CN103594220A - Functionalized grapheme/superparamagnetic ferroferric oxide nano particle composite material and preparation method thereof - Google Patents
Functionalized grapheme/superparamagnetic ferroferric oxide nano particle composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a functionalized grapheme/superparamagnetic ferroferric oxide nano particle composite material and a preparation method of the functionalized grapheme/superparamagnetic ferroferric oxide nano particle composite material, and belongs to the technical field of grapheme magnetic composite materials. The functionalized grapheme/superparamagnetic ferroferric oxide nano particle composite material solves the technical problems that a grapheme/superparamagnetic ferroferric oxide nano particle composite material is poor in hydrophilia and can not modify a functional group easily in the prior art. According to the composite material, superparamagnetic ferroferric oxide nano particles are loaded on the surface of functionalized grapheme, the diameter of the particles is smaller than 30nm, and the functionalized grapheme is polyacrylamide functionalized grapheme, or polyacrylic acid functionalized grapheme, or polymine functionalized grapheme, or tween-20 functionalized grapheme. Not only is the diameter of the particles smaller than 30nm, but also the composite material has the superparamagnetic characteristic and the strong external magnetic field correspondence, can be dispersed in a water solution excellently, and can further modify biological giant molecules.
Description
Technical field
The present invention relates to a kind of functionalization graphene/SPIO composite material and preparation method thereof, belong to Graphene magnetic composite technical field.
Background technology
SPIO have under normal temperature without can metabolism in coercive force and remanent magnetism, nontoxic, body, the handling advantage such as good under magnetic field.Graphene, is a kind of carbon atom single layer structure by sp2 hybridized orbit bonding, has graphitization planar structure and the low cost of high conductivity, high-specific surface area, uniqueness.The graphene nanometer composite that Graphene and nano material form, owing to having the advantage of Graphene and function nano material concurrently, makes it at aspects such as sensing, catalysis, electricity, magnetic, photoelectric properties, show abnormal good performance.Graphene/tri-iron tetroxide super-paramagnetism nano composite material wherein, because its outstanding magnetic and electrochemical properties are widely used in transducer, the fields such as biological medicine carrying.
Now in technology, preparing Graphene/tri-iron tetroxide super-paramagnetism nano composite material great majority adopts graphene oxide as substrate, when iron chloride Hydrothermal Synthesis is SPIO, graphene oxide is reduced to Graphene, if SPIO/graphene composite material is at the application (J.Mater.Chem. aspect stored energy, 2011, 21, 5069 – 5075), yet, this method is in preparation process, the Graphene obtaining due to reduction does not have functional group protection, and between graphene sheet layer, there are stronger Van der Waals force and π-π active force, cause the Graphene/tri-iron tetroxide super-paramagnetism nano composite material obtaining easily to produce gathering, its difficulty is scattered in water and conventional organic solvent, limited its application, simultaneously, Graphene/tri-iron tetroxide super-paramagnetism nano the composite material obtaining is owing to showing there is no functional group, need the further extra functional group of modifying to carry out mark function molecule, this modification step is loaded down with trivial details, caused a lot of difficulties to further research and the application of Graphene/tri-iron tetroxide super-paramagnetism nano composite material, if functionalization graphene/magnetic Nano material is for multi-modal imaging photo-thermal therapy (Adv.Mater.2012,24,1868 – 1872).
Summary of the invention
A little less than the object of the invention is to solve existing Graphene/tri-iron tetroxide super-paramagnetism nano composite material hydrophily, the technical problem that is difficult for modifying functional group, provides a kind of functionalization graphene/SPIO composite material and preparation method thereof.
Functionalization graphene/SPIO composite material of the present invention is comprised of functionalization graphene and SPIO, SPIO is carried on functionalization graphene surface, and the particle diameter of each SPIO is all less than 30 nanometers, described functionalization graphene is amine functional polyacrylate functionalized graphene, polyacrylic acid functionalization graphene, polymine functionalization graphene or polysorbas20 functionalization graphene.
