CN109078587A - A kind of graphene oxide-chitin nano fiber hybridized nanometer particle and preparation method thereof, application - Google Patents
A kind of graphene oxide-chitin nano fiber hybridized nanometer particle and preparation method thereof, application Download PDFInfo
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- 229920002101 Chitin Polymers 0.000 title claims abstract description 209
- 239000002121 nanofiber Substances 0.000 title claims abstract description 201
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 186
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 185
- 239000002245 particle Substances 0.000 title claims abstract description 122
- 238000002360 preparation method Methods 0.000 title claims abstract description 46
- 239000006185 dispersion Substances 0.000 claims abstract description 68
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 14
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 13
- 230000004044 response Effects 0.000 claims description 8
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 239000002105 nanoparticle Substances 0.000 claims description 5
- 239000002070 nanowire Substances 0.000 claims description 5
- 206010039509 Scab Diseases 0.000 claims description 4
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 3
- 235000013339 cereals Nutrition 0.000 claims description 3
- 239000000835 fiber Substances 0.000 claims description 3
- 238000004108 freeze drying Methods 0.000 claims description 3
- 238000001879 gelation Methods 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 240000007594 Oryza sativa Species 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 235000009566 rice Nutrition 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 7
- 239000007788 liquid Substances 0.000 description 29
- 238000004630 atomic force microscopy Methods 0.000 description 22
- 238000010586 diagram Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 14
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 238000002156 mixing Methods 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 150000001450 anions Chemical class 0.000 description 5
- 125000002091 cationic group Chemical group 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000004964 aerogel Substances 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 4
- 239000004575 stone Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000012286 potassium permanganate Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
- 229910021382 natural graphite Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000008055 phosphate buffer solution Substances 0.000 description 2
- 230000004043 responsiveness Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 241000271566 Aves Species 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 210000003746 feather Anatomy 0.000 description 1
- 244000144992 flock Species 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012761 high-performance material Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000007777 multifunctional material Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0091—Preparation of aerogels, e.g. xerogels
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Abstract
The invention belongs to field of nanometer material technology, and in particular to a kind of graphene oxide-chitin nano fiber hybridized nanometer particle and preparation method thereof, application.The embodiment of the invention provides a kind of graphene oxide-chitin nano fiber hybridized nanometer particles: graphene oxide is in conjunction with double electrical chitin nano fiber hydridization and the graphene oxide-chitin nano fiber hybridized nanometer particle can stable dispersion in water.The graphene oxide that the embodiment of the present invention obtains-chitin nano fiber hybridized nanometer particle has high charge density, can stable dispersion in water, and its viscosity is higher, has diversified assembling mode and machinability.
Description
Technical field
The invention belongs to field of nanometer material technology, and in particular to a kind of graphene oxide-chitin nano fiber hybridized nanometer
Particle and preparation method thereof, application.
Background technique
Hydridization refers to the combination that two different components are realized to Nano grade or molecular scale by Specific Interactions,
As an entirety.Hydridization provides a possibility that one kind constructs high-performance and more efficient multi-functional material to people.
Graphene oxide is the most important presoma of graphene, and there are a large amount of oxygen-containing groups, such as carboxylic for surface and edge
Base, hydroxyl and epoxy group etc., to be conducive to be modified and be modified, and graphene oxide can rebuild sp by reduction2Structure
Obtain high performance grapheme material.
Chitin is a kind of nitrogenous natural macromolecular material, and nature reserves are only second to cellulose, since this birdss of the same feather flock together
Intramolecular and the intermolecular hydrogen bonding effect of polysaccharose substance are stronger, therefore indissoluble solution, infusibility melt.It is mentioned by top-to-bottom method
Obtaining nanofiber is the important channel using biological materials such as chitins.
The prior art is not yet able to achieve preparation stable bond and graphene oxide-chitin with extensive machinability is received
Rice fiber hybrid particle.
The information disclosed in the background technology section is intended only to increase the understanding to general background of the invention, without answering
When being considered as recognizing or imply that the information constitutes the prior art already known to those of ordinary skill in the art in any form.
Summary of the invention
Goal of the invention
The purpose of the present invention is to provide a kind of graphene oxide-chitin nano fiber hybridized nanometer particle and its preparations
Method, application.By the present invention in that realizing graphene oxide and chitin nano fiber with double electrical chitin nano fibers
Hydridization, obtained graphene oxide-chitin nano fiber hybridized nanometer particle, which has high charge close
Degree, can stable dispersion in water, and its viscosity is higher, has diversified assembling mode and machinability.
Solution
Purpose to realize the present invention, the embodiment of the invention provides a kind of graphene oxide-chitin nano fiber hydridization
Nanoparticle, in which: graphene oxide is in conjunction with double electrical chitin nano fiber hydridization and the graphene oxide-chitin
Nanofiber hybridized nanometer particle can stable dispersion in water.When graphene oxide-chitin nano fiber hybridized nanometer particle
Aqueous dispersions Zeta potential absolute value be less than 30mV when, show that this aqueous dispersions system is unstable；Conversely, working as oxygen
When the Zeta potential absolute value of graphite alkene-chitin nano fiber hybridized nanometer particle aqueous dispersions is more than or equal to 30mV,
Then show that this aqueous dispersions system can be stabilized.
