CN107556522A - Silk/the sodium alginate for loading graphene and nano silver wire is composite porous - Google Patents
Silk/the sodium alginate for loading graphene and nano silver wire is composite porous Download PDFInfo
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- CN107556522A CN107556522A CN201710836887.1A CN201710836887A CN107556522A CN 107556522 A CN107556522 A CN 107556522A CN 201710836887 A CN201710836887 A CN 201710836887A CN 107556522 A CN107556522 A CN 107556522A
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Abstract
The invention discloses a kind of silk/sodium alginate for loading graphene and nano silver wire is composite porous and preparation method, preparation process are as follows：Use PAMAM modified sodium alginates；It is composite porous that silk/sodium alginate is obtained using liquid nitrogen, frozen dried；By silk/sodium alginate is composite porous be immersed in graphene oxide solution fully absorption after, reduce to obtain the three-dimensional porous composite of silk/sodium alginate of load graphene using reducing agent；It is composite porous in the three-dimensional porous composite surface layer layer self assembly nano silver wire of silk/sodium alginate of load graphene, silk/sodium alginate that load graphene and nano silver wire is finally prepared finally by means of electrostatic attraction.The present invention uses sodium alginate and silk as base material, graphene and nano silver wire are subjected to effective self assembly, obtain loading graphene and silk/sodium alginate of nano silver wire is composite porous, there is huge application value in fields such as photoelectric material, sorbing material, biomaterial, medical materials.
Description
Technical field
The present invention relates to a kind of silk/sodium alginate for loading graphene and nano silver wire is composite porous, belong to nanometer
Field of compound material.
Background technology
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）.
With the birth of petroleum base high polymer material, high polymer material extensive use in every field, but its institute's band
The pollution problem come has a strong impact on the living environment of the mankind.And native biopolymer material is with its unique performance and to environment
Close friend, turn into the study hotspot of current new material.Wherein, sodium alginate excellent has biocompatibility, nontoxic as a kind of
And the material of biodegradable, it has been widely used in the fields such as grocery trade, agricultural, medical industry, commodity at present.Sea
Mosanom is also known as algin, sodium alginate or seaweed gel, be extracted from the sea-tangle or sargassum of brown algae iodine and mannitol with
Byproduct afterwards.Sodium alginate is the main component of alginic cell wall and cytoplasm, and marine alga acid molecule is by β-D-MANNOSE
Aldehydic acid（M areas）With α-L- guluronic acids（G areas）The block linear polymer of 2 kinds of monomer compositions.In 1 marine alga acid molecule,
The continuous segment that wherein a kind of uronic acid is formed may be comprised only, it is also possible to form block copolymer by 2 kinds of uronic acid chain links.And
Sodium alginate is the product after alginic acid is neutralized with alkali.Sodium alginate is soluble in water, is the very high poly- electrolysis of a kind of charge density
Matter, there is good biological degradability and compatibility（New Chemical Materials, 2007, (08):20-22）.In sodium alginate structure
Containing substantial amounts of hydroxyl and carboxyl, therefore sodium alginate is the initiation material of an ideal chemistry functional.Pass through
Modification to hydroxyl in structure and carboxyl, its dissolubility, hydrophobicity and some physical and chemical performances is changed, form sea
Mosanom derivation function compound, can widen its application field.At present, the modification for sodium alginate hydroxyl and carboxyl is main
There are oxidation, sulfonation, esterification, amidatioon and graft copolymerization etc.（Huang Panli, Shen Xiaojun, Chen Jinghuan, Wu Yuying, Sun Run storehouse marine algas
The extraction of sour sodium and functional modification progress [J] chemistry of forest product and industry, 2017）.
The existing literature research of silk/sodium alginate composite, but it is mostly film and fiber.Such as Agricultural University Of Anhui's system
For fibroin-sodium alginate-glycerine blend film（Agricultural University Of Anhui's journal, 2013,40 (2): 321-325）, Dalian industry
University utilizes polyethyleneglycol diglycidylether（PEGDE）It is chemically crosslinked fibroin albumen（SF）, with CaCl2Crossslinked sodium alginate
（SA）, SF/SA dual network type composite fibres are prepared for using the method for substep crosslinking（Wish national wealth, Zhang Hong, Li Huitao, Chen Tao, in
Jump, preparation and performance [J] composite journals of the chemical crosslinking modified fibroin albumens of Guo Jing/sodium alginate fiber,
2017）.
