CN105712316B - A kind of preparation of zinc oxide nano-wire array/carbon nano-fiber composite material - Google Patents
A kind of preparation of zinc oxide nano-wire array/carbon nano-fiber composite material Download PDFInfo
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Abstract
A kind of preparation of zinc oxide nano-wire array/carbon nano-fiber composite material, is related to a kind of preparation method of nano composite material.The present invention is to solve existing carbon nano-fiber surface area is small, in the application with solution contact surface product it is limited the problem of.Preparation method of the present invention is as follows：First, method of electrostatic spinning；2nd, hydrothermal synthesis method.A kind of zinc oxide nano-wire array/carbon nano-fiber composite material has the characteristics that surface area is big and conductivity is excellent.Present invention is mainly used for prepare a kind of zinc oxide nano-wire array/carbon nano-fiber composite material.
Description
Technical field
The present invention relates to a kind of preparation method of novel nanocomposite materials.
Background technology
Carbon nano-fiber is the fibrous nano carbon material formed by the curling of Multi-layer graphite piece, has excellent physics, power
Learn performance and chemical stability, such as good electrical and thermal conductivity performance and outstanding mechanical performance.Carbon nano-fiber is typically derived from
Electrostatic spinning polymer nanofiber, such as use polyacrylonitrile and pitch.Polyacrylonitrile is the master for preparing nanometer carbon nano-fiber
Presoma is wanted, because can be by controlling later stage carbonization and stabilization temperature flexibly to control the intensity and elasticity of carbon nano-fiber
Modulus.
Nano zine oxide refers to nano material of the crystallite dimension between 1nm~100nm, due to crystallite dimension drastically
Reduce, nano zine oxide shows the special nature not available for many block materials, as non-migratory, fluorescence, piezoelectricity,
Absorption and scatters ultraviolet ability etc..Wherein one-dimension zinc oxide nano-wire array, because morphology controllable and surface area turn into greatly mesh
One of preceding most important research object of field of nanometer material technology.The synthetic method of one-dimension zinc oxide nano-wire array generally has chemical gas
Mutually the methods of deposition, physical vapour deposition (PVD) and Hydrothermal Synthesiss.Wherein hydrothermal synthesis method has that synthesis temperature is low, cost it is cheap and
Can be with large-scale production, therefore receive much concern.
The content of the invention
The present invention is to solve carbon nano-fiber surface area is small, in the application with solution contact surface product it is limited the problem of, open
Zinc oxide nano-wire array/carbon nano-fiber composite material that to send out a kind of new, so as to provide a kind of zinc oxide nano-wire array/
The preparation method of carbon nano-fiber composite material.
A kind of preparation method of zinc oxide nano-wire array/carbon nano-fiber composite material provided by the invention is by following
Step is carried out：
First, method of electrostatic spinning
1）1g polyacrylonitrile powders are dissolved in 10mL dimethyl formamide solutions, and are 100 DEG C ~ 150 DEG C in temperature
Under conditions of heating stirring 1h ~ 2h, obtain electrostatic spinning solution.The solution is transferred in 10mL syringe, then will injection
Device is fixed on syringe pump, and it is 10KV ~ 20KV to control electrostatic spinning voltage, the distance of reception device to spinning syringe needle for 5cm ~
15cm, solution flow rate are 1mL/h ~ 2mL/h, and electrostatic spinning is carried out in electrostatic spinning apparatus and obtains polyacrylonitrile fibre.
2）Polyacrylonitrile fibre is placed in air dry oven, 250 DEG C ~ 300 DEG C is warming up to 1 DEG C/min speed, protects
Warm 1h ~ 1.5h carries out stabilization processes.
