CN108797097A - A kind of preparation of graphene/carbon nano-fiber composite material - Google Patents
A kind of preparation of graphene/carbon nano-fiber composite material Download PDFInfo
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- D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
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- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
- D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
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Abstract
A kind of preparation of graphene/carbon nano-fiber composite material, is related to a kind of preparation method and applications of nanocomposite, and sensitivity is low when being detected applied to levodopa the present invention is to solve current material and detection limits higher problem.Method is as follows：One, method of electrostatic spinning；Two, chemically coated nickel method；Three, chemical vapour deposition technique.A kind of graphene/carbon nano-fiber composite material can be used as electrode material to detect levodopa.Present invention is mainly used for prepare a kind of graphene/carbon nano-fiber composite material.
Description
Technical field
The present invention relates to a kind of preparation method of graphene/carbon nano-fiber composite material and Electrochemical Detection are left-handed more
Bar.
Background technology
Carbon nano-fiber is the one-dimensional carbon material between carbon nanotube and common carbon fibers, and carbon nano-fiber has excellent
Good physical property, mechanical property and chemical stability, such as larger surface area, higher mechanical strength and Young's modulus.Mesh
Before, the application of carbon nano-fiber is concentrated mainly in traditional aerospace and sports and amusement product, and in hydrogen storage material, energy storage material
The fields such as material, catalyst carrier, electronic component cause extensive concern and application.Polyacrylonitrile is to prepare nano-sized carbon Nanowire
The main precursor of dimension, because the intensity of carbon nano-fiber can flexibly be controlled by controlling later stage carbonization and stabilization temperature
And elasticity modulus.There is higher specific surface area and porosity by the carbon nano-fiber of electrospinning, but conductivity is low, greatly limits
Its application in biosensor is made.
Graphene is a kind of carbon material with hexagonal lattice structure, has unique electronic structure and physico
Learn property, such as big surface area, high conductivity, excellent mechanical performance and biocompatibility.These characteristics make it super
Capacitor, lithium ion battery, solar cell, storing hydrogen, sensor and other field receive significant attention.Currently, graphene
Main preparation methods be mechanical stripping, redox, epitaxial growth and chemical vapour deposition technique.Wherein, chemical vapor deposition
Graphene prepared by method (CVD) has the characteristics that high quality defect is few.
Parkinson's disease (PD) is since dopamine can not penetrate caused by blood-brain barrier enters central nervous system, is old
The common neurodegenerative disease of people.Levodopa (LD) is the precursor of dopamine (DA), it can be by blood-brain barrier in enzyme
Under the action of be converted into DA, it be treat Parkinson's disease effective therapeutic agent.However, Excess free enthalpy LD is harmful, can cause
The side effects such as nausea, anorexia and dyskinesia.Therefore, accurately detection LD concentration is very important.
Invention content
Sensitivity is low when being detected applied to levodopa the present invention is to solve current material and detection limits higher technology
Problem, to provide a kind of preparation method of graphene/carbon nano-fiber composite material.