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）.Only have grinding for a small amount of three-dimensional porous composite of metal nanometer line at present
Study carefully report.Yu Shuhong seminars of China Science ＆ Technology University are prepared for gold/cerium dioxide nano line three-dimensional material by template of sponge
Material（Using sponge as the preparation of carrier loaded gold/cerium dioxide nano line three-dimensional material and its in continuous-flow system situ also
Former p-nitrophenol (English) [J] Science Bulletin, 2016,61 (09):700-705）；Macroscopic view three is used as using sponge
Framework template is tieed up, by simple nano pulp dip-coating means, makes nano silver wire（AgNWs）In the guide of sponge framework template
Under, form the AgNWs three-dimensional macro assemblies with dual-network structure.
The content of the invention
In view of the above problems, the present invention provides a kind of silk/sodium alginate for loading graphene and nano silver wire is porous multiple
Condensation material and preparation method.
The technical scheme is that：
（1）Sodium alginate is scattered in deionized water under normal temperature, bath raio 1:50, it is slowly added to 1-100g/L polyamide-amide
The PAMAM aqueous solution, the wherein volume ratio of the PAMAM aqueous solution and sodium alginate aqueous solution are 1:1-1:10, after reacting 24h, with steaming
Distilled water and ethanol wash, obtain PAMAM modified sodium alginates after drying repeatedly.（2）Silk-fibroin is dissolved in deionized water, prepared
Into the 1g/L-100g/L aqueous solution, the 1g/L-100g/L trivalent iron salt aqueous solution is slowly dropped under conditions of 50-80 DEG C
In silk protein aqueous solution, stir, wherein the mass ratio of the silk-fibroin and trivalent iron salt is 1:1-10:1,60 DEG C is at the uniform velocity stirred
After mixing 1h, the PAMAM modified sodium alginates that are slowly added in step 1, the mass ratio of the modified sodium alginate and silk-fibroin is
1:1-1:10, after ultrasonic mixing is uniform, pour into mould, be put into 1min in liquid nitrogen, pre-freeze in -20 DEG C of refrigerators is placed in after taking-up
6h, 6h is freezed in -80 DEG C of Thermo ultra low temperature freezers, being then placed in 48h in freeze dryer, to obtain silk/sodium alginate porous multiple
Condensation material.（3）Compound concentration 1-100g/L graphene oxide water solution, ultrasonic 1h, by silk/sodium alginate in step 2
It is composite porous to be immersed in 24h in graphene oxide solution, bath raio 1:50, after being cleaned repeatedly with ethanol and deionized water, put
Reduced in reducing agent, cleaned repeatedly with ethanol and deionized water, obtain loading silk/sea of graphene after vacuum drying
The three-dimensional porous composite of mosanom.（4）Nano silver wire is configured to the 1-10g/L aqueous solution, then adds 1-10g/L end
Amino dissaving polymer or the Hyperbranched Polymer with Terminal Hydroxyl aqueous solution, the Hyperbranched Polymer with Terminal Amido or the terminal hydroxy group
The volume ratio of the dissaving polymer aqueous solution and the nano silver wire aqueous solution is 1:1-1:10, under normal temperature after at the uniform velocity stirring reaction 24h,
Washed repeatedly with deionized water and ethanol, Hyperbranched Polymer with Terminal Amido modification nano silver wire or terminal hydroxy group over-expense are obtained after drying
Fluidized polymer modifies nano silver wire.（5）Hyperbranched Polymer with Terminal Amido is modified into nano silver wire and Hyperbranched Polymer with Terminal Hydroxyl
Modification nano silver wire is configured to the 0.1-10g/L aqueous solution respectively, then by silk/marine alga of the load graphene in step 3
The sour three-dimensional porous composite of sodium is immersed in 10- in 80 DEG C of the Hyperbranched Polymer with Terminal Amido modification nano silver wire aqueous solution
60min, bath raio 1:50, rinsed, dried repeatedly with deionized water after taking-up；Then above-mentioned three-dimensional porous composite is immersed in
10-60min in 80 DEG C of the Hyperbranched Polymer with Terminal Hydroxyl modification nano silver wire aqueous solution, bath raio 1:50, use deionization after taking-up
Water rinses repeatedly, drying, one layer of nano silver wire is so far assembled into the surface of three-dimensional porous composite, then held successively
Amino dissaving polymer is modified repeatedly above-mentioned in nano silver wire and Hyperbranched Polymer with Terminal Hydroxyl modification nano silver wire dressing liquid
Operation, the number of plies of three-dimensional porous composite material surface nano silver wire assembling is determined as needed.
