CN105712316A - Preparation method of zinc oxide nanowire array/carbon nanofiber composite material - Google Patents
Preparation method of zinc oxide nanowire array/carbon nanofiber composite material Download PDFInfo
- Publication number
- CN105712316A CN105712316A CN201510607850.2A CN201510607850A CN105712316A CN 105712316 A CN105712316 A CN 105712316A CN 201510607850 A CN201510607850 A CN 201510607850A CN 105712316 A CN105712316 A CN 105712316A
- Authority
- CN
- China
- Prior art keywords
- zinc oxide
- carbon nano
- fiber
- solution
- nano
- 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.)
- Granted
Links
Abstract
The invention discloses a preparation method of zinc oxide nanowire array/carbon nanofiber composite material, relates to preparation methods of nano composite materials, and aims to solve the problems that existing carbon nanofibers are low in surface area, and the contact area of the carbon nanofibers with solution is limited during application. The preparation method includes the steps of firstly, using an electrospinning method; secondly, using a hydrothermal synthesizing method. The zinc oxide nanowire array/carbon nanofiber composite material is large in surface area, excellent in conductivity, and the like. The preparation method is mainly used for preparing the zinc oxide nanowire array/carbon nanofiber composite material.
Description
Technical field
The preparation method that the present invention relates to a kind of novel nanocomposite materials.
Background technology
Carbon nano-fiber is the fibrous nano material with carbon element curling by Multi-layer graphite sheet, has Physical and mechanical properties and the chemical stability of excellence, such as good electrical and thermal conductivity performance and outstanding mechanical performance.Carbon nano-fiber is typically derived from electrostatic spinning polymer nanofiber, as with polyacrylonitrile and Colophonium etc..Polyacrylonitrile is the main precursor preparing nano-sized carbon nanofiber, because intensity and the elastic modelling quantity of carbon nano-fiber can be controlled flexibly by control later stage carbonization and stabilization temperature.
Nano zine oxide refers to crystallite dimension nano material between 1nm～100nm, due to strongly reducing of crystallite dimension, nano zine oxide shows the special nature not available for many block materials, such as non-migratory, fluorescence, piezoelectricity, absorption and scatters ultraviolet ability etc..Wherein one-dimension zinc oxide nano-wire array, owing to morphology controllable and surface area become greatly one of most important object of study of current field of nanometer material technology.The synthetic method of one-dimension zinc oxide nano-wire array generally has the methods such as chemical vapour deposition (CVD), physical vapour deposition (PVD) and Hydrothermal Synthesis.Wherein to have synthesis temperature low for hydrothermal synthesis method, with low cost and can large-scale production, therefore receive much concern.
Summary of the invention
The present invention is to solve that carbon nano-fiber surface area is little, limited problem is amassed in the application with solution contact surface, develop a kind of novel zinc oxide nano-wire array/carbon nano-fiber composite material, thus the preparation method that a kind of zinc oxide nano-wire array/carbon nano-fiber composite material is provided.
The preparation method of a kind of zinc oxide nano-wire array/carbon nano-fiber composite material provided by the invention is to sequentially include the following steps:
One, method of electrostatic spinning
1) 1g polyacrylonitrile powder is dissolved in 10mL dimethyl formamide solution, and when temperature is 100 DEG C ~ 150 DEG C heated and stirred 1h ~ 2h, obtain electrostatic spinning solution.This solution is transferred in the syringe of 10mL, again syringe is fixed on syringe pump, controlling electrostatic spinning voltage is 10KV ~ 20KV, reception device is 5cm ~ 15cm to the distance of spinning syringe needle, solution flow rate is 1mL/h ~ 2mL/h, carries out electrostatic spinning and obtain polyacrylonitrile fibre in electrostatic spinning apparatus；
2) being placed in air dry oven by polyacrylonitrile fibre, be warmed up to 250 DEG C ~ 300 DEG C with the speed of 1 DEG C/min, insulation 1h ~ 1.5h carries out stabilizing treatment；
3) carbonisation carries out in quartz tube furnace.By step 2) polyacrylonitrile fibre after stabilizing treatment is placed in boiler tube central authorities; it is warmed up to 700 DEG C ~ 1000 DEG C from room temperature with the speed of 3 DEG C/min ~ 8 DEG C/min under argon shield; and 60min ~ 120min it is incubated when temperature 700 DEG C ~ 1000 DEG C; then furnace cooling is to room temperature, obtains carbon nano-fiber.Step one 1) described in the flow velocity of argon be 380sccm ~ 400sccm；
4) carbon nano-fiber that step 3) obtains cutting into area is 1cm2~2cm2Sheet, then the carbon nano-fiber of well cutting is fixed on clean glass, have 50 μ L ~ 100 μ L's to make consumption by every square centimeter again, sample loading gun is utilized to be added drop-wise on the carbon nano-fiber on glass by zinc oxide seed layer solution, it is placed in insulation 60min ~ 90min when temperature is 200 DEG C ~ 300 DEG C again, obtains being prefabricated with the carbon nano-fiber/glass of zinc oxide seed layer；Step one 4) described in zinc oxide seed layer solution prepare according to the following steps: zinc acetate is dissolved in methanol, then with the rotating speed magnetic agitation 3min ~ 5min of 300r/min ~ 500r/min, obtaining zinc oxide seed layer solution, in wherein said zinc oxide seed layer solution, acetic acid zinc concentration is 0.005mol/L ~ 0.05mol/L.
