CN106346019B - A kind of micron chickens nucleocapsid of graphene support and preparation method thereof - Google Patents
A kind of micron chickens nucleocapsid of graphene support and preparation method thereof Download PDFInfo
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- CN106346019B CN106346019B CN201610948594.8A CN201610948594A CN106346019B CN 106346019 B CN106346019 B CN 106346019B CN 201610948594 A CN201610948594 A CN 201610948594A CN 106346019 B CN106346019 B CN 106346019B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 36
- 241000287828 Gallus gallus Species 0.000 title claims abstract description 27
- 235000013330 chicken meat Nutrition 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000004793 Polystyrene Substances 0.000 claims abstract description 59
- 229920002223 polystyrene Polymers 0.000 claims abstract description 47
- 239000004005 microsphere Substances 0.000 claims abstract description 45
- 239000010931 gold Substances 0.000 claims abstract description 37
- 229910052737 gold Inorganic materials 0.000 claims abstract description 37
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000006210 lotion Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 14
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 80
- SJUCACGNNJFHLB-UHFFFAOYSA-N O=C1N[ClH](=O)NC2=C1NC(=O)N2 Chemical compound O=C1N[ClH](=O)NC2=C1NC(=O)N2 SJUCACGNNJFHLB-UHFFFAOYSA-N 0.000 claims description 26
- 239000011259 mixed solution Substances 0.000 claims description 21
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 14
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 229960002163 hydrogen peroxide Drugs 0.000 claims description 7
- 229920002873 Polyethylenimine Polymers 0.000 claims description 6
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 6
- 239000012279 sodium borohydride Substances 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 239000001509 sodium citrate Substances 0.000 claims description 4
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 4
- 235000007164 Oryza sativa Nutrition 0.000 claims description 3
- 238000010276 construction Methods 0.000 claims description 3
- 235000009566 rice Nutrition 0.000 claims description 3
- 229940038773 trisodium citrate Drugs 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 229910021505 gold(III) hydroxide Inorganic materials 0.000 claims 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims 1
- 239000011257 shell material Substances 0.000 description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 235000019441 ethanol Nutrition 0.000 description 8
- 238000004140 cleaning Methods 0.000 description 7
- 239000011258 core-shell material Substances 0.000 description 7
- 238000005119 centrifugation Methods 0.000 description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000007654 immersion Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 235000019263 trisodium citrate Nutrition 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 230000001404 mediated effect Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920006389 polyphenyl polymer Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012296 anti-solvent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- -1 chlorauric acid-potassium carbonate Chemical compound 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- LRDFRRGEGBBSRN-UHFFFAOYSA-N isobutyronitrile Chemical compound CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Manufacturing Of Micro-Capsules (AREA)
- Medicinal Preparation (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
Micron chickens nucleocapsid the invention discloses a kind of support of graphene and preparation method thereof；Preparation method includes the following steps：(1) polystyrene microsphere lotion is obtained, and is stirred after adding in modified solution in polystyrene microsphere lotion, obtains the polystyrene microsphere lotion that surface is modified；(2) gel solution of microballoon gold seeds is obtained；(3) gel solution that there is the polystyrene microsphere of golden shell layer on surface is obtained；(4) surface there is the gel solution of the polystyrene microsphere of golden shell layer to obtain powdered sample after being dried；It it is made to grow graphene multilayer in golden shell layer inner wall and removes polystyrene microsphere by the way that sample is impregnated in tetrahydrofuran solution, then the micron chickens nucleocapsid of graphene support is obtained after being dried.The polystyrene microsphere size tunable system that in the present invention prepared by improved monodisperse method can be controlled in tens to hundreds of nanometers at 4 microns~10 microns by the golden shell layer thickness of graphene Multi-layer supporting.
Description
Technical field
The invention belongs to field of nanocomposite materials, more particularly, to a kind of micron chickens nucleocapsid knot of graphene support
Structure and preparation method thereof.
Background technology
Nanocomposite as a kind of new material, suffered from terms of mechanics, electricity and energy absorption at present compared with
Good performance has the characteristics such as absorption and converted electromagnetic wave, can be widely applied to the pulse power, electro-magnetic wave shield etc..Polyphenyl
The preparation of ethylene microballoon (PS balls) largely belongs to nanometer scale, the preparation method of graphene mostly using vapor deposition growth as
It is main.
