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 PDF

Info

Publication number
CN108797097A
CN108797097A CN201810430250.7A CN201810430250A CN108797097A CN 108797097 A CN108797097 A CN 108797097A CN 201810430250 A CN201810430250 A CN 201810430250A CN 108797097 A CN108797097 A CN 108797097A
Authority
CN
China
Prior art keywords
graphene
carbon nano
temperature
fiber
sccm
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201810430250.7A
Other languages
Chinese (zh)
Inventor
岳红彦
王婉秋
俞泽民
高鑫
关恩昊
王钊
张宏杰
宋珊珊
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Harbin University of Science and Technology
Original Assignee
Harbin University of Science and Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Harbin University of Science and Technology filed Critical Harbin University of Science and Technology
Priority to CN201810430250.7A priority Critical patent/CN108797097A/en
Publication of CN108797097A publication Critical patent/CN108797097A/en
Pending legal-status Critical Current

Links

Classifications

    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00Treating 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
    • D06M11/73Treating 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
    • D06M11/74Treating 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 with carbon or graphite; with carbides; with graphitic acids or their salts
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/20Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
    • D01F9/21Carbon 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
    • D01F9/22Carbon 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
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/416Systems
    • G01N27/48Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02Natural fibres, other than mineral fibres
    • D06M2101/04Vegetal fibres
    • D06M2101/06Vegetal fibres cellulosic

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Health & Medical Sciences (AREA)
  • Biochemistry (AREA)
  • Textile Engineering (AREA)
  • Molecular Biology (AREA)
  • Electrochemistry (AREA)
  • Physics & Mathematics (AREA)
  • Analytical Chemistry (AREA)
  • Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Fibers (AREA)
  • Carbon And Carbon Compounds (AREA)

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

A kind of preparation of graphene/carbon nano-fiber composite material
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.
CN201810430250.7A 2018-05-08 2018-05-08 A kind of preparation of graphene/carbon nano-fiber composite material Pending CN108797097A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810430250.7A CN108797097A (en) 2018-05-08 2018-05-08 A kind of preparation of graphene/carbon nano-fiber composite material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810430250.7A CN108797097A (en) 2018-05-08 2018-05-08 A kind of preparation of graphene/carbon nano-fiber composite material

Publications (1)

Publication Number Publication Date
CN108797097A true CN108797097A (en) 2018-11-13

Family

ID=64092134

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810430250.7A Pending CN108797097A (en) 2018-05-08 2018-05-08 A kind of preparation of graphene/carbon nano-fiber composite material

Country Status (1)

Country Link
CN (1) CN108797097A (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110016803A (en) * 2019-04-04 2019-07-16 碳翁(北京)科技有限公司 A kind of high temperature resistant fibre electroheating and its application
CN110022623A (en) * 2019-04-04 2019-07-16 碳翁(北京)科技有限公司 A kind of preparation and application of high temperature resistant fibre electroheating
CN110165229A (en) * 2019-05-28 2019-08-23 东旭光电科技股份有限公司 A kind of compound carbon fiber paper of graphene and its preparation method and application
CN110616561A (en) * 2019-10-28 2019-12-27 天津工业大学 Novel method for preparing carbon nano tube/carbon nano fiber composite material film
CN114150497A (en) * 2020-09-07 2022-03-08 北京大学 Graphene-carbon nanofiber composite material and preparation method thereof

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102644069A (en) * 2012-05-22 2012-08-22 东北林业大学 Method for chemically plating nickel on surface of carbon fiber
CN103144356A (en) * 2013-03-12 2013-06-12 南京航空航天大学 High-conductivity composite carbon fiber and preparation method thereof
CN103724930A (en) * 2013-05-28 2014-04-16 太仓派欧技术咨询服务有限公司 Nickel coating carbon fiber composite material and preparation method thereof
CN103981513A (en) * 2014-05-30 2014-08-13 北京理工大学 Chemical nickel plating method on carbon fiber surface
WO2015038612A1 (en) * 2013-09-11 2015-03-19 University Of Kentucky Research Foundation Potential of zero charge modified carbon based electrode for desalination
CN105712316A (en) * 2015-09-23 2016-06-29 哈尔滨理工大学 Preparation method of zinc oxide nanowire array/carbon nanofiber composite material
CN106198665A (en) * 2016-06-27 2016-12-07 衡阳师范学院 A kind of electrochemical sensor for levodopa amine detection by quantitative and preparation method thereof
CN106990149A (en) * 2017-05-02 2017-07-28 哈尔滨理工大学 A kind of preparation of molybdenum disulfide graphene composite nano plate biological sensor electrode

