CN104671277A - 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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- CN104671277A CN104671277A CN201310626956.8A CN201310626956A CN104671277A CN 104671277 A CN104671277 A CN 104671277A CN 201310626956 A CN201310626956 A CN 201310626956A CN 104671277 A CN104671277 A CN 104671277A
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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 preparation method and this zinc oxide composite of zinc oxide composite of high-specific surface area.
Background technology
2006, mechanical energy was successfully converted to electric energy by georgia ,u.s.a Institute of Technology professor Wang Zhonglin etc. within the scope of nanoscale, develops generator-nano generator minimum in the world.The ultimate principle of nano generator is: such as, when nano wire (NWs, zinc oxide nanowire) during dynamic tensile, generates piezoelectricity electromotive force under external force in nano wire, and corresponding transient current flows at two ends to balance fermi level.
The method of routine growth zinc oxide nanowire is chemically grown method, such as hydrothermal method, and zinc oxide nanowire is grown at the metal level substrate surface with Seed Layer.In the past, in zinc oxide nanowire process of growth, the bubble produced in nutrient solution rises to solution surface and is often caught by ventricumbent substrate surface, inhibits zinc oxide nanowire homoepitaxial on large-area metal layer substrate surface.
Summary of the invention
The method of routine growth nano wire, such as hydrothermal method, zinc oxide nanowire is poor at metal level substrate surface growth orientation degree, and specific surface area is not high.The technical problem that the present invention solves is to provide a kind of method and this zinc oxide composite of preparing zinc oxide composite, adds the specific surface area in zinc-oxide nano column array unit volume.
The present invention adopts method of electrostatic spinning to generate preparing zinc oxide nanometer film in substrate, after calcining, generate hexagon wurtzite crystalline phase preparing zinc oxide nanometer film on the surface with every root zinc oxide nanowire for axle growth of zinc oxide nano post is to form zinc-oxide nano column array, this zinc-oxide nano column is the hexagonal column in (001) face advantage orientation.Because the ratio of width to height of the zinc-oxide nano column (hexagonal column) of synthesis is higher, the specific surface area in zinc-oxide nano column array unit volume can be increased.Gained zinc oxide of the present invention may be used for LED, solar cell or photocatalytic surfaces etc.
In order to solve the problems of the technologies described above, the first technical scheme that the present invention adopts is: a kind of method preparing zinc oxide composite, and the method comprises the following steps:
(1) preparing zinc oxide nanometer film electrostatic spinning liquid is prepared
Polyethylene based polymers is joined in solvent, after polyethylene based polymers is dissolved, in liquid, add zinc salt, then mix and obtain electrostatic spinning liquid; Wherein, the weight ratio of polyethylene based polymers and zinc salt is 1-5:0.5-3;
(2) electrostatic spinning
Step (1) gained electrostatic spinning liquid is joined in electrostatic spinning apparatus, then electrostatic spinning liquid is expelled in substrate and carries out electrostatic spinning, substrate obtains polyethylene based polymers/zinc salt tunica fibrosa fiber sprinning;
(3) calcine
Calcined together with substrate by step (2) gained polyethylene based polymers/zinc salt tunica fibrosa, calcination condition is: be warming up to 500-600 DEG C according to the temperature rise rate of 2-10 DEG C/min, calcining at constant temperature 1-6 hour; Then cool to room temperature, obtains preparing zinc oxide nanometer film, and described preparing zinc oxide nanometer film is made up of the zinc oxide nanowire of hexagon wurtzite crystalline phase; And
(4) growth of zinc oxide nano post array
With step (3) gained preparing zinc oxide nanometer film for Seed Layer, in described Seed Layer with every root zinc oxide nanowire for axle, growth of zinc oxide nano post, to form zinc-oxide nano column array, obtains the matrix material of preparing zinc oxide nanometer film-zinc-oxide nano column array.
