CN106917071B - Graphene-nano-noble metal multiple tube preparation method - Google Patents
Graphene-nano-noble metal multiple tube preparation method Download PDFInfo
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- CN106917071B CN106917071B CN201710113579.6A CN201710113579A CN106917071B CN 106917071 B CN106917071 B CN 106917071B CN 201710113579 A CN201710113579 A CN 201710113579A CN 106917071 B CN106917071 B CN 106917071B
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/17—Metallic particles coated with metal
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Abstract
The invention discloses a kind of graphene-nano-noble metal multiple tube preparation methods, comprising: (1) after taking wire to be impregnated with dust technology, is placed in ultrasound in dehydrated alcohol, then dries；(2) wire of drying is put into chemical vapor depsotition equipment and grows graphene on its surface, obtain graphene/metal wire composite structure；(3) nano noble metal particles clad is deposited in graphene/metal wire composite structure graphene surface；(4) obtained composite construction is put into after removing wire in etching liquid, cleaning, drying obtains graphene-nano-noble metal multiple tube.Preparation method of the invention has the characteristics of operation is simple, and repeatability is strong, no pollution to the environment.Graphene provided by the invention-nano-noble metal multiple tube has excellent mobility, mechanical strength, thermal conductivity and corrosion resistance, is suitable for the numerous areas such as microelectronics, transparent electrode, organic electro-optic device, energy-storage battery, multifunctional composite and biomedicine.
Description
Technical field
The invention belongs to technical field of nano material, and in particular to a kind of preparation method of graphene-nanogold multiple tube.
Background technique
Graphene is a kind of two-dimentional allotrope of carbon, since the research group of Univ Manchester UK in 2004 is first
After single-layer graphene has successfully been obtained in secondary utilization micromechanics stripping method, graphene obtains the extensive pass of various countries researcher
Note.Although other allotropes such as carbon nanotube, fullerene of carbon etc. are all similar with graphene by sp2 hydbridized carbon atoms group
At, however in properties sides such as mobility, room temperature Hall effect, diracelectron structure, translucency, mechanical strength and thermal conductivities
Face, these allotropes cannot match in excellence or beauty with graphene.Exactly because these tempting speciality, graphene such as microelectronics,
The numerous areas such as transparent electrode, organic electro-optic device, energy-storage battery, multifunctional composite and biomedicine have wide
Application prospect.[specific visible document: L.Guo et al.J Phys C, 2012,116 (5): 3594.X.Wang et
al.Nano Lett,2008,8:323.K.K.Manga et al.Adv Mater,2012,24:1697.Y.Zhu et
al.Carbon,2010,48:2118.Y.Wang et al.J Phys Chem C,2011,115:23192.Y Wang et
al.J Am Chem Soc,2010,132:9274.]
Publication number CN102586869A discloses a kind of preparation method of three-dimensional grapheme tube, the grapheme tube skeleton material
Material is the organic materials such as Kynoar, polyethylene glycol, polymethylacrylic acid, and above-mentioned material is enhancing grapheme tube machinery by force
While spending, the important parameters such as the electric conductivity of graphene are undoubtedly also reduced.In addition, there is document report using noble metal and nanometer
The compound method of carbon material can effectively promote its electric conductivity.However, at present there has been no using wire as growth substrate, in gold
Belong to silk table face and deposit obtained graphene/metal wire composite structure, and then coat noble metal nano particles on the surface of graphene, finally
Graphene-nano-noble metal multiple tube relevant report is prepared by removing substrate (wire).
Summary of the invention
It is excellent it is an object of the invention to solve at least the above problems and/or defect, and provide at least to will be described later
Point.
In order to realize these purposes and other advantages according to the present invention, it is multiple to provide a kind of graphene-nano-noble metal
Close the preparation method of pipe, comprising the following steps:
Step 1: it is placed in ultrasound in dehydrated alcohol after taking wire dust technology to impregnate removal surface impurity and passivation layer,
Then it is dried for standby；
Step 2: being put into chemical vapor depsotition equipment and being grown on its surface using the wire of drying as growth substrate
Graphene obtains graphene/metal wire composite structure；
Step 3: depositing nano noble metal particles clad, shape in graphene/metal wire composite structure graphene surface
At noble metal clad/graphene/metal wire composite structure；
Step 4: noble metal clad/graphene/metal wire composite structure is put into etching liquid after removal wire,
It is dried after being cleaned with dehydrated alcohol and deionized water to products therefrom, obtains graphene-nano-noble metal multiple tube.
