CN105969330B - A kind of preparation method of graphene nano material - Google Patents
A kind of preparation method of graphene nano material Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
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- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
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- 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
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- 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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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/54—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing zinc or cadmium
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/65—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing carbon
Abstract
The present invention provides a kind of preparation method of graphene nano material, prepares ZnO quantum dot and the Fe with meso-hole structure respectively first3O4Nano particle, then wrap up one layer of SiO in both nanoparticle surfaces2Shell and to its amination.Amidized composite nanometer particle is grafted onto to the surface of graphene oxide of the pre- carboxylated in surface by way of covalent cross-linking, finally gives a kind of graphene oxide composite material with magnetic fluorescent dual-function.The graphene oxide composite material prepared using the present invention has obvious magnetic behavior, and its excellent fluorescence property is expected to realize when as pharmaceutical carrier carries out tracer to its transmission path.
Description
The present patent application is for the applying date 2014 year 09 month 26, the patent of invention of application number 201410502642.1
Divisional application.
Technical field
The present invention relates to a kind of graphene nanocomposite material and preparation method, belong to technical field of inorganic nanometer material.
Background technology
In recent years, metal nanoparticle, magnetic nano-particle are loaded into surface of graphene oxide and prepares composite, and
The research and development that it is explored in the application of the fields such as material, chemistry, biomedicine is rapid.At present both at home and abroad it is existing on it in life
In terms of application in terms of thing medical science is mainly used in bio-imaging, biological detection, oncotherapy and pharmaceutical carrier, these researchs all take
Obtained gratifying achievement.In terms of research of the graphene oxide as pharmaceutical carrier：Graphene has the specific surface area of superelevation first
With pi-electron conjugated system.Graphene oxide can be by pi-pi accumulation and hydrogen bond action carrying medicament, and can be with superfine small
Particulate form is suspended in the aqueous solution or physiological environment system, but prepares grinding for target medicine carrier currently with graphene oxide
Study carefully also relatively seldom, it is therefore necessary to increase this research dynamics, realize graphene oxide based medicine carrier early in practice
Application.
Magnetic nanoparticle is loaded into the magnetic targeting drug carrier of graphenic surface preparation, in actual disease treatment
With great application potential.At present under study for action, used magnetic particle is all solid Fe3O4Nano particle, wherein magnetic particle
Only play a part of making material that there is magnetic property in the composite, and the structure of nano-particle does not embody in the composite
Go out obvious effect.Quantum dot is used as structure and activity or even the progress animal of fluorescent marker tracer observation living cells or tissue
Living imaging and the research for following the trail of drug particles trend in vivo and effect have largely been reported.In these reports
Quantum dot used is synthesized using colloid chemistry method in organic system mostly, therefore obtained quantum dot poorly water-soluble, and
And the quantum dot composition of synthesis is mainly Cd oxygen group elements binary compound and its core shell structure.Cd is a kind of weight for having severe toxicity
Metallic element, quantum dot containing Cd easily discharge Cd during biomarker2+And damage biological body.Although the system of cadmium content point
The detection of standby and properity is highly developed, and numerous studies have shown that using surface modification technology or synthesis in water
Method can substantially improve the stability and security of the quantum dot containing Cd, but this kind of quantum dot, which can not still be completely eliminated, to be made
Free Cd can be decomposited during2+Possibility, therefore cadmium content point biological safety still do not obtain it is basic
Solve.Therefore, for biological safety and application angle, the system of hypotoxicity or bio-compatibility quanta point material is actively developed
The research of standby, structure and performance is by as the developing direction of following quanta point material.At present, applied to the low of bioluminescence detection
Toxicity or bio-compatibility quantum dot are mainly ZnS, ZnSe and ZnO quantum dot.Quantum dots of the ZnO as biological fluorescent labelling,
Bio-toxicity compared with the quantum dot containing Cd is smaller, all fool proof for tested animal and testing research person.Make
For a kind of safe and non-toxic, cheap and good-quality advanced luminescent material, ZnO quantum dot is in terms of basic research and practical application two, all
There is highly important value.
The content of the invention
It is an object of the invention to provide a kind of preparation method with magnetic, the graphene nano material of fluorescent functional.