Two, hydrothermal synthesis method
1) zinc nitrate, hexamethylenetetramine and polymine are dissolved in deionized water, add the rotating speed magnetic agitation 3min ~ 5min with 300r/min ~ 500r/min after ammonia, obtain hydro-thermal reaction solution: step 2 1) described in hydro-thermal reaction solution in nitric acid zinc concentration be 0.01mol/L ~ 0.1mol/L；The concentration of hexamethylenetetramine is 0.01mol/L ~ 0.1mol/L；The concentration of polymine is 0.001mol/L ~ 0.005mol/L；The concentration of ammonia is 0.1mol/L ~ 1mol/L；
2) by step 2 1) the hydro-thermal reaction solution that obtains pours in reactor, then by step one 4) it is prefabricated with the carbon nano-fiber of zinc oxide seed layer/glass and stands upside down in the mixed solution being positioned in reactor, cover reactor lid, 8h ~ 15h is reacted under the temperature conditions of 80 DEG C ~ 120 DEG C, then take out and naturally cool to room temperature in atmosphere, obtain nano composite material, open reactor distilled water to be cleaned up by this composite, and at 400 DEG C ~ 450 DEG C, it is incubated 1h ~ 1.5h, cool to room temperature with the furnace, namely zinc oxide nano-wire array/carbon nano-fiber composite material is obtained.
Advantages of the present invention:
(1) the inventive method prepares carbon nano-fiber by electrospinning process, and technique is simple, and can be controlled the diameter of fiber by the composition and electrospinning parameters regulating electrostatic spinning solution, obtains the uniform carbon nano-fiber of diameter Distribution；
(2) present invention adopts the method for Hydrothermal Synthesis to obtain orthotropic, the uniform zinc oxide nano-wire array of diameter Distribution on carbon nano-fiber surface.Zinc oxide nano-wire array considerably increases the surface area of carbon nano-fiber, provides countless active site on the surface of carbon nano-fiber.
Accompanying drawing illustrates:
Fig. 1 is the stereoscan photograph of carbon nano-fiber (CNF) prepared by electrostatic spinning；
Fig. 2 is the diameter of the carbon nano-fiber that different temperatures carbonization obtains under an argon atmosphere；
Fig. 3 is the electrical conductance of the carbon nano-fiber that carbonization obtains under different temperatures；
Fig. 4 is the stereoscan photograph of the zinc oxide nano-wire array/carbon nano-fiber composite material of synthesis；
Fig. 5 is the stereoscan photograph in the zinc oxide nano-wire array/carbon nano-fiber composite material cross 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, ● the diffraction maximum of carbon nano-fiber, ◆ the diffraction maximum of zinc oxide.