Above-mentioned graphene oxide-chitin nano fiber hybridized nanometer particle is in one possible implementation, described
The Zeta potential absolute value of graphene oxide-chitin nano fiber hybridized nanometer particle aqueous dispersions is 35-90mV；It is optional
Ground is 60-90mV.
Above-mentioned graphene oxide-chitin nano fiber hybridized nanometer particle is in one possible implementation, described
The viscosity of graphene oxide-chitin nano fiber hybridized nanometer particle aqueous dispersions can be by changing the dense of aqueous dispersions
The pH value of the mass ratio and/or aqueous dispersions of graphene oxide and chitin nano fiber is regulated and controled in degree, hybrid particle.
Above-mentioned graphene oxide-chitin nano fiber hybridized nanometer particle in one possible implementation, 25
DEG C, graphene oxide-chitin nano fiber hybridized nanometer particle water dispersion liquid pH is less than or equal to double electrical chitin nanometers
The isoelectric point of fiber, graphene oxide-chitin nano fiber hybridized nanometer particle water dispersion liquid concentration are 3mg/mL and oxidation
Graphene oxide is with double electrical chitin nano fiber mass ratioes in graphene-chitin nano fiber hybridized nanometer particle
Under the conditions of 0.5-100: 1, graphene oxide-chitin nano fiber hybridized nanometer particle water dispersion liquid k value is 50-
350mPa.s；Graphene oxide-chitin nano fiber hybridized nanometer particle water dispersion liquid k value and same under this condition
Under the conditions of graphene oxide aqueous dispersions k value compared to improving 3-80 times, with lower pair of equal conditions electrical property chitin Nanowire
The k value of dimension is compared to 10-80 times of raising.
Above-mentioned graphene oxide-chitin nano fiber hybridized nanometer particle in one possible implementation, works as oxygen
When graphite alkene-chitin nano fiber hybridized nanometer particle water dispersion liquid is in high concentration (9-30mg/ml) range, pass through
The gelation that quick response may be implemented in adjusting pH changes with gel phenomenon is removed.
The embodiment of the invention also provides a kind of graphene oxide-chitin nano fiber hybridized nanometer particle preparation sides
Method includes the following steps: with double electrical chitin nano fibers to mix graphene oxide in water reaction system, adjusts oxidation
The pH value of the quality of graphene and double electrical chitin nano fibers when reaction system, so that graphene oxide and double electrical first
Shell element nanofiber hydridization in conjunction with and the graphene oxide-chitin nano fiber hybridized nanometer particle can in water stable point
It dissipates, obtains containing graphene oxide-chitin nano fiber hybridized nanometer particle aqueous dispersions.It can be using arbitrary acid or alkali
Adjust the pH value of reaction system.
Above-mentioned preparation method is in one possible implementation, further includes: will obtain containing graphene oxide-chitin
The aqueous dispersions of nanofiber hybridized nanometer particle are stirred and are dried, and it is miscellaneous to obtain graphene oxide-chitin nano fiber
Change nanoparticle.
In one possible implementation, graphene oxide and double electrical chitin nano fibers are mixed for above-mentioned preparation method
The mass ratio of conjunction is 0.5-100: 1；It is optionally 0.5-20: 1；It is still optionally further 0.5-5:1, such as: 0.5: 1,1: 1,2:
1,3: 1 or 5: 1.
Above-mentioned preparation method in one possible implementation, adjusts the pH value of reaction system to less than is equal to double electrical
The isoelectric point of chitin nano fiber, and make the bis- electrical chitin nano fiber hybrid particle aqueous dispersions of graphene oxide-
Zeta potential absolute value be more than or equal to 30mV.PH value is excessively high to make graphene oxide and double electrical chitin nano fibers not
In conjunction with pH value is too low to make graphene oxide and double electrical chitin nano fibers that clustering phenomena occur.
Above-mentioned preparation method in one possible implementation, when amino in double electrical chitin nano fibers and
When the mass percent of carboxyl is respectively 10% and 4%, adjusts the pH value of reaction system to less than be equal to 8, and make to aoxidize stone
The Zeta potential absolute value of the bis- electrical chitin nano fiber hydridization grain aqueous dispersions of black alkene-is more than or equal to 30mV；Optionally,
Adjust pH to 3-7；Still optionally further, pH to 5-7 is adjusted；Further optionally, pH to 5.8-6.5 is adjusted.