The preparation method of above-mentioned functions functionalized graphene/SPIO composite material, comprises the following steps:
(1) functionalization graphene is joined in the reaction unit that fills ethylene glycol and diethylene glycol mixed solvent, ultrasonic, functionalization graphene is dispersed in mixed solvent;
(2) in reaction unit, add FeCl again
36H
2o and anhydrous sodium acetate, be stirred to solution clarification, obtains settled solution;
Described FeCl
36H
2the mass ratio of O, anhydrous sodium acetate, functionalization graphene is 1:3:(0.1-0.5);
(3) settled solution is added under the condition of 195-210 ℃ to thermal response 8-12h, obtain functionalization graphene/SPIO composite material.
Preferably, in described step (1), the excusing from death time is 1-10min.
Preferably, in described mixed solvent, the volume ratio of ethylene glycol and diethylene glycol is 1:(1-9).
Preferably, in described step (2), stir speed (S.S.) is turn/min of 150-400, and the time is 10-20min.
Beneficial effect of the present invention:
The particle diameter that is carried on the ferriferrous oxide nano-particle on functionalization graphene surface in functionalization graphene/SPIO composite material of the present invention is less than 30 nanometers, by regulating the mass ratio of reactant, can grain-size, there is superparamagnetism, there is stronger external magnetic field correspondence simultaneously, and due to it, there is the functional groups such as hydrophilic amino, carboxyl or hydroxyl, can in the aqueous solution, obtain fabulous dispersion, persistence is good, and the while is the large molecule of modified biological, protein, DNA etc. further.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope photo of functionalization graphene/SPIO composite material of embodiment 5 preparations;
Fig. 2 is the B-H loop of functionalization graphene/SPIO composite material of embodiment 5 preparations;
Fig. 3 is the transmission electron microscope photo of functionalization graphene/SPIO composite material of embodiment 6 preparations;
Fig. 4 is the transmission electron microscope photo of functionalization graphene/SPIO composite material of embodiment 7 preparations;
Fig. 5 is the transmission electron microscope photo of functionalization graphene/SPIO composite material of embodiment 8 preparations;
Fig. 6 is the transmission electron microscope photo of functionalization graphene/SPIO composite material of embodiment 9 preparations;
Fig. 7 is the transmission electron microscope photo of functionalization graphene/SPIO composite material of embodiment 10 preparations.
Embodiment
Functionalization graphene/SPIO composite material, by functionalization graphene and SPIO, formed, described SPIO is carried on functionalization graphene surface, and the particle diameter of each SPIO is all less than 30 nanometers, wherein, functionalization graphene is amine functional polyacrylate functionalized graphene, polyacrylic acid functionalization graphene, polymine functionalization graphene or polysorbas20 functionalization graphene.
When functionalization graphene is amine functional polyacrylate functionalized graphene, polyacrylic acid functionalization graphene, polysorbas20 functionalization graphene, preparation method is:
(1) aqueous solution of polymer is joined in graphene oxide dispersion liquid (GO dispersion liquid), add hydrazine hydrate, under normal temperature, ultrasonic and stirring, obtains mixture;
Described polymer is polypropylene amine, polyacrylic acid or polysorbas20;
(2) mixture is added to thermal response, obtain dark solution;
(3) dark solution is centrifugal, washing, obtains functionalization graphene.
In the preparation method of above-mentioned functions functionalized graphene, the aqueous solution of polymer can be by commercially available, and wherein, the mean molecule quantity of polypropylene amine is 15000, and polyacrylic mean molecule quantity is 240000; Centrifugal, washing process is centrifugal and use deionized water rinsing under can the rotating speed of turn 15000/min.
When functionalization graphene is polymine functionalization graphene, it is prepared as prior art (Nanoscale, 2013,5,663 – 670).
As preferred version, the preparation method of amine functional polyacrylate functionalized graphene:
(1) the polypropylene amine aqueous solution (mean molecule quantity of polypropylene amine is 15000) is joined in GO dispersion liquid, add hydrazine hydrate, ultrasonic and stir after 20min-1h the mixture obtaining under normal temperature;
The mass ratio of described polypropylene amine, graphene oxide and hydrazine hydrate is (7-9): 1:(8-12);
(2) mixture is reacted after 2-6h at 120-160 ℃, obtain dark solution;
(3) dark solution is centrifugal, washing, to remove polypropylene amine unnecessary in solution, obtains amine functional polyacrylate functionalized graphene.