3）Carbonisation is carried out in quartz tube furnace.By step 2）Polyacrylonitrile fibre after stabilization processes is put
In boiler tube center, 700 DEG C ~ 1000 DEG C are warming up to from room temperature with 3 DEG C/min ~ 8 DEG C/min speed under argon gas protection, and in temperature
60min ~ 120min is incubated under conditions of 700 DEG C ~ 1000 DEG C of degree, then furnace cooling to room temperature, obtains carbon nano-fiber.Step
One 3）Described in the flow velocity of argon gas be 380sccm ~ 400sccm；
4）By step 3）It is 1cm that obtained carbon nano-fiber, which cuts into area,2~2cm2Piece, then by the carbon of well cutting
Nanofiber is fixed on clean glass, then by the usage amount every square centimeter for having the μ L of 50 μ L ~ 100, using sample loading gun by oxygen
Change zinc Seed Layer solution to be added drop-wise on the carbon nano-fiber on glass, then be placed under conditions of temperature is 200 DEG C ~ 300 DEG C and be incubated
60min ~ 90min, obtain being prefabricated with carbon nano-fiber/glass of zinc oxide seed layer；Step 14）Described in zinc oxide kind
Sublayer solution is prepared according to the following steps：Zinc acetate is dissolved in methanol, then with 300r/min ~ 500r/min rotating speed magnetic
Power stirs 3min ~ 5min, zinc oxide seed layer solution is obtained, wherein acetic acid zinc concentration in described zinc oxide seed layer solution
For 0.005mol/L ~ 0.05mol/L.
2nd, hydrothermal synthesis method
1）Zinc nitrate, hexa and polyethyleneimine are dissolved in deionized water, added after ammoniacal liquor with 300r/
Min ~ 500r/min rotating speed magnetic agitation 3min ~ 5min, obtains hydro-thermal reaction solution：Step 21）Described hydro-thermal reaction is molten
Nitric acid zinc concentration is 0.01mol/L ~ 0.1mol/L in liquid；The concentration of hexa is 0.01mol/L ~ 0.1mol/L；
The concentration of polyethyleneimine is 0.001mol/L ~ 0.005mol/L；The concentration of ammoniacal liquor is 0.1mol/L ~ 1mol/L.
2）By step 21）Obtained hydro-thermal reaction solution is poured into reactor, then by step 14）It is prefabricated with oxidation
The carbon nano-fiber of zinc Seed Layer/glass, which stands upside down, to be positioned in the mixed solution in reactor, reactor lid is covered, at 80 DEG C
8h ~ 15h is reacted under ~ 120 DEG C of temperature conditionss, then takes out and naturally cools to room temperature in atmosphere, obtain nano composite material,
Open reactor to be cleaned up the composite with distilled water, and 1h ~ 1.5h, furnace cooling are incubated at 400 DEG C ~ 450 DEG C
To room temperature, that is, obtain zinc oxide nano-wire array/carbon nano-fiber composite material.
Advantages of the present invention：
（1）The inventive method prepares carbon nano-fiber by electrospinning process, and technique is simple, and can pass through regulation
The composition of electrostatic spinning solution controls the diameter of fiber with electrospinning parameters, obtains the carbon Nanowire that diameter is evenly distributed
Dimension.
（2）The present invention obtains vertical-growth, diameter distribution on carbon nano-fiber surface using the method for Hydrothermal Synthesiss
Even zinc oxide nano-wire array.Zinc oxide nano-wire array considerably increases the surface area of carbon nano-fiber, in carbon Nanowire
The surface of dimension provides countless active sites.
Brief description of the drawings
Fig. 1 is the stereoscan photograph of carbon nano-fiber (CNF) prepared by electrostatic spinning；
Fig. 2 is the diameter that different temperatures is carbonized obtained carbon nano-fiber under an argon atmosphere；
Fig. 3 is the electrical conductance of carbon nano-fiber for being carbonized to obtain under different temperatures；
Fig. 4 is the stereoscan photograph of zinc oxide nano-wire array/carbon nano-fiber composite material of synthesis；
Fig. 5 is the stereoscan photograph in zinc oxide nano-wire array/carbon nano-fiber composite material section of synthesis；
Fig. 6 is the Raman collection of illustrative plates of carbon nano-fiber prepared by electrostatic spinning；
Fig. 7 is the X ray diffracting spectrum of the zinc oxide nano-wire array/carbon nano-fiber composite material prepared, ● carbon is received
The diffraction maximum of rice fiber, ◆ the diffraction maximum of zinc oxide.