Invention content
In view of the drawbacks of the prior art, the purpose of the present invention is to provide a kind of micron chickens nucleocapsids of graphene support
Preparation method, it is intended to solve the preparation of hollow metal nucleocapsid and grow asking for graphene in metal shell layer inner wall
Topic.
The preparation method of the micron chickens nucleocapsid of graphene support provided by the invention, includes the following steps：
(1) polystyrene microsphere lotion is obtained, and is stirred after adding in modified solution in polystyrene microsphere lotion,
Obtain the polystyrene microsphere lotion that surface is modified；
(2) gel solution of microballoon gold seeds is obtained：
(2.1) being stirred after addition trisodium citrate in the first mixed solution of deionized water and tetra chlorauric acid makes it
The second mixed solution is obtained after reaction fully, and being stirred after addition sodium borohydride in second mixed solution makes it anti-
Gold seeds gel solution should be fully obtained afterwards；
(2.2) it is obtained after the polystyrene microsphere lotion that the gold seeds gel solution is modified with the surface is mixed
Obtain the gel solution of microballoon gold seeds；The microballoon gold seeds have the polystyrene microsphere of gold seeds for surface growth；
(3) gel solution that there is the polystyrene microsphere of golden shell layer on surface is obtained；
It is carried out after the gel solution of the mixed solution of tetra chlorauric acid and potassium carbonate, deionized water and microballoon gold seeds is mixed
Hydrogenperoxide steam generator is added dropwise until surface is obtained after color is graying the polystyrene microsphere of golden shell layer in whipping process in stirring
Gel solution and it is made to grow graphene multilayer in golden shell layer inner wall；
(4) surface there is the gel solution of the polystyrene microsphere of golden shell layer to obtain powdered sample after being dried
Product；Polystyrene microsphere is removed by the way that sample is impregnated in tetrahydrofuran solution, then graphene support is obtained after being dried
Micron chickens nucleocapsid.
Further, in step (1), polystyrene microsphere lotion is prepared using surfactant- free emulsion polymerization：Select second
Alcohol is as reaction dissolvent, and styrene is as monomer；Polyvinylpyrrolidone is taken to be dissolved in ethyl alcohol as stabilizer, takes azo two
Isobutyronitrile is dissolved in as initiator in styrene, is stirred 20 hours or more after being mixed, and obtains polystyrene microsphere lotion.
Further, modified solution is polyethyleneimine or polyvinylpyrrolidone.
Further, in step (2), deionized water described in the first mixed solution and mass fraction are the four of 1%
The volume ratio of chlorauric acid solution is more than or equal to 10:1；Mass fraction is 1% citric acid three sodium solution in second mixed solution
The volume ratio of tetra chlorauric acid solution for being 1% with mass fraction is 2:1；Mass fraction is in gold seeds gel solution
The volume ratio of tetra chlorauric acid solution that 0.075% sodium borohydride solution is 1% with mass fraction is 1:1；Microballoon gold seeds
Gel solution in mass fraction be 1% polyethylenimine solution and mass fraction be 1% tetra chlorauric acid liquor capacity ratio
Example is 1:12.
Further, in step (3), the mixed solution of the tetra chlorauric acid and potassium carbonate by 0.5g potassium carbonate with
The tetra chlorauric acid solution that 30ml mass fractions are 1% mixes in proportion.
Further, in step (3), there is K-H solution in the gel solution of the polystyrene microsphere of golden shell layer on surface
The tetra chlorauric acid liquor capacity ratio for being 1% with mass fraction in the gel solution of microballoon gold seeds is 7.5:1.
Further, in step (3), a hydrogenperoxide steam generator is added dropwise every 30 seconds equivalent in whipping process；
And it also needs to continue stirring 15 minutes or more after color is graying.
The present invention also provides a kind of micron chickens nucleocapsids obtained based on above-mentioned preparation method.
Further, golden shell layer thickness is in micron chickens nucleocapsid：Tens nanometers to hundreds of nanometers.
Further, support construction is graphene multilayer in micron chickens nucleocapsid.
