CN104671277B - Method for preparing zinc oxide composite material with high specific surface area and zinc oxide composite material - Google Patents
Method for preparing zinc oxide composite material with high specific surface area and zinc oxide composite material Download PDFInfo
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- CN104671277B CN104671277B CN201310626956.8A CN201310626956A CN104671277B CN 104671277 B CN104671277 B CN 104671277B CN 201310626956 A CN201310626956 A CN 201310626956A CN 104671277 B CN104671277 B CN 104671277B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention provides a method for preparing a zinc oxide composite material with a high specific surface area and the zinc oxide composite material. The method comprises the following steps: (1) preparing an electrostatic spinning solution for a zinc oxide nanofilm; (2) electrostatically spinning; and (3) calcining, namely, calcining a polyethylene polymer/zinc salt fiber film prepared in the step (2) and a substrate under the calcining conditions that the temperature is increased to 500-600 DEG C at a temperature-increasing rate of 2-10 DEG C per min and the constant-temperature time is 1-6 hours, and subsequently cooling to the room temperature to obtain the zinc oxide nanofilm which is formed by zinc oxide nanolines having hexagonal wurtzite crystalline phase; and (4) growing a zinc oxide nanorod array to prepare a composite material of a zinc oxide nanofilm-zinc oxide nanorod array. By virtue of the zinc oxide composite material, the specific surface area of the zinc oxide nanorod array in unit volume is increased.
Description
Technical field
The present invention relates to the preparation field of nano zine oxide, especially relate to a kind of zinc oxide composite wood of high-specific surface area
The preparation method of material and this zinc oxide composite.
Background technology
2006, mechanical energy was successfully turned in the range of nanoscale by georgia ,U.S.A Institute of Technology professor Wang Zhonglin etc.
Change electric energy into, develop generator-nano generator minimum in the world.The general principle of nano generator is：Work as nano wire
(NWs, such as zinc oxide nanowire) during dynamic tensile, generates piezoelectricity potential under external force in nano wire, corresponding transient current exists
Flow to balance fermi level in two ends.
The method of routine growth zinc oxide nanowire is chemically grown method, and such as hydro-thermal method makes zinc oxide nanowire exist
Metal level substrate surface growth with Seed Layer.In the past, in zinc oxide nanowire growth course, the gas of generation in nutrient solution
Bubble rises to solution surface and is often captured it is suppressed that zinc oxide nanowire is in large-area metal layer by face-down substrate surface
Homoepitaxial on substrate surface.
Content of the invention
The method of routine growth nano wire, such as hydro-thermal method, zinc oxide nanowire is in the metal level substrate surface orientation of growth
Degree is poor, and specific surface area is not high.Present invention solves the technical problem that be provide a kind of method preparing zinc oxide composite and
This zinc oxide composite, increased the specific surface area in zinc-oxide nano column array unit volume.
The present invention generates preparing zinc oxide nanometer film using method of electrostatic spinning in substrate, after calcining, fine on six sides generating
With every zinc oxide nanowire for axle growth of zinc oxide nano post to form oxidation on the preparing zinc oxide nanometer film surface of zinc ore crystalline phase
Zinc nano column array, this zinc-oxide nano column is the hexagon prism in (001) face advantage orientation.Zinc-oxide nano column due to synthesis
The ratio of width to height of (hexagon prism) is higher, can increase the specific surface area in zinc-oxide nano column array unit volume.Gained of the present invention
Zinc oxide can be used for LED, solar cell or photocatalytic surfaces etc..
In order to solve above-mentioned technical problem, the first technical scheme that the present invention adopts is：One kind prepares zinc oxide composite wood
The method of material, the method comprises the following steps：
(1) prepare preparing zinc oxide nanometer film electrostatic spinning liquid
Polyethylene based polymers are added in solvent, after polyethylene based polymers dissolving, in liquid, add zinc salt,
Then mix and obtain electrostatic spinning liquid；Wherein, the weight of polyethylene based polymers and zinc salt is than for 1-5：0.5-3；
(2) electrostatic spinning
Step (1) gained electrostatic spinning liquid is added in electrostatic spinning apparatus, then electrostatic spinning liquid is expelled to base
Carry out electrostatic spinning on bottom, polyethylene based polymers/zinc salt tunica fibrosa fibre spinning is obtained on substrate；
(3) calcine
Step (2) gained polyethylene based polymers/zinc salt tunica fibrosa is calcined together with substrate, calcination condition
For：Heating rate according to 2-10 DEG C/min is warming up to 500-600 DEG C, calcining at constant temperature 1-6 hour；Then it is cooled to room temperature, obtain
To preparing zinc oxide nanometer film, described preparing zinc oxide nanometer film is made up of the zinc oxide nanowire of six side buergerite crystalline phases；And
(4) growth of zinc oxide nano post array
With step (3) gained preparing zinc oxide nanometer film as Seed Layer, described Seed Layer with every zinc oxide nanowire is
Axle, growth of zinc oxide nano post, to form zinc-oxide nano column array, obtains preparing zinc oxide nanometer film-zinc-oxide nano column array
Composite.
The aforesaid method preparing zinc oxide composite, in step (1), described zinc salt is zinc acetate, zinc nitrate, oxalic acid
Zinc and their hydrate；Described solvent is NMF (DMF), ethanol (ethanol) or oxolane (THF)；Described
Polyethylene based polymers are polyvinyl alcohol (PVA) or polyvinylpyrrolidone (PVP).
The aforesaid method preparing zinc oxide composite, in step (1), doping oxide or gold in electrostatic spinning liquid
Belong to, oxide is Al2O3Or SnO2, metal is Ag, Au, Pt or Cu.