Embodiment
Embodiment one：A kind of zinc oxide nano-wire array/carbon nano-fiber composite material in present embodiment
Preparation method, specifically carry out according to the following steps：
First, method of electrostatic spinning
1）1g polyacrylonitrile powders are dissolved in 10mL dimethyl formamide solutions, and are 100 DEG C ~ 150 DEG C in temperature
Under conditions of heating stirring 1h ~ 2h, obtain electrostatic spinning solution.The solution is transferred in 10mL syringe, then will injection
Device is fixed on syringe pump, and it is 10KV ~ 20KV to control electrostatic spinning voltage, the distance of reception device to spinning syringe needle for 5cm ~
15cm, solution flow rate are 1mL/h ~ 2mL/h, and electrostatic spinning is carried out in electrostatic spinning apparatus and obtains polyacrylonitrile fibre.
2）Polyacrylonitrile fibre is placed in air dry oven, 250 DEG C ~ 300 DEG C is warming up to 1 DEG C/min speed, protects
Warm 1h ~ 1.5h carries out stabilization processes.
3）Carbonisation is carried out in quartz tube furnace.By step 2）Polyacrylonitrile fibre after stabilization processes is put
In boiler tube center, 700 DEG C ~ 1000 DEG C are warming up to from room temperature with 3 DEG C/min ~ 8 DEG C/min speed under argon gas protection, and in temperature
60min ~ 120min is incubated under conditions of 700 DEG C ~ 1000 DEG C of degree, then furnace cooling to room temperature, obtains carbon nano-fiber.Step
One 3）Described in the flow velocity of argon gas be 380sccm ~ 400sccm.
4）By step 3）It is 1cm that obtained carbon nano-fiber, which cuts into area,2~2cm2Piece, then by the carbon of well cutting
Nanofiber is fixed on clean glass, then by the usage amount profit sample loading gun every square centimeter for having a μ L of 50 μ L ~ 100 by zinc oxide
Seed Layer solution is added drop-wise on the carbon nano-fiber on glass, then is placed under conditions of temperature is 200 DEG C ~ 300 DEG C and is incubated 60min
~ 90min, obtain being prefabricated with carbon nano-fiber/glass of zinc oxide seed layer；Step 14）Described in clean glass successively
It is cleaned by ultrasonic 15min ~ 20min in acetone successively, is cleaned by ultrasonic in ethanol in 15min ~ 20min and deionized water and is cleaned by ultrasonic
15min ~ 20min, spontaneously dry what is obtained at room temperature；Step 14）Described in zinc oxide seed layer solution be by following step
Suddenly prepare：Zinc acetate is dissolved in methanol, then with 300r/min ~ 500r/min rotating speed magnetic agitation 3min ~ 5min, obtained
To zinc oxide seed layer solution, wherein in described zinc oxide seed layer solution acetic acid zinc concentration be 0.001mol/L ~
0.05mol/L。
2nd, hydrothermal synthesis method
1）Zinc nitrate, hexa and polyethyleneimine are dissolved in deionized water, added after ammoniacal liquor with 300r/
Min ~ 500r/min rotating speed magnetic agitation 3min ~ 5min, obtains hydro-thermal reaction solution：Step 21）Described hydro-thermal reaction is molten
Nitric acid zinc concentration is 0.01mol/L ~ 0.1mol/L in liquid；The concentration of hexa is 0.01mol/L ~ 0.1mol/L；
The concentration of polyethyleneimine is 0.001mol/L ~ 0.005mol/L；The concentration of ammoniacal liquor is 0.1mol/L ~ 1mol/L.
2）By step 21）Obtained hydro-thermal reaction solution is poured into reactor, then by step 14）It is prefabricated with oxidation
The carbon nano-fiber of zinc Seed Layer/glass, which stands upside down, to be positioned in the mixed solution in reactor, reactor lid is covered, at 80 DEG C
8h ~ 15h is reacted under ~ 120 DEG C of temperature conditionss, then takes out and naturally cools to room temperature in atmosphere, obtain nano composite material,
Open reactor to be cleaned up the composite with distilled water, and 1h ~ 1.5h, furnace cooling are incubated at 400 DEG C ~ 450 DEG C
To room temperature, that is, obtain zinc oxide nano-wire array/carbon nano-fiber composite material.