Above-mentioned graphene oxide-chitin nano fiber hybridized nanometer particle, preparation method are in a kind of possible realization side
In formula, the graphene oxide includes graphene oxide made from Hummers method or improved Hummers method oxidation stone obtained
Black alkene.Improved Hummers method, which refers to, aoxidizes graphite using potassium permanganate and the concentrated sulfuric acid in keeping Hummers method
On the basis of carried out improved method, such as: temperature, the mass ratio parameter in step are improved, can also to step into
Gone other adjustment.Optionally, the preparation method of the graphene oxide include the following steps: by natural graphite, the concentrated sulfuric acid and
Potassium permanganate stirs 1-3h at a temperature of being less than or equal to 4 DEG C；System temperature is increased to 45-60 DEG C, insulation reaction 4-8h；Instead
After answering, distilled water and hydrogen peroxide is added, persistently stirs 20-50min, then carries out centrifuge washing, remove extra acid and
Impurity obtains graphene oxide dispersion.
Above-mentioned graphene oxide-chitin nano fiber hybridized nanometer particle, preparation method are in a kind of possible realization side
In formula, double electrical chitin nano fibers are chitin nano fiber of the surface simultaneous with amino and carboxyl；Optionally,
Amino in double electrical chitin nano fibers accounts for the 5%-40% of double electrical chitin nano fiber gross masses, and carboxyl accounts for
The 2%-30% of double electrical property chitin nano fiber gross masses；Still optionally further, in double electrical chitin nano fibers
Amino and carboxyl mass ratio be 1: 1.
Above-mentioned graphene oxide-chitin nano fiber hybridized nanometer particle, preparation method are in a kind of possible realization side
In formula, the preparation method of double electrical chitin nano fibers can refer to CN 106868629A or Fuku S, Hori T,
Method preparation in Izawa H, et al.Carbohydr Polym, 2015,122:1-4.Optionally, double electrical crusts
The preparation method of plain nanofiber includes the following steps: to mix chitin powder with the sodium hydroxide of 20-45%, in 80-95
It stirs, is dried to get the chitin powder after deacetylated at DEG C；Take it is above-mentioned it is deacetylated after chitin powder, be put into burning
In bottle, TEMPO reagent, NaClO is added2And phosphate buffer solution, NaClO solution, sealed flask, in 50-65 is then added
After reacting at DEG C, ultrasound, centrifugation is to get double electrical chitin nano fiber dispersion liquids.
The embodiment of the invention also provides a kind of above-mentioned graphene oxide-chitin nano fiber hybridized nanometer particle or on
It states graphene oxide-chitin nano fiber hybridized nanometer particle that preparation method is prepared and is preparing graphene-chitin
Nanofiber hybridized nanometer particle aeroge or preparation nanometer silver-graphene-chitin nano fiber hybridized nanometer particle airsetting
Application in glue.
The embodiment of the invention also provides a kind of graphene-chitin nano fiber hybridized nanometer particle aeroges, lead to
The method included the following steps is crossed to be prepared: by above-mentioned graphene oxide-chitin nano fiber hybridized nanometer particle or on
Graphene oxide-chitin nano fiber hybridized nanometer particle that preparation method is prepared is stated, is assembled by hydro-thermal method,
It is carbonized in atmosphere of inert gases after freeze-drying；Optionally, the step of hydro-thermal method includes: to be put into reaction kettle in 160-
200 DEG C of reaction 8-15h；The step of being carbonized in the atmosphere of inert gases includes: to be carbonized in 750-850 DEG C, nitrogen atmosphere.
The embodiment of the invention also provides a kind of nanometer of silver-graphene-chitin nano fiber hybridized nanometer particle airsettings
Glue is prepared: by above-mentioned graphene oxide-chitin nano fiber hybridized nanometer grain by the method included the following steps
The graphene oxide that sub or above-mentioned preparation method is prepared-chitin nano fiber hybridized nanometer particle is carried out with silver nitrate
Mixing, is assembled by hydro-thermal method；Optionally, the silver nitrate and graphene oxide-chitin nano fiber hybridized nanometer
The mass ratio of particle is 0.5-3: 1；The step of hydro-thermal method includes: to be put into reaction kettle in 160-200 DEG C of reaction 8-15h.
Beneficial effect
(1) graphene oxide provided in the embodiment of the present invention-chitin nano fiber hybridized nanometer particle, have compared with
The Zeta potential of high charge density, aqueous dispersions can achieve -80mV or more, higher than the glue of current most of nano materials
Body stability.
(2) graphene oxide provided in the embodiment of the present invention-chitin nano fiber hybridized nanometer particle water dispersion
The k value of liquid is higher, and under equal conditions, the viscosity compared to graphene oxide aqueous dispersions can be improved 3-80 times, compared to double electricity
The viscosity of property chitin nano fiber aqueous dispersions can be improved 10-80 times.
(3) graphene oxide provided in the embodiment of the present invention-chitin nano fiber hybridized nanometer particle, can basis
Graphene oxide-chitin nano fiber hybridized nanometer particle different application adjusts its concentration: (9-30mg/ in higher concentrations
Ml), the gelation of quick response may be implemented by adjusting pH to change with gel phenomenon is removed, drug load with discharge and
Responsiveness devices field has potential practical value.