Preferably, the wire is copper wire or nickel wire, and the diameter of the wire is 10nm~1cm, and length is
10nm~1m.
Preferably, the dust technology concentration be 0.001~1mol/L, wire in dust technology soaking time be 1s~
60min, a length of 1~60min when ultrasonic in dehydrated alcohol；The drying is dried temperature using in air dry oven
It is 40~200 DEG C, the processing time is 0.1~36h.
Preferably, in the step 3, the expensive gold of nanometer is deposited in graphene/metal wire composite structure graphene surface
The deposition method for belonging to particle clad is in magnetron sputtering, hot evaporation, pulse laser deposition, chemical plating or electrochemical deposition method
Any one；The deposition rate for depositing nano noble metal particles clad is 0.1nm/s~10 μm/s, and the noble metal is
Gold, platinum, palladium, titanium, ruthenium, any one or more alloy material being combined into niobium.
Preferably, the graphene-nano-noble metal multiple tube diameter is 10nm~1cm, and length is 10nm~1m.
Preferably, in the step 2, in chemical vapor depsotition equipment, wire surface grows graphene process
Reaction atmosphere is the gaseous mixture of hydrogen and inert gas, under the premise of heating rate is 5~30 DEG C/min, is heated to reaction temperature
800~1500 DEG C, 0~120min of constant temperature of degree is cooled to room temperature after importing carbon source is reacted, and it is multiple to obtain graphene/wire
Close structure；The carbon source is one of methanol steam, alcohol vapour, acetone steam, xylene steam or a variety of mixing；Institute
The flow for stating carbon source is 10~30sccm.
Preferably, in the step 4, etching liquid is liquor potassic permanganate and/or ferric chloride solution.
Preferably, the process replacement of the step 2 are as follows: using the wire of drying as the Rotation of receiver of electrostatic spinning
Device is blended on the polymer spin dope electrostatic spinning to the wire of rotation of graphene oxide, while by graphene
Dispersion liquid ultrasonic atomizatio forms the wire of electrostatic spinning film and graphene coated on the wire of rotation；The step
In four, after noble metal clad/graphene/metal wire composite structure is put into and removes wire in etching liquid, it is added into N,
12h is impregnated in dinethylformamide or toluene, is dried, is obtained after then being cleaned with dehydrated alcohol and deionized water to products therefrom
Obtain graphene-nano-noble metal multiple tube.
Preferably, the polymer spin dope is PLA solution, polymethyl acrylate solution, polyimide solution
One of；The concentration of the polymer spin dope is 5~10wt%；The graphene oxide and polymer spin dope
Mass ratio is 1:50~100；The mixed process of the graphene oxide and polymer spin dope are as follows: by graphene oxide and gather
The mixing of object spinning solution is closed, dispersing agent 1- ethyl -3- methylimidazolium chloride is then added, low whipping speed is 500r/min condition
Under, mixed solution is heated to 50 DEG C, its reaction is kept for 24 hours, is cooled to room temperature, obtains the polymer for being mixed with graphene oxide
Spinning solution；The weight ratio of the dispersing agent 1- ethyl -3- methylimidazolium chloride and graphene oxide is 1:5~10；
The graphene dispersing solution includes the raw material of following parts by weight: 10~15 parts of graphene, 1- ethyl-3-methylimidazole
1~3 part of lactic acid, 30~50 parts of cyclohexanone, 30~50 parts of N- cyclohexyl pyrrolidone, 30~50 parts of propylene glycol butyl ether acetate.
Preferably, the electrospinning process are as follows: be blended with the polymer spin dope injection band of graphene oxide
It in the spray containers of stainless steel spray head, is then applied the voltage on stainless steel spray head with high voltage power supply, and held using with injection
The propulsion pump of device connection connects the polymer spin dope in spray containers by the wire that stainless steel spray head is sprayed to rotation
On receiving apparatus, the injection conditions of the electrostatic spinning are as follows: environment temperature is 40~80 DEG C, the output voltage of high voltage power supply be 15~
Distance is 10~15cm between 25kv, wire and stainless steel spray head, flow velocity is 5~12mL/h, the rotation of wire reception device
Rotary speed is 50~500r/min；
The power of the graphene dispersing solution ultrasonic atomizatio is 80W, and frequency 2.5MHz, condensation rate is 2~10mL/min,
The ejiction opening of ultrasonic atomizatio is 5~15cm at a distance from wire.