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.
Nano silver wire is synthesized using polyol process, and specific steps refer to document：Peng Yongyi, Xu Guojun, Dai Guozhang, Li Hong
Build polyol process preparation process condition research [J] material Leaders of nano silver wires, 2015,29 (22):79-81+86；Xia Xing
Reach, Yang Bingchu, Zhang Xiang, the hot method of Zhou Conghua polyalcohols prepares nano silver wire and its application [J] in transparent conductive film
Functional material, 2016,47 (05):5091-5095；Li Yiqun liquid phases polyol process controlledly synthesis metal silver nanowires and its
Application [D] Lanzhou University in nesa coating, 2015；Ma Xiao, You Fangfang, Feng Jinyang, Zhao Xiujian polyol process prepare one
Tie up Ag nano wires [J] artificial lens journals, 2014,43 (03):587-591；Guo Ruiping, Zheng Min, Zhang Haixia microwave radiation technologies
Polyol process quickly prepares research [J] the Institutes Of Technology Of Taiyuan journal of Ag nano wires, 2013,44 (01):76-80；Middle promulgated by the State Council
Bright patent CN201610804238.9；Chinese invention patent CN201710357029.9.
Compared with prior art, the advantage of the invention is that：PAMAM is polyamidoamine dendrimer, and surface is rich
Containing amino, imido grpup.Using PAMAM modified sodium alginates and silk-fibroin as carrier, firm Covalent bonding together is produced between the two,
Then nano ferriferrous oxide granule is generated, and it is porous compound to obtain after liquid nitrogen, freeze-drying process silk/sodium alginate
Material, graphene is then loaded, ensure that dispersing uniformity and silk/marine alga of the graphene in silk/sodium alginate matrix
The Stability Analysis of Structures and mechanical strength of sour sodium porous material.Finally by means of electrostatic attraction, in silk/alginic acid of load graphene
The three-dimensional porous composite surface layer layer self assembly nano silver wire of sodium, the silkworm of load graphene and nano silver wire is finally prepared
Silk/sodium alginate is composite porous, there is huge answer in fields such as photoelectric material, sorbing material, biomaterial, medical materials
With value.
Embodiment
The invention will be further elucidated with reference to specific embodiments.