The aforesaid method preparing zinc oxide composite, in step (2), is 10kV-20kV in voltage, receiving range is
8cm-20cm, under the conditions of driving velocity 0.1ml/hr-1ml/hr, electrostatic spinning liquid is expelled in substrate and carries out electrostatic spinning.
The aforesaid method preparing zinc oxide composite, the spinning time is 30 seconds to 10 minutes.
The aforesaid method preparing zinc oxide composite, in step (3), described zinc oxide nanowire a diameter of
200nm-300nm.
The aforesaid method preparing zinc oxide composite, in step (4), using hydrothermal synthesis method or microwave heating method,
In the zinc solution containing hydrogen-oxygen, with every zinc oxide nanowire for axle growth of zinc oxide nano post to form zinc-oxide nano
Post array.
The aforesaid method preparing zinc oxide composite, the described zinc solution containing hydrogen-oxygen is zinc acetate, zinc nitrate
Or the aqueous solution of zinc oxalate；Hydrogen-oxygen used is NaOH, ammoniacal liquor, ammonium carbonate or hexa.
The aforesaid method preparing zinc oxide composite, in step (4), described hydrothermal synthesis method is：At 80-100 DEG C
Under, in the zinc solution containing hydrogen-oxygen, with every zinc oxide nanowire for axle growth of zinc oxide nano post 2-12 hour.
The aforesaid method preparing zinc oxide composite, in step (4), described zinc-oxide nano column is that (001) face is excellent
The hexagon prism of gesture orientation, described hexagon prism cross section Breadth Maximum is 200nm-300nm, and hexagon prism height is 2-3 μm.
The aforesaid method preparing zinc oxide composite, the thickness of described zinc oxide composite is 5-8 μm.
The aforesaid method preparing zinc oxide composite, in step (2), the method also includes obtaining fibre spinning orderly
Polyethylene based polymers/zinc salt the tunica fibrosa of arrangement.
The aforesaid method preparing zinc oxide composite, before electrostatic spinning, places the substrate above the accommodating cavity of carrier
In；Wherein, this carrier includes first vector ground, is arranged on the Second support ground and the 3rd of first vector ground one side surface
Carrier substrate, Second support ground and the setting of the 3rd carrier substrate parallel, spaced-apart, are provided with the first gold medal on Second support ground
Belong to bar, the 3rd carrier substrate is provided with the second bonding jumper, the first bonding jumper is be arranged in parallel with the second bonding jumper；Second support bottom
Form accommodating cavity between material and the first bonding jumper, and the 3rd carrier substrate and the second bonding jumper.
The aforesaid method preparing zinc oxide composite, described first bonding jumper and material used by the second bonding jumper are aluminium
Paper tinsel, Copper Foil, aluminium flake or copper sheet；Described first vector ground, Second support ground and material used by the 3rd carrier substrate are insulation
Material, such as glass.
The aforesaid method preparing zinc oxide composite, described preparing zinc oxide nanometer film is by the oxidation of six side buergerite crystalline phases
The parallel composition of zinc nano wire.
The aforesaid method preparing zinc oxide composite, every cu μ m preparing zinc oxide nanometer film is averagely aoxidized by 2-3 root
Zinc nano wire is constituted, and zinc-oxide nano column is entwined each other.
The present invention provide the second technical scheme be：A kind of zinc oxide composite, is made using any of the above-described method.
The present invention provide the 3rd technical scheme be：A kind of zinc oxide composite, including preparing zinc oxide nanometer film and oxidation
Zinc nano column array；Described preparing zinc oxide nanometer film is made up of the zinc oxide nanowire of six side buergerite crystalline phases, zinc-oxide nano column
Grown for axle with every zinc oxide nanowire, constitute described zinc-oxide nano column array, described zinc-oxide nano column is (001) face
The hexagon prism of advantage orientation.
Aforesaid zinc oxide composite, described hexagon prism cross section Breadth Maximum is 200-300nm, and hexagon prism height is
2-3μm.
Aforesaid zinc oxide composite, a diameter of 200-300nm of described zinc oxide nanowire.
Aforesaid zinc oxide composite, described preparing zinc oxide nanometer film via calcining electrostatic spinning polyethylene based polymers/
Zinc salt tunica fibrosa is made.
Aforesaid zinc oxide composite, the thickness of described zinc oxide composite is 5-8 μm.
Aforesaid zinc oxide composite, described preparing zinc oxide nanometer film by six side buergerite crystalline phases zinc oxide nanowire
Parallel composition.
Aforesaid zinc oxide composite, every cu μ m preparing zinc oxide nanometer film is averagely by 2-3 root zinc oxide nanowire structure
Become, zinc-oxide nano column is entwined each other.
Gained zinc oxide composite of the present invention, in the preparing zinc oxide nanometer film Seed Layer through being sintered into six side buergerite crystalline phases
On, with the zinc oxide nanowire of every for axle growth of zinc oxide nano post to form zinc-oxide nano column array, zinc-oxide nano
Post grows into the hexagon prism of (001) face advantage orientation.Because the ratio of width to height of synthesizing zinc oxide nano-pillar is higher, unit can be increased
Surface area in volume.Gained zinc oxide composite of the present invention can be used for LED based on ZnO, solar cell, light are urged
Change surface etc..Zinc oxide composite preparation process is simple of the present invention.
Brief description
Fig. 1 is the preparing zinc oxide nanometer film XRD spectra that electrostatic spinning is made up of zinc oxide nanowire after calcining, wherein aoxidizes
Zinc is deposited on gold-plated silicon.