The present invention is include at least the following beneficial effects: preparation method of the invention have operation is simple, repeatability
By force, the characteristics of no pollution to the environment.Graphene provided by the invention-nano-noble metal multiple tube has excellent mobility, machine
Tool intensity, thermal conductivity and corrosion resistance are suitable for microelectronics, transparent electrode, organic electro-optic device, energy-storage battery, multi-functional multiple
The numerous areas such as condensation material and biomedicine.
Further advantage, target and feature of the invention will be partially reflected by the following instructions, and part will also be by this
The research and practice of invention and be understood by the person skilled in the art.
Detailed description of the invention:
Fig. 1 is the noble metal clad/graphene/copper wire composite construction scanning electron microscope prepared in the embodiment of the present invention 1
The EDS of photo (a) and corresponding position is swept at facet as a result, being carbon (b), copper (c) and gold (d) respectively；
Fig. 2 is noble metal clad/graphene/copper wire composite construction face the EDS score prepared in the embodiment of the present invention 1
Figure；
Fig. 3 is the graphene-nano-noble metal multiple tube optical microscopy sectional view prepared in the embodiment of the present invention 1.
Specific embodiment:
Present invention will be described in further detail below with reference to the accompanying drawings, to enable those skilled in the art referring to specification text
Word can be implemented accordingly.
It should be appreciated that such as " having ", "comprising" and " comprising " term used herein do not allot one or more
The presence or addition of a other elements or combinations thereof.,
Embodiment 1:
A kind of preparation method of graphene-nano-noble metal multiple tube, comprising the following steps:
Step 1: the copper wire of 15 μm of diameter, length 5cm is taken to impregnate 2min removal surface impurity with the dust technology of 0.1mol/L
And after passivation layer, it is placed in ultrasound 20min in dehydrated alcohol, 60 DEG C of drying 2h in air dry oven is then placed into and is dried for standby；
Step 2: being put into chemical vapor depsotition equipment using the copper wire of drying as growth substrate, reaction atmosphere is hydrogen
1000 DEG C are heated under the heating rate of 30 DEG C/min with the gaseous mixture of nitrogen, constant temperature 60min is passed through alcohol vapour
10sccm is reacted, and is stopped being passed through alcohol vapour after reaction, is rapidly cooled to room temperature, it is compound to obtain graphene/copper wire
Structure；
Step 3: by magnetron sputtering method, under conditions of deposition velocity is 20nm/s, in graphene/copper wire obtained
Composite structure surface deposits nanogold clad, forms nanogold clad/graphene/copper wire composite construction；Fig. 1, which is shown, to be received
Golden clad/graphene/the scanning electron microscope (SEM) photograph (a) of copper wire composite construction of rice and the EDS of corresponding position are swept at facet as a result, respectively
It is carbon (b), copper (c) and gold (d)；Fig. 2 shows nanogold clad/total spectrograms in graphene/copper wire composite construction face EDS；
Step 4: nanogold clad/graphene/copper wire composite construction to be put into iron chloride etching liquid and remove copper wire
Afterwards, it is placed in 60 DEG C of drying 2h in air dry oven after being cleaned with dehydrated alcohol and deionized water to products therefrom, obtains graphite
Alkene-nanogold multiple tube；Fig. 3 shows graphene-nano metal multiple tube optics after present invention removal growth substrate copper wire
Microscope sectional view.