(4) graphene oxide provided in the embodiment of the present invention-chitin nano fiber hybridized nanometer particle has more
Macroscopical assembling mode of sample, available different macroscopic material, and obtained macroscopic material all has excellent performance.Example
Such as it can be assembled into natural latex composite material, aeroge, can be applied to high performance material, supercapacitor, electrochemical response
Equal fields.
Detailed description of the invention
One or more embodiments are illustrated by the picture in corresponding attached drawing, these exemplary theorys
The bright restriction not constituted to embodiment.Dedicated word " exemplary " means " being used as example, embodiment or illustrative " herein.
Here as any embodiment illustrated by " exemplary " should not necessarily be construed as preferred or advantageous over other embodiments.
Fig. 1 is graphene oxide in the embodiment of the present invention 1-chitin nano fiber hybridized nanometer particle atomic force microscopy
Mirror figure.
Fig. 2 is graphene oxide in the embodiment of the present invention 1-chitin nano fiber hybridized nanometer particle in different pH
Charge-distribution curve figure.
Fig. 3 is graphene oxide in the embodiment of the present invention 2-chitin nano fiber hybridized nanometer particle atomic force microscopy
Mirror figure.
Fig. 4 is graphene oxide in the embodiment of the present invention 3-chitin nano fiber hybridized nanometer particle atomic force microscopy
Mirror figure.
Fig. 5 is graphene oxide in the embodiment of the present invention 4-chitin nano fiber hybridized nanometer particle atomic force microscopy
Mirror figure.
Fig. 6 is graphene oxide in the embodiment of the present invention 5-chitin nano fiber hybridized nanometer particle atomic force microscopy
Mirror figure.
Fig. 7 is graphene oxide in the embodiment of the present invention 6-chitin nano fiber hybridized nanometer particle atomic force microscopy
Mirror figure.
Fig. 8 is graphene oxide in the embodiment of the present invention 7-chitin nano fiber hybridized nanometer particle atomic force microscopy
Mirror figure.
Fig. 9 is graphene oxide in the embodiment of the present invention 8-chitin nano fiber hybridized nanometer particle atomic force microscopy
Mirror figure.
Figure 10 is that graphene oxide in the embodiment of the present invention 9-chitin nano fiber hybridized nanometer particle atomic force is aobvious
Micro mirror figure.
Figure 11 a is that the structure of the only cationic chitin nano fiber with amino prepared in comparative example 1 of the present invention is shown
It is intended to.
Figure 11 b is that the atomic force of 1 graphene oxide of comparative example of the present invention and single electrical chitin nano fiber mixed liquor is aobvious
Micro mirror figure, wherein the right is the enlarged drawing on the left side.
Figure 11 c is that the structure of the only anion chitin nano fiber with carboxyl prepared in comparative example 2 of the present invention is shown
It is intended to.
Figure 11 d is the atomic force of graphene oxide and single electrical chitin nano fiber mixed liquor in comparative example 2 of the present invention
Microscope figure, wherein the right is the enlarged drawing on the left side.
Figure 12 is that the atomic force of graphene oxide and double electrical chitin nano fiber mixed liquors is aobvious in comparative example 3 of the present invention
Micro mirror figure.
Figure 13 is that the atomic force of graphene oxide and double electrical chitin nano fiber mixed liquors is aobvious in comparative example 4 of the present invention
Micro mirror figure.
Figure 14 is that the atomic force of graphene oxide and double electrical chitin nano fiber mixed liquors is aobvious in comparative example 5 of the present invention
Micro mirror figure.
Figure 15 is that the atomic force of graphene oxide and double electrical chitin nano fiber mixed liquors is aobvious in comparative example 6 of the present invention
Micro mirror figure.
Figure 16 is graphene in application examples 1 of the present invention-chitin nano fiber hybridized nanometer particle aeroge capacitor row
For curve.Wherein, GO refers to the graphene aerogel being prepared by graphene oxide in caption；Refer to by this hair at G: C=1: 2
Graphene-chitin Nanowire that the graphene oxide of bright embodiment 9-chitin nano fiber hybridized nanometer particle is prepared
Tie up hybridized nanometer particle aeroge.
Figure 17 is nanometer silver-graphene in application examples 2 of the present invention-chitin nano fiber hybridized nanometer particle aeroge pair
The electrochemical response behavior of hydrogen peroxide.Wherein, it is referred to by the graphene oxide-of the embodiment of the present invention 9 at G: C=1: 2 in caption
Nanometer silver-graphene made from chitin nano fiber hybridized nanometer particle-chitin nano fiber hybridized nanometer particle airsetting
Glue.