Embodiment two：Present embodiment is unlike embodiment one：Step 1）It is middle by 1g polypropylene
Nitrile powder is dissolved in 10mL dimethyl formamide solutions, and heating stirring 1h under conditions of being 110 DEG C ~ 130 DEG C in temperature ~
2h, obtain electrostatic spinning solution.The solution is transferred in 10mL syringe, then syringe is fixed on syringe pump, is controlled
Electrostatic spinning voltage processed is 10KV ~ 20KV, and the distance of reception device to spinning syringe needle is 8cm ~ 12cm, solution flow rate be 1mL/h ~
2mL/h, progress electrostatic spinning obtains polyacrylonitrile fibre in electrostatic spinning apparatus.It is other identical with embodiment one.
Embodiment three：Unlike one of present embodiment and embodiment one or two：Step 12）In
Polyacrylonitrile fibre is placed in batch-type furnace, is warming up to 270 DEG C ~ 290 DEG C with 1 DEG C/min speed, insulation 1h ~ 1.5h carries out steady
Determining processing.It is other identical with one of embodiment one or two.
Embodiment four：Unlike one of present embodiment and embodiment one to three：Step 13）In
By step 2）Polyacrylonitrile fibre after stabilization processes be placed in boiler tube center, argon gas protection under from room temperature with 3 DEG C/min ~
8 DEG C/min speed is warming up to 800 DEG C ~ 900 DEG C, and is incubated 80min ~ 100min under conditions of 800 DEG C ~ 900 DEG C of temperature, so
Furnace cooling obtains carbon nano-fiber to room temperature afterwards.Step 13）Described in the flow velocity of argon gas be 400sccm.Other and tool
One of body embodiment one to three is identical.
Embodiment five：Unlike one of present embodiment and embodiment one to four：Step 14）In
By step 3）It is 1cm that obtained carbon nano-fiber, which cuts into area,2~1.5cm2Piece, then the carbon nano-fiber of well cutting is consolidated
It is fixed on clean glass, it is using sample loading gun that zinc oxide seed layer is molten then by the usage amount every square centimeter for having the μ L of 70 μ L ~ 90
Drop is added on the carbon nano-fiber on glass, then is placed under conditions of temperature is 230 DEG C ~ 280 DEG C and is incubated 60min ~ 90min,
Obtain being prefabricated with carbon nano-fiber/glass of zinc oxide seed layer；Step 14）Described in clean glass successively exist successively
Be cleaned by ultrasonic 15min ~ 20min in acetone, be cleaned by ultrasonic in ethanol in 15min ~ 20min and deionized water be cleaned by ultrasonic 15min ~
20min, spontaneously dry what is obtained at room temperature；Step 14）Described in zinc oxide seed layer solution be to prepare according to the following steps
's：Zinc acetate is dissolved in methanol, then with 300r/min ~ 500r/min rotating speed magnetic agitation 3min ~ 5min, aoxidized
Zinc Seed Layer solution, wherein acetic acid zinc concentration is 0.005mol/L ~ 0.01mol/L in described zinc oxide seed layer solution.
It is other identical with one of embodiment one to four.
Embodiment six：Unlike one of present embodiment and embodiment one to five：Rapid 21）Middle institute
Nitric acid zinc concentration is 0.04mol/L ~ 0.06mol/L in the hydro-thermal reaction solution stated；The concentration of hexa is
0.04mol/L~0.06mol/L；The concentration of polyethyleneimine is 0.001mol/L ~ 0.003mol/L；The concentration of ammoniacal liquor is
0.3mol/L~0.6mol/L.It is other identical with one of embodiment one to five.
Embodiment seven：Unlike one of present embodiment and embodiment one to six：Step 22）In
By step 21）Obtained hydro-thermal reaction solution is poured into reactor, then by step 14）It is prefabricated with the carbon of zinc oxide seed layer
Nanofiber, which stands upside down, to be positioned in the mixed solution in reactor, reactor lid is covered, in 90 DEG C ~ 110 DEG C of temperature conditionss
Lower reaction 8h ~ 12h, then takes out and naturally cools to room temperature in atmosphere, obtains nano composite material, opens reactor distillation
Water cleans up the composite, and 1h ~ 1.5h is incubated at 430 DEG C ~ 450 DEG C, cools to room temperature with the furnace, that is, is aoxidized
Zinc nano-wire array/carbon nano-fiber composite material.It is other identical with one of embodiment one to six.