As preferred version, the preparation method of polyacrylic acid functionalization graphene is:
(1) the polyacrylic acid aqueous solution (polyacrylic mean molecule quantity is 240000) is joined in GO dispersion liquid, add hydrazine hydrate, ultrasonic and stir after 20min-1h the mixture obtaining under normal temperature;
The mass ratio of described polyacrylic acid, graphene oxide and hydrazine hydrate is (50-70): 1:(8-12);
(2) mixture is reacted after 2-6h at 120-160 ℃, obtain dark solution;
(3) dark solution is centrifugal, washing, to remove polyacrylic acid unnecessary in solution, obtains polyacrylic acid functionalization graphene.
As preferred version, the preparation method of polymine functionalization graphene is:
(1) polyethyleneimine: amine aqueous solution (mean molecule quantity of polymine is 25000) is joined in GO dispersion liquid, ultrasonic and stir after 20min-1h the mixture obtaining under normal temperature;
The mass ratio of described polymine, graphene oxide is (8-12): 1;
(2) mixture is reacted after 2h at 90 ℃, obtain dark solution;
(3) dark solution is centrifugal, washing, to remove polymine unnecessary in solution, obtains polymine functionalization graphene.
As preferred version, the preparation method of polysorbas20 functionalization graphene:
(1) the polysorbas20 aqueous solution is joined in GO dispersion liquid, add hydrazine hydrate, ultrasonic and stir after 20min-1h the mixture obtaining under normal temperature;
The mass ratio of described polysorbas20, graphene oxide and hydrazine hydrate is (40-60): 1:(8-12);
(2) mixture is reacted after 2-6h at 120-160 ℃, obtain dark solution;
(3) dark solution is centrifugal, washing, to remove polysorbas20 unnecessary in solution, obtains polysorbas20 functionalization graphene.
The preparation of functionalization graphene/SPIO composite material, directly utilizes solvent thermal process by FeCl
36H
2o is synthetic at functionalization graphene surface in situ, comprises the following steps:
(1) functionalization graphene is joined in the reactor that fills ethylene glycol and diethylene glycol mixed solvent, ultrasonic 1-10min is dispersed in mixed solvent functionalization graphene;
In mixed solvent, the volume ratio of ethylene glycol and diethylene glycol is 1:(1-9), preferred 1:1,1:2,1:4.3 or 1:9;
(2) under agitation, in reactor, add FeCl
36H
2o and anhydrous sodium acetate, turn at 150-400/min, preferably 200 turn/rotating speed of min under, stir 10-20min until solution becomes clarification, obtain settled solution;
Wherein, add FeCl
36H
2the mass ratio of O, anhydrous sodium acetate and functionalization graphene is 1:3:(0.1-0.5);
(3) settled solution is transferred in reactor, at 195-210 ℃, add thermal response 8-12h, preferably add thermal response 10h at 200 ℃, be cooled to room temperature, separated by magnet adsorption, use successively second alcohol and water cyclic washing, obtain functionalization graphene/SPIO composite material.
Below in conjunction with embodiment and accompanying drawing, further illustrate the present invention.
Embodiment 1
The preparation of amine functional polyacrylate functionalized graphene:
The polypropylene amine aqueous solution of 2.4mL58mg/mL (mean molecule quantity of polypropylene amine is 15000) is joined in the even GO dispersion liquid of 40mL0.4mg/mL, add 160 μ L hydrazine hydrates, ultrasonic and stir after 30min under normal temperature, the mixture obtaining reacts 4h at 140 ℃, obtain dark solution, by centrifugal under the rotating speed of turn 15000/min of dark solution and with deionized water rinsing 3 times, remove polypropylene amine unnecessary in solution, obtain amine functional polyacrylate functionalized graphene.
Embodiment 2
The preparation of polyacrylic acid functionalization graphene:
By the 3.5mL25wt% polyacrylic acid aqueous solution (density 1.09g/mL, polyacrylic mean molecule quantity is 240000) join in the even GO dispersion liquid of 40mL0.4mg/mL, add 160 μ L hydrazine hydrates, under normal temperature, stir after 20min, the mixture obtaining reacts 4h at 140 ℃, obtains dark solution product, by centrifugal under the rotating speed of turn 15000/min of dark solution and with deionized water rinsing 3 times, to remove polyacrylic acid unnecessary in solution, obtain polyacrylic acid functionalization graphene.
