quality of the silk-fibroin and trivalent iron salt
Than for 1:1-10:1, calcium chloride solution of the concentration as 1-5wt%, the calcium chloride and silk are added dropwise using 30 drops/min speed
The mass ratio of albumen is 1:50, regulation pH value is to 10-12, after 60 DEG C are at the uniform velocity stirred 1h, the poly- DOPA that is slowly added in step 1
Amine modified cellulose, the mass ratio of the poly-dopamine modified lithium cellulose and silk-fibroin is 1:1, after ultrasonic mixing is uniform, pour into
In mould, 1min in liquid nitrogen is put into, pre-freeze 6h in -20 DEG C of refrigerators is placed in after taking-up, is freezed in -80 DEG C of Thermo ultra low temperature freezers
6h, it is then placed in 48h in freeze dryer and obtains cellulose/silk magnetic porous composite material.（3）Nano silver wire is configured to 1-
The 10g/L aqueous solution, then add the 1-10g/L Hyperbranched Polymer with Terminal Amido aqueous solution, the amine-terminated hyperbrancedization polymerization
The volume ratio of thing and the nano silver wire aqueous solution is 1:1-1:10, under normal temperature after at the uniform velocity stirring reaction 24h, with deionized water and ethanol
Wash repeatedly, Hyperbranched Polymer with Terminal Amido modification nano silver wire is obtained after drying.（4）By cellulose/silk in step 2
Magnetic porous composite material is immersed in 10-60min in the 1-10g/L Hyperbranched Polymer with Terminal Amido modification nano silver wire aqueous solution,
Bath raio 1:10, rinsed, dried repeatedly with deionized water after taking-up；Then above-mentioned magnetic porous composite material is immersed in 1-10g/
10-60min in L graphene oxide water solutions, bath raio 1:10, rinsed, dried, so far by one repeatedly with deionized water after taking-up
Layer nano silver wire/graphene oxide is assembled into the surface of magnetic porous composite material, then polymerize successively in amine-terminated hyperbrancedization
Thing is modified and aforesaid operations is repeated in nano silver wire and graphene oxide dressing liquid, determines magnetic porous composite material table as needed
The number of plies of face nano silver wire/graphene oxide assembling, is finally placed in reducing agent and is reduced, after washing, filter, being dried in vacuo
Obtain the cellulose based on graphene/nano silver wire/silk magnetic porous composite material.
Preferably, the silk-fibroin is that silk is made after degumming, dissolving, dialysis, purification.
Preferably, the trivalent iron salt is the one or more in iron chloride, ferric sulfate, ferric nitrate.
Preferably, the reducing agent is that hydrazine hydrate, sodium borohydride, sodium citrate, vitamin C, hydroiodic acid, tea are more
One or more in phenol.
Compared with prior art, the advantage of the invention is that：Poly-dopamine is a kind of biology with superpower Adhesion property
Compatibility material, almost can be in any material surface film forming.The forming process of poly-dopamine is simple, and reaction condition is gentle, as long as
Poly-dopamine layer can be formed in material surface by immersing the material in the Tris-HCl buffer solutions of alkalescence containing dopamine.It is thus poly- more
Bar amine modified cellulose effectively increases the bonding between cellulose and fibroin.Using modified cellulose and silk-fibroin as load
Body, nano ferriferrous oxide granule is loaded, and it is more to obtain after crosslinking, liquid nitrogen, freeze-drying process cellulose/silk magnetic
Hole composite material, final load graphene and nano silver wire, it ensure that graphene and nano silver wire in cellulose/silk matrix
Dispersing uniformity and cellulose/silk porous material Stability Analysis of Structures and mechanical strength.Cellulose/silk is magnetic porous compound
Material has certain magnetic, it is possible to achieve effective to recycle.
Embodiment
The invention will be further elucidated with reference to specific embodiments.
Embodiment 1：
（1）1g/L dopamine Tris-HCl buffer solutions are prepared, cotton is immersed in above-mentioned buffering by regulation pH value at room temperature to 8.5
24h in liquid, bath raio 1:50, after deionized water is cleaned repeatedly, obtain poly-dopamine modified lithium cotton.（2）Silk-fibroin is dissolved in deionization
In water, the 1g/L aqueous solution is configured to, it is water-soluble that 1g/L ferric chloride in aqueous solution is slowly dropped into silk-fibroin under conditions of 50 DEG C
In liquid, stir, wherein the mass ratio of the silk-fibroin and iron chloride is 1:1, it is added dropwise with 30 drops/min speed dense
The calcium chloride solution for 1wt% is spent, the mass ratio of the calcium chloride and silk-fibroin is 1:50, regulation pH value is at the uniform velocity stirred to 10,60 DEG C
After mixing 1h, the poly-dopamine modified lithium cotton that is slowly added in step 1, the mass ratio of the poly-dopamine modified lithium cotton and silk-fibroin is
1:1, after ultrasonic mixing is uniform, pour into mould, be put into 1min in liquid nitrogen, be placed in pre-freeze 6h in -20 DEG C of refrigerators after taking-up, -80
6h is freezed in DEG C Thermo ultra low temperature freezers, 48h in freeze dryer is then placed in and obtains cotton/silk magnetic porous composite material.