Embodiment 2:
A kind of preparation method of graphene-nano-noble metal multiple tube, comprising the following steps:
Step 1: the nickel wire of 15 μm of diameter, length 5cm is taken to impregnate 2min removal surface impurity with the dust technology of 0.1mol/L
And after passivation layer, it is placed in ultrasound 20min in dehydrated alcohol, 60 DEG C of drying 2h in air dry oven is then placed into and is dried for standby；
Step 2: being put into chemical vapor depsotition equipment using the nickel wire of drying as growth substrate, reaction atmosphere is hydrogen
1000 DEG C are heated under the heating rate of 30 DEG C/min with the gaseous mixture of nitrogen, constant temperature 60min is passed through alcohol vapour
10sccm is reacted, and is stopped being passed through alcohol vapour after reaction, is rapidly cooled to room temperature, it is compound to obtain graphene/nickel silk
Structure；
Step 3: by magnetron sputtering method, under conditions of deposition velocity is 20nm/s, in graphene/nickel silk obtained
Composite structure surface deposits nanogold clad, forms nanogold clad/graphene/nickel filament composite structure；
Copper wire is removed Step 4: nanogold clad/graphene/nickel filament composite structure is put into iron chloride etching liquid
Afterwards, it is placed in 60 DEG C of drying 2h in air dry oven after being cleaned with dehydrated alcohol and deionized water to products therefrom, obtains graphite
Alkene-nanogold multiple tube.
Embodiment 3:
A kind of preparation method of graphene-nano-noble metal multiple tube, which comprises the following steps:
Step 1: the copper wire of 15 μm of diameter, length 5cm is taken to impregnate 2min removal surface impurity with the dust technology of 0.1mol/L
And after passivation layer, it is placed in ultrasound 20min in dehydrated alcohol, 60 DEG C of drying 2h in air dry oven is then placed into and is dried for standby；
Step 2: being put into chemical vapor depsotition equipment using the copper wire of drying as growth substrate, reaction atmosphere is hydrogen
1050 DEG C are heated under the heating rate of 20 DEG C/min with the gaseous mixture of nitrogen, constant temperature 30min is passed through alcohol vapour
20sccm is reacted, and is stopped being passed through alcohol vapour after reaction, is rapidly cooled to room temperature, it is compound to obtain graphene/copper wire
Structure；
Step 3: by magnetron sputtering method, under conditions of deposition velocity is 20nm/s, in graphene/copper wire obtained
Composite structure surface deposits nanogold clad, forms nanogold clad/graphene/copper wire composite construction；
Step 4: nanogold clad/graphene/copper wire composite construction to be put into iron chloride etching liquid and remove copper wire
Afterwards, it is placed in 60 DEG C of drying 2h in air dry oven after being cleaned with dehydrated alcohol and deionized water to products therefrom, obtains graphite
Alkene-nanogold multiple tube.
Embodiment 4:
A kind of preparation method of graphene-nano-noble metal multiple tube, comprising the following steps:
Step 1: the copper wire of 15 μm of diameter, length 5cm is taken to impregnate 2min removal surface impurity with the dust technology of 0.1mol/L
And after passivation layer, it is placed in ultrasound 20min in dehydrated alcohol, 60 DEG C of drying 2h in air dry oven is then placed into and is dried for standby；
Step 2: being put into chemical vapor depsotition equipment using the copper wire of drying as growth substrate, reaction atmosphere is hydrogen
1000 DEG C are heated under the heating rate of 30 DEG C/min with the gaseous mixture of nitrogen, constant temperature 60min is passed through alcohol vapour
10sccm is reacted, and is stopped being passed through alcohol vapour after reaction, is rapidly cooled to room temperature, it is compound to obtain graphene/copper wire
Structure；
Step 3: by chemical plating method, in graphene obtained/copper wire composite structure surface deposition nanogold cladding
Layer forms nanogold clad/graphene/copper wire composite construction；
Step 4: nanogold clad/graphene/copper wire composite construction to be put into iron chloride etching liquid and remove copper wire
Afterwards, it is placed in 60 DEG C of drying 2h in air dry oven after being cleaned with dehydrated alcohol and deionized water to products therefrom, obtains graphite
Alkene-nanogold multiple tube.