Fig. 2 is the preparing zinc oxide nanometer film that the first specific embodiment electrostatic spinning is made up of zinc oxide nanowire after calcining
Shape appearance figure under light microscope (1000 times).
Fig. 3 is the preparing zinc oxide nanometer film that the first specific embodiment electrostatic spinning is made up of zinc oxide nanowire after calcining
Shape appearance figure under SEM (10000 times).
Fig. 4 is the carrier schematic diagram of substrate used by the present invention second specific embodiment.
Fig. 5 is the carrier generalized section of substrate used by the present invention second specific embodiment.
Fig. 6 is the process carrying out electrostatic spinning on the carrier of substrate used by the present invention second specific embodiment.
Fig. 7 is the state after completing electrostatic spinning on the carrier of substrate used by the present invention second specific embodiment.
Fig. 8 is the process taking off substrate from the carrier of substrate used by the present invention second specific embodiment.
Fig. 9 be the present invention the second specific embodiment electrostatic spinning calcining before have orientation preparing zinc oxide nanometer film in optics
Pattern under microscope (1000 times).
Figure 10 is the present invention second specific embodiment growth of zinc oxide nano on the preparing zinc oxide nanometer film have orientation
Pattern under SEM (500 times) for the preparing zinc oxide nanometer film that the post obtains-zinc-oxide nano column array composite.
Figure 11 is the present invention second specific embodiment growth of zinc oxide nano on the preparing zinc oxide nanometer film have orientation
Pattern under SEM (2000 times) for the preparing zinc oxide nanometer film that the post obtains-zinc-oxide nano column array composite.
Figure 12 is the present invention second specific embodiment growth of zinc oxide nano on the preparing zinc oxide nanometer film have orientation
Pattern under SEM (10000 times) for the preparing zinc oxide nanometer film that the post obtains-zinc-oxide nano column array composite.
Specific embodiment
For being fully understood by purpose, feature and effect of the present invention, by following specific embodiments, the present invention is done in detail
Describe in detail bright.
The first specific embodiment the following detailed description of the present invention once.
A kind of method preparing zinc oxide composite, the method comprises the following steps：
(1) prepare preparing zinc oxide nanometer film electrostatic spinning liquid
Polyethylene based polymers are added in solvent, after polyethylene based polymers dissolving, in liquid, add zinc salt,
Then mix and obtain electrostatic spinning liquid.Wherein, the weight of polyethylene based polymers and zinc salt is than for 1-5：0.5-3.For example,
Add 1-5g polyethylene based polymers in every 10ml solvent, in mixed solution, then add zinc salt, the mixed solution of every 10ml
Add 0.5-3g zinc salt.
Described zinc salt can be zinc acetate, zinc nitrate, zinc oxalate and their hydrate.Described solvent can be methyl first
Acid amides (DMF), ethanol (ethanol) or oxolane (THF).Described polyethylene based polymers can be polyvinyl alcohol (PVA)
Or polyvinylpyrrolidone (PVP).
Preferably, in this step, in electrostatic spinning liquid doping oxide or metal to promote zinc oxide in certain party
The performance in face, oxide can be Al2O3Or SnO2, metal can be Ag, Au, Pt or Cu.
(2) electrostatic spinning
Step (1) gained electrostatic spinning liquid is added in electrostatic spinning apparatus, then electrostatic spinning liquid is expelled to base
Carry out electrostatic spinning on bottom, polyethylene based polymers/zinc salt tunica fibrosa is obtained on substrate.
Electrostatic spinning apparatus used by the present invention are conventional commercial electrostatic spinning apparatus.Specifically, by step (1) gained electrostatic
Spinning solution is added in the liquid dispensing apparatus such as injection needle of electrostatic spinning apparatus, and syringe needle is metal such as stainless steel, and syringe needle is connect
High-voltage power supply, receiving terminal is grounded.Then it is 10kV-20kV in voltage, under the conditions of receiving range is 8cm-20cm, with micro pump to push away
Dynamic speed 0.1ml/hr-1ml/hr, electrostatic spinning liquid is expelled in substrate by injection apparatus and carries out electrostatic spinning, in substrate
Upper acquisition polyethylene based polymers/zinc salt tunica fibrosa.
The present invention does not have particular/special requirement to substrate, and conventional substrate all can apply to the present invention, for example gold-plated silicon.
(3) calcine
Step (2) gained polyethylene based polymers/zinc salt fiber membrane is calcined together with substrate, calcination condition
For：Heating rate according to 2-10 DEG C/min is warming up to 500-600 DEG C, calcining at constant temperature 1-6 hour；Then it is cooled to room temperature, obtain
To preparing zinc oxide nanometer film.
Gained preparing zinc oxide nanometer film is made up of the zinc oxide nanowire of six side buergerite crystalline phases, this zinc oxide nanowire straight
Footpath is 200nm-300nm.
It is the preparing zinc oxide nanometer film that this step of a preferred embodiment of the invention is made up of zinc oxide nanowire shown in Fig. 1
XRD spectra.ZnO is six side buergerite crystalline phases as seen from Figure 1, and peak the strongest is 001 face.Fig. 2 is a preferred embodiment
Shape appearance figure under the preparing zinc oxide nanometer film light microscope (1000 times) that this step is made up of zinc oxide nanowire.Fig. 3 is one
Shape appearance figure under the preparing zinc oxide nanometer film SEM (10000 times) that this step of preferred embodiment is made up of zinc oxide nanowire.By Fig. 2
With Fig. 3 it can be seen that preparing zinc oxide nanometer film of the present invention is made up of zinc oxide nanowire.Can be seen that nano-pillar is hexagonal by SEM figure
Post shapes, it can be seen that zinc oxide growth is (001) face advantage orientation.