（3）Nano silver wire is configured to the 1g/L aqueous solution, then adds the 1g/L Hyperbranched Polymer with Terminal Amido aqueous solution, the end
The volume ratio of amino dissaving polymer and the nano silver wire aqueous solution is 1:1, under normal temperature after at the uniform velocity stirring reaction 24h, spend from
Sub- water and ethanol wash, Hyperbranched Polymer with Terminal Amido modification nano silver wire are obtained after drying repeatedly.（4）By in step 2
Cotton/silk magnetic porous composite material is immersed in 10min in the 1g/L Hyperbranched Polymer with Terminal Amido modification nano silver wire aqueous solution,
Bath raio 1:10, rinsed, dried repeatedly with deionized water after taking-up；Then above-mentioned magnetic porous composite material is immersed in 1g/L oxygen
10min in graphite aqueous solution, bath raio 1:10, rinsed repeatedly with deionized water after taking-up, dry, be placed in hydrazine hydrate solution
90 DEG C of reductase 12 h, washing, filter, obtain the magnetic porous composite wood of cotton/silk based on graphene/nano silver wire after vacuum drying
Material.
Embodiment 2：
（1）10g/L dopamine Tris-HCl buffer solutions are prepared, regulation pH value to 8.5, are at room temperature immersed in stalk above-mentioned slow
24h in fliud flushing, bath raio 1:50, after deionized water is cleaned repeatedly, obtain poly-dopamine modified lithium stalk.（2）Silk-fibroin is dissolved in
In ionized water, the 10g/L aqueous solution is configured to, 10g/L ferric sulfate aqueous solution is slowly dropped into silk egg under conditions of 70 DEG C
In white water solution, stir, wherein the mass ratio of the silk-fibroin and ferric sulfate is 5:1, with 30 drops/min speed dropwise
The calcium chloride solution that concentration is 2wt% is added, the mass ratio of the calcium chloride and silk-fibroin is 1:50, regulation pH value is to 11,60 DEG C
After at the uniform velocity stirring 1h, the poly-dopamine modified lithium stalk that is slowly added in step 1, the poly-dopamine modified lithium stalk and silk-fibroin
Mass ratio be 1:1, after ultrasonic mixing is uniform, pour into mould, be put into 1min in liquid nitrogen, be placed in after taking-up in -20 DEG C of refrigerators
Pre-freeze 6h, 6h is freezed in -80 DEG C of Thermo ultra low temperature freezers, being then placed in 48h in freeze dryer, to obtain stalk/silk magnetic more
Hole composite material.（3）Nano silver wire is configured to the 5g/L aqueous solution, then adds 5g/L Hyperbranched Polymer with Terminal Amido water
The volume ratio of solution, the Hyperbranched Polymer with Terminal Amido and the nano silver wire aqueous solution is 1:5, at the uniform velocity stirring reaction under normal temperature
After 24h, washed repeatedly with deionized water and ethanol, Hyperbranched Polymer with Terminal Amido modification nano silver wire is obtained after drying.（4）Will
Stalk/silk magnetic porous composite material in step 2 is immersed in 5g/L Hyperbranched Polymer with Terminal Amido modification nano silver wire water
30min in solution, bath raio 1:10, rinsed, dried repeatedly with deionized water after taking-up；Then by above-mentioned magnetic porous composite material
It is immersed in 30min in 5g/L graphene oxide water solutions, bath raio 1:10, rinsed, dried, so far repeatedly with deionized water after taking-up
One layer of nano silver wire/graphene oxide is assembled into the surface of magnetic porous composite material, then successively amine-terminated hyperbranced
Fluidized polymer is modified in nano silver wire and graphene oxide dressing liquid and is repeated once aforesaid operations, is placed in sodium citrate 90 DEG C also
Former 12h, washing, filter, obtain the stalk based on graphene/nano silver wire/silk magnetic porous composite material after vacuum drying.