Embodiment 5:
A kind of preparation method of graphene-nano-noble metal multiple tube, comprising the following steps:
Step 1: taking the nickel wire of 30 μm of diameter, length 10cm miscellaneous with the dust technology immersion 20min removal surface of 0.5mol/L
After matter and passivation layer, it is placed in ultrasound 30min in dehydrated alcohol, it is standby to be then placed into 100 DEG C of drying 1h drying in air dry oven
With；
Step 2: being put into chemical vapor depsotition equipment using the nickel wire of drying as growth substrate, reaction atmosphere is hydrogen
1200 DEG C are heated under the heating rate of 15 DEG C/min with the gaseous mixture of nitrogen, constant temperature 30min is passed through acetone steam
30sccm is reacted, and is stopped being passed through acetone steam after reaction, is rapidly cooled to room temperature, it is compound to obtain graphene/nickel silk
Structure；
Step 3: depositing nanogold on graphene/nickel filament composite structure obtained surface by pulse laser sediment method
Clad forms nanogold clad/graphene/nickel filament composite structure；
Nickel wire is removed Step 4: nanogold clad/graphene/nickel filament composite structure is put into potassium permanganate etching liquid
Afterwards, it is placed in 60 DEG C of drying 2h in air dry oven after being cleaned with dehydrated alcohol and deionized water to products therefrom, obtains graphite
Alkene-nanogold multiple tube.
Embodiment 6:
A kind of preparation method of graphene-nano-noble metal multiple tube, which comprises the following steps:
Step 1: taking the copper wire of 50 μm of diameter, length 10cm miscellaneous with the dust technology immersion 10min removal surface of 0.5mol/L
After matter and passivation layer, it is placed in ultrasound 30min in dehydrated alcohol, it is standby to be then placed into 80 DEG C of drying 2h drying in air dry oven
With；
Step 2: being put into chemical vapor depsotition equipment using the copper wire of drying as growth substrate, reaction atmosphere is hydrogen
1500 DEG C are heated under the heating rate of 10 DEG C/min with the gaseous mixture of nitrogen, constant temperature 100min is passed through xylene steam
20sccm is reacted, and is stopped being passed through xylene steam after reaction, is rapidly cooled to room temperature, it is multiple to obtain graphene/copper wire
Close structure；
Step 3: depositing Technique of Nano Pd packet in graphene obtained/copper wire composite structure surface by electrochemical deposition method
Coating forms Technique of Nano Pd clad/graphene/copper wire composite construction；
Step 4: Technique of Nano Pd clad/graphene/copper wire composite construction to be put into iron chloride etching liquid and remove copper wire
Afterwards, it is placed in 60 DEG C of drying 2h in air dry oven after being cleaned with dehydrated alcohol and deionized water to products therefrom, obtains graphite
Alkene-Technique of Nano Pd multiple tube.
Embodiment 7:
A kind of preparation method of graphene-nano-noble metal multiple tube, comprising the following steps:
Step 1: taking the copper wire of 50 μm of diameter, length 10cm miscellaneous with the dust technology immersion 10min removal surface of 0.5mol/L
After matter and passivation layer, it is placed in ultrasound 30min in dehydrated alcohol, it is standby to be then placed into 80 DEG C of drying 2h drying in air dry oven
With；
Step 2: being blended with the poly- of graphene oxide using the copper wire of drying as the Rotation of receiver device of electrostatic spinning
It closes on object spinning solution electrostatic spinning to the copper wire of rotation, while by graphene dispersing solution ultrasonic atomizatio on the copper wire of rotation,
Form the copper wire of electrostatic spinning film and graphene coated；
Step 3: by electrochemical deposition method, it is compound in the copper wire of electrostatic spinning film obtained and graphene coated
Body structure surface deposits Platinum Nanoparticles clad；
Step 4: the composite construction that step 3 is obtained is put into after removing copper wire in iron chloride etching liquid, it is added into N,
12h is impregnated in dinethylformamide or toluene, is placed in after then being cleaned with dehydrated alcohol and deionized water to products therefrom
60 DEG C of drying 2h in air dry oven obtain graphene-Platinum Nanoparticles multiple tube；
Wherein, the polymer spin dope is PLA solution；The concentration of the polymer spin dope is 5wt%；
The mass ratio of the graphene oxide and polymer spin dope is 1:50；The graphene oxide and polymer spin dope
Mixed process are as follows: graphene oxide is mixed with polymer spin dope, dispersing agent 1- ethyl -3- methyl chloride miaow is then added
Mixed solution is heated to 50 DEG C under the conditions of low whipping speed is 500r/min by azoles, is kept its reaction for 24 hours, is cooled to room temperature,