(4) growth of zinc oxide nano post array
With step (3) gained preparing zinc oxide nanometer film as Seed Layer, in described Seed Layer, growth of zinc oxide nano post is with shape
Become zinc oxide nano array, obtain the composite of preparing zinc oxide nanometer film-zinc-oxide nano column array.The present invention adopts hydro-thermal to close
One-tenth method or microwave heating method, growth of zinc oxide nano post in the zinc solution containing hydrogen-oxygen.
Hydrothermal synthesis method is a kind of method of hydro-thermal method synthesizing zinc oxide nanometer stick array.Specifically described containing hydrogen-oxygen
Zinc solution is the aqueous solution of zinc acetate, zinc nitrate or zinc oxalate；Hydrogen-oxygen used is NaOH, ammoniacal liquor, ammonium carbonate or six
Methenamine.Zinc salt is added in the container (sealed bottle or water heating kettle) equipped with deionized water, then reinjects part and go
Ionized water, the concentration of zinc salt is 5～50mM (mM every liter).Add hydrogen-oxygen (as instilled ammoniacal liquor) to mix after zinc salt dissolving
Close uniformly, then at 80-100 DEG C, (for example utilize baking oven), step (3) gained preparing zinc oxide nanometer film is placed in containing hydrogen-oxygen
In zinc solution, zinc-oxide nano column is made to grow 2-12 hour.
This step gained zinc-oxide nano column is the hexagon prism of (001) face advantage orientation, and described hexagon prism cross section is maximum
Width is 200-300nm, and hexagon prism height is 2-3 μm.
Zinc oxide composite is obtained according to said method, this zinc oxide composite includes preparing zinc oxide nanometer film and oxygen
Change zinc nano column array, zinc-oxide nano column vertical-growth constitutes described oxidation on a side surface of described preparing zinc oxide nanometer film
Zinc nano column array, described zinc-oxide nano column is the hexagon prism of (001) face advantage orientation.Described preparing zinc oxide nanometer film is by six sides
The zinc oxide nanowire of buergerite crystalline phase is constituted, a diameter of 200-300nm of described zinc oxide nanowire, and gained zinc oxide is combined
The thickness of material is 5-8 μm.
Gained zinc oxide composite of the present invention, in the preparing zinc oxide nanometer film Seed Layer through being sintered into six side buergerite crystalline phases
To form zinc-oxide nano column array, zinc-oxide nano column grows into (001) face advantage orientation to upper growth of zinc oxide nano post
Hexagon prism.Because the ratio of width to height of synthesizing zinc oxide nano-pillar is higher, the surface area in unit volume can be increased.
The present invention is in order to obtain, by the parallel preparing zinc oxide nanometer film constituting of zinc oxide nanowire of six side buergerite crystalline phases, adopting
With the second specific embodiment.The following detailed description of the second specific embodiment.
This embodiment has the electrostatic spinning steps different from above-mentioned first embodiment, also includes obtaining fibre spinning
The polyethylene based polymers of ordered arrangement/zinc salt tunica fibrosa.Before electrostatic spinning, by substrate 6 be placed on carrier (as Fig. 4 and
Shown in Fig. 5) accommodating cavity in.This carrier includes first vector ground 1, is arranged on the second load of first vector ground one side surface
Body ground 2 and the 3rd carrier substrate 3, Second support ground 2 and the setting of the 3rd carrier substrate 3 parallel, spaced-apart.In Second support
Ground 2 is provided with the first bonding jumper 4, and the first bonding jumper 4 sets along Second support ground 2 side parallel with the 3rd carrier substrate
Put.Second bonding jumper 5 is provided with the 3rd carrier substrate 3, the second bonding jumper 5 is along the 3rd carrier substrate 3 and Second support bottom
The parallel side setting of material 2.Second support ground 2 and the first bonding jumper 4, shape and the 3rd carrier substrate 3 and the second bonding jumper 5 between
Become accommodating cavity.
Fig. 6 is the process that this embodiment carries out electrostatic spinning, is ejected into electrostatic spinning liquid via electrospinning device 7
In substrate 6, form zinc oxide nanowire 8.Fig. 7 is the state after this embodiment completes electrostatic spinning.Fig. 8 is this embodiment
The process of substrate is taken off from carrier.Can be seen that by Fig. 6-Fig. 8 preparing zinc oxide nanometer film can be constituted by zinc oxide nanowire is parallel.
In this embodiment, every cu μ m preparing zinc oxide nanometer film is averagely made up of 2-3 root zinc oxide nanowire, zinc-oxide nano column that
This entwines.For example, the total surface area of preparing zinc oxide nanometer film is 4.15 μm2, averagely have in every cu μ m preparing zinc oxide nanometer film
2.56 root zinc oxide nanowire.
In electrostatic spinning, injection head connects positive electricity, and the metal strips for grounding on carrier, thus produce an electricity in-between
?.And electrostatic spinning itself can be considered as the fiber of positively charged, stress is deposited on the carrier of ground connection under the electric field.Work as spinning
Move to bonding jumper neighbouring when, electrically contrary due to both, in the presence of Coulomb force, two ends on bonding jumper for the spinning
By maximum Coulomb force attraction, therefore pull the two ends of spinning and make it vertical with the direction of bonding jumper.On the other hand, different
In the part on bonding jumper, the spinning between bonding jumper can positively charged.Coulomb repulsion between due to spinning and strengthen spinning
Between ordered arrangement.