Method provided by the invention is by Silica-coated（Mesoporous Fe3O4Magnetic nanoparticle-ZnO quantum dot）It is logical
The mode for crossing covalent cross-linking is incorporated into surface of graphene oxide, obtains a kind of graphene oxide based composites.Wherein, stone is aoxidized
Black alkene is in itself and Fe3O4Meso-hole structure in magnetic nanoparticle makes whole material have a higher specific surface area, and hypotoxicity
The selection of ZnO quantum dot and the cladding of silica shell further increase the biocompatibility of graphene oxide composite material, most
The graphene oxide composite material with magnetic fluorescent dual-function, high-specific surface area and good biocompatibility is obtained eventually, is expected to
There is good application prospect in terms of pharmaceutical carrier.Specifically include following steps：
（1）The preparation of graphene oxide
Powdered graphite is added into H2SO4、K2S2O8、P2O5Mixed liquor in, 70 ~ 85 DEG C reaction 3 ~ 6h.Then it is diluted with water,
And filtration washing is to remove unnecessary acid.Gained pre-product is dried at room temperature for overnight, is then added the graphite of pre-oxidation dense
H2SO4, KMnO is gradually added under ice-water bath protection4, this mixture at 30 ~ 35 DEG C the min of stirring reaction 30 after 85 ~ 95
DEG C carry out 1 ~ 2h of reaction, after be diluted with water, make 20 ~ 40min of its boiling reaction, after being stirred for 1 ~ 2 hour, add water and 30wt%
H2O2Solution left standstill precipitates.Rinsed for several times with watery hydrochloric acid after mixture filtering, then rinsed with water to neutrality.Finally gained is produced
Thing, which dialyses one week to purify, removes remaining metal ion, and ultrasound peels off 30 ~ 50min to obtained graphite oxide at ambient temperature,
It is about 0.1 ~ 1mgmL to obtain concentration-1Graphene oxide storing solution.Use 1- (3- dimethylamino-propyls) -3- ethyl carbon
Diimine（EDC）And n-hydroxysuccinimide（NHS）Make the activated carboxylic at graphene oxide plane and edge.
（2）Mesoporous Fe3O4The preparation of magnetic nanoparticle
At room temperature by Fe (NO3) 3·9H2O is dissolved in ethylene glycol, and stirring is heated to being formed dry for 3 hours after 70 ~ 80 DEG C
Fe(NO3)3- ethylene glycol gel.By the Fe (NO of formation3)3- ethylene glycol gel is placed on 380 ~ 450 DEG C of progress in horizontal pipe furnace
Room temperature is naturally cooled to after pyrolysis, by product respectively with pure water and ethanol wash after dry in 70 ~ 80 DEG C of drying boxes.Finally plus
Enter appropriate TMA to modify ferroso-ferric oxide, rear ultrasound, shake up and disperse Jie for obtaining various concentrations in deionized water
Hole Fe3O4Nano-particle storing solution.
（3）Preparation with the adjustable ZnO quantum dot of fluorescence color
At room temperature, by Zn (OAc)2·2H2O and LiOHH2O is according to mol ratio 2:3 are dissolved in TEG, are stirred continuously until
Solution luminescence.Afterwards according to certain mol proportion B（Mg：Zn）By Mg (OAc)2·4H2O is added in above-mentioned solution, ice-water bath condition
2 ~ 5min of lower supersound process, purifying, obtains the ZnO quantum dot of different glow colors.
（4）(mesoporous Fe3O4- ZnO quantum dot)@SiO2Preparation
By hexamethylene, triton x-100 and n-hexyl alcohol according to volume ratio 4:1:1 adds beaker, adds after stirring 15 ~ 30min
Enter 200ul Fe3O4Nano-particle solution and 800ulZnO quantum dot solutions（Concentration：1~10mmol/l）, stir 10 ~ 30min
Afterwards, 120ul NH are added4OH and 120ul PDDA solution（0.075%V/V）.Continue to add into system after stirring 20min
80ul TEOS, continue to be stirred vigorously 12 ~ 24h under the conditions of lucifuge.20 ~ 30ml acetone is finally added into the system again, is obtained
(mesoporous Fe3O4- ZnO quantum dot)@SiO2Composite nanoparticle, compound particle surface is finally subjected to ammonia using APS and THPMP
Base functionalization.