Detailed description of the invention
Detailed description of the invention one: the preparation method of a kind of zinc oxide nano-wire array/carbon nano-fiber composite material in present embodiment, specifically carries out according to the following steps:
One, method of electrostatic spinning
1) 1g polyacrylonitrile powder is dissolved in 10mL dimethyl formamide solution, and when temperature is 100 DEG C ~ 150 DEG C heated and stirred 1h ~ 2h, obtain electrostatic spinning solution.This solution is transferred in the syringe of 10mL, again syringe is fixed on syringe pump, controlling electrostatic spinning voltage is 10KV ~ 20KV, reception device is 5cm ~ 15cm to the distance of spinning syringe needle, solution flow rate is 1mL/h ~ 2mL/h, carries out electrostatic spinning and obtain polyacrylonitrile fibre in electrostatic spinning apparatus；
2) being placed in air dry oven by polyacrylonitrile fibre, be warmed up to 250 DEG C ~ 300 DEG C with the speed of 1 DEG C/min, insulation 1h ~ 1.5h carries out stabilizing treatment；
3) carbonisation carries out in quartz tube furnace.By step 2) polyacrylonitrile fibre after stabilizing treatment is placed in boiler tube central authorities; it is warmed up to 700 DEG C ~ 1000 DEG C from room temperature with the speed of 3 DEG C/min ~ 8 DEG C/min under argon shield; and 60min ~ 120min it is incubated when temperature 700 DEG C ~ 1000 DEG C; then furnace cooling is to room temperature, obtains carbon nano-fiber.Step one 1) described in the flow velocity of argon be 380sccm ~ 400sccm；
4) carbon nano-fiber that step 3) obtains cutting into area is 1cm2~2cm2Sheet, then the carbon nano-fiber of well cutting is fixed on clean glass, by every square centimeter of consumption profit sample loading gun that makes having 50 μ L ~ 100 μ L, zinc oxide seed layer solution is added drop-wise on the carbon nano-fiber on glass again, it is placed in insulation 60min ~ 90min when temperature is 200 DEG C ~ 300 DEG C again, obtains being prefabricated with the carbon nano-fiber/glass of zinc oxide seed layer；Step one 4) described in clean glass successively ultrasonic cleaning 15min ~ 20min in acetone successively, in ethanol, ultrasonic cleaning 15min ~ 20min and deionized water for ultrasonic clean 15min ~ 20min, and at room temperature natural drying obtains；Step one 4) described in zinc oxide seed layer solution prepare according to the following steps: zinc acetate is dissolved in methanol, then with the rotating speed magnetic agitation 3min ~ 5min of 300r/min ~ 500r/min, obtaining zinc oxide seed layer solution, in wherein said zinc oxide seed layer solution, acetic acid zinc concentration is 0.001mol/L ~ 0.05mol/L.
Two, hydrothermal synthesis method
1) zinc nitrate, hexamethylenetetramine and polymine are dissolved in deionized water, add the rotating speed magnetic agitation 3min ~ 5min with 300r/min ~ 500r/min after ammonia, obtain hydro-thermal reaction solution: step 2 1) described in hydro-thermal reaction solution in nitric acid zinc concentration be 0.01mol/L ~ 0.1mol/L；The concentration of hexamethylenetetramine is 0.01mol/L ~ 0.1mol/L；The concentration of polymine is 0.001mol/L ~ 0.005mol/L；The concentration of ammonia is 0.1mol/L ~ 1mol/L；
2) by step 2 1) the hydro-thermal reaction solution that obtains pours in reactor, then by step one 4) it is prefabricated with the carbon nano-fiber of zinc oxide seed layer/glass and stands upside down in the mixed solution being positioned in reactor, cover reactor lid, 8h ~ 15h is reacted under the temperature conditions of 80 DEG C ~ 120 DEG C, then take out and naturally cool to room temperature in atmosphere, obtain nano composite material, open reactor distilled water to be cleaned up by this composite, and at 400 DEG C ~ 450 DEG C, it is incubated 1h ~ 1.5h, cool to room temperature with the furnace, namely zinc oxide nano-wire array/carbon nano-fiber composite material is obtained；
Detailed description of the invention two: present embodiment and detailed description of the invention one the difference is that: 1g polyacrylonitrile powder is dissolved in 10mL dimethyl formamide solution by step 1), and heated and stirred 1h ~ 2h when temperature is 110 DEG C ~ 130 DEG C, obtains electrostatic spinning solution.This solution is transferred in the syringe of 10mL, again syringe is fixed on syringe pump, controlling electrostatic spinning voltage is 10KV ~ 20KV, reception device is 8cm ~ 12cm to the distance of spinning syringe needle, solution flow rate is 1mL/h ~ 2mL/h, carries out electrostatic spinning and obtain polyacrylonitrile fibre in electrostatic spinning apparatus.Other is identical with detailed description of the invention one；