Figure 18 is nano silver-graphene aerogel for being prepared in application examples 2 of the present invention by graphene oxide to dioxygen
The electrochemical response behavior of water.Wherein, GO refers to the nano silver-graphene aerogel being prepared by graphene oxide.
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described, it is clear that described embodiments are some of the embodiments of the present invention, rather than
Whole embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not making creative work premise
Under every other embodiment obtained, shall fall within the protection scope of the present invention.Unless otherwise explicitly stated, otherwise whole
In a specification and claims, it is to include that the term " include " or its transformations will be understood as
The element or component stated, and do not exclude other elements or other components.
In addition, in order to better illustrate the present invention, numerous details is given in specific embodiment below.
It will be appreciated by those skilled in the art that without certain details, the present invention equally be can be implemented.In some embodiments, right
It is not described in detail in raw material well known to those skilled in the art, element, method, means etc., in order to highlight master of the invention
Purport.
Embodiment 1
1. the preparation of graphene oxide
Modified Hummers method prepares graphene oxide:
By 2g natural graphite, the 120mL concentrated sulfuric acid and 6g potassium permanganate, pours into 250mL three-necked flask, be placed in ice-water bath
In, in 4 DEG C of 2h stirred below；System temperature is increased to 50 DEG C, insulation reaction 6h；After reaction, 240mL distilled water is added
With 2-5mL hydrogen peroxide, persistently stir 30min, centrifuge washing then carried out to obtained graphene oxide, remove extra acid and
Obtained graphene oxide dispersion is finally placed in spare in 4 DEG C of refrigerators by impurity.The Zeta potential of obtained graphene oxide
For -41mV, at 25 DEG C, the viscosity of its dispersion liquid is 17.52mPa.s (concentration 3mg/ml).
2. the preparation of pair electrical chitin nano fiber
Firstly, the chitin powder of 10g is mixed with the sodium hydroxide of 200mL 35%, the agitating and heating 1h at 90 DEG C,
Caustic washing is washed away using ethyl alcohol, is dried, can obtain it is deacetylated after chitin powder, utilize titration test ammonia
Base content is 12%；By it is above-mentioned it is deacetylated after chitin powder take out 1g be put into flask, the TEMPO of 0.1mmol is added
The NaClO of reagent, 10mmol2, the phosphate buffer solution (0.1mol/l, pH are equal to 6.86) of 90mL, subsequent addition 1mmol's
NaClO solution, sealed flask, after reacting 2h at 60 DEG C, 300W ultrasound 30min, 7000r are centrifuged 15min, and can obtain yield is
80%, all can be stable dispersion two months or more under acid and alkalinity, that amino content accounts for double electrical chitin nano fibers is total
Quality 10%, carboxyl-content account for 4% double electrical chitin nano fibers point of double electrical chitin nano fiber gross masses
Dispersion liquid.The Zeta potential absolute value of obtained double electrical chitin nano fiber aqueous dispersions is 35mV, the viscosity at 25 DEG C
For 4.125mPa.s (concentration 3mg/ml).
3. the preparation of graphene oxide-chitin nano fiber hybridized nanometer particle
Double electrical chitin nano fiber dispersion liquid concentrations prepared by graphene oxide prepared by step 1 and step 2 are equal
It is adjusted to 3mg/ml, is mixed with the ratio of mass ratio 2: 1, the pH for adjusting mixed liquor is equal to 3.0, stirs 0.5h, obtains graphite oxide
Alkene-chitin nano fiber hybridized nanometer particle water dispersion liquid, then to be drying to obtain graphene oxide-chitin nano fiber miscellaneous
Change nanoparticle.
Wherein, the graphene oxide obtained-chitin nano fiber hybridized nanometer particle water dispersion liquid Zeta potential be-
37mV, at 25 DEG C, graphene oxide-chitin nano fiber hybridized nanometer particle water dispersion liquid (concentration 3mg/ml) is glutinous
Degree is 200mPa.s.
The graphene oxide being prepared-chitin nano fiber hybridized nanometer particle atomic force microscopy diagram such as Fig. 1
It is shown.Obtained graphene oxide-chitin nano fiber hybridized nanometer particle water dispersion liquid charge-distribution curve figure is shown in figure
2, as shown in Figure 2, as pH < 8, the graphene oxide-chitin nano fiber hybridized nanometer particle water dispersion liquid system is single
Peak, that is, show to only exist a kind of nano material in system, i.e. graphene oxide and double electrical chitin nano fibers is complete
It is combined together entirely；As pH > 8, graphene oxide-chitin nano fiber hybridized nanometer particle water dispersion liquid system occurs
Multimodal, that is, show in system there are two kinds of nano materials, i.e. graphene oxide and double electrical chitin nano fibers are not
It is completely combined.
Embodiment 2
With embodiment 1, difference is only that the pH for adjusting mixed liquor is equal to 5.0.