Using following verification experimental verifications effect of the present invention：
A kind of preparation method of zinc oxide nano-wire array/carbon nano-fiber composite material of this experiment is by the following method
Realize：
First, method of electrostatic spinning
1）1g polyacrylonitrile powders are dissolved in 10mL dimethyl formamide solutions, and in the condition that temperature is 120 DEG C
Lower heating stirring 2h, obtains electrostatic spinning solution.The solution is transferred in 10mL syringe, then syringe is fixed on note
Penetrate on pump, it is 20KV to control electrostatic spinning voltage, and the distance of reception device to spinning syringe needle is 10cm, solution flow rate 1mL/h,
Electrostatic spinning is carried out in electrostatic spinning apparatus and obtains polyacrylonitrile fibre.
2）Polyacrylonitrile fibre is placed in batch-type furnace, is warming up to 280 DEG C with 1 DEG C/min speed, insulation 1h carries out steady
Determining processing.
3）Carbonisation is carried out in quartz tube furnace.By step 2）Polyacrylonitrile fibre after stabilization processes is put
In boiler tube center, 900 DEG C are warming up to from room temperature with 5 DEG C/min speed under argon gas protection, and under conditions of 900 DEG C of temperature
60min is incubated, then furnace cooling to room temperature, obtains carbon nano-fiber.Step 13）Described in the flow velocity of argon gas be
400sccm。
4）By step 3）It is 1cm that obtained carbon nano-fiber, which cuts into area,2Piece, then by the carbon nanometer of well cutting
Fiber is fixed on clean glass, then by the usage amount every square centimeter for having 90 μ L, using sample loading gun by zinc oxide seed layer
Solution is added drop-wise on the carbon nano-fiber on glass, then is placed under conditions of temperature is 250 DEG C and is incubated 60min, is prefabricated with
Carbon nano-fiber/glass of zinc oxide seed layer；Step 14）Described in zinc oxide seed layer solution be to make according to the following steps
Standby：Zinc acetate is dissolved in methanol, then with 400r/min rotating speed magnetic agitation 5min, it is molten to obtain zinc oxide seed layer
Liquid, wherein acetic acid zinc concentration is 0.01mol/L in described zinc oxide seed layer solution.
2nd, hydrothermal synthesis method
1）Zinc nitrate, hexa and polyethyleneimine are dissolved in deionized water, added after ammoniacal liquor with 400r/
Min rotating speed magnetic agitation 5min, obtains hydro-thermal reaction solution：Step 21）Zinc nitrate and six in described hydro-thermal reaction solution
The concentration of methenamine is 0.05mol/L；The concentration of polyethyleneimine is 0.002mol/L；The concentration of ammoniacal liquor is
0.5mol/L。
2）By step 21）Obtained hydro-thermal reaction solution is poured into reactor, then by step 14）It is prefabricated with oxidation
The carbon nano-fiber of zinc Seed Layer, which stands upside down, to be positioned in the mixed solution in reactor, reactor lid is covered, 80 DEG C ~ 120
DEG C temperature conditionss under react 8h ~ 15h, then take out and naturally cool to room temperature in atmosphere, obtain nano composite material, open
Reactor is cleaned up the composite with distilled water, and is incubated 1h at 450 DEG C, is cooled to room temperature with the furnace, that is, is obtained oxygen
Change zinc nano-wire array/carbon nano-fiber composite material.
Fig. 1 is the stereoscan photograph of carbon nano-fiber (CNF) prepared by electrostatic spinning, it can be seen that carbon is received
Rice fiber surface is slided light diameter and is evenly distributed, a diameter of 200~300nm of carbon nano-fiber.
Fig. 2 is the diameter that different temperatures is carbonized obtained carbon nano-fiber under an argon atmosphere.It can be seen that with
The extension of carbonization time and the raising of carburizing temperature, the diameter of carbon nano-fiber is gradually reduced.