（5）The preparation of the graphene oxide composite material of magnetic fluorescent dual-function
By amidized (mesoporous Fe3O4- ZnO quantum dot)@SiO2Nano composite granules are introduced by the method for covalent cross-linking
To the surface of graphene oxide of carboxylated, the graphene oxide composite material with magnetic fluorescent dual-function is obtained.
In the present invention, step（1）Described in H2SO4、K2S2O8、P2O5Mixed liquor, the mass ratio of middle each component be：10:
1:1。
In the present invention, step（3）Described in mol ratio B (Mg：Zn)=(0~0.1).
In the present invention, step（4）Described in Fe3O4Nano-particle solution concentration is 1 ~ 10mmol/l, ZnO quantum dot solution
Concentration is 1 ~ 10mmol/l.
Compared with prior art, the present invention has the advantages that：
The graphene nanocomposite material that the present invention prepares is by mesoporous Fe3O4The magnetic of nano particle, Hole bottom cavity blast, height
The phases such as the extra specific surface area of the fluorescence property and graphene oxide of specific surface area and ZnO quantum dot, good bio-compatibility
Fusion, can be as a kind of new drug carrier with magnetic target tropism, fluorescence and high drug load.Target product not only can be with
The targeting transport of medicine is realized, fluorescent tracing can also be carried out to medicament transport process.
Brief description of the drawings
Fig. 1 is the SEM figures of the magnetic fluorescent dual-function stannic oxide/graphene nano composite prepared.
Fig. 2 is the TEM figures of the magnetic fluorescent dual-function stannic oxide/graphene nano composite prepared.
Fig. 3 is the PL spectrograms of the magnetic fluorescent dual-function stannic oxide/graphene nano composite prepared.
Fig. 4 is the magnetization curve figure of the magnetic fluorescent dual-function stannic oxide/graphene nano composite prepared.
Embodiment
The present invention is further described below by embodiment.
Embodiment 1
（1）The preparation of graphene oxide
2g graphite powders are added into the dense H of 25g2SO4、2.5g K2S2O8With 2.5g P2O5Mixed liquor in, 80 DEG C reaction 3h.So
Afterwards plus the dilution of 500ml water, and filtration washing is to remove unnecessary acid.Gained pre-product is dried at room temperature for overnight, then will be pre-
The graphite of oxidation adds the dense H of 100ml2SO4In, it is gradually added 13g KMnO under ice-water bath protection4, this mixture is at 35 DEG C
The min of stirring reaction 30 carries out reaction 2h after 85 DEG C, after be diluted with water, make its boiling reaction 30min, be stirred for 1 hour
Afterwards, 500ml water and 20ml and 30% H are added2O2Solution left standstill precipitates.With 1 after mixture filtering:10 watery hydrochloric acid rinses 5 times, then
Rinsed with water to neutrality.Finally products therefrom is dialysed one week to purify and remove remaining metal ion, obtained graphite oxide exists
Ultrasound peels off 30min under room temperature condition, is configured to the graphene oxide storing solution that concentration is about 0.5mg/ml.Aoxidized to 50ml
1 mg 1- (3- dimethylamino-propyls) -3- ethyl carbodiimides are added in the dispersion liquid of graphene（EDC）With 0.5 mg N- hydroxyls
Base succinimide（NHS）, 30min is stirred, makes the activated carboxylic at GO planes and edge.
（2）Mesoporous Fe3O4The preparation of magnetic nanoparticle
At room temperature by 0.02mol Fe (NO3) 3·9H2O is dissolved in 25ml ethylene glycol, and stirring is heated for 3 hours after 80 DEG C
Fe (the NO dry to formation3)3- ethylene glycol gel.Fe (the NO that 1g is formed3)3- ethylene glycol gel is placed in horizontal pipe furnace,
Room temperature is naturally cooled to after keeping 12h to 400 DEG C with 10 DEG C/min heating rate, product is washed with pure water and alcohol respectively
Wash after dry 12h in 70 DEG C of drying boxes.Appropriate TMA will be added in dried product, 10ml is dispersed in after ultrasonic 1min
In deionized water, the mesoporous Fe that concentration is about 10 mmol/L is obtained3O4Nano-particle storing solution.