Embodiment 3
The preparation of polymine functionalization graphene:
The polyethyleneimine: amine aqueous solution of 2mL86mg/mL (mean molecule quantity of polymine is 25000) is joined in the even GO dispersion liquid of 40mL0.4mg/mL, under normal temperature, stir after 20min, the mixture obtaining continues to stir 2h at 90 ℃, obtain dark solution, by centrifugal under the rotating speed of turn 15000/min of dark solution and with deionized water rinsing 3 times, to remove polymine unnecessary in solution, obtain polymine functionalization graphene.
Embodiment 4
The preparation of polysorbas20 functionalization graphene:
0.8mL polysorbas20 is joined in the even GO dispersion liquid of 40mL0.4mg/mL, add 160 μ L hydrazine hydrates, ultrasonic and stir after 20min under normal temperature, the mixture obtaining obtains dark solution react 4h at 140 ℃ after, by centrifugal under the rotating speed of turn 15000/min of dark solution and with deionized water rinsing 3 times, to remove polysorbas20 unnecessary in solution, obtain polysorbas20 functionalization graphene.
Embodiment 5
In conjunction with Fig. 1 and Fig. 2, embodiment 5 is described
0.15g polyacrylic acid functionalization graphene ultrasonic dissolution, in the mixed solvent of 20mL ethylene glycol and diethylene glycol volume ratio 1:4.3, is then added to 0.35gFeCl
36H
2o and 1.05g acetic anhydride are received, after stirring, transfer to 40mL polytetrafluoroethylliner liner, in the hydrothermal reaction kettle of stainless steel outer sleeve, at 200 ℃, react 10h, be cooled to room temperature, separated by magnet adsorption, use successively second alcohol and water cyclic washing, obtain functionalization graphene/SPIO composite material.
Functionalization graphene/SPIO the composite material obtaining is dissolved in water, can see that composite material well scatter in water; By being dissolved with under the aqueous solution room temperature of composite material standing three months, still there is good dispersiveness; Continue to place, in dispersion liquid, there will be a small amount of aggregation, but these aggregations are by vibration or slight ultrasonicly just can again be scattered in water.
Fig. 1 is the transmission electron microscope photo of functionalization graphene/SPIO composite material of embodiment 5 preparations, as can be seen from the figure, SPIO loads on functionalization graphene surface, and particle diameter is all less than 15 nanometers.
Fig. 2 is the B-H loop of functionalization graphene/SPIO composite material of embodiment 5 preparations.
Embodiment 6
In conjunction with Fig. 3, embodiment 6 is described
In the mixed solvent that is 1:2 to 20mL ethylene glycol and diethylene glycol volume ratio by 0.15g polyacrylic acid functionalization graphene ultrasonic dissolution, then add 0.35gFeCl
36H
2o and 1.05g anhydrous sodium acetate, after stirring, transfer to 40mL polytetrafluoroethylliner liner, in the hydrothermal reaction kettle of stainless steel outer sleeve, at 200 ℃, react 10h, be cooled to room temperature, separated by magnet adsorption, use successively second alcohol and water cyclic washing, obtain functionalization graphene/SPIO composite material.
Functionalization graphene/SPIO the composite material obtaining is dissolved in water, can see that composite material well scatter in water; By being dissolved with under the aqueous solution room temperature of composite material standing three months, still there is good dispersiveness; Continue to place, in dispersion liquid, there will be a small amount of aggregation, but these aggregations are by vibration or slight ultrasonicly just can again be scattered in water.
Fig. 3 is the transmission electron microscope photo of functionalization graphene/SPIO composite material of embodiment 6 preparations, as can be seen from the figure, SPIO loads on functionalization graphene surface, and particle diameter is all less than 22 nanometers.