Described first bonding jumper and material used by the second bonding jumper are aluminium foil, Copper Foil, aluminium flake or copper sheet；Described first vector
Ground, Second support ground and material used by the 3rd carrier substrate are isolation material, such as glass.
Step (1) gained electrostatic spinning liquid is added in electrostatic spinning apparatus, then electrostatic spinning liquid is ejected into and puts
Put and carry out electrostatic spinning in the substrate in the accommodating cavity of carrier, polyethylene based polymers/zinc salt tunica fibrosa is obtained on substrate.
After calcining, gained preparing zinc oxide nanometer film is constituted by the zinc oxide nanowire of six side buergerite crystalline phases is parallel.Aoxidize in present embodiment
Zinc nanometer film has certain orientation so that the zinc-oxide nano column being grown on zinc oxide nanowire more has order, obtains
The specific surface area arriving is bigger.That is, when with parallel silk for Seed Layer, because the density of parallel silk is very high, Hydrothermal Synthesiss
The zinc-oxide nano column of method synthesis is entwined each other and makes surface become orderly zinc oxide carpet.The zinc oxide of this specific embodiment
Composite specific surface area is bigger.Carry out electrostatic spinning preparation polyethylene based polymers/zinc salt tunica fibrosa using this carrier, have
Process is simple, repeatability is high, and preparation every time only need to change substrate, and the polyethylene based polymers/zinc salt tunica fibrosa of preparation has
Sequence is high, through calcining rear oxidation zinc nano wire arranged in parallel so that the zinc-oxide nano column growing thereon has bigger ratio
Surface area.
To illustrate the enforcement of the method for the present invention below by specific embodiment, skilled artisan would appreciate that
It is that this is understood not to the restriction to scope of the invention as claimed.
Embodiment 1
The thickness of composite material of the present embodiment gained preparing zinc oxide nanometer film-zinc-oxide nano column array is 5 μm, constitutes oxidation
The a diameter of 300nm of zinc oxide nanowire of zinc nanometer film, zinc-oxide nano column a size of diameter 300nm, highly 2 μm.
The preparation method of this composite is described below
(1) prepare preparing zinc oxide nanometer film electrostatic spinning liquid
22.7g polyvinylpyrrolidone (PVP, molecular weight 1.3M) is slowly added in 10ml NMF (DMF),
After polyvinylpyrrolidone dissolving, it is slow added into 0.9g zinc acetate, then mixes and obtain electrostatic spinning liquid.
(2) electrostatic spinning
Step (1) gained electrostatic spinning liquid is added in injection needle, syringe needle (stainless steel) connects high-voltage power supply, receives termination
Ground.Then it is 15kV in voltage, under the conditions of receiving range is 14cm, with micro pump with driving velocity 0.5ml/hr, by Static Spinning
Silk liquid is expelled to and carries out electrostatic spinning on the gold-plated silicon of substrate, obtains PVP/ zinc salt tunica fibrosa in substrate.
(3) calcine
Step (2) gained fiber membrane is calcined in high temperature furnace together with substrate, calcination condition is：According to 10
DEG C/heating rate of min is warming up to 500 DEG C, calcining at constant temperature 1 hour；Then it is cooled to room temperature, obtain preparing zinc oxide nanometer film.
It is the preparing zinc oxide nanometer film XRD spectra that this step is made up of zinc oxide nanowire shown in Fig. 1.As seen from Figure 1
ZnO is six side buergerite crystalline phases, and peak the strongest is 001 face.Fig. 2 is the zinc-oxide nano that this step is made up of zinc oxide nanowire
Shape appearance figure under film light microscope (1000 times).Fig. 3 is the preparing zinc oxide nanometer film SEM that this step is made up of zinc oxide nanowire
Shape appearance figure under (10000 times).Can be seen that preparing zinc oxide nanometer film is made up of zinc oxide nanowire by Fig. 2 and Fig. 3.Gained aoxidizes
Zinc nanometer film is made up of the zinc oxide nanowire of six side buergerite crystalline phases, a diameter of 300nm of this zinc oxide nanowire.
(4) growth of zinc oxide nano post array
0.238g zinc nitrate is added in the sealed bottle equipped with 250ml deionized water, then reinjects 40ml deionization
Water, instills 1ml ammoniacal liquor (percentage by weight is 25%) after zinc nitrate dissolving again and mixes, then at 90 DEG C in an oven
Reaction 5 hours, makes zinc-oxide nano column grow.
This step gained zinc-oxide nano column is the hexagon prism of (001) face advantage orientation, and described hexagon prism cross section is maximum
Width is 300nm, and hexagon prism height is 2 μm.
Embodiment 2
The thickness of composite material of the present embodiment gained preparing zinc oxide nanometer film-zinc-oxide nano column array is 8 μm, constitutes oxidation
The a diameter of 300nm of zinc oxide nanowire of zinc nanometer film, zinc-oxide nano column a size of diameter 300nm, highly 2 μm.Say below
The preparation method of this composite bright
(1) prepare preparing zinc oxide nanometer film electrostatic spinning liquid
22.7g polyvinylpyrrolidone (PVP, molecular weight 1.3M) is slowly added in 10ml NMF (DMF),
After polyvinylpyrrolidone dissolving, it is slow added into 0.9g zinc acetate, then mixes and obtain electrostatic spinning liquid.
(2) electrostatic spinning
Step (1) gained electrostatic spinning liquid is added in injection needle, syringe needle (stainless steel) connects high-voltage power supply, receives termination
Ground.Then it is 15kV in voltage, under the conditions of receiving range is 14cm, with micro pump with driving velocity 0.5ml/hr, by Static Spinning
Silk liquid is expelled to and carries out electrostatic spinning on the gold-plated silicon of substrate, obtains PVP/ zinc salt tunica fibrosa in substrate.