Detailed description of the invention three: one of present embodiment and detailed description of the invention one or two are the difference is that step one 2) in polyacrylonitrile fibre is placed in batch-type furnace, be warmed up to 270 DEG C ~ 290 DEG C with the speed of 1 DEG C/min, insulation 1h ~ 1.5h carries out stabilizing treatment.Other is identical with one of detailed description of the invention one or two；
Detailed description of the invention four: one of present embodiment and detailed description of the invention one to three are the difference is that step one 3) in by step 2) polyacrylonitrile fibre after stabilizing treatment is placed in boiler tube central authorities; it is warmed up to 800 DEG C ~ 900 DEG C from room temperature with the speed of 3 DEG C/min ~ 8 DEG C/min under argon shield; and 80min ~ 100min it is incubated when temperature 800 DEG C ~ 900 DEG C; then furnace cooling is to room temperature, obtains carbon nano-fiber.Step one 1) described in the flow velocity of argon be 400sccm.Other is identical with one of detailed description of the invention one to three；
Detailed description of the invention five: one of present embodiment and detailed description of the invention one to four are the difference is that step one 4) in carbon nano-fiber that step 3) is obtained to cut into area be 1cm2~1.5cm2Sheet, then the carbon nano-fiber of well cutting is fixed on clean glass, have 70 μ L ~ 90 μ L's to make consumption by every square centimeter again, sample loading gun is utilized to be added drop-wise on the carbon nano-fiber on glass by zinc oxide seed layer solution, it is placed in insulation 60min ~ 90min when temperature is 230 DEG C ~ 280 DEG C again, obtains being prefabricated with the carbon nano-fiber/glass of zinc oxide seed layer；Step one 4) described in clean glass successively ultrasonic cleaning 15min ~ 20min in acetone successively, in ethanol, ultrasonic cleaning 15min ~ 20min and deionized water for ultrasonic clean 15min ~ 20min, and at room temperature natural drying obtains；Step one 4) described in zinc oxide seed layer solution prepare according to the following steps: zinc acetate is dissolved in methanol, then with the rotating speed magnetic agitation 3min ~ 5min of 300r/min ~ 500r/min, obtaining zinc oxide seed layer solution, in wherein said zinc oxide seed layer solution, acetic acid zinc concentration is 0.005mol/L ~ 0.01mol/L.Other is identical with one of detailed description of the invention one to four；
Detailed description of the invention six: one of present embodiment and detailed description of the invention one to five the difference is that: rapid 2 1) described in hydro-thermal reaction solution in nitric acid zinc concentration be 0.04mol/L ~ 0.06mol/L；The concentration of hexamethylenetetramine is 0.04mol/L ~ 0.06mol/L；The concentration of polymine is 0.001mol/L ~ 0.003mol/L；The concentration of ammonia is 0.3mol/L ~ 0.6mol/L.Other is identical with one of detailed description of the invention one to five；
Detailed description of the invention seven: one of present embodiment and detailed description of the invention one to six are the difference is that step 2 2) in by step 2 1) the hydro-thermal reaction solution that obtains pours in reactor, then by step one 4) be prefabricated with zinc oxide seed layer carbon nano-fiber stand upside down be positioned in reactor mixed solution in, cover reactor lid, 8h ~ 12h is reacted under the temperature conditions of 90 DEG C ~ 110 DEG C, then take out and naturally cool to room temperature in atmosphere, obtain nano composite material, open reactor distilled water to be cleaned up by this composite, and at 430 DEG C ~ 450 DEG C, it is incubated 1h ~ 1.5h, cool to room temperature with the furnace, namely zinc oxide nano-wire array/carbon nano-fiber composite material is obtained.Other is identical with one of detailed description of the invention one to six.
