CN102153065B - Gold nanorod-graphene composite membrane and preparation method thereof - Google Patents
Gold nanorod-graphene composite membrane and preparation method thereof Download PDFInfo
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- CN102153065B CN102153065B CN2010105365297A CN201010536529A CN102153065B CN 102153065 B CN102153065 B CN 102153065B CN 2010105365297 A CN2010105365297 A CN 2010105365297A CN 201010536529 A CN201010536529 A CN 201010536529A CN 102153065 B CN102153065 B CN 102153065B
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Abstract
The invention relates to a composite membrane, in particular to a gold nanorod-graphene composite membrane and a preparation method thereof. The composite membrane comprises graphene oxide, oleyl amine modified graphene and gold nanorods, wherein the graphene oxide and the oleyl amine modified graphene are mixed with each other and stacked to form a graphene membrane; the gold nanorods are doped on the surface and among the layers of the graphene membrane; and an absorption peak appears within 500-1000nm in a visible light-near infrared region. The method comprises the following steps: firstly preparing the oleyl amine modified graphene; then preparing graphene oxide aqueous solution; preparing oleyl amine modified graphene toluene solution; and finally taking and adding gold nanorod aqueous solution to the graphene oxide aqueous solution, adding the oleyl amine modified graphene toluene solution, sealing the obtained two phases of mixed solution and standing, thus the graphene oxide, the gold nanorods and the oleyl amine modified graphene can self assemble the composite membrane on the water-toluene interface, and volatilizing the toluene to completely remove the toluene, thus obtaining the unbraced gold nanorod-graphene composite membrane on the water-air interface.
Description
Technical field
The present invention relates to a kind of composite package, especially relate to a kind of gold nanorods-Graphene composite package and preparation method thereof.
Background technology
2004 Graphene (Graphene) appearance caused the research boom that the whole world is new.Graphene is a kind of carbonaceous novel material that the monolayer carbon atom closely is arranged in two-dimentional hexagonal structure.The thickness of this graphite crystal film has only 0.335nm, and Graphene has a series of unique characteristics.In August, 2008, U.S. scientist confirms that Graphene is the highest material of intensity on the present the known world.Graphene still is the outstanding material of present known conductivity, fast tens of times than silicon of its electric transmission speed.Employing Hummers etc. (J.Am.Chem.Soc., 2009,131 (3): 1043-1049) chemistry redox method, as raw material, can produce Graphene with natural graphite in large quantity.
Golden nanometer particle is just causing more and more keen interest of scientific and technological circle because of its distinctive optics and chemistry and catalytic performance.Usually these characteristics are decided by the particle diameter and the form of these metallicss.Because nonspherical particle has more superior performance than isotropic spheroidal particle, the nano Au particle of different shape and particle diameter can produce the special property that much is different from the body gold.Utilize the seed law can prepare the gold nano stub of surface band CTAB (CTAB) in large quantity.
Because the peculiar property of Graphene and nanometer gold is also more and more about the research report of Graphene and nanometer gold composite material and preparation method thereof recently.But at present relevant research is conceived to mostly that growth in situ goes out nano Au particle on Graphene, is difficult to the pattern of regulation and control nano Au particle.
Summary of the invention
The object of the present invention is to provide a kind of gold nanorods-Graphene composite package and preparation method thereof.
A kind of gold nanorods according to the invention-Graphene composite package is made up of graphene oxide, oleyl amine modified graphene and gold nanorods; Wherein graphene oxide and oleyl amine modified graphene mix mutually and are stacked into graphene film; Gold nanorods is entrained in the surface and the interlayer of graphene film; The length of gold nanorods is 20～100nm; Length-to-diameter ratio is 2～10; Weight ratio is 200nm～20 μ m for the thickness of
composite package, and 500～1000nm place has absorption peak in visible light-near-infrared region.
The preparation method of a kind of gold nanorods according to the invention-Graphene composite package may further comprise the steps:
1) preparation of oleyl amine modified graphene: graphite oxide is dissolved in the oleyl amine, is mixed with suspending liquid A, supersound process gets graphene oxide oleyl amine solution, adds sulfuric acid as catalyzer, heating, and products therefrom promptly obtains the oleyl amine modified graphene through washing and drying;
In step 1), the concentration of said suspending liquid A can be 0.5～100mg/ml, and the time of said supersound process can be 0.5～10h, and ultrasonic power can be 20～200W; Said graphene oxide oleyl amine solution and vitriolic volume ratio can be (5～20): (0.01～0.05); Said heating can be adopted microwave heating, and the temperature of microwave heating can be 100～250 ℃, and the time of microwave heating can be 0.5～10h.