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102644069A (en) * 2012-05-22 2012-08-22 东北林业大学 Method for chemically plating nickel on surface of carbon fiber
CN103144356A (en) * 2013-03-12 2013-06-12 南京航空航天大学 High-conductivity composite carbon fiber and preparation method thereof
CN103724930A (en) * 2013-05-28 2014-04-16 太仓派欧技术咨询服务有限公司 Nickel coating carbon fiber composite material and preparation method thereof
WO2015038612A1 (en) * 2013-09-11 2015-03-19 University Of Kentucky Research Foundation Potential of zero charge modified carbon based electrode for desalination
CN103981513A (en) * 2014-05-30 2014-08-13 北京理工大学 Chemical nickel plating method on carbon fiber surface
CN105712316A (en) * 2015-09-23 2016-06-29 哈尔滨理工大学 Preparation method of zinc oxide nanowire array/carbon nanofiber composite material
CN106198665A (en) * 2016-06-27 2016-12-07 衡阳师范学院 A kind of electrochemical sensor for levodopa amine detection by quantitative and preparation method thereof
CN106990149A (en) * 2017-05-02 2017-07-28 哈尔滨理工大学 A kind of preparation of molybdenum disulfide graphene composite nano plate biological sensor electrode

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110016803A (en) * 2019-04-04 2019-07-16 碳翁(北京)科技有限公司 A kind of high temperature resistant fibre electroheating and its application
CN110022623A (en) * 2019-04-04 2019-07-16 碳翁(北京)科技有限公司 A kind of preparation and application of high temperature resistant fibre electroheating
CN110022623B (en) * 2019-04-04 2020-01-10 碳翁(北京)科技有限公司 Preparation and application of high-temperature-resistant electric heating fiber
CN110165229A (en) * 2019-05-28 2019-08-23 东旭光电科技股份有限公司 A kind of compound carbon fiber paper of graphene and its preparation method and application
CN110165229B (en) * 2019-05-28 2022-06-28 东旭光电科技股份有限公司 Graphene composite carbon fiber paper and preparation method and application thereof
CN110616561A (en) * 2019-10-28 2019-12-27 天津工业大学 Novel method for preparing carbon nano tube/carbon nano fiber composite material film
CN110616561B (en) * 2019-10-28 2023-02-03 天津工业大学 Novel method for preparing carbon nano tube/carbon nano fiber composite material film
CN114150497A (en) * 2020-09-07 2022-03-08 北京大学 Graphene-carbon nanofiber composite material and preparation method thereof
CN114150497B (en) * 2020-09-07 2023-08-15 北京大学 Graphene-carbon nanofiber composite material and preparation method thereof

Similar Documents

Publication Publication Date Title
CN108797097A (en) A kind of preparation of graphene/carbon nano-fiber composite material
CN108467023A (en) A kind of preparation of the graphene/carbon nano-fiber composite material of three-dimensional structure
Zheng et al. Review of vertical graphene and its applications
Yadav et al. Recent advances in carbon nanofibers and their applications–a review
Lee et al. Fabrication of ultrafine metal-oxide-decorated carbon nanofibers for DMMP sensor application
Lu et al. CuO nanoparticles/nitrogen-doped carbon nanofibers modified glassy carbon electrodes for non-enzymatic glucose sensors with improved sensitivity
Su et al. Electrospinning: A facile technique for fabricating polymeric nanofibers doped with carbon nanotubes and metallic nanoparticles for sensor applications
Zhou et al. Tungsten carbide nanofibers prepared by electrospinning with high electrocatalytic activity for oxygen reduction
Yang et al. Polyacrylonitrile‐based electrospun carbon paper for electrode applications
CN105322146B (en) A kind of selenizing molybdenum/carbon nano-fiber/graphene composite material and preparation method thereof
CN109859954B (en) Nanofiber-based flexible array structure electrode and preparation method thereof
JP2008195599A (en) Platinum nano catalyst-carrying carbon nano-tube electrode and its manufacturing method
Fang et al. Construction of carbon nanorods supported hydrothermal carbon and carbon fiber from waste biomass straw for high strength supercapacitor
CN102810406A (en) Super capacitor taking polyaniline/aligned carbon nanotube compound film as electrode and manufacturing method thereof
Qiu et al. Preparation of nitrogen-doped carbon submicrotubes by coaxial electrospinning and their electrocatalytic activity for oxygen reduction reaction in acid media
JP2006342011A (en) Carbon nanotube-carbon fiber composite and method for producing the same
CN106390766B (en) A kind of imitative nasal cavity ciliary structures filtering material with self-cleaning function
CN110517900B (en) Preparation method of nitrogen-doped low-temperature carbon nanofiber electrode material for supercapacitor
CN109369185A (en) A kind of preparation method of nitrogen-doped graphene complex carbon material
CN109205595A (en) Highly conductive Flexible graphene pipe and preparation method thereof
Yang et al. Highly sensitive hydrogen peroxide sensor based on a glassy carbon electrode modified with platinum nanoparticles on carbon nanofiber heterostructures
Garcia-Gomez et al. Enhancement of electrochemical properties on TiO 2/carbon nanofibers by electrospinning process
Safe et al. Hollow polyaniline nanofibers for highly sensitive ammonia detection applications
CN109900758B (en) Silver/carbon nanotube composite material and preparation method and application thereof
Wenrui et al. Fabrication and specific functionalisation of carbon fibers for advanced flexible biosensors

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20181113

WD01 Invention patent application deemed withdrawn after publication