Adopt following verification experimental verification effect of the present invention:
The preparation method of a kind of zinc oxide nano-wire array/carbon nano-fiber composite material of this test realizes by the following method:
One, method of electrostatic spinning
1) 1g polyacrylonitrile powder is dissolved in 10mL dimethyl formamide solution, and when temperature is 120 DEG C heated and stirred 2h, obtain electrostatic spinning solution.This solution is transferred in the syringe of 10mL, being fixed on syringe pump by syringe again, controlling electrostatic spinning voltage is 20KV, and reception device is 10cm to the distance of spinning syringe needle, solution flow rate is 1mL/h, carries out electrostatic spinning and obtain polyacrylonitrile fibre in electrostatic spinning apparatus；
2) being placed in batch-type furnace by polyacrylonitrile fibre, be warmed up to 280 DEG C with the speed of 1 DEG C/min, insulation 1h carries out stabilizing treatment；
3) carbonisation carries out in quartz tube furnace.By step 2) polyacrylonitrile fibre after stabilizing treatment is placed in boiler tube central authorities, is warmed up to 900 DEG C from room temperature with the speed of 5 DEG C/min, and is incubated 60min when temperature 900 DEG C under argon shield, and then furnace cooling is to room temperature, obtains carbon nano-fiber.Step one 1) described in the flow velocity of argon be 400sccm；
4) carbon nano-fiber that step 3) obtains cutting into area is 1cm2Sheet, then the carbon nano-fiber of well cutting is fixed on clean glass, have 90 μ L's to make consumption by every square centimeter again, sample loading gun is utilized to be added drop-wise on the carbon nano-fiber on glass by zinc oxide seed layer solution, it is placed in insulation 60min when temperature is 250 DEG C again, obtains being prefabricated with the carbon nano-fiber/glass of zinc oxide seed layer；Step one 4) described in zinc oxide seed layer solution prepare according to the following steps: zinc acetate is dissolved in methanol, then with the rotating speed magnetic agitation 5min of 400r/min, obtaining zinc oxide seed layer solution, in wherein said zinc oxide seed layer solution, acetic acid zinc concentration is 0.01mol/L.
Two, hydrothermal synthesis method
1) zinc nitrate, hexamethylenetetramine and polymine are dissolved in deionized water, add the rotating speed magnetic agitation 5min with 400r/min after ammonia, obtain hydro-thermal reaction solution: step 2 1) described in hydro-thermal reaction solution in the concentration of zinc nitrate and hexamethylenetetramine be 0.05mol/L；The concentration of polymine is 0.002mol/L；The concentration of ammonia is 0.5mol/L；
2) by step 2 1) the hydro-thermal reaction solution that obtains pours in reactor, then by step one 4) be prefabricated with zinc oxide seed layer carbon nano-fiber stand upside down be positioned in reactor mixed solution in, cover reactor lid, 8h ~ 15h is reacted under the temperature conditions of 80 DEG C ~ 120 DEG C, then take out and naturally cool to room temperature in atmosphere, obtain nano composite material, open reactor distilled water to be cleaned up by this composite, and at 450 DEG C, it is incubated 1h, cool to room temperature with the furnace, namely obtain zinc oxide 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 the sliding light diameter Distribution in carbon nano-fiber surface is uniform, the diameter of carbon nano-fiber is 200～300nm.
Fig. 2 is the diameter of the carbon nano-fiber that different temperatures carbonization obtains under an argon atmosphere.It can be seen that along with the raising of the prolongation of carbonization time and carburizing temperature, the diameter of carbon nano-fiber is gradually reduced.
Fig. 3 is the electrical conductance of the carbon nano-fiber that different temperatures carbonization obtains under argon gas atmosphere.During low temperature, the electrical conductance of carbon nano-fiber is very low, and temperature raises electrical conductance to be increased, and during 900 DEG C of heat treatments, the electrical conductance of carbon nano-fiber reaches～3S/cm.
Fig. 4 is the stereoscan photograph of the zinc oxide nano-wire array/carbon nano-fiber composite material of synthesis, it can be seen that there is the countless zinc oxide nano-wire arrays being perpendicular to carbon nano-fiber on the surface of each carbon nano-fiber.
Fig. 5 is the stereoscan photograph in the zinc oxide nano-wire array/carbon nano-fiber composite material cross section of synthesis, and zinc oxide nano-wire array around vertical-growth on each carbon nano-fiber and is evenly distributed as seen from the figure.The diameter of zinc oxide nanowire is ~ 40nm, and length is 2 μm.
Fig. 6 is the Raman collection of illustrative plates of the carbon nano-fiber that electrostatic spinning obtains, wherein at～1380cm-1With～1618cm-1Two characteristic peaks at place correspondence respectivelysp 2Graphite-structure carbon andsp 3Disordered structure carbon, is that D is with (1360cm respectively-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, ● the diffraction maximum of carbon nano-fiber, the diffraction maximum at 22.6 ° of places is corresponding to (002) crystal face of graphite-structure.◆ the diffraction maximum of zinc oxide, all diffraction maximums are corresponding with the characteristic peak of ZnO very well.Show to obtain zinc oxide nano-wire array/carbon nano-fiber composite material.