The present invention prepares polystyrene microsphere as substrate material, modified polyphenyl second using improved surfactant- free emulsion polymerization
Alkene microballoon；Using seed mediated growth method and its self-assembling technique, the gel solution of PS package gold seeds is grown；Using improved table
Bright seed mediated growth method prepares the controllable golden shell layer of thickness；Finally by chemical immersion remove polystyrene microsphere kernel, formed by
The micron chickens nucleocapsid of graphene Multi-layer supporting.Micron chickens Core-shell structure material inner wall of the present invention is using graphene multilayer as branch
Support body forms graphene multilayer and the composite shell structure of gold, the stability of reinforcing material.
Description of the drawings
The micron chickens Core-shell structure material preparation method that Fig. 1 is the present invention realizes flow chart.
Fig. 2 is the micron chickens Core-shell structure material scanning electron microscope image of the present invention.
Fig. 3 is the micron chickens Core-shell structure material transmission electron microscope image of the present invention.
Fig. 4 is the polystyrene microsphere scanning electron microscope image of the present invention.
Fig. 5 is the micron chickens Core-shell structure material X-ray diffraction spectrum of the present invention.
Fig. 6 is the micron chickens Core-shell structure material Raman collection of illustrative plates of the present invention.
Specific embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to the accompanying drawings and embodiments, it is right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.
The micron chickens nucleocapsid of graphene support provided by the invention includes：The golden shell layer of outer layer and shell inner wall
Graphene multilayer as backing material.The PS in golden shell layer is removed using a kind of method of new chemical immersion, in gold nano
The controllable graphene multilayer of thickness is grown under layer catalytic action.It is micro- to grow 4 by improving surfactant- free emulsion polymerization by the present invention
The PS controllable in micron range of rice~10.With room temperature chemical method in the present invention, the nucleocapsid using graphene as substrate is prepared
Structure.
As shown in Figure 1, the preparation method of the micron chickens nucleocapsid of graphene support provided by the invention includes following steps
Suddenly：
(1) polystyrene microsphere lotion is obtained, and is stirred after adding in modified solution in polystyrene microsphere lotion,
Obtain the polystyrene microsphere lotion that surface is modified；
Wherein it is possible to polystyrene microsphere lotion is prepared using surfactant- free emulsion polymerization, specially：Ethyl alcohol is selected as anti-
Solvent is answered, styrene is as monomer；Polyvinylpyrrolidone is taken to be dissolved in ethyl alcohol as stabilizer, azodiisobutyronitrile is taken to make
It is dissolved in styrene for initiator, is stirred 20 hours or more after being mixed, obtain polystyrene microsphere lotion.
Wherein, modified solution can be polyethyleneimine, polyvinylpyrrolidone etc..
(2) the gel solution step of microballoon gold seeds is obtained：
It is stirred and (is more than or equal to after addition trisodium citrate in the first mixed solution of deionized water and tetra chlorauric acid
5 minutes) make the second mixed solution of acquisition after its reaction fully, and carried out after adding in sodium borohydride in second mixed solution
Stirring (being more than or equal to 5 minutes) obtains gold seeds gel solution after making its reaction fully；
The polystyrene microsphere lotion mixing that the gold seeds gel solution is modified with the surface (is more than or equal to
15 minutes) afterwards obtain microballoon gold seeds gel solution；The microballoon gold seeds have the polystyrene of gold seeds for surface growth
Microballoon；
(3) gel solution that there is the polystyrene microsphere of golden shell layer on surface is obtained；
By the solidifying of the mixed solution of tetra chlorauric acid and potassium carbonate (referred to as K-H solution), deionized water and microballoon gold seeds
It is stirred after sol solution mixing, hydrogenperoxide steam generator is added dropwise in whipping process until surface is obtained after color is graying golden shell
The gel solution of the polystyrene microsphere of layer simultaneously makes it grow graphene multilayer in golden shell layer inner wall；
Wherein, a hydrogenperoxide steam generator is added dropwise every 30 seconds equivalent in whipping process；And it is also needed after color is graying
Continue stirring 15 minutes or more.