Embodiment 1：
（1）Sodium alginate is scattered in deionized water under normal temperature, bath raio 1:50, it is slowly added to 1g/L polyamide-amide PAMAM
The aqueous solution, the wherein volume ratio of the PAMAM aqueous solution and sodium alginate aqueous solution are 1:1, after reacting 24h, with distilled water and ethanol
Wash repeatedly, obtain PAMAM modified sodium alginates after drying.（2）Silk-fibroin is dissolved in deionized water, is configured to 1g/L water
Solution, 1g/L ferric chloride in aqueous solution is slowly dropped into silk protein aqueous solution under conditions of 50 DEG C, stirred, wherein institute
The mass ratio for stating silk-fibroin and iron chloride is 1:After 1,60 DEG C is at the uniform velocity stirred 1h, the PAMAM being slowly added in step 1 is modified sea
Mosanom, the mass ratio of the modified sodium alginate and silk-fibroin is 1:1, after ultrasonic mixing is uniform, pour into mould, be put into liquid
1min in nitrogen, pre-freeze 6h in -20 DEG C of refrigerators is placed in after taking-up, 6h is freezed in -80 DEG C of Thermo ultra low temperature freezers, is then placed in
It is composite porous to obtain silk/sodium alginate by 48h in freeze dryer.（3）Compound concentration 1g/L graphene oxide water solution, surpass
Sound 1h, 24h in graphene oxide solution, bath raio 1 are immersed in by silk/sodium alginate in step 2 is composite porous:50,
After being cleaned repeatedly with ethanol and deionized water, 90 DEG C of reductase 12 h in hydrazine hydrate solution are placed in, it is repeatedly clear with ethanol and deionized water
Wash, obtain loading the three-dimensional porous composite of silk/sodium alginate of graphene after vacuum drying.（4）Nano silver wire is prepared
Into the Hyperbranched Polymer with Terminal Amido or the Hyperbranched Polymer with Terminal Hydroxyl aqueous solution of the 1g/L aqueous solution, then addition 1g/L, institute
The volume ratio for stating Hyperbranched Polymer with Terminal Amido or the Hyperbranched Polymer with Terminal Hydroxyl aqueous solution and the nano silver wire aqueous solution is
1:1, under normal temperature after at the uniform velocity stirring reaction 24h, washed repeatedly with deionized water and ethanol, dry after obtain amine-terminated hyperbrancedization and gather
Compound modifies nano silver wire or Hyperbranched Polymer with Terminal Hydroxyl modification nano silver wire.（5）Hyperbranched Polymer with Terminal Amido is modified
Nano silver wire and Hyperbranched Polymer with Terminal Hydroxyl modification nano silver wire are configured to the 0.1g/L aqueous solution respectively, then by step 3
In the three-dimensional porous composite of silk/sodium alginate of load graphene be immersed in 80 DEG C of Hyperbranched Polymer with Terminal Amido and repair
Adorn 10min in the nano silver wire aqueous solution, bath raio 1:50, rinsed, dried repeatedly with deionized water after taking-up；Then by above-mentioned three-dimensional
10min in the composite porous Hyperbranched Polymer with Terminal Hydroxyl modification nano silver wire aqueous solution for being immersed in 80 DEG C, bath raio 1:50,
Rinsed, dried repeatedly with deionized water after taking-up, obtained loading graphene and silk/sodium alginate of nano silver wire is porous compound
Material.
Embodiment 2：
（1）Sodium alginate is scattered in deionized water under normal temperature, bath raio 1:50, it is slowly added to 10g/L polyamide-amide
The PAMAM aqueous solution, the wherein volume ratio of the PAMAM aqueous solution and sodium alginate aqueous solution are 1:5, after reacting 24h, with distilled water and
Ethanol washs, obtains PAMAM modified sodium alginates after drying repeatedly.（2）Silk-fibroin is dissolved in deionized water, is configured to 10g/
The L aqueous solution, 10g/L ferric sulfate aqueous solution is slowly dropped into silk protein aqueous solution under conditions of 70 DEG C, stirring is equal
It is even, wherein the mass ratio of the silk-fibroin and ferric sulfate is 5:After 1,60 DEG C is at the uniform velocity stirred 1h, it is slowly added in step 1
PAMAM modified sodium alginates, the mass ratio of the modified sodium alginate and silk-fibroin is 1:5, after ultrasonic mixing is uniform, pour into mould
In tool, 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, being then placed in 48h in freeze dryer, to obtain silk/sodium alginate composite porous.（3）Compound concentration 10g/L oxidation
Graphene aqueous solution, ultrasonic 1h, graphene oxide solution is immersed in by silk/sodium alginate in step 2 is composite porous
Middle 24h, bath raio 1:50, after being cleaned repeatedly with ethanol and deionized water, be placed in sodium citrate 90 DEG C of reduction 12h, with ethanol and
Deionized water is cleaned repeatedly, obtains loading the three-dimensional porous composite of silk/sodium alginate of graphene after vacuum drying.（4）
Nano silver wire is configured to the 5g/L aqueous solution, then 5g/L Hyperbranched Polymer with Terminal Amido is added or superbrnaching end-hydroxy gathers