Fig. 3 is the electrical conductance that different temperatures is carbonized obtained carbon nano-fiber under argon gas atmosphere.During low temperature, carbon nano-fiber
Electrical conductance it is very low, temperature rise electrical conductance increase, 900 DEG C heat treatment when, the electrical conductance of carbon nano-fiber reaches~3S/cm.
Fig. 4 is the stereoscan photograph of zinc oxide nano-wire array/carbon nano-fiber composite material of synthesis, can from figure
To find out, there are the countless zinc oxide nano-wire arrays perpendicular to carbon nano-fiber on the surface of each carbon nano-fiber.
Fig. 5 is the stereoscan photograph in zinc oxide nano-wire array/carbon nano-fiber composite material section of synthesis, by scheming
It can be seen that zinc oxide nano-wire array surrounds vertical-growth on each carbon nano-fiber and is evenly distributed.Zinc oxide nanowire
A diameter of ~ 40nm, length be 2 μm.
Fig. 6 is the Raman collection of illustrative plates for the carbon nano-fiber that electrostatic spinning obtains, wherein in~1380cm-1With~1618cm-1Place
Two characteristic peaks correspond to respectivelysp 2Graphite-structure carbon andsp 3Disordered structure carbon, it is D bands respectively（1360cm-1）And G（1590cm-1）Band.
Fig. 7 is the X ray diffracting spectrum of the zinc oxide nano-wire array/carbon nano-fiber composite material prepared, ● carbon is received
The diffraction maximum of rice fiber, the diffraction maximum at 22.6 ° of places is corresponding to graphite-structure（002）Crystal face.◆ the diffraction maximum of zinc oxide, own
Diffraction maximum is corresponding with ZnO characteristic peak very well.Show to have obtained zinc oxide nano-wire array/carbon nano-fiber composite material.
Claims (7)
- A kind of 1. preparation method of zinc oxide nano-wire array/carbon nano-fiber composite material, it is characterised in that zinc-oxide nano The preparation method of linear array/carbon nano-fiber composite material is carried out according to the following steps：First, method of electrostatic spinning1）1g polyacrylonitrile powders are dissolved in 10mL dimethyl formamide solutions, and in the bar that temperature is 100 DEG C ~ 150 DEG C Heating stirring 1h ~ 2h under part, obtain the solution of electrostatic spinning；The solution is transferred in 10mL syringe, then by syringe Be fixed on syringe pump, it is 10kV ~ 20kV to control electrostatic spinning voltage, the distance of reception device to spinning syringe needle for 5cm ~ 15cm, solution flow rate are 1mL/h ~ 2mL/h, and electrostatic spinning is carried out in electrostatic spinning apparatus and obtains polyacrylonitrile fibre；2）Polyacrylonitrile fibre is placed in air dry oven, 250 DEG C ~ 300 DEG C is warming up to 1 DEG C/min speed, is incubated 1h ~ 1.5h carries out stabilization processes；3）Carbonisation is carried out in quartz tube furnace；By step 2）Polyacrylonitrile fibre after stabilization processes is placed in stove Pipe center, 700 DEG C ~ 1000 DEG C are warming up to from room temperature with 3 DEG C/min ~ 8 DEG C/min speed under argon gas protection, and in temperature 60min ~ 120min is incubated under conditions of 700 DEG C ~ 1000 DEG C, then furnace cooling to room temperature, obtains carbon nano-fiber；Step 1 3）Described in the flow velocity of argon gas be 380sccm ~ 400sccm；4）By step 3）It is 1cm that obtained carbon nano-fiber, which cuts into area,2~2cm2Piece, then by the carbon nanometer of well cutting Fiber is fixed on clean glass, then by the usage amount every square centimeter for having the μ L of 50 μ L ~ 100, using sample loading gun by zinc oxide Seed Layer solution is added drop-wise on the carbon nano-fiber on glass, then is placed under conditions of temperature is 200 DEG C ~ 300 DEG C and is incubated 60min ~ 90min, obtain being prefabricated with the carbon nano-fiber of zinc oxide seed layer；Step 14）Described in zinc oxide seed layer solution be Prepare according to the following steps：Zinc acetate is dissolved in methanol, then with 300r/min ~ 500r/min rotating speed magnetic agitation 3min ~ 5min, zinc oxide seed layer solution is obtained, wherein acetic acid