(4) surface there is the gel solution of the polystyrene microsphere of golden shell layer to obtain powdered sample after being dried
Product；Polystyrene microsphere is removed by the way that sample is impregnated in tetrahydrofuran solution, then graphene support is obtained after being dried
Micron chickens nucleocapsid.
Wherein it is possible to it is repeatedly impregnated and is dried；Preferably, more than or equal to 3 times.
As one embodiment of the present of invention, deionized water and the tetrachloro that mass fraction is 1% are golden in the first mixed solution
The volume ratio of acid solution is more than or equal to 10:1.Citric acid three sodium solution and the matter that mass fraction is 1% in second mixed solution
It is 2 to measure the volume ratio of tetra chlorauric acid solution that score is 1%:1.Mass fraction is 0.075% in gold seeds gel solution
The volume ratio of tetra chlorauric acid solution that sodium borohydride solution is 1% with mass fraction is 1:1.The gel solution of microballoon gold seeds
The tetra chlorauric acid liquor capacity ratio that the polyethylenimine solution and mass fraction that middle mass fraction is 1% are 1% is 1:12.
In embodiments of the present invention, K-H solution is by tetra chlorauric acid solution that 0.5g potassium carbonate and 30ml mass fractions are 1%
It mixes in proportion.There is the solidifying of K-H solution and microballoon gold seeds in the gel solution of the polystyrene microsphere of golden shell layer on surface
The tetra chlorauric acid liquor capacity ratio that mass fraction is 1% in sol solution is 7.5:1.
The present invention prepares the hollow golden shell (MG@Au) of graphene Multi-layer supporting using a kind of new chemical immersion methods.Tool
Body step is as follows：Sample in tetrahydrofuran solution is impregnated and removes PS, under the catalysis of gold, graphene is grown in golden inner wall
Multilayer.Retain lower floor's lotion and carry out multiple eccentric cleaning, be put into baking oven and be dried into powder；It is repeated 3 times, prepares in high quality
Empty MG@Au powder.
Support construction therein is graphene multilayer.It is micro- in 4-10 to improve polystyrene microsphere grain size prepared by monodisperse method
It is controllable in the range of rice.Golden shell layer thickness can be controlled in tens to hundreds of nanometers.
Beneficial effects of the present invention：The preparation of PS balls largely belongs to nanometer scale, and the present invention improves emulsifier-free emulsion polymerization
The parameter of method grows PS controllable in 4 microns~10 micron ranges.The preparation method of graphene mostly based on high growth temperature,
With low-temperature chemical routes in the present invention, the core-shell material using graphene as substrate is prepared.Micron chickens nucleocapsid of the present invention
Material inner wall using graphene multilayer as supporter, formed graphene multilayer with gold composite shell structure, reinforcing material it is steady
It is qualitative.
For the micron chickens nucleocapsid and its system of further description graphene support provided in an embodiment of the present invention
Preparation Method, in conjunction with attached drawing and specific example, details are as follows：
(1) three-necked flask is fixed in constant speed stirring, and is put into water-bath and heats；Take total amount 100.0ml ethyl alcohol,
45.0ml styrene is in three-necked flask；0.8g polyvinylpyrrolidones is taken to be scattered in ethanol in proper amount (polyvinylpyrrolidone
The amount that can be completely dissolved), 0.45g azodiisobutyronitriles is taken to be scattered in appropriate styrene, and (azodiisobutyronitrile can be completely dissolved
Amount), and be added in three-necked flask；
(2) vacuum pump access three-necked flask is vacuumized, closes vacuum pump and be filled with nitrogen, cycle is multiple, makes three-necked flask
In be full of nitrogen；It is 120rpm to adjust mechanical agitation speed, and keeping water-bath constant temperature, reaction is for 24 hours at 70 DEG C；
(3) using deionized water, each eccentric cleaning of alcohol for several times, the residue during cleaning reaction is finally stored in
It is spare in deionized water；
(4) PS lotions are taken in conical flask；Deionized water is added in in conical flask, is placed on magnetic stirrer, is added in
0.25mlPEI solution, the PS balls total surface area that 1mlPEI is modified are 1.14 × 106cm2, stir more than 1h；
(5) supernatant liquid is removed, retains lower floor's lotion, carries out eccentric cleaning operation, is cleaned for several times with deionized water, centrifugation