Claims (7)
1. the preparation method of zinc oxide nano-wire array/carbon nano-fiber composite material, it is characterised in that the preparation method of zinc oxide nano-wire array/carbon nano-fiber composite material carries out according to the following steps:
One. method of electrostatic spinning
1) 1g polyacrylonitrile powder is dissolved in 10mL dimethyl formamide solution, and when temperature is 100 DEG C ~ 150 DEG C heated and stirred 1h ~ 2h, obtain the solution of electrostatic spinning；This solution is transferred in the syringe of 10mL, again syringe is fixed on syringe pump, controlling electrostatic spinning voltage is 10KV ~ 20KV, reception device is 5cm ~ 15cm to the distance of spinning syringe needle, solution flow rate is 1mL/h ~ 2mL/h, carries out electrostatic spinning and obtain polyacrylonitrile fibre in electrostatic spinning apparatus；
2) being placed in air dry oven by polyacrylonitrile fibre, be warmed up to 250 DEG C ~ 300 DEG C with the speed of 1 DEG C/min, insulation 1h ~ 1.5h carries out stabilizing treatment；
3) carbonisation carries out in quartz tube furnace; by step 2) polyacrylonitrile fibre after stabilizing treatment is placed in boiler tube central authorities; it is warmed up to 700 DEG C ~ 1000 DEG C from room temperature with the speed of 3 DEG C/min ~ 8 DEG C/min under argon shield; and 60min ~ 120min it is incubated when temperature 700 DEG C ~ 1000 DEG C; then furnace cooling is to room temperature; obtain carbon nano-fiber, step one 1) described in the flow velocity of argon be 380sccm ~ 400sccm；
4) carbon nano-fiber that step 3) obtains cutting into area is 1cm2~2cm2Sheet, then the carbon nano-fiber of well cutting is fixed on clean glass, have 50 μ L ~ 100 μ L's to make consumption by every square centimeter again, sample loading gun is utilized to be added drop-wise on the carbon nano-fiber on glass by zinc oxide seed layer solution, it is placed in insulation 60min ~ 90min when temperature is 200 DEG C ~ 300 DEG C again, obtains being prefabricated with the carbon nano-fiber of zinc oxide seed layer；Step one 4) described in zinc oxide seed layer solution prepare according to the following steps: zinc acetate is dissolved in methanol, then with the rotating speed magnetic agitation 3min ~ 5min of 300r/min ~ 500r/min, obtaining zinc oxide seed layer solution, in wherein said zinc oxide seed layer solution, acetic acid zinc concentration is 0.005mol/L ~ 0.05mol/L；
Two. hydrothermal synthesis method
1) zinc nitrate, hexamethylenetetramine and polymine are dissolved in deionized water, add the rotating speed magnetic agitation 3min ~ 5min with 300r/min ~ 500r/min after ammonia, obtain hydro-thermal reaction solution: step 2 1) described in hydro-thermal reaction solution in nitric acid zinc concentration be 0.01mol/L ~ 0.1mol/L；The concentration of hexamethylenetetramine is 0.01mol/L ~ 0.1mol/L；The concentration of polymine is 0.001mol/L ~ 0.005mol/L；The concentration of ammonia is 0.1mol/L ~ 1mol/L；
2) by step 2 1) the hydro-thermal reaction solution that obtains pours in reactor, then by step one 4) it is prefabricated with the carbon nano-fiber of zinc oxide seed layer/glass and stands upside down in the mixed solution being positioned in reactor, cover reactor lid, 8h ~ 15h it is incubated under the temperature conditions of 80 DEG C ~ 120 DEG C, then take out and naturally cool to room temperature in atmosphere, obtain nano composite material, open reactor distilled water to be cleaned up by this composite, and at 400 DEG C ~ 450 DEG C, it is incubated 1h ~ 1.5h, cool to room temperature with the furnace, namely zinc oxide nano-wire array/carbon nano-fiber composite material is obtained.