The compound aqueous solution, the Hyperbranched Polymer with Terminal Amido or the Hyperbranched Polymer with Terminal Hydroxyl aqueous solution and nano silver wire are water-soluble
The volume ratio of liquid is 1:5, under normal temperature after at the uniform velocity stirring reaction 24h, washed repeatedly with deionized water and ethanol, dry after held
Amino dissaving polymer modifies nano silver wire or Hyperbranched Polymer with Terminal Hydroxyl modification nano silver wire.（5）Will be amine-terminated hyperbranced
Fluidized polymer modifies nano silver wire and Hyperbranched Polymer with Terminal Hydroxyl modification nano silver wire is configured to the 5g/L aqueous solution respectively, with
The three-dimensional porous composite of silk/sodium alginate of the load graphene in step 3 is immersed in 80 DEG C amine-terminated hyperbranced afterwards
30min in the fluidized polymer modification nano silver wire aqueous solution, bath raio 1:50, rinsed, dried repeatedly with deionized water after taking-up；Then
Above-mentioned three-dimensional porous composite is immersed in 80 DEG C of the Hyperbranched Polymer with Terminal Hydroxyl modification nano silver wire aqueous solution
30min, bath raio 1:50, rinsed, dried repeatedly with deionized water after taking-up, it is more that one layer of nano silver wire so far has been assembled into three-dimensional
The surface of hole composite material, then modify nano silver wire and Hyperbranched Polymer with Terminal Hydroxyl in Hyperbranched Polymer with Terminal Amido successively
Aforesaid operations are repeated twice in modification nano silver wire dressing liquid, obtain loading silk/sodium alginate of graphene and nano silver wire
It is composite porous.
Embodiment 3：
（1）Sodium alginate is scattered in deionized water under normal temperature, bath raio 1:50, it is slowly added to 50g/L polyamide-amide
The PAMAM aqueous solution, the wherein volume ratio of the PAMAM aqueous solution and sodium alginate aqueous solution are 1:10, after reacting 24h, use distilled water
Washed repeatedly with ethanol, obtain PAMAM modified sodium alginates after drying.（2）Silk-fibroin is dissolved in deionized water, is configured to
The 50g/L aqueous solution, 50g/L iron nitrate aqueous solution is slowly dropped into silk protein aqueous solution under conditions of 80 DEG C, stirred
Uniformly, wherein the mass ratio of the silk-fibroin and ferric nitrate is 10:After 1,60 DEG C is at the uniform velocity stirred 1h, it is slowly added in step 1
PAMAM modified sodium alginates, the mass ratio of the modified sodium alginate and silk-fibroin is 1:10, 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, being then placed in 48h in freeze dryer, to obtain silk/sodium alginate composite porous.（3）Compound concentration 50g/L oxidation
Graphene aqueous solution, ultrasonic 1h, graphene oxide solution is immersed in by silk/sodium alginate in step 2 is composite porous
Middle 24h, bath raio 1:50, after being cleaned repeatedly with ethanol and deionized water, 60 DEG C of reduction 5h in sodium borohydride are placed in, with ethanol and are gone
Ionized water cleans repeatedly, obtains loading the three-dimensional porous composite of silk/sodium alginate of graphene after vacuum drying.（4）Will
Nano silver wire is configured to the 10g/L aqueous solution, then adds 10g/L Hyperbranched Polymer with Terminal Amido or superbrnaching end-hydroxy gathers
The compound aqueous solution, the Hyperbranched Polymer with Terminal Amido or the Hyperbranched Polymer with Terminal Hydroxyl aqueous solution and nano silver wire are water-soluble
The volume ratio of liquid is 1:10, under normal temperature after at the uniform velocity stirring reaction 24h, washed repeatedly with deionized water and ethanol, dry after obtain
Hyperbranched Polymer with Terminal Amido modifies nano silver wire or Hyperbranched Polymer with Terminal Hydroxyl modification nano silver wire.（5）Amino End Group is surpassed
Branched polymer modifies nano silver wire and Hyperbranched Polymer with Terminal Hydroxyl modification nano silver wire is configured to the water-soluble of 10g/L respectively
Liquid, the three-dimensional porous composite of silk/sodium alginate of the load graphene in step 3 is then immersed in 80 DEG C of end ammonia
60min in the base dissaving polymer modification nano silver wire aqueous solution, bath raio 1:50, rinsed, dried repeatedly with deionized water after taking-up
It is dry；Then the Hyperbranched Polymer with Terminal Hydroxyl for above-mentioned three-dimensional porous composite being immersed in 80 DEG C modifies the nano silver wire aqueous solution
Middle 60min, bath raio 1:50, rinsed repeatedly with deionized water after taking-up, dry, one layer of nano silver wire is so far assembled into three-dimensional
Composite porous surface, then modify nano silver wire and superbrnaching end-hydroxy polymerization in Hyperbranched Polymer with Terminal Amido successively
Aforesaid operations in triplicate in thing modification nano silver wire dressing liquid, obtain loading silk/alginic acid of graphene and nano silver wire
Sodium is composite porous.