Obtain the polymer spin dope for being mixed with graphene oxide；The dispersing agent 1- ethyl -3- methylimidazolium chloride and oxidation stone
The weight ratio of black alkene is 1:5；The graphene dispersing solution includes the raw material of following parts by weight: 10 parts of graphene, 1- ethyl -3- first
1 part of base imidazole lactic acid, 30 parts of cyclohexanone, 30 parts of N- cyclohexyl pyrrolidone, 30 parts of propylene glycol butyl ether acetate；
The electrospinning process are as follows: be blended with the polymer spin dope injection band stainless steel spray head of graphene oxide
Spray containers in, then applied the voltage on stainless steel spray head with high voltage power supply, and utilize pushing away of connecting with spray containers
The polymer spin dope in spray containers is sprayed by stainless steel spray head to the wire reception device of rotation into pump, institute
State the injection conditions of electrostatic spinning are as follows: environment temperature is 40 DEG C, the output voltage of high voltage power supply is 15kv, wire and stainless steel
Distance is 10cm between spray head, the rotation speed of flow velocity 5mL/h, wire reception device is 50r/min；
The power of the graphene dispersing solution ultrasonic atomizatio is 80W, frequency 2.5MHz, condensation rate 2mL/min, ultrasound
The ejiction opening of atomization is 5cm at a distance from wire.
Embodiment 8:
A kind of preparation method of graphene-nano-noble metal multiple tube, comprising the following steps:
Step 1: taking the copper wire of diameter 1cm, length 30cm miscellaneous with the dust technology immersion 10min removal surface of 0.5mol/L
After matter and passivation layer, it is placed in ultrasound 30min in dehydrated alcohol, it is standby to be then placed into 80 DEG C of drying 2h drying in air dry oven
With；
Step 2: being blended with the poly- of graphene oxide using the copper wire of drying as the Rotation of receiver device of electrostatic spinning
It closes on object spinning solution electrostatic spinning to the copper wire of rotation, while by graphene dispersing solution ultrasonic atomizatio on the copper wire of rotation,
Form the copper wire of electrostatic spinning film and graphene coated；
Step 3: by magnetically controlled sputter method, in the copper wire composite junction of electrostatic spinning film obtained and graphene coated
Structure surface deposits nano-titanium clad；
Step 4: the composite construction that step 3 is obtained is put into after removing copper wire in iron chloride etching liquid, it is added into N,
12h is impregnated in dinethylformamide or toluene, is placed in after then being cleaned with dehydrated alcohol and deionized water to products therefrom
60 DEG C of drying 2h in air dry oven obtain graphene-nanometer composite ti pipe；
Wherein, the polymer spin dope is polymethyl acrylate solution；The concentration of the polymer spin dope is
10wt%；The mass ratio of the graphene oxide and polymer spin dope is 1:100；The graphene oxide and polymer spun
The mixed process of silk stock solution are as follows: graphene oxide is mixed with polymer spin dope, dispersing agent 1- ethyl -3- first is then added
Mixed solution is heated to 50 DEG C under the conditions of low whipping speed is 500r/min by base imidazolitm chloride, keeps its reaction for 24 hours, cooling
To room temperature, the polymer spin dope for being mixed with graphene oxide is obtained；The dispersing agent 1- ethyl -3- methylimidazolium chloride with
The weight ratio of graphene oxide is 1:10；The graphene dispersing solution includes the raw material of following parts by weight: 15 parts of graphene, 1- second
3 parts of base -3- methylimidazole lactic acid, 50 parts of cyclohexanone, 50 parts of N- cyclohexyl pyrrolidone, 50 parts of propylene glycol butyl ether acetate；
The electrospinning process are as follows: be blended with the polymer spin dope injection band stainless steel spray head of graphene oxide
Spray containers in, then applied the voltage on stainless steel spray head with high voltage power supply, and utilize pushing away of connecting with spray containers
The polymer spin dope in spray containers is sprayed by stainless steel spray head to the wire reception device of rotation into pump, institute
State the injection conditions of electrostatic spinning are as follows: environment temperature is 80 DEG C, the output voltage of high voltage power supply is 25kv, wire and stainless steel
Distance is 15cm between spray head, the rotation speed of flow velocity 12mL/h, wire reception device is 500r/min；
The power of the graphene dispersing solution ultrasonic atomizatio is 80W, frequency 2.5MHz, condensation rate 10mL/min, is surpassed
The ejiction opening of sound atomization is 15cm at a distance from wire.