(3) calcine
Step (2) gained fiber membrane is calcined in high temperature furnace together with substrate, calcination condition is：According to 5
DEG C/heating rate of min is warming up to 600 DEG C, calcining at constant temperature 2 hours；Then it is cooled to room temperature, obtain preparing zinc oxide nanometer film.
Via XRD detection it can be seen that preparing zinc oxide nanometer film is made up of zinc oxide nanowire.Gained preparing zinc oxide nanometer film by
The zinc oxide nanowire of six side buergerite crystalline phases is constituted, a diameter of 300nm of this zinc oxide nanowire.
(4) growth of zinc oxide nano post array
0.238g zinc nitrate is added in the sealed bottle equipped with 250ml deionized water, then reinjects 40ml deionization
Water, instills 1ml ammoniacal liquor (percentage by weight 28%) again after zinc nitrate dissolving and mixes, then anti-in an oven at 90 DEG C
Answer 5 hours, so that zinc-oxide nano column is grown.
This step gained zinc-oxide nano column is the hexagon prism of (001) face advantage orientation, and described hexagon prism cross section is maximum
Width is 300nm, and hexagon prism height is 2 μm.
Comparative example 1
This comparative example gained thickness of composite material is 1.5 μm, and the zinc oxide nanowire constituting preparing zinc oxide nanometer film is a diameter of
120nm, zinc-oxide nano column a size of diameter 120nm, highly 0.8 μm.The preparation method of this composite is described below
(1) prepare preparing zinc oxide nanometer film electrostatic spinning liquid
22.7g polyvinylpyrrolidone (PVP, molecular weight 1.3M) is slowly added in 10ml NMF (DMF),
After polyvinylpyrrolidone dissolving, it is slow added into 0.9g zinc acetate, then mixes and obtain electrostatic spinning liquid.
(2) electrostatic spinning
Step (1) gained electrostatic spinning liquid is added in injection needle, syringe needle (stainless steel) connects high-voltage power supply, receives termination
Ground.Then it is 15kV in voltage, under the conditions of receiving range is 14cm, with micro pump with driving velocity 0.5ml/hr, by Static Spinning
Silk liquid is expelled to and carries out electrostatic spinning on the gold-plated silicon of substrate, obtains PVP/ zinc salt tunica fibrosa in substrate.
(3) calcine
Step (2) gained fiber membrane is calcined in high temperature furnace together with substrate, calcination condition is：According to 2
DEG C/heating rate of min is warming up to 450 DEG C, calcining at constant temperature 3 hours；Then it is cooled to room temperature, obtain preparing zinc oxide nanometer film.
(4) growth of zinc oxide nano post array
0.238g zinc nitrate is added in the sealed bottle equipped with 250ml deionized water, then reinjects 40ml deionization
Water, instills 1ml ammoniacal liquor (percentage by weight 28%) again after zinc nitrate dissolving and mixes, then anti-in an oven at 90 DEG C
Answer 5 hours, so that zinc-oxide nano column is grown.
In this comparative example ZnO/PVP composite cellulosic membrane, PVP incomplete combustion, spinning may still have the presence of PVP, causes
Zinc oxide crystallite grain in spinning cannot be assembled and grow up, and reduce the crystallinity of zinc oxide.Cause the oxygen growing thereon
The density changing zinc nano-pillar declines, and crystal column is less, and crystal face preferred orientation changes etc..
Comparative example 2
This comparative example gained thickness of composite material is 1.3 μm, and the zinc oxide nanowire constituting preparing zinc oxide nanometer film is a diameter of
150nm, zinc-oxide nano column a size of 150nm, highly 1 μm.The preparation method of this composite is described below
(1) prepare preparing zinc oxide nanometer film electrostatic spinning liquid
22.7g polyvinylpyrrolidone (PVP, molecular weight 1.3M) is slowly added in 10ml NMF (DMF),
After polyvinylpyrrolidone dissolving, it is slow added into 0.9g zinc acetate, then mixes and obtain electrostatic spinning liquid.
(2) electrostatic spinning
Step (1) gained electrostatic spinning liquid is added in injection needle, syringe needle (stainless steel) connects high-voltage power supply, receives termination
Ground.Then it is 15kV in voltage, under the conditions of receiving range is 14cm, with micro pump with driving velocity 0.5ml/hr, by Static Spinning
Silk liquid is expelled to and carries out electrostatic spinning on the gold-plated silicon of substrate, obtains PVP/ zinc salt tunica fibrosa in substrate.
(3) calcine
Step (2) gained tunica fibrosa is calcined in high temperature furnace together with substrate, calcination condition is：According to 2 DEG C/
The heating rate of min is warming up to 650 DEG C, calcining at constant temperature 3 hours；Then it is cooled to room temperature, obtain preparing zinc oxide nanometer film.
(4) growth of zinc oxide nano post array
0.238g zinc nitrate is added in the sealed bottle equipped with 250ml deionized water, then reinjects 40ml deionization
Water, instills 1ml ammoniacal liquor (percentage by weight 28%) again after zinc nitrate dissolving and mixes, then anti-in an oven at 90 DEG C
Answer 5 hours, so that zinc-oxide nano column is grown.
This comparative example is more than the preparing zinc oxide nanometer film of 600 DEG C of calcining gained, and zinc oxide grain becomes big, in identical hydro-thermal method
Under the conditions of the ZnO nano post that grows thereon larger, therefore can affect specific surface area.