Can realize separation, the residue during cleaning reaction adds the lotion after centrifugation for the adjusting of rotating speed and centrifugation time
Deionized water is scattered in test tube；
(6) deionized water is successively added in conical flask, the 1ml tetra chlorauric acids that mass fraction is 1%, mass fraction are
1% 2ml trisodium citrates, the 1ml sodium borohydrides that mass fraction is 0.075%, often add in a kind of solution magnetic stirrer and stir
It mixes several minutes；The modification PS lotions of 1/3rd amounts in step (5) are eventually adding in conical flask, more than magnetic agitation 15min
After stand；After layering to appear, remove layer turbid and carry out eccentric cleaning operation for several times with ionized water, be finally stored in deionized water
In；
(7) mass fraction is taken as 1% tetra chlorauric acid solution 30ml, is added in the stirring of 0.5g potassium carbonate, is treated that potassium carbonate is completely molten
Solution is aged more than for 24 hours, is prepared into tetra chlorauric acid-potassium carbonate mixed solution (K-H solution)；
(8) it is molten that the gold seeds lotion of 1/10th amounts, 7.5mlK-H in deionized water, step (6) are added in conical flask
Liquid；It is placed on magnetic stirrer and stirs；Hydrogenperoxide steam generator is added dropwise, until mixed liquor color is graying；
(9) it after standing, removes layer turbid and carries out eccentric cleaning operation for several times with ionized water, finally the lotion after centrifugation exists
It is dried into powder.
(10) PS@Au samples grind into powder in grinding pot after drying is taken, it is spare to be put into test tube；It adds in test tube
Appropriate tetrahydrofuran solution, makes sample be fully immersed in tetrahydrofuran, impregnates more than 12h at room temperature；Supernatant liquid is removed, is protected
Leaving layer lotion simultaneously adds in ethanol in proper amount；It is put into centrifuge and carries out centrifugally operated, the adjusting of centrifugal rotational speed and centrifugation time is with energy
Realize separation, repeated washing for several times afterwards dries the lotion after centrifugation；
(11) (9) step is repeated several times, removes internal PS residuals, after be put into baking oven drying, prepare hollow G@Au powder
End.
Table one：Polystyrene microsphere lotion parameter table
Table two：
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, all any modification, equivalent and improvement made all within the spirits and principles of the present invention etc., should all include
Within protection scope of the present invention.
Claims (9)
1. a kind of preparation method of the micron chickens nucleocapsid of graphene support, which is characterized in that include the following steps：
(1) polystyrene microsphere lotion is obtained, and is stirred after adding in modified solution in polystyrene microsphere lotion, is obtained
The polystyrene microsphere lotion that surface is modified；
(2) gel solution of microballoon gold seeds is obtained：
(2.1) being stirred after addition trisodium citrate in the first mixed solution of deionized water and tetra chlorauric acid makes its reaction
The second mixed solution is obtained after fully, and being stirred after addition sodium borohydride in second mixed solution fills its reaction
Gold seeds gel solution is obtained after point；
(2.2) it is obtained after the gold seeds gel solution is mixed with the polystyrene microsphere lotion that the surface is modified micro-
The gel solution of ball gold seeds；
The microballoon gold seeds have the polystyrene microsphere of gold seeds for surface growth；
(3) gel solution that there is the polystyrene microsphere of golden shell layer on surface is obtained；
It is stirred after the gel solution of the mixed solution of tetra chlorauric acid and potassium carbonate, deionized water and microballoon gold seeds is mixed
It mixes, hydrogenperoxide steam generator is added dropwise in whipping process until there is the polystyrene microsphere of golden shell layer on acquisition surface after color is graying
Gel solution simultaneously makes it grow graphene multilayer in golden shell layer inner wall；
(4) surface there is the gel solution of the polystyrene microsphere of golden shell layer to obtain powdered sample after being dried；
Polystyrene microsphere is removed by the way that sample is impregnated in tetrahydrofuran solution, then the micro- of graphene support is obtained after being dried
The golden nucleocapsid of rice.
2. preparation method as described in claim 1, which is characterized in that in step (1), prepared using surfactant- free emulsion polymerization
Polystyrene microsphere lotion.