（3）Preparation with the adjustable ZnO quantum dot of fluorescence color
At room temperature, by 0.002molZn (OAc)2·2H2O and 0.003mol LiOHH2O is dissolved in 40ml TEG, is held
Continuous stirring purifies until solution luminescence, is configured to 10mmol/l ZnO quantum dot.
（4）(mesoporous Fe3O4- ZnO quantum dot)@SiO2Preparation
15ml hexamethylenes, 3.6ml triton x-100s and 3.6ml n-hexyl alcohols are added into beaker, added after stirring 15min
200ul concentration 10mmol/l Fe3O4The ZnO quantum dot solution of nano-particle solution and 800ul concentration 10mmol/l, is stirred
After mixing 10min, 120ul NH are added4OH and 120ul PDDA solution（0.075%V/V）.Continue to stir after 20min to being
80ul TEOS are added in system, continue to be stirred vigorously 24h under the conditions of lucifuge.20ml acetone is finally added into the system again, is obtained
To (mesoporous Fe3O4- ZnO quantum dot)@SiO2Composite nanoparticle.30ulAPS and 80ulTHPMP are added to (being situated between for preparation
Hole Fe3O4- ZnO quantum dot)@SiO2In composite nanoparticle, 24h is stirred, finally obtains (the mesoporous Fe of surface amination3O4 -
ZnO quantum dot)@SiO2Composite nanoparticle.
（5）The preparation of the graphene oxide composite material of magnetic fluorescent dual-function
By 20ml（4）In obtained amino functional (mesoporous Fe3O4- ZnO quantum dot)@SiO2Composite nanoparticle adds
2 h are reacted into the GO dispersion liquids of 50ml concentration 0.5mg/ml activated carboxylics, make (mesoporous Fe3O4- ZnO quantum dot)@SiO2It is multiple
The carboxyl covalent cross-linking of the amino and GO that close nanoparticle surface forms amido link.Then by the way that the step with Magneto separate is cleaned multiple times
Suddenly, the multi-functional GO composite nanometer particles of target product magnetic fluorescence are obtained.
Embodiment 2
（1）The preparation of graphene oxide
2g graphite powders are added into the dense H of 25g2SO4、2.5g K2S2O8With 2.5g P2O5Mixed liquor in, 70 DEG C reaction 5h.So
Afterwards plus the dilution of 500ml water, and filtration washing is to remove unnecessary acid.Gained pre-product is dried at room temperature for overnight, then will be pre-
The graphite of oxidation adds the dense H of 150ml2SO4In, it is gradually added 20g KMnO under ice-water bath protection4, this mixture is at 30 DEG C
The min of stirring reaction 30 carries out reaction 2h after 85 DEG C, after be diluted with water, make its boiling reaction 30min, be stirred for 1 hour
Afterwards, 500ml water 20ml and 30% H is added2O2Solution left standstill precipitates.With 1 after mixture filtering:10 watery hydrochloric acid rinses 5 times, then uses
Water is rinsed to neutrality.Finally products therefrom is dialysed one week to purify and remove remaining metal ion, obtained graphite oxide is in room
Ultrasound peels off 30min under the conditions of temperature, is configured to the graphene oxide storing solution that concentration is about 0.2 mg/ml.Aoxidized to 50ml
0.5 mg 1- (3- dimethylamino-propyls) -3- ethyl carbodiimides are added in the dispersion liquid of graphene（EDC）With 0.2 mg N-
HOSu NHS（NHS）, 30min is stirred, makes the activated carboxylic at GO planes and edge.
（2）Mesoporous Fe3O4The preparation of magnetic nanoparticle
At room temperature by 0.02mol Fe (NO3) 3·9H2O is dissolved in 25ml ethylene glycol, and stirring is heated for 3 hours after 70 DEG C
Fe (the NO dry to formation3)3- ethylene glycol gel.Fe (the NO that 1g is formed3)3- ethylene glycol gel is placed in horizontal pipe furnace,
Room temperature is naturally cooled to after keeping 12h to 400 DEG C with 10 DEG C/min heating rate, product is washed with pure water and alcohol respectively
Wash after dry 12h in 70 DEG C of drying boxes.Appropriate TMA will be added in dried product, 100ml is dispersed in after ultrasonic 1min
In deionized water, the mesoporous Fe that concentration is about 1 mmol/L is obtained3O4Nano-particle storing solution.