Embodiment 3
The thickness of composite material of the present embodiment gained preparing zinc oxide nanometer film-zinc-oxide nano column array is 6 μm, zinc oxide nano
Rice film thickness is 200nm, zinc-oxide nano column a size of diameter 200nm, highly 2 μm.The preparation of this composite is described below
Method
(1) prepare preparing zinc oxide nanometer film electrostatic spinning liquid
22.7g polyvinylpyrrolidone (PVP, molecular weight 1.3M) is slowly added in 10ml NMF (DMF),
After polyvinylpyrrolidone dissolving, it is slow added into 0.9g zinc acetate, then mixes and obtain electrostatic spinning liquid.
(2) electrostatic spinning
Step (1) gained electrostatic spinning liquid is added in injection needle, syringe needle (stainless steel) connects high-voltage power supply, receives termination
Ground.Silicon gold-plated for substrate is placed in the accommodating cavity of carrier as shown in Figure 4 and Figure 5.
It is 15kV in voltage, under the conditions of receiving range is 14cm, with micro pump with driving velocity 0.5ml/hr, by Static Spinning
Silk liquid is expelled to and carries out electrostatic spinning on the gold-plated silicon of substrate, obtains PVP/ zinc salt tunica fibrosa in substrate.Fig. 9 is to take
Pattern under light microscope (1000 times) for the tropism preparing zinc oxide nanometer film.
(3) calcine
Step (2) gained tunica fibrosa is calcined in high temperature furnace together with substrate, calcination condition is：According to 10
DEG C/heating rate of min is warming up to 500 DEG C, calcining at constant temperature 1 hour；Then it is cooled to room temperature, obtain preparing zinc oxide nanometer film.
Gained preparing zinc oxide nanometer film is constituted by the zinc oxide nanowire of six side buergerite crystalline phases is parallel, this zinc oxide nanowire
A diameter of 200nm.
(4) growth of zinc oxide nano post array
0.238g zinc nitrate is added in the sealed bottle equipped with 250ml deionized water, then reinjects 40ml deionization
Water, instills 1ml ammoniacal liquor (percentage by weight 28%) again after zinc nitrate dissolving and mixes, then anti-in an oven at 90 DEG C
Answer 5 hours, so that zinc-oxide nano column is grown.
This step gained zinc-oxide nano column is the hexagon prism of (001) face advantage orientation, and described hexagon prism cross section is maximum
Width is 200nm.Hexagon prism height is 2 μm.Figure 10 is that this embodiment grows oxidation on the preparing zinc oxide nanometer film have orientation
Pattern under SEM (500 times) for the preparing zinc oxide nanometer film that the zinc nano-pillar obtains-zinc-oxide nano column array composite.Figure 11
It is preparing zinc oxide nanometer film-zinc oxide that this embodiment growth of zinc oxide nano post on the preparing zinc oxide nanometer film have orientation obtains
Pattern under SEM (2000 times) for the nano column array composite.Figure 12 is that this embodiment is having the zinc-oxide nano of orientation
The preparing zinc oxide nanometer film that on film, growth of zinc oxide nano post obtains-zinc-oxide nano column array composite is at SEM (10000 times)
Under pattern.
The present invention generates preparing zinc oxide nanometer film using method of electrostatic spinning-calcining in substrate, and this preparing zinc oxide nanometer film is by six
The zinc oxide nanowire of side buergerite crystalline phase is constituted, can be unordered can also be parallel.Then in preparing zinc oxide nanometer film
With every zinc oxide nanowire for axle growth of zinc oxide nano post to form zinc-oxide nano column array on surface, this zinc oxide nano
Meter Zhu is the hexagon prism in (001) face advantage orientation.Because the ratio of width to height of the zinc-oxide nano column (hexagon prism) of synthesis is higher, can
To increase the specific surface area in zinc-oxide nano column array unit volume.Gained zinc oxide of the present invention can be used for LED, solar energy
Battery or photocatalytic surfaces etc..
Claims (19)
1. a kind of method preparing zinc oxide composite, the method comprises the following steps：
(1) prepare preparing zinc oxide nanometer film electrostatic spinning liquid
Polyethylene based polymers are added in solvent, after polyethylene based polymers dissolving, add zinc salt in liquid, then
Mix and obtain electrostatic spinning liquid；Wherein, the weight of polyethylene based polymers and zinc salt is than for 1-5：0.5-3；
(2) electrostatic spinning
Step (1) gained electrostatic spinning liquid is added in electrostatic spinning apparatus, then electrostatic spinning liquid is expelled in substrate
Carry out electrostatic spinning, polyethylene based polymers/zinc salt tunica fibrosa is obtained on substrate；
(3) calcine
Step (2) gained polyethylene based polymers/zinc salt tunica fibrosa is calcined together with substrate, calcination condition is：Press
Heating rate according to 2-10 DEG C/min is warming up to 500-600 DEG C, calcining at constant temperature 1-6 hour；Then it is cooled to room temperature, aoxidized
Zinc nanometer film, described preparing zinc oxide nanometer film is made up of the zinc oxide nanowire of six side buergerite crystalline phases；And
(4) growth of zinc oxide nano post array
With step (3) gained preparing zinc oxide nanometer film as Seed Layer, with every zinc oxide nanowire as axle in described Seed Layer, raw
Long zinc-oxide nano column, to form zinc-oxide nano column array, obtains the compound of preparing zinc oxide nanometer film-zinc-oxide nano column array
Material；
Wherein, before electrostatic spinning, place the substrate above in the accommodating cavity of carrier；Wherein, this carrier includes first vector ground,
It is arranged on Second support ground and the 3rd carrier substrate, Second support ground and the 3rd carrier of first vector ground one side surface
Ground parallel, spaced-apart is arranged, and is provided with the first bonding jumper, is provided with the second gold medal in the 3rd carrier substrate on Second support ground
Belong to bar, the first bonding jumper is be arranged in parallel with the second bonding jumper；Second support ground and the first bonding jumper, with the 3rd carrier substrate and
Form accommodating cavity between second bonding jumper.