Obtained graphene oxide-chitin nano fiber hybridized nanometer particle water dispersion liquid Zeta potential is -56mV,
At 25 DEG C, graphene oxide-chitin nano fiber hybridized nanometer particle water dispersion liquid (concentration 3mg/ml) viscosity is
250mPa.s。
The graphene oxide-chitin nano fiber hybridized nanometer particle atomic force microscopy diagram is as shown in Figure 3.
Embodiment 3
With embodiment 1, difference is only that the pH for adjusting mixed liquor is equal to 6.2.
Obtained graphene oxide-chitin nano fiber hybridized nanometer particle water dispersion liquid Zeta potential is -54mV,
(25 DEG C, concentration 3mg/ml) of viscosity are 325mPa.s.
The graphene oxide-chitin nano fiber hybridized nanometer particle atomic force microscopy diagram is as shown in Figure 4.
Embodiment 4
With embodiment 1, difference is only that the pH for adjusting mixed liquor is equal to 7.0.
Obtained graphene oxide-chitin nano fiber hybridized nanometer particle water dispersion liquid Zeta potential is -55mV,
(25 DEG C, concentration 3mg/ml) of viscosity are 100mPa.s.
The graphene oxide-chitin nano fiber hybridized nanometer particle atomic force microscopy diagram is as shown in Figure 5.
Embodiment 5
With embodiment 1, difference is only that the pH for adjusting mixed liquor is equal to 8.0.
Obtained graphene oxide-chitin nano fiber hybridized nanometer particle water dispersion liquid Zeta potential is -78mV,
(25 DEG C, concentration 3mg/ml) of viscosity are 50mPa.s.
The graphene oxide-chitin nano fiber hybridized nanometer particle atomic force microscopy diagram is as shown in Figure 6.
Embodiment 6
With embodiment 1, difference is only that graphene oxide and double electrical chitin nano fibers with the ratio of mass ratio 5: 1
Example mixing, the pH for adjusting mixed liquor are equal to 6.2, and graphene oxide is in conjunction with the complete hydridization of double electrical chitin nano fibers.
Obtained graphene oxide-chitin nano fiber hybridized nanometer particle water dispersion liquid Zeta potential is -88mV,
(25 DEG C, concentration 3mg/ml) of viscosity are 150mPa.s.
The graphene oxide-chitin nano fiber hybridized nanometer particle atomic force microscopy diagram is as shown in Figure 7.
Embodiment 7
With embodiment 1, difference is only that graphene oxide and double electrical chitin nano fibers with the ratio of mass ratio 3: 1
Example mixing, the pH for adjusting mixed liquor are equal to 6.2, and graphene oxide is in conjunction with the complete hydridization of double electrical chitin nano fibers.
Obtained graphene oxide-chitin nano fiber hybridized nanometer particle water dispersion liquid Zeta potential is -76mV,
(25 DEG C, concentration 3mg/ml) of viscosity are 220mPa.s.
The graphene oxide-chitin nano fiber hybridized nanometer particle atomic force microscopy diagram is as shown in Figure 8.
Embodiment 8
With embodiment 1, difference is only that graphene oxide and double electrical chitin nano fibers with the ratio of mass ratio 1: 1
Example mixing, the pH for adjusting mixed liquor are equal to 6.2, and graphene oxide is in conjunction with the complete hydridization of double electrical chitin nano fibers.
Obtained graphene oxide-chitin nano fiber hybridized nanometer particle water dispersion liquid Zeta potential is -45mV,
(25 DEG C, concentration 3mg/ml) of viscosity are 239mPa.s.
The graphene oxide-chitin nano fiber hybridized nanometer particle atomic force microscopy diagram is as shown in Figure 9.
Embodiment 9
With embodiment 1, difference is only that graphene oxide and double electrical chitin nano fibers with the ratio of mass ratio 1: 2
Example mixing, the pH for adjusting mixed liquor are equal to 6.2, and graphene oxide is in conjunction with the complete hydridization of double electrical chitin nano fibers.
Obtained graphene oxide-chitin nano fiber hybridized nanometer particle water dispersion liquid Zeta potential is -40mV,
(25 DEG C, concentration 3mg/ml) of viscosity are 185mPa.s.
The graphene oxide-chitin nano fiber hybridized nanometer particle atomic force microscopy diagram is as shown in Figure 10.
Comparative example 1
1. the preparation of graphene oxide
Step 1 that the preparation method is the same as that of Example 1.
2. the only preparation of the cationic chitin nano fiber with amino
Preparation method: document Carbohydrate Polymers, 2010,79 (4): the method system in 1046-1051 are used
The standby cationic chitin nano fiber for only having amino, structural schematic diagram is as shown in fig. 11a.
3. the cationic chitin Nanowire for only having amino prepared by graphene oxide and step 2 prepared by step 1
Dimension is mixed with the ratio of mass ratio 2: 1, at this point, adjusting pH does not influence result, therefore is not required to control pH value.As a result, it has been found that only
Cationic chitin nano fiber with amino can be settled with graphene oxide, can only obtain dusty material, such as Figure 11 b
It is shown.