Embodiment 9:
A kind of preparation method of graphene-nano-noble metal multiple tube, comprising the following steps:
Step 1: taking the nickel wire of diameter 0.5cm, length 20cm miscellaneous with the dust technology immersion 10min removal surface of 1mol/L
After matter and passivation layer, it is placed in ultrasound 60min in dehydrated alcohol, it is standby to be then placed into 80 DEG C of drying 2h drying in air dry oven
With；
Step 2: being blended with the poly- of graphene oxide using the nickel wire of drying as the Rotation of receiver device of electrostatic spinning
It closes on object spinning solution electrostatic spinning to the nickel wire of rotation, while by graphene dispersing solution ultrasonic atomizatio on the nickel wire of rotation,
Form the nickel wire of electrostatic spinning film and graphene coated；
Step 3: by magnetically controlled sputter method, in the nickel wire composite junction of electrostatic spinning film obtained and graphene coated
Structure surface deposits nanogold clad；
Step 4: the composite construction that step 3 is obtained is put into after removing nickel wire in iron chloride etching liquid, it is added into N,
12h is impregnated in dinethylformamide or toluene, is placed in after then being cleaned with dehydrated alcohol and deionized water to products therefrom
60 DEG C of drying 2h in air dry oven obtain graphene-nanogold multiple tube；
Wherein, the polymer spin dope is polyimide solution；The concentration of the polymer spin dope is
10wt%；The mass ratio of the graphene oxide and polymer spin dope is 1:60；The graphene oxide and polymer spun
The mixed process of silk stock solution are as follows: graphene oxide is mixed with polymer spin dope, dispersing agent 1- ethyl -3- first is then added
Mixed solution is heated to 50 DEG C under the conditions of low whipping speed is 500r/min by base imidazolitm chloride, keeps its reaction for 24 hours, cooling
To room temperature, the polymer spin dope for being mixed with graphene oxide is obtained；The dispersing agent 1- ethyl -3- methylimidazolium chloride with
The weight ratio of graphene oxide is 1:8；The graphene dispersing solution includes the raw material of following parts by weight: 12 parts of graphene, 1- second
2 parts of base -3- methylimidazole lactic acid, 40 parts of cyclohexanone, 40 parts of N- cyclohexyl pyrrolidone, 40 parts of propylene glycol butyl ether acetate；
The electrospinning process are as follows: be blended with the polymer spin dope injection band stainless steel spray head of graphene oxide
Spray containers in, then applied the voltage on stainless steel spray head with high voltage power supply, and utilize pushing away of connecting with spray containers
The polymer spin dope in spray containers is sprayed by stainless steel spray head to the wire reception device of rotation into pump, institute
State the injection conditions of electrostatic spinning are as follows: environment temperature is 60 DEG C, the output voltage of high voltage power supply is 20kv, wire and stainless steel
Distance is 12cm between spray head, the rotation speed of flow velocity 8mL/h, wire reception device is 150r/min；
The power of the graphene dispersing solution ultrasonic atomizatio is 80W, frequency 2.5MHz, condensation rate 5mL/min, ultrasound
The ejiction opening of atomization is 10cm at a distance from wire.
Although the embodiments of the present invention have been disclosed as above, but its is not only in the description and the implementation listed
With it can be fully applied to various fields suitable for the present invention, for those skilled in the art, can be easily
Realize other modification, therefore without departing from the general concept defined in the claims and the equivalent scope, the present invention is simultaneously unlimited
In specific details and legend shown and described herein.