2. the method preparing zinc oxide composite according to claim 1 is it is characterised in that in step (1), described zinc
Salt is zinc acetate, zinc nitrate, zinc oxalate and their hydrate；Described solvent is NMF DMF, ethanol ethanol or
Tetrahydrofuran THF；Described polyethylene based polymers are PVAC polyvinylalcohol or polyvinylpyrrolidone PVP.
3. the method preparing zinc oxide composite according to claim 1 and 2 is it is characterised in that in step (1),
Doping oxide or metal in electrostatic spinning liquid, oxide is Al2O3Or SnO2, metal is Ag, Au, Pt or Cu.
4. the method preparing zinc oxide composite according to claim 1 is it is characterised in that in step (2), in voltage
For 10kV-20kV, receiving range is 8cm-20cm, under the conditions of driving velocity 0.1ml/hr-1ml/hr, electrostatic spinning liquid is injected
Electrostatic spinning is carried out on substrate.
5. the method preparing zinc oxide composite according to claim 4 it is characterised in that the spinning time arrived for 30 seconds
10 minutes.
6. the method preparing zinc oxide composite according to claim 1 is it is characterised in that in step (3), described oxygen
Change a diameter of 200nm-300nm of zinc nano wire.
7. the method preparing zinc oxide composite according to claim 1 is it is characterised in that in step (4), using water
Thermal synthesis method or microwave heating method, in the zinc solution containing hydrogen-oxygen, with every zinc oxide nanowire for axle developing zinc oxide
Nano-pillar is to form zinc-oxide nano column array.
8. the method preparing zinc oxide composite according to claim 7 is it is characterised in that the described zinc containing hydrogen-oxygen
Salting liquid is the aqueous solution of zinc acetate, zinc nitrate or zinc oxalate；Hydrogen-oxygen used is that NaOH, ammoniacal liquor, ammonium carbonate or six are sub-
Tetramine.
9. the method preparing zinc oxide composite according to claim 8 is it is characterised in that in step (4), described water
Thermal synthesis method is：At 80-100 DEG C, in the zinc solution containing hydrogen-oxygen, oxidation is grown for axle with every zinc oxide nanowire
Zinc nano-pillar 2-12 hour.
10. the method preparing zinc oxide composite according to claim 1 is it is characterised in that in step (4), described
Zinc-oxide nano column is the hexagon prism of (001) face advantage orientation, and described hexagon prism cross section Breadth Maximum is 200nm-300nm,
Hexagon prism height is 2-3 μm.
11. methods preparing zinc oxide composite according to claim 1 are it is characterised in that described zinc oxide is combined
The thickness of material is 5-8 μm.
12. methods preparing zinc oxide composite according to claim 1 are it is characterised in that described first bonding jumper
It is aluminium flake or copper sheet with material used by the second bonding jumper；Described first vector ground, Second support ground and the 3rd carrier substrate
Material used is insulating materials.
13. methods preparing zinc oxide composite according to claim 1 are it is characterised in that every cu μ m aoxidizes
Zinc nanometer film is averagely made up of 2-3 root zinc oxide nanowire, and zinc-oxide nano column is entwined each other.
A kind of 14. zinc oxide composites, are made using the method described in any one of claim 1-13.
A kind of 15. zinc oxide composites are it is characterised in that include preparing zinc oxide nanometer film and zinc-oxide nano column array；Described
Preparing zinc oxide nanometer film is made up of the zinc oxide nanowire of six side buergerite crystalline phases, and zinc-oxide nano column is with every zinc oxide nanowire
For axle growth, constitute described zinc-oxide nano column array, described zinc-oxide nano column is the hexagon prism of (001) face advantage orientation；
Wherein, described preparing zinc oxide nanometer film be using method of electrostatic spinning in substrate growth of zinc oxide nano film, then calcine
Arrive；Wherein, before electrostatic spinning, place the substrate above in the accommodating cavity of carrier；Wherein, this carrier includes first vector ground,
It is arranged on Second support ground and the 3rd carrier substrate, Second support ground and the 3rd carrier of first vector ground one side surface
Ground parallel, spaced-apart is arranged, and is provided with the first bonding jumper, is provided with the second gold medal in the 3rd carrier substrate on Second support ground
Belong to bar, the first bonding jumper is be arranged in parallel with the second bonding jumper；Second support ground and the first bonding jumper, with the 3rd carrier substrate and
Form accommodating cavity between second bonding jumper；
Wherein, described preparing zinc oxide nanometer film is constituted by the zinc oxide nanowire of six side buergerite crystalline phases is parallel.
16. zinc oxide composites according to claim 15 are it is characterised in that described hexagon prism cross section Breadth Maximum
For 200-300nm, hexagon prism height is 2-3 μm.
17. zinc oxide composites according to claim 15 or 16 it is characterised in that described zinc oxide nanowire straight
Footpath is 200-300nm.
18. zinc oxide composites according to claim 15 or 16 are it is characterised in that described zinc oxide composite
Thickness is 5-8 μm.
19. zinc oxide composites according to claim 15 are it is characterised in that every cu μ m preparing zinc oxide nanometer film is put down
Constituted by 2-3 root zinc oxide nanowire, zinc-oxide nano column is entwined each other.
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