（3）Preparation with the adjustable ZnO quantum dot of fluorescence color
At room temperature, by 0.002molZn (OAc)2·2H2O and 0.003mol LiOHH2O is dissolved in 40ml TEG, is held
Continuous stirring is until solution luminescence.By 0.0002mol Mg (OAc)2·4H2O is added in above-mentioned solution, under the conditions of ice-water bath
5min is ultrasonically treated, is purified, is configured to 10mmol/l ZnO quantum dot.
（4）(mesoporous Fe3O4- ZnO quantum dot)@SiO2Preparation
15ml hexamethylenes, 3.6ml triton x-100s and 3.6ml n-hexyl alcohols are added into beaker, added after stirring 15min
200ul concentration 1mmol/l Fe3O4The ZnO quantum dot solution of nano-particle solution and 800ul concentration 10mmol/l, stirring
After 10min, 120ul NH are added4OH and 120ul PDDA solution（0.075%V/V）.Continue to stir after 20min to system
Middle addition 80ul TEOS, continue to be stirred vigorously 24h under the conditions of lucifuge.20ml acetone is finally added into the system again, is obtained
(mesoporous Fe3O4- ZnO quantum dot)@SiO2Composite nanoparticle.30ulAPS and 80ulTHPMP are added to the (mesoporous of preparation
Fe3O4- ZnO quantum dot)@SiO2In composite nanoparticle, 24h is stirred, finally obtains (the mesoporous Fe of surface amination3O4 -
ZnO quantum dot)@SiO2Composite nanoparticle.
（5）The preparation of the graphene oxide composite material of magnetic fluorescent dual-function
By 20ml（4）In obtained amino functional (mesoporous Fe3O4- ZnO quantum dot)@SiO2Composite nanoparticle solution
It is added in the mg/ml of 50ml concentration 0.2 activated carboxylic GO dispersion liquids and reacts 2 h, makes (mesoporous Fe3O4- ZnO quantum dot)@
SiO2The amino on composite nanoparticle surface and GO carboxyl covalent cross-linking form amido link.Then by being cleaned multiple times and magnetic point
From the step of, obtain the multi-functional GO composite nanometer particles of target product magnetic fluorescence.
Embodiment 3
（1）The preparation of graphene oxide
2g graphite powders are added into the dense H of 25g2SO4、2.5g K2S2O8With 2.5g P2O5Mixed liquor in, 80 DEG C reaction 3h.So
Afterwards plus the dilution of 500ml water, and filtration washing is to remove unnecessary acid.Gained pre-product is dried at room temperature for overnight, then will be pre-
The graphite of oxidation adds the dense H of 100ml2SO4In, it is gradually added 13g KMnO under ice-water bath protection4, this mixture is at 35 DEG C
The min of stirring reaction 30 carries out reaction 2h after 85 DEG C, after be diluted with water, make its boiling reaction 30min, be stirred for 1 hour
Afterwards, 500ml water and 20ml and 30% H are added2O2Solution left standstill precipitates.With 1 after mixture filtering:10 watery hydrochloric acid rinses 5 times, then
Rinsed with water to neutrality.Finally products therefrom is dialysed one week to purify and remove remaining metal ion, obtained graphite oxide exists
Ultrasound peels off 30min under room temperature condition, is configured to the graphene oxide storing solution that concentration is about 0.1mg/ml.Aoxidized to 50ml
2mg 1- (3- dimethylamino-propyls) -3- ethyl carbodiimides are added in the dispersion liquid of graphene（EDC）With 0.1mg N- hydroxyls
Succinimide（NHS）, 30min is stirred, makes the activated carboxylic at GO planes and edge.