2. the preparation method of a kind of zinc oxide nano-wire array/carbon nano-fiber composite material according to claim 1, it is characterized in that step one 1) in 1g polyacrylonitrile powder is dissolved in 10mL dimethyl formamide solution, and heated and stirred 1h ~ 2h when temperature is 110 DEG C ~ 130 DEG C, obtain electrostatic spinning solution, this solution is transferred in the syringe of 10mL, again syringe is fixed on syringe pump, controlling electrostatic spinning voltage is 10KV ~ 20KV, reception device is 8cm ~ 12cm to the distance of spinning syringe needle, solution flow rate is 1mL/h ~ 2mL/h, in electrostatic spinning apparatus, carry out electrostatic spinning obtain polyacrylonitrile fibre.
3. the preparation method of a kind of zinc oxide nano-wire array/carbon nano-fiber composite material according to claim 1, it is characterized in that step one 2) in polyacrylonitrile fibre is placed in air dry oven, being warmed up to 270 DEG C ~ 290 DEG C with the speed of 1 DEG C/min, insulation 1h ~ 1.5h carries out stabilizing treatment.
4. the preparation method of a kind of zinc oxide nano-wire array/carbon nano-fiber composite material according to claim 1; it is characterized in that step one 3) in by step 2) polyacrylonitrile fibre after stabilizing treatment is placed in tubular type boiler tube central authorities; it is warmed up to 800 DEG C ~ 900 DEG C from room temperature with the speed of 3 DEG C/min ~ 8 DEG C/min under argon shield; and 80min ~ 100min it is incubated when temperature 800 DEG C ~ 900 DEG C; then furnace cooling is to room temperature; obtain carbon nano-fiber, step one 1) described in the flow velocity of argon be 400sccm.
5. the preparation method of a kind of zinc oxide nano-wire array/carbon nano-fiber composite material according to claim 1, it is characterised in that step one 4) in carbon nano-fiber that step 3) is obtained to cut into area be 1cm2~1.5cm2Sheet, then the carbon nano-fiber of well cutting is fixed on clean glass, have 70 μ L ~ 90 μ L's to make consumption by every square centimeter again, sample loading gun is utilized to be added drop-wise on the carbon nano-fiber on glass by zinc oxide seed layer solution, it is placed in insulation 60min ~ 90min when temperature is 230 DEG C ~ 280 DEG C again, obtains being prefabricated with the carbon nano-fiber/glass of zinc oxide seed layer；Step one 4) described in zinc oxide seed layer solution prepare according to the following steps: zinc acetate is dissolved in methanol, then with the rotating speed magnetic agitation 3min ~ 5min of 300r/min ~ 500r/min, obtaining zinc oxide seed layer solution, in wherein said zinc oxide seed layer solution, acetic acid zinc concentration is 0.005mol/L ~ 0.01mol/L.
6. the preparation method of a kind of zinc oxide nano-wire array/carbon nano-fiber composite material according to claim 1, it is characterised in that step 2 1) described in hydro-thermal reaction solution in nitric acid zinc concentration be 0.04mol/L ~ 0.06mol/L；The concentration of hexamethylenetetramine is 0.04mol/L ~ 0.06mol/L；The concentration of polymine is 0.001mol/L ~ 0.003mol/L；The concentration of ammonia is 0.3mol/L ~ 0.6mol/L.
7. the preparation method of a kind of zinc oxide nano-wire array/carbon nano-fiber composite material according to claim 1, it is characterized in that step 2 2) in by step 2 1) the hydro-thermal reaction solution that obtains pours in reactor, then by step one 4) it is prefabricated with the carbon nano-fiber of zinc oxide seed layer/glass and stands upside down in the mixed solution being positioned in reactor, cover reactor lid, 8h ~ 12h is reacted under the temperature conditions of 90 DEG C ~ 110 DEG C, then take out and naturally cool to room temperature in atmosphere, obtain composite, open reactor distilled water to be cleaned up by composite, and at 430 DEG C ~ 450 DEG C, it is incubated 1h ~ 1.5h, cool to room temperature with the furnace, namely zinc oxide nano-wire array/carbon nano-fiber composite material is obtained.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510607850.2A CN105712316B (en) | 2015-09-23 | 2015-09-23 | A kind of preparation of zinc oxide nano-wire array/carbon nano-fiber composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510607850.2A CN105712316B (en) | 2015-09-23 | 2015-09-23 | A kind of preparation of zinc oxide nano-wire array/carbon nano-fiber composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105712316A true CN105712316A (en) | 2016-06-29 |
| CN105712316B CN105712316B (en) | 2017-12-26 |
Family
ID=56144942