Comparative example 2
1. the preparation of graphene oxide
Step 1 that the preparation method is the same as that of Example 1.
2. the preparation of the anion chitin nano fiber with carboxyl
Preparation method: use document Biomacromolecules, 2008,9 (1): the method in 192-198. prepares a band
There is the anion chitin nano fiber of carboxyl, structural schematic diagram is as shown in fig. 11c.
3. the anion chitin Nanowire for only having carboxyl prepared by graphene oxide and step 2 prepared by step 1
Dimension dispersion liquid concentration is adjusted to 3mg/ml, is mixed with the ratio of mass ratio 2: 1, at this point, adjusting pH does not influence result, therefore
It is not required to control pH value.As a result, it has been found that only the anion chitin nano fiber with carboxyl can be steady after mixing with graphene oxide
Fixed dispersion, but fail to be combined together from both known to atomic force microscopy diagram, as illustrated in fig. 11d.Obtained graphite oxide
Alkene-anion chitin nano fiber aqueous dispersions Zeta potential is -38mV, and at 25 DEG C, the viscosity of dispersion liquid is
15.67mPa.s。
Comparative example 3
With embodiment 1, difference is only that the pH for adjusting mixed liquor is equal to 9.0.
From atomic force microscopy diagram it is found that graphene oxide is not combined together with double electrical chitin nano fibers,
As shown in figure 12.Obtained graphene oxide-chitin nano fiber aqueous dispersions Zeta potential is -44mV, at 25 DEG C
The viscosity of dispersion liquid is 14.59mPa.s.
Comparative example 4
With embodiment 1, difference is only that the pH for adjusting mixed liquor is equal to 11.0.
From atomic force microscopy diagram it is found that graphene oxide is not combined together with double electrical chitin nano fibers,
As shown in figure 13, the graphene oxide obtained-chitin nano fiber aqueous dispersions Zeta potential is -45mV, at 25 DEG C
The viscosity of dispersion liquid be 119.8mPa.s, viscosity increase mainly due to alkalinity it is stronger when graphene oxide liquid crystal by
To caused by destruction.
Comparative example 5
With embodiment 1, difference is only that graphene oxide and double electrical chitin nano fibers with the ratio of mass ratio 1: 3
Example mixing.
From atomic force microscopy diagram it is found that serious aggregation has occurred in graphene oxide and double electrical chitin nano fibers
Phenomenon, as shown in figure 14.
Comparative example 6
With embodiment 1, difference is only that graphene oxide and double electrical chitin nano fibers with the ratio of mass ratio 1: 5
Example mixing.
From atomic force microscopy diagram it is found that serious aggregation has occurred in graphene oxide and double electrical chitin nano fibers
Phenomenon, as shown in figure 15.
1 graphene of application examples-chitin nano fiber hybridized nanometer particle aeroge
The graphene oxide that embodiment 9 is prepared-chitin nano fiber hybridized nanometer particle, is put into reaction kettle
In 180 DEG C of reaction 12h, after taking-up after freeze-drying, then at 800 DEG C, it is carbonized in nitrogen atmosphere, the stone after being restored
Black alkene-chitin nano fiber hybridized nanometer particle aeroge.
The graphene-chitin nano fiber hybridized nanometer particle aeroge is assembled into double electric layers supercapacitor, electricity
Chemical response the study found that its specific capacitance reaches as high as 131F/g, with the specific capacitance of pure graphene aerogel improve 2 times with
On, as a result as shown in figure 16.
2 nanometers of silver-graphenes of application examples-chitin nano fiber hybridized nanometer particle aeroge
The graphene oxide that embodiment 9 is prepared-chitin nano fiber hybridized nanometer particle, with etc. quality nitre
Sour silver is mixed, and is put into reaction kettle in 180 DEG C of reaction 12h, is realized the reduction to graphene oxide, obtain nano silver-stone
Black alkene-chitin nano fiber hybridized nanometer particle aeroge.
By the graphene of the loading nano silvery-chitin nano fiber hybridized nanometer particle aeroge assembling modification glass carbon electricity
Pole finds that it has excellent responsiveness to hydrogen peroxide, and as shown in figure 17, CV scanning curve has the peak of reduction at -0.6V.And
After individual graphene oxide is mixed with silver nitrate, the aeroge being assembled into can't show the electrochemical response of hydrogen peroxide
Property, as shown in figure 18, there is not recovering signal, shows that individual graphene oxide can not load a large amount of nano silvers.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although
Present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: it still may be used
To modify the technical solutions described in the foregoing embodiments or equivalent replacement of some of the technical features；
And these are modified or replaceed, technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution spirit and
Range.
Claims (10)
1. a kind of graphene oxide-chitin nano fiber hybridized nanometer particle, it is characterised in that: graphene oxide and double electrical property
Chitin nano fiber hydridization in conjunction with and the graphene oxide-chitin nano fiber hybridized nanometer particle can be stable in water
Dispersion.