Embodiment 3：
（1）Prepare 50g/L dopamine Tris-HCl buffer solutions, regulation pH value to 8.5, at room temperature by flax retting above-mentioned slow
24h in fliud flushing, bath raio 1:50, after deionized water is cleaned repeatedly, obtain poly-dopamine modified lithium flax.（2）Silk-fibroin is dissolved in
In ionized water, the 50g/L aqueous solution is configured to, the 50g/L trivalent iron salt aqueous solution is slowly dropped into silk under conditions of 80 DEG C
In protein solution, stir, wherein the mass ratio of the silk-fibroin and trivalent iron salt is 10:1, with 30 drops/min speed
The calcium chloride solution that concentration is 5wt% is added dropwise, the mass ratio of the calcium chloride and silk-fibroin is 1:50, regulation pH value to 12,
After 60 DEG C are at the uniform velocity stirred 1h, poly-dopamine modified lithium flax for being slowly added in step 1, described poly-dopamine modified lithium flax and silk
The mass ratio of albumen is 1:1, after ultrasonic mixing is uniform, pour into mould, be put into 1min in liquid nitrogen, -20 DEG C of ice are placed in after taking-up
Pre-freeze 6h in case, 6h is freezed in -80 DEG C of Thermo ultra low temperature freezers, 48h in freeze dryer is then placed in and obtains Flax/Silk magnetic
Property is composite porous.（3）Nano silver wire is configured to the 10g/L aqueous solution, amine-terminated hyperbrancedization for then adding 10g/L is gathered
The volume ratio of the compound aqueous solution, the Hyperbranched Polymer with Terminal Amido and the nano silver wire aqueous solution is 1:10, at the uniform velocity stir under normal temperature
After mixing reaction 24h, washed repeatedly with deionized water and ethanol, Hyperbranched Polymer with Terminal Amido modification silver nanoparticle is obtained after drying
Line.（4）Flax/Silk magnetic porous composite material in step 2 is immersed in the modification of 10g/L Hyperbranched Polymer with Terminal Amido
60min in the nano silver wire aqueous solution, bath raio 1:10, rinsed, dried repeatedly with deionized water after taking-up；Then it is above-mentioned magnetic is more
Hole composite material is immersed in 60min in 10g/L graphene oxide water solutions, bath raio 1:10, rushed repeatedly with deionized water after taking-up
Wash, dry, one layer of nano silver wire/graphene oxide is so far assembled into the surface of magnetic porous composite material, then successively
Modified in Hyperbranched Polymer with Terminal Amido and five aforesaid operations are repeated in nano silver wire and graphene oxide dressing liquid, be placed in boron hydrogen
Change 60 DEG C of reduction 5h in sodium, it is more to obtain the Flax/Silk magnetic based on graphene/nano silver wire after washing, suction filtration, vacuum drying
Hole composite material.
Obviously, the above embodiment of the present invention is only intended to clearly illustrate example of the present invention, and is not pair
The restriction of embodiments of the present invention.For those of ordinary skill in the field, may be used also on the basis of the above description
To make other changes in different forms.Here all embodiments can not be exhaustive.It is every to belong to this hair
Row of the obvious changes or variations that bright technical scheme is amplified out still in protection scope of the present invention.
Claims (7)
1. the preparation method of the cellulose based on graphene/nano silver wire/silk magnetic porous composite material, it is characterised in that：
Step 1：1-100g/L dopamine Tris-HCl buffer solutions are prepared, regulation pH value at room temperature soaks cellulose to 8.5
Stain 24h in above-mentioned buffer solution, bath raio 1:50, after deionized water is cleaned repeatedly, obtain poly-dopamine modified lithium cellulose；
Step 2：Silk-fibroin is dissolved in deionized water, is configured to the 1g/L-100g/L aqueous solution, will under conditions of 50-80 DEG C
The 1g/L-100g/L trivalent iron salt aqueous solution is slowly dropped into silk protein aqueous solution, is stirred, wherein the silk-fibroin
Mass ratio with trivalent iron salt is 1:1-10:1, it is molten as 1-5wt% calcium chloride that concentration is added dropwise using 30 drops/min speed
Liquid, regulation pH value is to 10-12, after 60 DEG C are at the uniform velocity stirred 1h, the poly-dopamine modified lithium cellulose that is slowly added in step 1, and ultrasound
After well mixed, pour into mould, be put into 1min in liquid nitrogen, pre-freeze 6h in -20 DEG C of refrigerators, -80 DEG C of Thermo are placed in after taking-up
6h is freezed in ultra low temperature freezer, 48h in freeze dryer is then placed in and obtains cellulose/silk magnetic porous composite material；
Step 3：Nano silver wire is configured to the 1-10g/L aqueous solution, then adds 1-10g/L amine-terminated hyperbrancedization polymerization