A kind of preparation method of graphene/carbon nano-fiber composite material provided by the invention is to carry out according to the following steps：
One, method of electrostatic spinning
1）1 g polyacrylonitrile powders are dissolved in 10 mL dimethyl formamide solutions, and are 80 DEG C ~ 150 DEG C in temperature
Under conditions of the heating stirring h of 1 h ~ 2, obtain electrostatic spinning solution.Then, the above-mentioned solution of the mL of 10 mL ~ 20 is taken to be transferred to injection
In device, syringe is fixed on syringe pump, electrostatic spinning, solution flow rate 1 are carried out in the case where voltage is the kV of 10 kV ~ 20
The mL/h of mL/h ~ 3, it is the cm of 10 cm ~ 15 to collect distance；
2）Polyacrylonitrile fibre is placed in air dry oven, 300 DEG C ~ 400 are warming up to the speed of 1 DEG C/min ~ 2 DEG C/min
DEG C, heat preservation 1 h ~ 2 h carry out stabilization processes；
3）By the polyacrylonitrile fibre after stabilization processes be placed in tube furnace center, under protection of argon gas from room temperature with 5 DEG C/
The speed of min ~ 10 DEG C/min is warming up to 800 DEG C ~ 1000 DEG C, and keep the temperature under conditions of 800 DEG C ~ 1000 DEG C of temperature 60 min ~
100 min, then furnace cooling to room temperature obtain carbon nano-fiber, step 13）Described in argon gas flow velocity be 300
sccm~500 sccm；
Two, chemically coated nickel method
1）By step 12）It is 1 cm that obtained carbon nano-fiber, which cuts into area,2 ~3 cm2 Second of the piece at 60 DEG C ~ 80 DEG C
Alcohol solution for soaking 30 min ~ 60 min degrease, and are washed with distilled water several times；It immerses and contains (NH4)2S2O8With it is dense
H2SO4Mixed solution in stir the min of 15 min ~ 30 and be roughened, and be washed with distilled water several times；Immerse SnCl2In solution
It stirs the min of 3 min ~ 10 to be sensitized, and is washed with distilled water several times；The PbCl of immersion2Solution stir the min of 3 min ~ 10 into
Row activation, and be washed with distilled water several times；
2）Immersion contains NiSO4·6H2O(25 g/L ~30 g/L)、NaH2PO2·H2O(30 g/L ~35 g/L)、
Na3C6H5O7·H2O (g/L of 30 g/L ~ 35) and NH4Start chemistry in the chemical nickel-plating solution of Cl (g/L of 70 g/L ~ 75)
Nickel plating takes alkaline condition to carry out nickel plating, uses NH3·H2O carries out the adjusting of pH, and pH value is 8 ~ 10, and temperature is 50 DEG C ~ 70 DEG C,
Time is the min of 30 min ~ 50, is freeze-dried；
Three, chemical vapour deposition technique
1）By step 22）The carbon nano-fiber of obtained nickel plating is placed in quartz tube furnace center, under the protection of argon gas and hydrogen
From room temperature with the heating rate of 10 DEG C/min ~ 20 DEG C/min be heated to temperature be 800 DEG C ~ 1000 DEG C, and temperature be 800 DEG C ~
The min of 10 min ~ 20 are kept the temperature under conditions of 1000 DEG C, into tube furnace with 10 under conditions of temperature is 800 DEG C ~ 1000 DEG C
The rate of the sccm of sccm ~ 20 is passed through the methane gas min of 20 min ~ 30, then by quartz tube furnace with 80 DEG C/min ~ 100
DEG C/cooling rate of min is 800 DEG C ~ 1000 DEG C from temperature and is cooled to room temperature, obtain the carbon fiber for the nickel plating wrapped up by graphene
Dimension;Step 3 1) described in the flow velocity of argon gas be the sccm of 480 sccm ~ 500, the flow velocity of hydrogen is 180 sccm ~ 200
sccm；
2）By step 3 1) by 1 h ~ 2 in the hydrochloric acid of carbon fiber immersion 3 mol/L ~ 5 mol/L of the nickel plating of graphene package
H gets rid of nickel, obtains graphene/carbon nano-fiber composite material.