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510607850.2A Expired - Fee Related CN105712316B (en) | 2015-09-23 | 2015-09-23 | A kind of preparation of zinc oxide nano-wire array/carbon nano-fiber composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105712316B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107808956A (en) * | 2017-10-27 | 2018-03-16 | 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 |
| CN108956713A (en) * | 2018-06-29 | 2018-12-07 | 五邑大学 | ZnO/ carbon nanocoils sensitive material of propagation path horizontal distribution and preparation method thereof and high sensitivity sensor |
| CN109781822A (en) * | 2019-01-29 | 2019-05-21 | 哈尔滨医科大学 | A kind of zinc-oxide nano chip arrays/three-dimensional foam graphene biosensor working electrode and its preparation method and application |
| CN109859954A (en) * | 2019-03-07 | 2019-06-07 | 河北科技大学 | A kind of 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 |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
-
2015
- 2015-09-23 CN CN201510607850.2A patent/CN105712316B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107808956A (en) * | 2017-10-27 | 2018-03-16 | 哈尔滨理工大学 | A kind of preparation method of titanium niobium oxygen nanometer rods/carbon nanofiber arrays electrode |
| 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 |
| CN108956713A (en) * | 2018-06-29 | 2018-12-07 | 五邑大学 | ZnO/ carbon nanocoils sensitive material of propagation path horizontal distribution and preparation method thereof and high sensitivity sensor |
| 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 |
| CN109781822A (en) * | 2019-01-29 | 2019-05-21 | 哈尔滨医科大学 | A kind of zinc-oxide nano chip arrays/three-dimensional foam graphene biosensor working electrode and its preparation method and application |
| 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 |
| CN109859954A (en) * | 2019-03-07 | 2019-06-07 | 河北科技大学 | A kind of 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105712316B (en) | 2017-12-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105712316A (en) | Preparation method of zinc oxide nanowire array/carbon nanofiber composite material | |
| Siddheswaran et al. | Preparation and characterization of ZnO nanofibers by electrospinning | |
| CN102886270B (en) | SiC is nanocrystalline/Graphene hetero-junctions and preparation method and application | |
| Qiu et al. | Large-scale production of aligned long boron nitride nanofibers by multijet/multicollector electrospinning | |
| CN105329876B (en) | A kind of preparation method of boron, nitrogen co-doped carbon quantum dot | |
| Panapoy et al. | Electrical conductivity of PAN-based carbon nanofibers prepared by electrospinning method | |
| CN107235484B (en) | A method of graphene is prepared using black liquor rugose wood element | |
| CN107128926B (en) | Preparation method of self-supporting carbide derived carbon nanowire | |
| Chen et al. | High yield silicon carbide whiskers from rice husk ash and graphene: growth method and thermodynamics | |
| CN104891479A (en) | Plant-based graphene and preparation method thereof | |
| CN104495796B (en) | The method preparing porous class grapheme material for raw material with Herba Eichhorniae | |
| CN103724043B (en) | High thermal conductivity C/C composite and preparation method | |
| CN101786597B (en) | TiO2 nuclear shell structure nano rod array coated with carbon bed and preparation method thereof | |
| CN106276881B (en) | A kind of preparation method of graphene | |
| Qi et al. | Graphene nanocluster decorated niobium oxide nanofibers for visible light photocatalytic applications | |
| CN106847554A (en) | A kind of preparation method based on bacteria cellulose carrying nano silver line flexible electrode | |
| CN107119348B (en) | A kind of graphite fibre and preparation method thereof | |
| Yu et al. | Preparation and piezoelectric catalytic performance of flexible inorganic Ba 1− x Ca x TiO 3 via electrospinning | |
| Chen et al. | Hydrothermal synthesis and hydrogen sensing properties of nanostructured SnO2 with different morphologies | |
| CN103757748A (en) | Preparation of tubular zinc stannate (ZnSnO3) material by using electrostatic spinning process | |
| CN103408060B (en) | Method of preparing ZnO array on multi-structure polymer surface | |
| CN102992392B (en) | Preparation method of strontium-titanate hollow nanorod array | |
| CN112875685A (en) | Graphene generated in situ based on lignin and preparation method thereof | |
| CN105601278B (en) | The preparation and its application of hafnium carbide precursor maceration extract | |
| CN109763203B (en) | Preparation method of silicon carbide nanowires |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20171226 Termination date: 20180923 |