Embodiment 7
In conjunction with Fig. 4, embodiment 7 is described
In the mixed solvent that is 1:1 to 20mL ethylene glycol and diethylene glycol volume ratio by 0.15g polyacrylic acid functionalization graphene ultrasonic dissolution, then add 0.35gFeCl
36H
2o and 1.05g anhydrous sodium acetate, after stirring, transfer to 40mL polytetrafluoroethylliner liner, in the hydrothermal reaction kettle of stainless steel outer sleeve, at 200 ℃, react 10h, be cooled to room temperature, separated by magnet adsorption, use successively second alcohol and water cyclic washing, obtain functionalization graphene/SPIO composite material.
Functionalization graphene/SPIO the composite material obtaining is dissolved in water, can see that composite material well scatter in water; By being dissolved with under the aqueous solution room temperature of composite material standing three months, still there is good dispersiveness; Continue to place, in dispersion liquid, there will be a small amount of aggregation, but these aggregations are by vibration or slight ultrasonicly just can again be scattered in water.
Fig. 4 is the transmission electron microscope photo of functionalization graphene/SPIO composite material of embodiment 7 preparations, as can be seen from the figure, SPIO loads on functionalization graphene surface, and particle diameter is all less than 30 nanometers.
Embodiment 8
In conjunction with Fig. 5, embodiment 8 is described
In the mixed solvent that is 1:9 to 20mL ethylene glycol and diethylene glycol volume ratio by 0.15g polymine functionalization graphene ultrasonic dissolution, then add 0.35gFeCl
36H
2o and 1.05g anhydrous sodium acetate, after stirring, transfer to 40mL polytetrafluoroethylliner liner, in the hydrothermal reaction kettle of stainless steel outer sleeve, at 200 ℃, react 10h, be cooled to room temperature, separated by magnet adsorption, use successively second alcohol and water cyclic washing, obtain functionalization graphene/SPIO composite material.
Functionalization graphene/SPIO the composite material obtaining is dissolved in water, can see that composite material well scatter in water; By being dissolved with under the aqueous solution room temperature of composite material standing one week, still there is good dispersiveness; Continue to place, in dispersion liquid, there will be a small amount of aggregation, but these aggregations just can be scattered in water again by ultrasonic.
Fig. 5 is the transmission electron microscope photo of functionalization graphene/SPIO composite material of embodiment 8 preparations, as can be seen from the figure, SPIO loads on functionalization graphene surface, and particle diameter is all less than 15 nanometers.
Embodiment 9
In conjunction with Fig. 6, embodiment 9 is described
In the mixed solvent that is 1:9 to 20mL ethylene glycol and diethylene glycol volume ratio by 0.1g amine functional polyacrylate functionalized graphene ultrasonic dissolution, then add 0.35gFeCl
36H
2o and 1.05g anhydrous sodium acetate, after stirring, transfer to 40mL polytetrafluoroethylliner liner, in the hydrothermal reaction kettle of stainless steel outer sleeve, at 200 ℃, react 10h, be cooled to room temperature, separated by magnet adsorption, use successively second alcohol and water cyclic washing, obtain functionalization graphene/SPIO composite material.
Functionalization graphene/SPIO the composite material obtaining is dissolved in water, can see that composite material well scatter in water; By being dissolved with under the aqueous solution room temperature of composite material standing three months, still there is good dispersiveness; Continue to place, in dispersion liquid, there will be a small amount of aggregation, but these aggregations are by vibration or slight ultrasonicly just can again be scattered in water.
Fig. 6 is the transmission electron microscope photo of functionalization graphene/SPIO composite material of embodiment 9 preparations, as can be seen from the figure, SPIO loads on functionalization graphene surface, and particle diameter is all less than 15 nanometers.
Embodiment 10
In conjunction with Fig. 7, embodiment 10 is described
In the mixed solvent that is 1:9 to 20mL ethylene glycol and diethylene glycol volume ratio by 0.1g polysorbas20 functionalization graphene ultrasonic dissolution, then add 0.35gFeCl
36H
2o and 1.05g anhydrous sodium acetate, after stirring, transfer to 40mL polytetrafluoroethylliner liner, in the hydrothermal reaction kettle of stainless steel outer sleeve, at 200 ℃, react 10h, be cooled to room temperature, separated by magnet adsorption, use successively second alcohol and water cyclic washing, obtain functionalization graphene/SPIO composite material.