zinc concentration is in described zinc oxide seed layer solution 0.005mol/L~0.05mol/L；2nd, hydrothermal synthesis method1）Zinc nitrate, hexa and polyethyleneimine are dissolved in deionized water, add ammoniacal liquor after with 300r/min ~ The min of 500 r/min rotating speed magnetic agitation 3min ~ 5, obtains hydro-thermal reaction solution：Step 21）Described hydro-thermal reaction solution Middle nitric acid zinc concentration is the mol/L of 0.01mol/L ~ 0.1；The concentration of hexa is the mol/L of 0.01mol/L ~ 0.1； The concentration of polyethyleneimine is the mol/L of 0.001mol/L ~ 0.005；The concentration of ammoniacal liquor is the mol/L of 0.1mol/L ~ 1；2）By step 21）Obtained hydro-thermal reaction solution is poured into reactor, then by step 14）It is prefabricated with zinc oxide kind The carbon nano-fiber of sublayer/glass, which stands upside down, to be positioned in the mixed solution in reactor, reactor lid is covered, 80 DEG C ~ 120 DEG C temperature conditionss under be incubated 8h ~ 15h, then take out and naturally cool to room temperature in atmosphere, obtain nano composite material, open Reactor is cleaned up the composite with distilled water, and 1h ~ 1.5h is incubated at 400 DEG C ~ 450 DEG C, cools to room with the furnace Temperature, that is, obtain zinc oxide nano-wire array/carbon nano-fiber composite material.
- 2. a kind of preparation method of zinc oxide nano-wire array/carbon nano-fiber composite material according to claim 1, its It is characterised by step 11）It is middle that 1g polyacrylonitrile powders are dissolved in 10mL dimethyl formamide solutions, and be 110 in temperature DEG C ~ 130 DEG C under conditions of heating stirring 1h ~ 2h, obtain electrostatic spinning solution；The solution is transferred in 10mL syringe, Syringe is fixed on syringe pump again, it is 10kV ~ 20kV to control electrostatic spinning voltage, distance of the reception device to spinning syringe needle For 8cm ~ 12cm, solution flow rate is 1mL/h ~ 2mL/h, and electrostatic spinning is carried out in electrostatic spinning apparatus and obtains polyacrylonitrile fibre Dimension.
- 3. a kind of preparation method of zinc oxide nano-wire array/carbon nano-fiber composite material according to claim 1, its It is characterised by step 12）It is middle that polyacrylonitrile fibre is placed in air dry oven, with 1 DEG C/min speed be warming up to 270 DEG C ~ 290 DEG C, insulation 1h ~ 1.5h carries out stabilization processes.
- 4. a kind of preparation method of zinc oxide nano-wire array/carbon nano-fiber composite material according to claim 1, its It is characterised by step 13）It is middle by step 2）Polyacrylonitrile fibre after stabilization processes is placed in tubular type boiler tube center, in argon gas Under protection 800 DEG C ~ 900 DEG C are warming up to from room temperature with 3 DEG C/min ~ 8 DEG C/min speed, and in the bar of 800 DEG C ~ 900 DEG C of temperature 80min ~ 100min is incubated under part, then furnace cooling to room temperature, obtains carbon nano-fiber；Step 13）Described in argon gas Flow velocity is 400sccm.
- 5. a kind of preparation method of zinc oxide nano-wire array/carbon nano-fiber composite material according to claim 1, its It is characterised by step 14）It is middle by step 3）It is 1cm that obtained carbon nano-fiber, which cuts into area,2~1.5cm2Piece, then will cut The carbon nano-fiber cut is fixed on clean glass, then by the usage amount every square centimeter for having the μ L of 70 μ L ~ 90, utilizes sample-adding Zinc oxide seed layer solution is added drop-wise on the carbon nano-fiber on glass by rifle, then is placed in the condition that temperature is 230 DEG C ~ 280 DEG C Lower insulation 60min ~ 90min, obtain being prefabricated with carbon nano-fiber/glass of zinc oxide seed layer；Step 14）Described in oxygen Change zinc Seed Layer solution to prepare according to the following steps：Zinc acetate is dissolved in methanol, then with 300r/min ~ 500r/min's Rotating speed magnetic agitation 3min ~ 5min, obtains zinc oxide seed layer solution, wherein zinc acetate in described zinc oxide seed layer solution Concentration be 0.005mol/L ~ 0.01mol/L.