Claims (7)
1. a kind of graphene-nano-noble metal multiple tube preparation method, which comprises the following steps:
Step 1: being placed in ultrasound in dehydrated alcohol after taking copper wire dust technology to impregnate removal surface impurity and passivation layer, then drying
It does spare；The diameter of the copper wire is 10nm~1cm, and length is 10nm~1m；The dust technology concentration is 0.001~1mol/
L, copper wire soaking time in dust technology is 1s~60min, a length of 1~60min when ultrasonic in dehydrated alcohol；The drying is adopted
In air dry oven, being dried temperature is 40~200 DEG C, and the processing time is 0.1~36h；
Step 2: being blended with the polymer of graphene oxide using the copper wire of drying as the Rotation of receiver device of electrostatic spinning
On spinning solution electrostatic spinning to the copper wire of rotation, while graphene dispersing solution ultrasonic atomizatio being formed on the copper wire of rotation
The copper wire of electrostatic spinning film and graphene coated；
Step 3: by magnetically controlled sputter method, in the copper wire composite construction table of electrostatic spinning film obtained and graphene coated
Face deposits nano-titanium clad；
Step 4: the composite construction that step 3 is obtained is put into after removing copper wire in potassium permanganate etching liquid, it is added into N, N-
12h is impregnated in dimethylformamide or toluene, is placed in drum after then being cleaned with dehydrated alcohol and deionized water to products therefrom
60 DEG C of drying 2h in wind drying box obtain graphene-nanometer composite ti pipe；
Wherein, the polymer spin dope is polymethyl acrylate solution；The concentration of the polymer spin dope be 5~
10wt%；The mass ratio of the graphene oxide and polymer spin dope is 1:50~100；The graphene oxide with polymerize
The mixed process of object spinning solution are as follows: graphene oxide is mixed with polymer spin dope, dispersing agent 1- ethyl-is then added
Mixed solution is heated to 50 DEG C under the conditions of low whipping speed is 500r/min by 3- methylimidazolium chloride, keeps its reaction for 24 hours,
It is cooled to room temperature, obtains the polymer spin dope for being mixed with graphene oxide；The dispersing agent 1- ethyl -3- methyl chloride miaow
The weight ratio of azoles and graphene oxide is 1:5~10；
The graphene dispersing solution includes the raw material of following parts by weight: 10~15 parts of graphene, 1- ethyl-3-methylimidazole lactic acid
1~3 part, 30~50 parts of cyclohexanone, 30~50 parts of N- cyclohexyl pyrrolidone, 30~50 parts of propylene glycol butyl ether acetate.
2. graphene as described in claim 1-nano-noble metal multiple tube preparation method, which is characterized in that the copper wire
Replace with nickel wire.
3. graphene as described in claim 1-nano-noble metal multiple tube preparation method, which is characterized in that the step
In three, magnetically controlled sputter method replaces with any one in hot evaporation, pulse laser deposition, chemical plating or electrochemical deposition method
Kind；The deposition rate for depositing nano-titanium clad is 0.1nm/s~10 μm/s, and the nano-titanium clad replaces with a nanometer ruthenium packet
Any one or more alloy material clad being combined into coating, nanometer niobium clad.
4. graphene as described in claim 1-nano-noble metal multiple tube preparation method, which is characterized in that the graphite
Alkene-nano-noble metal multiple tube diameter is 10nm~1cm, and length is 10nm~1m.
5. graphene as described in claim 1-nano-noble metal multiple tube preparation method, which is characterized in that the step
In four, liquor potassic permanganate replaces with ferric chloride solution.
6. graphene as described in claim 1-nano-noble metal multiple tube preparation method, which is characterized in that the polymerization
Object spinning solution replaces with one of PLA solution, polyimide solution.
7. graphene as described in claim 1-nano-noble metal multiple tube preparation method, which is characterized in that the electrostatic
Spinning process are as follows: be blended in spray containers of the polymer spin dope injection with stainless steel spray head of graphene oxide, so
It is applied the voltage on stainless steel spray head with high voltage power supply afterwards, and will be in spray containers using the propulsion pump being connect with spray containers
Polymer spin dope sprayed by stainless steel spray head to the wire reception device of rotation, the injection of the electrostatic spinning
Condition are as follows: environment temperature is 40~80 DEG C, the output voltage of high voltage power supply is 15~25kv, between wire and stainless steel spray head
Distance is 10~15cm, flow velocity is 5~12mL/h, the rotation speed of wire reception device is 50~500r/min；
The power of the graphene dispersing solution ultrasonic atomizatio is 80W, and frequency 2.5MHz, condensation rate is 2~10mL/min, ultrasound
The ejiction opening of atomization is 5~15cm at a distance from wire.
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