2) preparation of graphite oxide aqueous solution: graphite oxide is dissolved in the water, is mixed with suspension-s B, supersound process promptly gets the graphite oxide aqueous solution;
In step 2) in, the concentration of said suspension-s B can be 0.1～5mg/ml; The time of said supersound process can be 0.5～10h, and ultrasonic power can be 20～200W.
3) preparation of oleyl amine modified graphene toluene solution: the oleyl amine modified graphene of step 1) gained is dissolved in the toluene, is mixed with suspension-s C, supersound process promptly gets oleyl amine modified graphene toluene solution;
In step 3), the concentration of said suspension-s C can be 0.1～5mg/ml, and the time of said supersound process can be 0.5～10h, and ultrasonic power can be 20～200W.
4) the gold nanorods aqueous solution 0.01～5ml that gets 0.5～5nM is added to 1～500ml step 2) in the graphite oxide aqueous solution of gained; Add oleyl amine modified graphene toluene solution then with equal concentration of graphite oxide aqueous solution and volume; Two phase mixing solutionss of gained seal and leave standstill; The Graphene of graphene oxide, gold nanorods, oleyl amine modification can be self-assembled into composite package on water-toluene interface; After again toluene being removed fully, can obtain unsupported a kind of gold nanorods-Graphene composite package in water-air interface.
In step 4), said two phase mixing solutionss seal and leave standstill, and preferably two phase mixing solutionss seal after leave standstill more than the 1h again behind ultrasonic or the stirring 30min～120h; Said toluene is removed fully, can be through drawing, topple over or uncovered to its volatilization is removed fully.
Said graphite oxide is to be raw material with the natural graphite, by the Hummers method (referring to document J.Am.Chem.Soc., 2009,131 (3): 1043-1049) make.
The gold nanorods of synthetic pattern homogeneous is assembled on the Graphene and composite membrane-forming to adopt direct self-assembling method of the present invention can make; Overcome the inhomogenous shortcoming of pattern of growth in situ nano Au particle on the present Graphene; The composite package of gained has the good absorption characteristic at visible light-near-infrared region 500nm～1000nm place, aspect photoelectric device, has potential and uses.Technology of the present invention is simple, and desired raw material cheaply is easy to get, and can be used for producing in batches.The present invention also has the potential of certain versatility in addition, can the nanometer gold of other patterns or the nanoparticle of other different qualities be assembled into the composite package that forms difference in functionality on the Graphene.
Description of drawings
Fig. 1 is the ESEM picture of the gold nanorods of embodiment 2 preparations.In Fig. 1, scale is 100nm.
Fig. 2 is the transmission electron microscope picture of the gold nanorods of embodiment 2 preparations.In Fig. 2, scale is 100nm.
Fig. 3 is the infrared spectrogram of Graphene of the oleyl amine modification of embodiment 3 preparation.In Fig. 3, X-coordinate is wave number Wavenumbers (cm
-1), ordinate zou is transsmissivity Transmittance (%).
Fig. 4 is the surface sweeping Electronic Speculum picture of the gold nanorods-Graphene composite package of embodiment 5 preparations.In Fig. 4, scale is 200nm.
Fig. 5 is the ultraviolet spectrogram of the gold nanorods-Graphene composite package of embodiment 5 preparations.In Fig. 5, X-coordinate is wavelength wavelength (nm), and ordinate zou is absorbance A bsorbance.
Embodiment
Through embodiment the present invention is specifically described below; Present embodiment only is used for the present invention is further described; Can not be interpreted as restriction to protection domain of the present invention; Some nonessential improvement and adjustment that those skilled in the art makes according to the content of foregoing invention all belong to protection domain of the present invention.
Embodiment 1: the preparation of graphite oxide aqueous solution
Take by weighing 5g natural graphite and 5g SODIUMNITRATE, the vitriol oil with 230ml in ice bath mixes, and slowly adds 30g KMnO in the stirring
4, treat KMnO
4With the solution thorough mixing evenly after, above-mentioned solution is transferred to 35 ± 5 ℃ of water-bath 1h, this moment, solution can form thick.Slowly add the 400ml pure water, and temperature is risen to 90 ± 5 ℃ of continuation reaction 30min, mixture becomes glassy yellow by brown.Further add pure water 100ml dilution at last, add the H of 30ml massfraction 30% simultaneously
2O
2Solution-treated is with the unreacted KMnO that neutralizes
4, treat suction filtration and repetitive scrubbing filter cake behind the above-mentioned solution cool to room temperature, promptly obtain graphite oxide after the vacuum-drying.Take by weighing a certain amount of graphite oxide and be distributed in the water, ultrasonic certain hour dissolves to it fully, can obtain the graphite oxide aqueous solution of homogeneous.