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 (8)
1. the composite porous preparation method of silk/sodium alginate of load graphene and nano silver wire, it is characterised in that：
（1）Sodium alginate is scattered in deionized water under normal temperature, bath raio 1:50, it is slowly added to 1-100g/L polyamide-amide
The PAMAM aqueous solution, the wherein volume ratio of the PAMAM aqueous solution and sodium alginate aqueous solution are 1:1-1:10, after reacting 24h, with steaming
Distilled water and ethanol wash, obtain PAMAM modified sodium alginates after drying repeatedly；
（2）Silk-fibroin is dissolved in deionized water, is configured to the 1g/L-100g/L aqueous solution, by 1g/ under conditions of 50-80 DEG C
The L-100g/L trivalent iron salt aqueous solution is slowly dropped into silk protein aqueous solution, is stirred, wherein the silk-fibroin and three
The mass ratio of valency molysite is 1:1-10:After 1,60 DEG C is at the uniform velocity stirred 1h, the PAMAM being slowly added in step 1 is modified alginic acid
Sodium, 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 DEG C
6h is freezed in Thermo ultra low temperature freezers, being then placed in 48h in freeze dryer, to obtain silk/sodium alginate composite porous；
（3）Compound concentration 1-100g/L graphene oxide water solution, ultrasonic 1h are more by silk/sodium alginate in step 2
Hole composite material is immersed in 24h in graphene oxide solution, bath raio 1:50, after being cleaned repeatedly with ethanol and deionized water, it is placed in
Reduced in reducing agent, cleaned repeatedly with ethanol and deionized water, obtain loading silk/marine alga of graphene after vacuum drying
The sour three-dimensional porous composite of sodium；
（4）Nano silver wire is configured to the 1-10g/L aqueous solution, then add 1-10g/L Hyperbranched Polymer with Terminal Amido or
The Hyperbranched Polymer with Terminal Hydroxyl aqueous solution, under normal temperature after at the uniform velocity stirring reaction 24h, washed, done repeatedly with deionized water and ethanol
Hyperbranched Polymer with Terminal Amido modification nano silver wire or Hyperbranched Polymer with Terminal Hydroxyl modification nano silver wire are obtained after dry；
（5）Hyperbranched Polymer with Terminal Amido is modified into nano silver wire and Hyperbranched Polymer with Terminal Hydroxyl modification nano silver wire is matched somebody with somebody respectively
The 0.1-10g/L aqueous solution is made, then by the three-dimensional porous composite wood of silk/sodium alginate of the load graphene in step 3
Material is immersed in 10-60min in 80 DEG C of the Hyperbranched Polymer with Terminal Amido modification nano silver wire aqueous solution, bath raio 1:50, after taking-up
Rinsed, dried repeatedly with deionized water；Then the superbrnaching end-hydroxy for above-mentioned three-dimensional porous composite being immersed in 80 DEG C gathers
10-60min in the compound modification nano silver wire aqueous solution, bath raio 1:50, rinsed, dried, so far repeatedly with deionized water after taking-up
One layer of nano silver wire has been assembled into the surface of three-dimensional porous composite, then modified successively in Hyperbranched Polymer with Terminal Amido
Aforesaid operations are repeated in nano silver wire and Hyperbranched Polymer with Terminal Hydroxyl modification nano silver wire dressing liquid, are determined as needed three-dimensional
The number of plies of composite porous surface nano silver wire assembling.