（2）Mesoporous Fe3O4The preparation of magnetic nanoparticle
At room temperature by 0.02mol Fe (NO3) 3·9H2O is dissolved in 25ml ethylene glycol, and stirring is heated for 3 hours after 80 DEG C
Fe (the NO dry to formation3)3- ethylene glycol gel.Fe (the NO that 1g is formed3)3- ethylene glycol gel is placed in horizontal pipe furnace,
Room temperature is naturally cooled to after keeping 12h to 400 DEG C with 10 DEG C/min heating rate, product is washed with pure water and alcohol respectively
Wash after dry 12h in 70 DEG C of drying boxes.Appropriate TMA will be added in dried product, 10ml is dispersed in after ultrasonic 1min
In deionized water, the mesoporous Fe that concentration is about 10 mmol/L is obtained3O4Nano-particle storing solution.
（3）Preparation with the adjustable ZnO quantum dot of fluorescence color
At room temperature, by 0.002molZn (OAc)2·2H2O and 0.003mol LiOHH2O is dissolved in 40ml TEG, is held
Continuous stirring is up to solution luminescence, by 0.0001mol Mg (OAc)2·4H2O is added in above-mentioned solution, under the conditions of ice-water bath
5min is ultrasonically treated, is purified, is configured to 10mmol/l ZnO quantum dot
（4）(mesoporous Fe3O4- ZnO quantum dot)@SiO2Preparation
15ml hexamethylenes, 3.6ml triton x-100s and 3.6ml n-hexyl alcohols are added into beaker, added after stirring 15min
200ul concentration 10mmol/l Fe3O4The ZnO quantum dot solution of nano-particle solution and 800ul concentration 10mmol/l, is stirred
After mixing 10min, 120ul NH are added4OH and 120ul PDDA solution（0.075%V/V）.Continue to stir after 20min to being
80ul TEOS are added in system, continue to be stirred vigorously 24h under the conditions of lucifuge.20ml acetone is finally added into the system again, is obtained
To (mesoporous Fe3O4- ZnO quantum dot)@SiO2Composite nanoparticle.30ulAPS and 80ulTHPMP are added to the (mesoporous of preparation
Fe3O4- ZnO quantum dot)@SiO2In composite nanoparticle, 24h is stirred, finally obtains (the mesoporous Fe of surface amination3O4 -
ZnO quantum dot)@SiO2Composite nanoparticle.
（5）The preparation of the graphene oxide composite material of magnetic fluorescent dual-function
By 20ml（4）In obtained amino functional (mesoporous Fe3O4- ZnO quantum dot)@SiO2Composite nanoparticle adds
2 h are reacted into the GO dispersion liquids of 50ml concentration 0.1mg/ml activated carboxylics, make (mesoporous Fe3O4- ZnO quantum dot)@SiO2It is multiple
The carboxyl covalent cross-linking of the amino and GO that close nanoparticle surface forms amido link.Then by the way that the step with Magneto separate is cleaned multiple times
Suddenly, the multi-functional GO composite nanometer particles of target product magnetic fluorescence are obtained.
Claims (1)
1. a kind of preparation method of graphene nano material, it is characterised in that prepare as follows：
（1）The preparation of graphene oxide
2g graphite powders are added into the dense H of 25g2SO4、2.5g K2S2O8With 2.5g P2O5Mixed liquor in, 80 DEG C reaction 3h, Ran Houjia
500mL water dilutes, and filtration washing, to remove unnecessary acid, gained pre-product is dried at room temperature for overnight, then adding 100mL
Dense H2SO4In, it is gradually added 13g KMnO under ice-water bath protection4, this mixture at 35 DEG C the min of stirring reaction 30 after
85 DEG C carry out reaction 2h, after be diluted with water, make its boiling reaction 30min, after being stirred for 1 hour, add 500mL water and 20mL and
30% H2O2Solution left standstill precipitates, with 1 after mixture filtering：10 watery hydrochloric acid rinses 5 times, then is rinsed with water to neutrality, finally
Products therefrom is dialysed one week to purify and removes remaining metal ion, obtained graphite oxide at ambient temperature peel off by ultrasound
30min, it is configured to the graphene oxide storing solution that concentration is 0.1mg/mL；Added into the dispersion liquid of 50mL graphene oxides