Embodiment 2: the preparation of the gold nanorods aqueous solution
The seed law is adopted in the preparation of gold nanorods, is divided into two steps:
The preparation seed solution: with 7.5ml, the CTAB of 0.01M and 0.25ml, the HAuCl of 0.01M
4Fully mixing adds the 0.6ml that at present joins, the ice NaBH of 0.01M again
4, stirred fast 2 minutes, be placed on then 25 the degree water-bath in left standstill at least 2 hours.
Preparation generates solution: add 4.75ml successively, the CTAB of 0.01M, 0.2ml, the HAuCl of 0.01M
4And 0.03ml, the AgNO of 0.01M
3, stir and make abundant mixing.Add 0.032ml then, the vitamins C of 0.1M, solution become colourless at once.Add 20 μ l seed solutions at last, stirred for 10 seconds fast, rest on 25 the degree water-baths in more than 3 hours.Gained solution 8500 leaves the heart 25～30min, removes supernatant, and deposition is gold nanorods, it is dispersed in the water can obtains the gold nanorods aqueous solution.
The ESEM picture of the gold nanorods of preparation is referring to Fig. 1, and the transmission electron microscope picture of the gold nanorods of preparation is referring to Fig. 2.
Embodiment 3: the preparation of oleyl amine modified graphene toluene solution microwave heating method
Take by weighing the about 200mg of embodiment 1 said graphite oxide, be dissolved in the 10ml oleyl amine.Ultrasonicly make graphite oxide fully peel off into graphene oxide and in oleyl amine, be uniformly dispersed.Above-mentioned homogeneous solution is transferred in the quartz reaction bottle, added stirrer, drips several vitriol oil rear pressing covers and seal, use microwave synthesizer (Shanghai know earnest scientific instrument ltd) to react 3 hours then at 140 ℃.After the question response system naturally cools to room temperature, open bottle cap, the gained black solid is washed centrifugal once collection with the ethanol that adds less ammonia earlier, washes centrifugal twice collecting precipitation with ethanol again, and drying in vacuum obtains the Graphene of oleyl amine modification.A certain amount of oleyl amine modified graphene is dissolved in the toluene the ultrasonic Graphene toluene solution that promptly obtains the oleyl amine modification after it is uniformly dispersed.
The infrared spectrogram of the Graphene of the oleyl amine modification of preparation is referring to Fig. 3.
Embodiment 4: the liquid-liquid interface self-assembling method prepares gold nanorods-Graphene composite package
Preparation 0.1mg/ml embodiment 1 described graphite oxide aqueous solution and 0.1mg/ml embodiment 3 described oleyl amine modified graphene toluene solutions.Get above-mentioned graphite oxide aqueous solution 40ml, drip the gold nanorods aqueous solution 1.2ml of embodiment 2 described 1nM.The oleyl amine modified graphene toluene solution 40ml that in above-mentioned solution, adds 0.1mg/ml then can be self-assembled into gold nanorods-Graphene composite package at water-toluene interface after sealing stirring 5h and then leaving standstill 3h.Uncovered then treat that toluene finishes after, gold nanorods-Graphene composite package floats over the water surface, can further collect.
Embodiment 5: the liquid-liquid interface self-assembling method prepares gold nanorods-Graphene composite package
Get 0.1mg/ml graphite oxide aqueous solution 50ml, drip 1nM gold nanorods solution 1.8ml.The Graphene toluene solution 50ml that in above-mentioned solution, adds the modification of 0.1mg/ml oleyl amine then seals and stops to stir after stirring 2d, leaves standstill 10h again and can form gold nanorods-Graphene self-assembly composite package at water-toluene interface.Drawn toluene solution with suction pipe then, can obtain unsupported composite package on the water surface.
The surface sweeping Electronic Speculum picture of the gold nanorods-Graphene composite package of preparation is referring to Fig. 4, and the ultraviolet spectrogram of the gold nanorods of preparation-Graphene composite package is referring to Fig. 5.
Claims (8)
1. gold nanorods-Graphene composite package; It is characterized in that forming by graphene oxide, oleyl amine modified graphene and gold nanorods; Wherein graphene oxide and oleyl amine modified graphene mix mutually and are stacked into graphene film; Gold nanorods is entrained in the surface and the interlayer of graphene film; The length of gold nanorods is 20～100nm, and length-to-diameter ratio is 2～10, and weight ratio is
; The thickness of composite package is 200nm～20 μ m, and 500～1000nm place has absorption peak in visible light-near-infrared region.