Advantage of the present invention：
1）The method of the present invention is prepared for carbon nano-fiber by electrostatic spinning, and is carrying out chemistry by chemical vapour deposition technique
Graphene is deposited on the carbon fiber of nickel plating, a kind of novel graphite alkene/carbon nano-fiber composite material has been obtained after nickel is etched away；
2）The composite material of the present invention can play the synergistic effect of high conductance graphene and high-specific surface area carbon nano-fiber, significantly
The chemical property for improving material may make the sensitivity of Electrochemical Detection levodopa to improve significantly to 0. 26 μ A μ
Μ-1。
Description of the drawings
Fig. 1 is the stereoscan photograph of carbon nano-fiber prepared by electrostatic spinning；
Fig. 2 is the stereoscan photograph of carbon nano-fiber after chemical nickel plating；
Fig. 3 is that carbon nano-fiber has carried out the stereoscan photograph of chemical vapor deposition graphene after chemical nickel plating；
Fig. 4 is the stereoscan photograph of graphene/carbon nano-fiber composite material；
Fig. 5 is the Raman collection of illustrative plates of the carbon nano-fiber that electrostatic spinning obtains and graphene/carbon nanofiber；
Fig. 6 is the differential pulse voltammetry figure of graphene/carbon nanofiber/ito glass electrode detection difference levodopa concentration；
Fig. 7 is the Linear Fit Chart of graphene/carbon nanofiber/ito glass electrode detection levodopa and oxidation spike potential；
Fig. 8 is graphene/carbon nanofiber/ito glass electrode detection in the case where 10 μM of uric acid interfere, different levodopa concentrations
Differential pulse voltammetry figure；
Fig. 9 is graphene/carbon nanofiber/ito glass electrode detection in the case where 10 μM of uric acid interfere, levodopa and oxidation peak
The Linear Fit Chart of current potential.
Specific implementation mode
Specific implementation mode one：A kind of preparation method of graphene/carbon nano-fiber composite material be according to the following steps into
Capable：
One, method of electrostatic spinning
1）1 g polyacrylonitrile powders are dissolved in 10 mL dimethyl formamide solutions, and are 80 DEG C ~ 150 DEG C in temperature
Under conditions of the heating stirring h of 1 h ~ 2, obtain electrostatic spinning solution.Then, the above-mentioned solution of the mL of 10 mL ~ 20 is taken to be transferred to injection
In device, syringe is fixed on syringe pump, electrostatic spinning, solution flow rate 1 are carried out in the case where voltage is the kV of 10 kV ~ 20
The mL/h of mL/h ~ 3, it is the cm of 10 cm ~ 15 to collect distance；
2）Polyacrylonitrile fibre is placed in air dry oven, 300 DEG C ~ 400 are warming up to the speed of 1 DEG C/min ~ 2 DEG C/min
DEG C, heat preservation 1 h ~ 2 h carry out stabilization processes；
3）By the polyacrylonitrile fibre after stabilization processes be placed in tube furnace center, under protection of argon gas from room temperature with 5 DEG C/
The speed of min ~ 10 DEG C/min is warming up to 800 DEG C ~ 1000 DEG C, and keep the temperature under conditions of 800 DEG C ~ 1000 DEG C of temperature 60 min ~
100 min, then furnace cooling to room temperature obtain carbon nano-fiber, step 13）Described in argon gas flow velocity be 300
sccm~500 sccm；
Two, chemically coated nickel method
1）By step 12）It is 1 cm that obtained carbon nano-fiber, which cuts into area,2 ~3 cm2 Second of the piece at 60 DEG C ~ 80 DEG C
Alcohol solution for soaking 30 min ~ 60 min degrease, and are washed with distilled water several times；It immerses and contains (NH4)2S2O8With it is dense
H2SO4Mixed solution in stir the min of 15 min ~ 30 and be roughened, and be washed with distilled water several times；Immerse SnCl2In solution
It stirs the min of 3 min ~ 10 to be sensitized, and is washed with distilled water several times；The PbCl of immersion2Solution stir the min of 3 min ~ 10 into
Row activation, and be washed with distilled water several times；
2）Immersion contains NiSO4·6H2O (25 g/L ~30 g/L)、NaH2PO2·H2O (30 g/L ~35 g/L)、
Na3C6H5O7·H2O (g/L of 30 g/L ~ 35) and NH4Beginning in the chemical nickel-plating solution of Cl (g/L of 70 g/L ~ 75)
Nickel plating is learned, takes alkaline condition to carry out nickel plating, uses NH3·H2O carries out the adjusting of pH, and pH value is 8 ~ 10, and temperature is 50 DEG C ~ 70