2mg 1- (3- dimethylamino-propyls) -3- ethyl carbodiimides（EDC）With 0.1mg n-hydroxysuccinimides（NHS）, stirring
30min, make the activated carboxylic at GO planes and edge；
（2）Mesoporous Fe3O4The preparation of magnetic nanoparticle
At room temperature by 0.02mol Fe (NO3) 3·9H2O is dissolved in 25mL ethylene glycol, and stirring is heated to shape in 3 hours after 80 DEG C
Cheng Gan Fe (NO3)3- ethylene glycol gel, the Fe (NO that 1g is formed3)3- ethylene glycol gel is placed in horizontal pipe furnace, with 10
DEG C/min heating rate naturally cools to room temperature after keeping 12h to 400 DEG C, by product respectively with after pure water and ethanol wash
12h is dried in 70 DEG C of drying boxes, TMA will be added in dried product, is dispersed in after ultrasonic 1min in 10mL deionized waters,
Obtain the mesoporous Fe that concentration is 10 mmol/L3O4Nano-particle storing solution；
（3）Preparation with the adjustable ZnO quantum dot of fluorescence color
At room temperature, by 0.002molZn (OAc)2·2H2O and 0.003mol LiOHH2O is dissolved in 40mL TEG, is persistently stirred
Mix up to solution luminescence, by 0.0001mol Mg (OAc)2·4H2O is added in above-mentioned solution, ultrasonic under the conditions of ice-water bath
5min is handled, is purified, is configured to 10mmol/L ZnO quantum dot；
（4）(mesoporous Fe3O4- ZnO quantum dot)@SiO2Preparation
15mL hexamethylenes, 3.6mL triton x-100s and 3.6mL n-hexyl alcohols are added into beaker, add 200 μ L's after stirring 15min
Concentration 10mmol/L Fe3O4The ZnO quantum dot solution of nano-particle solution and 800 μ L concentration 10mmol/L, stir 10min
Afterwards, 120 μ LNH are added4OH and concentration are 0.075%V/V 120 μ L PDDA solution, are continued to stir after 20min into system
80 μ LTEOS are added, continue to be stirred vigorously 24h under the conditions of lucifuge, finally add 20mL acetone into the system again, obtain (being situated between
Hole Fe3O4- ZnO quantum dot)@SiO2Composite nanoparticle, 30 μ LAPS and 80 μ L THPMP are added to (the mesoporous Fe of preparation3O4
- ZnO quantum dot)@SiO2In composite nanoparticle, 24h is stirred, finally obtains (the mesoporous Fe of surface amination3O4- ZnO quantum
Point)@SiO2Composite nanoparticle；
（5）The preparation of the graphene oxide composite material of magnetic fluorescent dual-function
By 20mL（4）In obtained amino functional (mesoporous Fe3O4- ZnO quantum dot)@SiO2Composite nanoparticle is added to
2 h are reacted in the GO dispersion liquids of 50mL concentration 0.1mg/mL activated carboxylics, make (mesoporous Fe3O4- ZnO quantum dot)@SiO2It is compound
The amino of nanoparticle surface and GO carboxyl covalent cross-linking form amido link；Then by cleaning and Magneto separate the step of, obtain
The GO composite nanometer particle multi-functional to target product magnetic fluorescence.
Priority Applications (1)
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| CN104946236B (en) * | 2015-04-28 | 2017-05-31 | 上海大学 | Compound upper conversion nano crystalline substance of silver-colored graphene coated silica and preparation method thereof |
| CN104910864A (en) * | 2015-07-16 | 2015-09-16 | 北京新怡源环保科技有限公司 | Flexible nano wave-absorbing material of ferroferric oxide composite silicon dioxide and grapheme and preparation method thereof |
| CN105086993A (en) * | 2015-09-11 | 2015-11-25 | 天津市中环量子科技有限公司 | Fluorescent quantum dot micro-nano encapsulated composite material structure |
| CN105241860B (en) * | 2015-11-20 | 2018-03-27 | 济南大学 | A kind of preparation method of magnetic fluorescence graphene composite Nano ion probe |
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| CN105969330A (en) | 2016-09-28 |
| CN104263358B (en) | 2016-04-13 |
| CN105860957A (en) | 2016-08-17 |
| CN104263358A (en) | 2015-01-07 |
| CN105969331A (en) | 2016-09-28 |
| CN105969331B (en) | 2017-12-26 |
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