2. the preparation method of a kind of gold nanorods as claimed in claim 1-Graphene composite package is characterized in that may further comprise the steps:
1) preparation of oleyl amine modified graphene: graphite oxide is dissolved in the oleyl amine, is mixed with suspending liquid A, supersound process gets graphene oxide oleyl amine solution, adds sulfuric acid as catalyzer, heating, and products therefrom promptly obtains the oleyl amine modified graphene through washing and drying;
2) preparation of graphite oxide aqueous solution: graphite oxide is dissolved in the water, is mixed with suspension-s B, supersound process promptly gets the graphite oxide aqueous solution;
3) preparation of oleyl amine modified graphene toluene solution: the oleyl amine modified graphene of step 1) gained is dissolved in the toluene, is mixed with suspension-s C, supersound process promptly gets oleyl amine modified graphene toluene solution;
4) the gold nanorods aqueous solution 0.01～5ml that gets 0.5～5nM is added to 1～500ml step 2) in the graphite oxide aqueous solution of gained; Add oleyl amine modified graphene toluene solution then with equal concentration of graphite oxide aqueous solution and volume; Two phase mixing solutionss of gained seal and leave standstill; The Graphene of graphene oxide, gold nanorods, oleyl amine modification can be self-assembled into composite package on water-toluene interface; After again toluene being removed fully, can obtain unsupported a kind of gold nanorods-Graphene composite package in water-air interface; Said two phase mixing solutionss seal and leave standstill, and are that two phase mixing solutionss seal after leave standstill more than the 1h behind ultrasonic or the stirring 30min～120h again.
3. the preparation method of a kind of gold nanorods as claimed in claim 2-Graphene composite package is characterized in that in step 1) the concentration of said suspending liquid A is 0.5～100mg/ml, and the time of said supersound process is 0.5～10h, and ultrasonic power is 20～200W.
4. the preparation method of a kind of gold nanorods as claimed in claim 2-Graphene composite package is characterized in that in step 1) said graphene oxide oleyl amine solution and vitriolic volume ratio are (5～20): (0.01～0.05).
5. the preparation method of a kind of gold nanorods as claimed in claim 2-Graphene composite package is characterized in that in step 1), saidly adds thermal recovery microwave heating, and the temperature of microwave heating is 100～250 ℃, and the time of microwave heating is 0.5～10h.
6. the preparation method of a kind of gold nanorods as claimed in claim 2-Graphene composite package is characterized in that in step 2) in, the concentration of said suspension-s B is 0.1～5mg/ml; The time of said supersound process is 0.5～10h, and ultrasonic power is 20～200W.
7. the preparation method of a kind of gold nanorods as claimed in claim 2-Graphene composite package is characterized in that in step 3) the concentration of said suspension-s C is 0.1～5mg/ml, and the time of said supersound process is 0.5～10h, and ultrasonic power is 20～200W.
8. the preparation method of a kind of gold nanorods as claimed in claim 2-Graphene composite package is characterized in that in step 4) said toluene is removed fully, is through drawing, topple over or uncovered to its volatilization is removed fully.
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| CN103219066B (en) * | 2012-01-19 | 2016-08-03 | 中国科学院上海硅酸盐研究所 | Flexible conductive film that two-dimensional graphene is compound with one-dimensional nano line and preparation method thereof |
| CN103668141B (en) * | 2012-08-30 | 2015-12-16 | 中国科学院上海微系统与信息技术研究所 | In the method for surface of graphene oxide growth noble metal nanocrystalline |
| CN105033276B (en) * | 2015-07-28 | 2017-05-03 | 同济大学 | Method for in situ synthesis of gold nanorods/graphene oxide composite material |
| CN105750558B (en) * | 2016-04-12 | 2017-12-08 | 同济大学 | A kind of method of one pot process gold nanorods/graphene oxide composite material |
| CN107973621A (en) * | 2017-11-03 | 2018-05-01 | 东南大学 | A kind of reaction island based on graphene/nanometer gold plating and its preparation method and application |
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| US20100038601A1 (en) * | 2008-08-12 | 2010-02-18 | Chaoyin Zhou | Durable transparent conductors on polymeric substrates |
| CN101710512A (en) * | 2009-11-20 | 2010-05-19 | 哈尔滨工程大学 | Composite material of graphene and carbon-encapsulated ferromagnetic nano metal and preparation method thereof |
| CN101837972A (en) * | 2010-05-28 | 2010-09-22 | 南京邮电大学 | Graphene three-dimensional structure and preparation method thereof |
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| US20100038601A1 (en) * | 2008-08-12 | 2010-02-18 | Chaoyin Zhou | Durable transparent conductors on polymeric substrates |
| CN101710512A (en) * | 2009-11-20 | 2010-05-19 | 哈尔滨工程大学 | Composite material of graphene and carbon-encapsulated ferromagnetic nano metal and preparation method thereof |
| CN101837972A (en) * | 2010-05-28 | 2010-09-22 | 南京邮电大学 | Graphene three-dimensional structure and preparation method thereof |
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