Functionalization graphene/SPIO the composite material obtaining is dissolved in water, can see that composite material well scatter in water; By being dissolved with under the aqueous solution room temperature of composite material standing one month, still there is good dispersiveness; Continue to place, in dispersion liquid, there will be a small amount of aggregation, but these aggregations are by vibration or slight ultrasonicly just can again be scattered in water.
Fig. 7 is the transmission electron microscope photo of functionalization graphene/SPIO composite material of embodiment 10 preparations, as can be seen from the figure, SPIO loads on functionalization graphene surface, and particle diameter is all less than 18 nanometers.
Embodiment 11
In the mixed solvent that is 1:3 to 20mL ethylene glycol and diethylene glycol volume ratio by 0.05g polymine functionalization graphene ultrasonic dissolution, then add 0.35gFeCl
36H
2o and 1.05g anhydrous sodium acetate, after stirring, transfer to 40mL polytetrafluoroethylliner liner, in the hydrothermal reaction kettle of stainless steel outer sleeve, at 195 ℃, react 8h, be cooled to room temperature, separated by magnet adsorption, use successively second alcohol and water cyclic washing, obtain functionalization graphene/SPIO composite material.
Functionalization graphene/SPIO the composite material obtaining is dissolved in water, can see that composite material well scatter in water; By being dissolved with under the aqueous solution room temperature of composite material standing one week, still there is good dispersiveness; Continue to place, in dispersion liquid, there will be a small amount of aggregation, but these aggregations just can be scattered in water again by ultrasonic.
Embodiment 12
In the mixed solvent that is 1:4.3 to 20mL ethylene glycol and diethylene glycol volume ratio by 0.175g polysorbas20 functionalization graphene ultrasonic dissolution, then add 0.35gFeCl
36H
2o and 1.05g anhydrous sodium acetate, after stirring, transfer to 40mL polytetrafluoroethylliner liner, in the hydrothermal reaction kettle of stainless steel outer sleeve, in 210 ℃, react 12h, be cooled to room temperature, separated by magnet adsorption, use successively second alcohol and water cyclic washing, obtain functionalization graphene/SPIO composite material.
Functionalization graphene/SPIO the composite material obtaining is dissolved in water, can see that composite material well scatter in water; By being dissolved with under the aqueous solution room temperature of composite material standing one month, still there is good dispersiveness; Continue to place, in dispersion liquid, there will be a small amount of aggregation, but these aggregations are by vibration or slight ultrasonicly just can again be scattered in water.
Obviously, the explanation of above embodiment is just for helping to understand method of the present invention and core concept thereof.It should be pointed out that the those of ordinary skill for described technical field, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection range of the claims in the present invention.
Claims (5)
1. functionalization graphene/SPIO composite material, it is characterized in that, this composite material is comprised of functionalization graphene and SPIO, SPIO is carried on functionalization graphene surface, and the particle diameter of each SPIO is all less than 30 nanometers;
Described functionalization graphene is amine functional polyacrylate functionalized graphene, polyacrylic acid functionalization graphene, polymine functionalization graphene or polysorbas20 functionalization graphene.
2. the preparation method of functionalization graphene/SPIO composite material claimed in claim 1, is characterized in that, comprises the following steps:
(1) functionalization graphene is joined in the reaction unit that fills ethylene glycol and diethylene glycol mixed solvent, ultrasonic, functionalization graphene is dispersed in mixed solvent;
(2) in reaction unit, add FeCl again
36H
2o and anhydrous sodium acetate, be stirred to solution clarification, obtains settled solution;
Described FeCl
36H
2the mass ratio of O, anhydrous sodium acetate, functionalization graphene is 1:3:(0.1-0.5);
(3) settled solution is added under the condition of 195-210 ℃ to thermal response 8-12h, obtain functionalization graphene/SPIO composite material.
3. the preparation method of functionalization graphene/SPIO composite material according to claim 2, is characterized in that, in described step (1), the excusing from death time is 1-10min.
4. the preparation method of functionalization graphene/SPIO composite material according to claim 2, is characterized in that, in mixed solvent, the volume ratio of ethylene glycol and diethylene glycol is 1:(1-9).
5. the preparation method of functionalization graphene/SPIO composite material according to claim 2, is characterized in that, in described step (2), stir speed (S.S.) is turn/min of 150-400, and the time is 10-20min.
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