2. the composite porous system of silk/sodium alginate of load graphene according to claim 1 and nano silver wire
Preparation Method, it is characterised in that the silk-fibroin is that silk is made after degumming, dissolving, dialysis, purification.
3. the composite porous system of silk/sodium alginate of load graphene according to claim 1 and nano silver wire
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 composite porous system of silk/sodium alginate of load graphene according to claim 1 and nano silver wire
Preparation Method, it is characterised in that the mass ratio of the modified sodium alginate and silk-fibroin is 1:1-1:10.
5. the composite porous system of silk/sodium alginate of load graphene according to claim 1 and nano silver wire
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.
6. the composite porous system of silk/sodium alginate of load graphene according to claim 1 and nano silver wire
Preparation Method, it is characterised in that the nano silver wire is synthesized using polyol process.
7. the composite porous system of silk/sodium alginate of load graphene according to claim 1 and nano silver wire
Preparation Method, it is characterised in that the Hyperbranched Polymer with Terminal Amido or the Hyperbranched Polymer with Terminal Hydroxyl aqueous solution and Yin Na
The volume ratio of the rice noodles aqueous solution is 1:1-1:10.
8. the load graphene and the porous composite wood of silk/sodium alginate of nano silver wire that are obtained by claim 1 preparation method
Material.
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| CN112832019A (en) * | 2021-02-01 | 2021-05-25 | 苏州大学 | Method for finishing fibers/fabrics by nano-silver graphene oxide composite nano-material and fibers/fabrics |
| CN112962161A (en) * | 2021-02-01 | 2021-06-15 | 苏州大学 | Preparation method of doped graphene oxide/nano-silver melt-blown nonwoven material |
| CN116392979A (en) * | 2023-06-08 | 2023-07-07 | 成都昱恒新瑞科技有限公司 | Visible light driven separation membrane, preparation method and application thereof in organic wastewater |
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| CN101941842A (en) * | 2010-10-11 | 2011-01-12 | 东华大学 | Method for preparing graphene loaded ferroferric oxide magnetic nanometer particle composite material |
| CN104371714A (en) * | 2014-11-28 | 2015-02-25 | 赵兵 | Molybdenum trioxide-graphene oxide composite material and preparation method thereof |
| CN104761749A (en) * | 2015-04-03 | 2015-07-08 | 四川大学 | Cellulose nanofiber hyperbranched modification method |
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| CN101941842A (en) * | 2010-10-11 | 2011-01-12 | 东华大学 | Method for preparing graphene loaded ferroferric oxide magnetic nanometer particle composite material |
| CN104371714A (en) * | 2014-11-28 | 2015-02-25 | 赵兵 | Molybdenum trioxide-graphene oxide composite material and preparation method thereof |
| CN104761749A (en) * | 2015-04-03 | 2015-07-08 | 四川大学 | Cellulose nanofiber hyperbranched modification method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112832019A (en) * | 2021-02-01 | 2021-05-25 | 苏州大学 | Method for finishing fibers/fabrics by nano-silver graphene oxide composite nano-material and fibers/fabrics |
| CN112962161A (en) * | 2021-02-01 | 2021-06-15 | 苏州大学 | Preparation method of doped graphene oxide/nano-silver melt-blown nonwoven material |
| CN112832019B (en) * | 2021-02-01 | 2022-04-08 | 苏州大学 | Method for finishing fibers/fabrics by nano-silver graphene oxide composite nano-material and fibers/fabrics |
| CN112962161B (en) * | 2021-02-01 | 2022-04-08 | 苏州大学 | Preparation method of doped graphene oxide/nano-silver melt-blown nonwoven material |
| CN116392979A (en) * | 2023-06-08 | 2023-07-07 | 成都昱恒新瑞科技有限公司 | Visible light driven separation membrane, preparation method and application thereof in organic wastewater |
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