2. graphene oxide according to claim 1-chitin nano fiber hybridized nanometer particle, it is characterised in that: institute
The Zeta potential absolute value for stating graphene oxide-chitin nano fiber hybridized nanometer particle aqueous dispersions is 35-90mV；It can
Selection of land is 60-90mV.
3. graphene oxide according to claim 1-chitin nano fiber hybridized nanometer particle, it is characterised in that: institute
The viscosity for stating graphene oxide-chitin nano fiber hybridized nanometer particle aqueous dispersions can be by changing the dense of aqueous dispersions
The pH value of the mass ratio and/or aqueous dispersions of graphene oxide and chitin nano fiber is regulated and controled in degree, hybrid particle；
And/or when graphene oxide-chitin nano fiber hybridized nanometer particle aqueous dispersions are in high concentration (9-30mg/
When ml) in range, the gelation that quick response may be implemented by adjusting pH changes with gel phenomenon is removed.
4. a kind of graphene oxide-chitin nano fiber hybridized nanometer particle preparation method, includes the following steps: to aoxidize
Graphene mixes in water reaction system with double electrical chitin nano fibers, adjusts graphene oxide and receives with double electrical chitins
The pH value of the quality when reaction system of rice fiber so that graphene oxide in conjunction with double electrical property chitin nano fiber hydridization and
The graphene oxide-chitin nano fiber hybridized nanometer particle can stable dispersion in water, obtain containing graphene oxide-first
The aqueous dispersions of shell element nanofiber hybridized nanometer particle.
5. the preparation method according to claim 4, it is characterised in that: further include: it will obtain containing graphene oxide-crust
The aqueous dispersions of plain nanofiber hybridized nanometer particle are stirred and are dried, and obtain graphene oxide-chitin nano fiber
Hybridized nanometer particle.
6. described in graphene oxide according to claim 1-chitin nano fiber hybridized nanometer particle or claim 4
Preparation method, it is characterised in that: the graphene oxide includes graphene oxide made from Hummers method or improved
Graphene oxide made from Hummers method；
And/or double electrical chitin nano fibers are chitin nano fiber of the surface simultaneous with amino and carboxyl；It can
Selection of land, the amino account for the 5%-40% of double electrical chitin nano fiber gross masses, and carboxyl accounts for double electrical chitin Nanowires
The 2%-30% of gross mass is tieed up, still optionally further, the mass ratio of amino and carboxyl is 1: 1.
7. the preparation method according to claim 4, it is characterised in that: graphene oxide and double electrical chitin nano fibers
Mixed mass ratio is 0.5-100: 1；It is optionally 0.5-20: 1；It is still optionally further 0.5-5:1；
And/or the pH value of reaction system to less than the isoelectric point equal to double electrical chitin nano fibers are adjusted, and make to aoxidize
The Zeta potential absolute value of the bis- electrical chitin nano fiber hybrid particle aqueous dispersions of graphene-is more than or equal to 30mV；
And/or when in double electrical chitin nano fibers the mass percent of amino and carboxyl be respectively 10% and 4%
When, it adjusts the pH value of reaction system to less than is equal to 8, and make the bis- electrical chitin nano fiber hydridization grains of graphene oxide-
The Zeta potential absolute value of aqueous dispersions is more than or equal to 30mV；Optionally, pH to 3-7 is adjusted；Still optionally further, pH is adjusted
To 5-7；Further optionally, pH to 5.8-6.5 is adjusted.
8. graphene oxide according to claim 1-3-chitin nano fiber hybridized nanometer particle or right
It is required that prepared by graphene oxide-chitin nano fiber hybridized nanometer particle of the described in any item preparation method preparations of 4-7
Graphene-chitin nano fiber hybridized nanometer particle aeroge or preparation nanometer silver-graphene-chitin nano fiber hydridization
Application in nanoparticle aeroge.
9. a kind of graphene-chitin nano fiber hybridized nanometer particle aeroge, the graphene-chitin nano fiber hydridization
The preparation method of nanoparticle aeroge includes the following steps: the described in any item graphene oxide-crusts of claim 1-3
Plain nanofiber hybridized nanometer particle or graphene oxide-crust of the described in any item preparation method preparations of claim 4-7
Plain nanofiber hybridized nanometer particle is assembled by hydro-thermal method, is carbonized in atmosphere of inert gases after freeze-drying.
10. a kind of nanometer of silver-graphene-chitin nano fiber hybridized nanometer particle aeroge, this nanometer of silver-graphene-first
The preparation method of shell element nanofiber hybridized nanometer particle aeroge includes the following steps: will be described in claim any one of 1-3
Graphene oxide-chitin nano fiber hybridized nanometer particle or claim 4-7 described in any item preparation methods preparation
Graphene oxide-chitin nano fiber hybridized nanometer particle mixed with silver nitrate, assembled by hydro-thermal method.
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