DEG C, the time is the min of 30 min ~ 50, is freeze-dried；
Three, chemical vapour deposition technique
By step 22）The carbon nano-fiber of obtained nickel plating be placed in quartz tube furnace center, under the protection of argon gas and hydrogen from
Room temperature with the heating rate of 10 DEG C/min ~ 20 DEG C/min be heated to temperature be 800 DEG C ~ 1000 DEG C, and temperature be 800 DEG C ~
The min of 10 min ~ 20 are kept the temperature under conditions of 1000 DEG C, into tube furnace with 10 under conditions of temperature is 800 DEG C ~ 1000 DEG C
The rate of the sccm of sccm ~ 20 is passed through the methane gas min of 20 min ~ 30, then by quartz tube furnace with 80 DEG C/min ~ 100
DEG C/cooling rate of min is 800 DEG C ~ 1000 DEG C from temperature and is cooled to room temperature, obtain the carbon fiber for the nickel plating wrapped up by graphene
Dimension;Step 3 1) described in the flow velocity of argon gas be the sccm of 480 sccm ~ 500, the flow velocity of hydrogen be 180 sccm ~
200 sccm；
2）By step 3 1) by graphene package nickel plating carbon fiber immerse the mol/L hydrochloric acid of 3 mol/L ~ 5 in the h of 1 h ~ 2,
Nickel is got rid of, graphene/carbon nano-fiber composite material is obtained.
Specific implementation mode two：The present embodiment is different from the first embodiment in that：Step 1 1) in by 1 g
Polyacrylonitrile powder is dissolved in 10 mL dimethyl formamide solutions, and is heated under conditions of temperature is 100 DEG C ~ 110 DEG C
The h of 1 h ~ 1.5 are stirred, electrostatic spinning solution is obtained, which are transferred in the syringe of 10 mL, then syringe is fixed on
On syringe pump, control electrostatic spinning voltage is the kV of 15 kV ~ 20, and the distance of reception device to spinning syringe needle is 10 cm, solution stream
Speed is the mL/h of 1 mL/h ~ 2, and electrostatic spinning is carried out in electrostatic spinning apparatus and obtains polyacrylonitrile fibre；Other and specific implementation
Mode one is identical；
Specific implementation mode three：Unlike one of present embodiment and specific implementation mode one to two：Step 13）It is middle to walk
Rapid 2）Polyacrylonitrile fibre after stabilization processes is placed in tubular type boiler tube center, under protection of argon gas from room temperature with 5 DEG C/
The speed of min ~ 7 DEG C/min is warming up to 850 DEG C ~ 900 DEG C, and keeps the temperature 60 min under conditions of 850 DEG C ~ 900 DEG C of temperature
~ 80 min, then furnace cooling to room temperature obtain carbon nano-fiber, step 11）Described in argon gas flow velocity be 400
sccm；It is other identical as one of specific implementation mode one to two；
Specific implementation mode four：Unlike one of present embodiment and specific implementation mode one to three：Step 22）Immersion contains
There is NiSO4·6H2O (28 g/L ~30 g/L)、NaH2PO2·H2O (33 g/L ~35 g/L)、Na3C6H5O7·H2O (33
The g/L of g/L ~ 35) and NH4Start chemical nickel plating in the chemical nickel-plating solution of Cl (g/L of 73 g/L ~ 75), takes alkaline item
Part carries out nickel plating, uses NH3·H2O carries out the adjusting of pH, and pH value is 7 ~ 8, and temperature is 60 DEG C ~ 70 DEG C, and the time is 30 min ~ 40
Min is freeze-dried；It is other identical as one of specific implementation mode one to three；
Specific implementation mode five：Unlike one of present embodiment and specific implementation mode one to four：Step 31）By step
25）The carbon nano-fiber of obtained nickel plating is placed in quartz tube furnace center, from room temperature with 10 DEG C under the protection of argon gas and hydrogen
The heating rate of/min ~ 15 DEG C/min is heated to 850 DEG C ~ 900 DEG C of temperature, and under conditions of temperature is 850 DEG C ~ 900 DEG C
The min of 25 min ~ 30 are kept the temperature, first is passed through with the rate of 20 sccm into tube furnace under conditions of temperature is 850 DEG C ~ 900 DEG C
30 min of alkane gas, then by quartz tube furnace with the cooling rate of 90 DEG C/min ~ 100 DEG C/min from temperature be 850 DEG C ~
900 DEG C are cooled to room temperature, and obtain the carbon fiber for the nickel plating wrapped up by graphene;Step 3 1) described in the flow velocity of argon gas be
500 sccm, the flow velocity of hydrogen is 200 sccm；It is other identical as one of specific implementation mode one to two.