- 6. a kind of preparation method of zinc oxide nano-wire array/carbon nano-fiber composite material according to claim 1, its It is characterised by step 21）Described in hydro-thermal reaction solution in nitric acid zinc concentration be 0.04mol/L ~ 0.06mol/L；Six is sub- The concentration of tetramine is 0.04mol/L ~ 0.06mol/L；The concentration of polyethyleneimine is 0.001mol/L ~ 0.003mol/L； The concentration of ammoniacal liquor is 0.3mol/L ~ 0.6mol/L.
- 7. a kind of preparation method of zinc oxide nano-wire array/carbon nano-fiber composite material according to claim 1, its It is characterised by step 22）It is middle by step 21）Obtained hydro-thermal reaction solution is poured into reactor, then by step 14）It is prefabricated Carbon nano-fiber/the glass for having zinc oxide seed layer, which stands upside down, to be positioned in the mixed solution in reactor, covers reactor lid, 8h ~ 12h is reacted under 90 DEG C ~ 110 DEG C of temperature conditionss, then takes out and naturally cools to room temperature in atmosphere, obtain composite wood Material, open reactor and cleaned up composite with distilled water, and 1h ~ 1.5h, furnace cooling are incubated at 430 DEG C ~ 450 DEG C To room temperature, that is, obtain zinc oxide nano-wire array/carbon nano-fiber composite material.
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| CN107808956B (en) * | 2017-10-27 | 2019-09-24 | 哈尔滨理工大学 | A kind of preparation method of titanium niobium oxygen nanometer rods/carbon nanofiber arrays electrode |
| CN108797097A (en) * | 2018-05-08 | 2018-11-13 | 哈尔滨理工大学 | A kind of preparation of graphene/carbon nano-fiber composite material |
| CN108956713B (en) * | 2018-06-29 | 2020-12-01 | 五邑大学 | ZnO/carbon nanowire sensitive material with horizontally distributed propagation paths, preparation method thereof and high-sensitivity sensor |
| CN109781822B (en) * | 2019-01-29 | 2021-04-20 | 哈尔滨医科大学 | Zinc oxide nanosheet array/three-dimensional foam graphene biosensor working electrode and preparation method and application thereof |
| CN109859954B (en) * | 2019-03-07 | 2020-11-03 | 河北科技大学 | Nanofiber-based flexible array structure electrode and preparation method thereof |
| CN111300812A (en) * | 2020-04-04 | 2020-06-19 | 南开大学 | Method for digitally controllable printing of P (VDF-TrFE) nanowire array |
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| CN104310459A (en) * | 2014-10-22 | 2015-01-28 | 上海大学 | Novel preparation method of zinc oxide nano-rod |
| CN104671277A (en) * | 2013-11-29 | 2015-06-03 | 纳米新能源（唐山）有限责任公司 | Method for preparing zinc oxide composite material with high specific surface area and zinc oxide composite material |
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| CN102659169A (en) * | 2012-04-27 | 2012-09-12 | 哈尔滨理工大学 | Method for preparing zinc oxide micro-nano tooth-shaped rods and zinc oxide micro-nano pine cones |
| CN102659168A (en) * | 2012-04-27 | 2012-09-12 | 哈尔滨理工大学 | Method for preparing zinc oxide nanoshuttle |
| CN103482683A (en) * | 2013-10-15 | 2014-01-01 | 哈尔滨理工大学 | Synthesis method of zinc oxide nano wire harness array/foam graphene composite material and application thereof |
| CN104671277A (en) * | 2013-11-29 | 2015-06-03 | 纳米新能源（唐山）有限责任公司 | Method for preparing zinc oxide composite material with high specific surface area and zinc oxide composite material |
| CN104310459A (en) * | 2014-10-22 | 2015-01-28 | 上海大学 | Novel preparation method of zinc oxide nano-rod |
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