3. preparation method as claimed in claim 1 or 2, which is characterized in that the modified solution is polyethyleneimine or poly- second
Alkene pyrrolidone.
4. preparation method as claimed in claim 1 or 2, which is characterized in that in step (2), described in the first mixed solution
Deionized water and the volume ratio for the tetra chlorauric acid solution that mass fraction is 1% are more than or equal to 10：1；
The tetra chlorauric acid solution that the citric acid three sodium solution that mass fraction is 1% in second mixed solution is 1% with mass fraction
Volume ratio be 2：1；
The tetra chlorauric acid that the sodium borohydride solution that mass fraction is 0.075% in gold seeds gel solution is 1% with mass fraction
The volume ratio of solution is 1：1；
The tetrachloro that the polyethylenimine solution that mass fraction is 1% in the gel solution of microballoon gold seeds is 1% with mass fraction
Auric acid liquor capacity ratio is 1：12.
5. preparation method as described in claim 1, which is characterized in that in step (3), the tetra chlorauric acid and potassium carbonate
Mixed solution is mixed in proportion by 0.5g potassium carbonate with 30ml mass fractions for 1% tetra chlorauric acid solution.
6. preparation method as described in claim 1, which is characterized in that in step (3), there is the polystyrene of golden shell layer on surface
The tetra chlorauric acid solution body that K-H solution is 1% with mass fraction in the gel solution of microballoon gold seeds in the gel solution of microballoon
Product ratio is 7.5:1.
7. preparation method as described in claim 1, which is characterized in that in step (3), every 30 seconds etc. in whipping process
A hydrogenperoxide steam generator is added dropwise in amount；And it also needs to continue stirring 15 minutes or more after color is graying.
8. a kind of micron chickens nucleocapsid obtained based on claim 1-7 any one of them preparation method.
9. micron chickens nucleocapsid as claimed in claim 8, which is characterized in that support construction in the micron chickens nucleocapsid
For graphene multilayer.
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| CN111421134B (en) * | 2020-04-04 | 2021-05-18 | 华中科技大学 | Micron gold cage shell structure material with broadband absorption characteristic and preparation thereof |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102358783A (en) * | 2011-07-27 | 2012-02-22 | 武汉大学 | Preparation method of polystyrene/gold composite microspheres |
| CN103754863A (en) * | 2013-12-26 | 2014-04-30 | 湖南大学 | Preparation method of gold-graphene composite nano material |
| CN103817322A (en) * | 2014-02-25 | 2014-05-28 | 中国科学院化学研究所 | PS@Au core-shell structure material, manufacturing method of PS@Au core-shell structure material, and application of PS@Au core-shell structure material |
| CN104952900A (en) * | 2015-05-13 | 2015-09-30 | 武汉工程大学 | Storage device based on graphene oxide/polystyrene/gold nanoparticle composite and preparation method thereof |
| CN105131596A (en) * | 2015-09-14 | 2015-12-09 | 江南大学 | Preparation method of graphene/polyaniline composite hollow microspheres |
| CN105542332A (en) * | 2015-12-15 | 2016-05-04 | 江南大学 | Preparation method of polystyrene/graphene/precious metal composite particle |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102358783A (en) * | 2011-07-27 | 2012-02-22 | 武汉大学 | Preparation method of polystyrene/gold composite microspheres |
| CN103754863A (en) * | 2013-12-26 | 2014-04-30 | 湖南大学 | Preparation method of gold-graphene composite nano material |
| CN103817322A (en) * | 2014-02-25 | 2014-05-28 | 中国科学院化学研究所 | PS@Au core-shell structure material, manufacturing method of PS@Au core-shell structure material, and application of PS@Au core-shell structure material |
| CN104952900A (en) * | 2015-05-13 | 2015-09-30 | 武汉工程大学 | Storage device based on graphene oxide/polystyrene/gold nanoparticle composite and preparation method thereof |
| CN105131596A (en) * | 2015-09-14 | 2015-12-09 | 江南大学 | Preparation method of graphene/polyaniline composite hollow microspheres |
| CN105542332A (en) * | 2015-12-15 | 2016-05-04 | 江南大学 | Preparation method of polystyrene/graphene/precious metal composite particle |
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