Using following verification experimental verifications effect of the present invention：
Experiment one：A kind of preparation method of graphene/carbon nano-fiber composite material of this experiment is to realize by the following method：
One, method of electrostatic spinning
1）1 g polyacrylonitrile powders are dissolved in 10 mL dimethyl formamide solutions, and the item for being 100 DEG C in temperature
1 h of heating stirring, obtains electrostatic spinning solution under part.Then, the above-mentioned solution of 10 mL is taken to be transferred in syringe, by syringe
It is fixed on syringe pump, electrostatic spinning is carried out in the case where voltage is 20 kV, solution flow rate is 1 mL/h, and it is 10 cm to collect distance；
2）Polyacrylonitrile fibre is placed in air dry oven, is warming up to 300 DEG C with the speed of 1 DEG C/min, 1 h of heat preservation is carried out
Stabilization processes；
3）By the polyacrylonitrile fibre after stabilization processes be placed in tube furnace center, under protection of argon gas from room temperature with 5 DEG C/
The speed of min is warming up to 900 DEG C, and keeps the temperature 60 min under conditions of 900 DEG C of temperature, and then furnace cooling to room temperature, obtains
Carbon nano-fiber, step 13）Described in argon gas flow velocity be 400 sccm；
Two, chemically coated nickel method
1）By step 12）It is 1 cm that obtained carbon nano-fiber, which cuts into area,2Piece impregnated in 60 DEG C of ethanol solution
30 min degrease, and are washed with distilled water several times；It immerses and contains (NH4)2S2O8With dense H2SO4Mixed solution in stir 15
Min is roughened, and is washed with distilled water several times；Immerse SnCl25 min are stirred in solution to be sensitized, and distillation is used in combination to wash
It washs several times；The PbCl of immersion2Solution stirs 5 min and is activated, and is washed with distilled water several times；
2）It immerses in chemical nickel-plating solution and starts chemical nickel plating, take alkaline condition to carry out nickel plating, use NH3·H2O carries out pH
Adjusting, pH value 8.5, temperature be 65 DEG C, the time be 30 min, be freeze-dried；
Three, chemical vapour deposition technique
1）By step 22）The carbon nano-fiber of obtained nickel plating is placed in quartz tube furnace center, under the protection of argon gas and hydrogen
Temperature is heated to as 900 DEG C from room temperature with the heating rate of 10 DEG C/min, and keeps the temperature 10 under conditions of temperature is 900 DEG C
Min is passed through 30 min of methane gas into tube furnace under conditions of temperature is 900 DEG C with the rate of 20 sccm, then will
Quartz tube furnace is 900 DEG C from temperature with the cooling rate of 100 DEG C/min and is cooled to room temperature, and obtains the plating wrapped up by graphene
The carbon fiber of nickel;Step 3 1) described in the flow velocity of argon gas be 500 sccm, the flow velocity of hydrogen is 200 sccm；
2）By step 31）By graphene package nickel plating carbon fiber immerse hydrochloric acid in 1 h, get rid of nickel, obtain graphene/
Carbon nano-fiber composite material.
Fig. 1 is the stereoscan photograph of carbon nano-fiber prepared by electrostatic spinning, it can be seen from the figure that carbon Nanowire
Light is slided in dimension table face, and diameter is evenly distributed, a diameter of nm of 200 nm~300.