The volume ratio of the thing aqueous solution, the Hyperbranched Polymer with Terminal Amido and the nano silver wire aqueous solution is 1:1-1:10, under normal temperature at the uniform velocity
After stirring reaction 24h, washed repeatedly with deionized water and ethanol, Hyperbranched Polymer with Terminal Amido modification silver nanoparticle is obtained after drying
Line；
Step 4：It is poly- that cellulose in step 2/silk magnetic porous composite material is immersed in 1-10g/L amine-terminated hyperbrancedization
10-60min in the compound modification nano silver wire aqueous solution, bath raio 1:10, rinsed, dried repeatedly with deionized water after taking-up；Then
Above-mentioned magnetic porous composite material is immersed in 10-60min in 1-10g/L graphene oxide water solutions, bath raio 1:10, after taking-up
Rinsed repeatedly with deionized water, dry, one layer of nano silver wire/graphene oxide is so far assembled into magnetic porous composite material
Surface, then modified successively in Hyperbranched Polymer with Terminal Amido and above-mentioned behaviour repeated in nano silver wire and graphene oxide dressing liquid
Make, determine the number of plies of magnetic porous composite material surface nano silver wire/graphene oxide assembling as needed, be finally placed in reduction
Reduced in agent, wash, filter, be dried in vacuo after to obtain cellulose/silk based on graphene/nano silver wire magnetic porous
Composite.
2. the system of the cellulose based on graphene/nano silver wire/silk magnetic porous composite material according to claim 1
Preparation Method, it is characterised in that the silk-fibroin is that silk is made after degumming, dissolving, dialysis, purification.
3. the system of the cellulose based on graphene/nano silver wire/silk magnetic porous composite material according to claim 1
Preparation Method, it is characterised in that the trivalent iron salt is the one or more in iron chloride, ferric sulfate, ferric nitrate.
4. the system of the cellulose based on graphene/nano silver wire/silk magnetic porous composite material according to claim 1
Preparation Method, it is characterised in that the mass ratio of the calcium chloride and silk-fibroin is 1:50.
5. the system of the cellulose based on graphene/nano silver wire/silk magnetic porous composite material according to claim 1
Preparation Method, it is characterised in that the mass ratio of the poly-dopamine modified lithium cellulose and silk-fibroin is 1:1.
6. the system of the cellulose based on graphene/nano silver wire/silk magnetic porous composite material according to claim 1
Preparation Method, it is characterised in that the reducing agent is hydrazine hydrate, sodium borohydride, sodium citrate, vitamin C, hydroiodic acid, Tea Polyphenols
In one or more.
7. the magnetic porous composite wood of cellulose/silk based on graphene/nano silver wire obtained by claim 1 preparation method
Material.
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| CN109786134A (en) * | 2019-02-28 | 2019-05-21 | 重庆文理学院 | A kind of preparation method of supercapacitor |
| CN110581278A (en) * | 2019-09-24 | 2019-12-17 | 浙江农林大学 | Positive electrode material for flexible lithium ion battery, preparation method and application thereof, and flexible lithium ion battery |
| CN111560173A (en) * | 2020-06-02 | 2020-08-21 | 杭州电子科技大学 | Flower-like graphene/silk fibroin nanoclusters and preparation method thereof |
| CN112574436A (en) * | 2019-09-12 | 2021-03-30 | 天津大学 | Composite gel based on silk fibroin and polydopamine and preparation method and application thereof |
| CN112915935A (en) * | 2021-01-25 | 2021-06-08 | 合肥工业大学 | Bionic magnetic fibroin-based composite aerogel, and preparation method and application thereof |
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| CN109786134A (en) * | 2019-02-28 | 2019-05-21 | 重庆文理学院 | A kind of preparation method of supercapacitor |
| CN109786134B (en) * | 2019-02-28 | 2020-10-09 | 重庆文理学院 | Preparation method of super capacitor |
| CN112574436A (en) * | 2019-09-12 | 2021-03-30 | 天津大学 | Composite gel based on silk fibroin and polydopamine and preparation method and application thereof |
| CN112574436B (en) * | 2019-09-12 | 2022-03-29 | 天津大学 | Composite gel based on silk fibroin and polydopamine and preparation method and application thereof |
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| CN111560173A (en) * | 2020-06-02 | 2020-08-21 | 杭州电子科技大学 | Flower-like graphene/silk fibroin nanoclusters and preparation method thereof |
| CN112915935A (en) * | 2021-01-25 | 2021-06-08 | 合肥工业大学 | Bionic magnetic fibroin-based composite aerogel, and preparation method and application thereof |
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Application publication date: 20180119 |