Fig. 2 is the stereoscan photograph of carbon nano-fiber after chemical nickel plating, it can be seen from the figure that carbon nano-fiber surface
Sliding light nickel plating is uniform, a diameter of nm of 300 nm~400.
Fig. 3 is that carbon nano-fiber has carried out the stereoscan photograph of chemical vapor deposition graphene after chemical nickel plating, from figure
In as can be seen that there are the graphene film of stacking, a diameter of nm of 300 nm~400 in carbon nano-fiber surface.
Fig. 4 is the stereoscan photograph of graphene/carbon nano-fiber composite material, it can be seen from the figure that carbon Nanowire
There are the graphene film stacked on a small quantity, a diameter of nm of 200 nm~300 in dimension table face.
Fig. 5 is the Raman collection of illustrative plates of the carbon nano-fiber that electrostatic spinning obtains and graphene/carbon nanofiber, wherein
1355,1580 and 2820 cm-1On have significant peak value, D, G and 2D wave band are corresponded respectively to, in the deposition of graphene
Under, D/G intensity ratios become 0.88 from 0.94 after depositing graphene, show that the defect in graphene/carbon nanofiber is reduced, 2D
Band becomes sharp.
Experiment two：Graphene/carbon nano-fiber composite material is tested as the detection of working electrode, and concrete operations are as follows：
Using graphene/carbon nano-fiber composite material together with ITO glass as working electrode, effective material area is 0.7
cm2, as reference electrode, platinum filament is used as to electrode silver/silver chlorate, passes through Pulse Voltammetry method using traditional three-electrode system
Test, current potential increase by 50 mV, 4 mV of pulse height, 8 mV/s of sweep speed, to obtain the material to a various concentration left side
Revolve the current-responsive of DOPA；The graphene/carbon nano-fiber composite material is prepared by experiment one.
Fig. 6 is the differential pulse voltammetry of graphene/carbon nanofiber/ito glass electrode detection difference levodopa concentration
Figure, obviously increases as levodopa concentration is continuously increased oxidation peak current.
Fig. 7 is the linear fit of graphene/carbon nanofiber/ito glass electrode detection levodopa and oxidation spike potential
Figure, by matched curve it is found that the oxidation peak current (Ip) of LD and corresponding concentration value are in a linear relationship, fit curve equation is：
Ip=(1.82±0.29)+(0.26±0.01)CLD, linearly dependent coefficient R2=0.9942.It follows that in a concentration of 0- of LD
At 60 μM, the sensitivity of electrode detection LD is 0.91 μ A μM-1, actually measured detection is limited to 1 μM.
Fig. 8 is graphene/carbon nanofiber/ito glass electrode detection in the case where 10 μM of uric acid interfere, different levodopas
The differential pulse voltammetry figure of concentration is obviously increased as levodopa concentration is continuously increased oxidation peak current.
Fig. 9 is graphene/carbon nanofiber/ito glass electrode detection in the case where 10 μM of uric acid interfere, levodopa and oxygen
Change spike potential Linear Fit Chart, by matched curve it is found that LD oxidation peak current (IP) it is linearly closed with corresponding concentration value
System, fit curve equation are：Ip=(0.63±0.31)+ (0.23±0.01)CLD, linearly dependent coefficient R2=0.9876.Thus
It is found that detection various concentration LD sensitivity is 0.23 μ A μM under uric acid interference-1, actually measured detection is limited to 1 μM.With
Individually when detection levodopa, sensitivity is very close, it was demonstrated that in the presence of uric acid, which still has levodopa good
Selectivity.
Claims (2)
1. a kind of preparation method of graphene/carbon nano-fiber composite material, it is characterised in that graphene/carbon nanofiber is compound
The preparation method of material carries out according to the following steps：
One, method of electrostatic spinning
1）1 g polyacrylonitrile powders are dissolved in 10 mL dimethyl formamide solutions, and are 80 DEG C ~ 150 DEG C in temperature
Under conditions of the heating stirring h of 1 h ~ 2, obtain electrostatic spinning solution；
Then, it takes the above-mentioned solution of the mL of 10 mL ~ 20 to be transferred in syringe, syringe is fixed on syringe pump, be in voltage
Electrostatic spinning is carried out under the kV of 10 kV ~ 20, solution flow rate is the mL/h of 1 mL/h ~ 3, and it is the cm of 10 cm ~ 15 to collect distance；
2）Polyacrylonitrile fibre is placed in air dry oven, 300 DEG C ~ 400 are warming up to the speed of 1 DEG C/min ~ 2 DEG C/min
DEG C, heat preservation 1 h ~ 2 h carry out stabilization processes；
3）By the polyacrylonitrile fibre after stabilization processes be placed in tube furnace center, under protection of argon gas from room temperature with 5 DEG C/
The speed of min ~ 10 DEG C/min is warming up to 800 DEG C ~ 1000 DEG C, and keep the temperature under conditions of 800 DEG C ~ 1000 DEG C of temperature 60 min ~
100 min, then furnace cooling to room temperature obtain carbon nano-fiber, step 13）Described in argon gas flow velocity be 300
sccm~500 sccm；
Two, chemically coated nickel method
1）By step 12）It is 1 cm that obtained carbon nano-fiber, which cuts into area,2 ~3 cm2 Second of the piece at 60 DEG C ~ 80 DEG C
Alcohol solution for soaking 30 min ~ 60 min degrease, and are washed with distilled water several times；It immerses and contains (NH4)2S2O8With it is dense
H2SO4Mixed solution in stir the min of 15 min ~ 30 and be roughened, and be washed with distilled water several times；Immerse SnCl2In solution
It stirs the min of 3 min ~ 10 to be sensitized, and is washed with distilled water several times；The PbCl of immersion2Solution stir the min of 3 min ~ 10 into
Row activation, and be washed with distilled water several times；
2）Immersion contains NiSO4·6H2O (25 g/L ~30 g/L)、NaH2PO2·H2O(30 g/L ~35 g/L)、
Na3C6H5O7·H2O (g/L of 30 g/L ~ 35) and NH4Beginning in the chemical nickel-plating solution of Cl (g/L of 70 g/L ~ 75)
Nickel plating is learned, takes alkaline condition to carry out nickel plating, uses NH3·H2O carries out the adjusting of pH, and pH value is 8 ~ 10, and temperature is 50 DEG C ~ 70
DEG C, the time is the min of 30 min ~ 50, is freeze-dried；
Three, chemical vapour deposition technique
1）By step 22）The carbon nano-fiber of obtained nickel plating is placed in quartz tube furnace center, under the protection of argon gas and hydrogen
From room temperature with the heating rate of 10 DEG C/min ~ 20 DEG C/min be heated to temperature be 800 DEG C ~ 1000 DEG C, and temperature be 800 DEG C ~
The min of 10 min ~ 20 are kept the temperature under conditions of 1000 DEG C, into tube furnace with 10 under conditions of temperature is 800 DEG C ~ 1000 DEG C
The rate of the sccm of sccm ~ 20 is passed through the methane gas min of 20 min ~ 30, then by quartz tube furnace with 80 DEG C/min ~ 100
DEG C/cooling rate of min is 800 DEG C ~ 1000 DEG C from temperature and is cooled to room temperature, obtain the carbon fiber for the nickel plating wrapped up by graphene
Dimension；Step 3 1) described in the flow velocity of argon gas be the sccm of 480 sccm ~ 500, the flow velocity of hydrogen be 180 sccm ~
200 sccm；
2）By step 3 1) by 1 h ~ 2 in the hydrochloric acid of carbon fiber immersion 3 mol/L ~ 5 mol/L of the nickel plating of graphene package
H gets rid of nickel, obtains graphene/carbon nano-fiber composite material.
2. preparation and the Electrochemical Detection levodopa of a kind of graphene/carbon nano-fiber composite material, it is characterised in that graphite
Working electrode Electrochemical Detection levodopas of the alkene/carbon nano-fiber/ITO as biosensor.
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