The aforesaid method preparing zinc oxide composite, in step (1), described zinc salt is zinc acetate, zinc nitrate, zinc oxalate and their hydrate; Described solvent is methylformamide (DMF), ethanol (ethanol) or tetrahydrofuran (THF) (THF); Described polyethylene based polymers is polyvinyl alcohol (PVA) or polyvinylpyrrolidone (PVP).
The aforesaid method preparing zinc oxide composite, in step (1), doping oxide or metal in electrostatic spinning liquid, oxide compound is Al
2o
3or SnO
2, metal is Ag, Au, Pt or Cu.
The aforesaid method preparing zinc oxide composite, in step (2), be 10kV-20kV at voltage, receiving range is 8cm-20cm, under driving velocity 0.1ml/hr-1ml/hr condition, is expelled to by electrostatic spinning liquid 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), the diameter of described zinc oxide nanowire is 200nm-300nm.
The aforesaid method preparing zinc oxide composite, in step (4), adopts hydrothermal synthesis method or microwave heating method, containing in the zinc solution of hydrogen-oxygen, with every root zinc oxide nanowire for axle growth of zinc oxide nano post is to form zinc-oxide nano column array.
The aforesaid method preparing zinc oxide composite, the described zinc solution containing hydrogen-oxygen is the aqueous solution of zinc acetate, zinc nitrate or zinc oxalate; Hydrogen-oxygen used is sodium hydroxide, ammoniacal liquor, volatile salt or vulkacit H.
The aforesaid method preparing zinc oxide composite, in step (4), described hydrothermal synthesis method is: at 80-100 DEG C, containing in the zinc solution of hydrogen-oxygen, with every root 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 the hexagonal column of (001) face advantage orientation, and described hexagonal column cross section maximum width is 200nm-300nm, and hexagonal column 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 comprises the polyethylene based polymers/zinc salt tunica fibrosa obtaining fiber sprinning ordered arrangement.
The aforesaid method preparing zinc oxide composite, before electrostatic spinning, is placed on substrate in the accommodating cavity of carrier; Wherein, this carrier comprises the first carrier substrate, be arranged on Second support ground and the 3rd carrier substrate of the first carrier substrate one side surface, Second support ground and the 3rd carrier substrate parallel, spaced-apart are arranged, Second support ground is provided with the first metal strip, 3rd carrier substrate is provided with the second metal strip, and the first metal strip and the second metal strip be arranged in parallel; Second support ground and the first metal strip, and form accommodating cavity between the 3rd carrier substrate and the second metal strip.
The aforesaid method preparing zinc oxide composite, described first metal strip and the second metal strip material used are aluminium foil, Copper Foil, aluminium flake or copper sheet; Described first carrier substrate, Second support ground and the 3rd carrier substrate material used are insulating material, such as glass.
The aforesaid method preparing zinc oxide composite, described preparing zinc oxide nanometer film is made up of the zinc-oxide nano line parallel of hexagon wurtzite crystalline phase.
The aforesaid method preparing zinc oxide composite, every cu μ m preparing zinc oxide nanometer film is on average made up of 2-3 root zinc oxide nanowire, and zinc-oxide nano column is entwined each other.
Second technical scheme provided by the invention is: a kind of zinc oxide composite, adopts above-mentioned any one method to make.
3rd technical scheme provided by the invention is: a kind of zinc oxide composite, comprises 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 hexagon wurtzite crystalline phase, zinc-oxide nano column with every root zinc oxide nanowire for axle grows, form described zinc-oxide nano column array, described zinc-oxide nano column is the hexagonal column of (001) face advantage orientation.
Aforesaid zinc oxide composite, described hexagonal column cross section maximum width is 200-300nm, and hexagonal column height is 2-3 μm.
Aforesaid zinc oxide composite, the diameter of described zinc oxide nanowire is 200-300nm.
Aforesaid zinc oxide composite, described preparing zinc oxide nanometer film is made via calcining electrostatic spinning polyethylene based polymers/zinc salt tunica fibrosa.
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 hexagon wurtzite crystalline phase zinc-oxide nano line parallel form.
Aforesaid zinc oxide composite, every cu μ m preparing zinc oxide nanometer film is on average made up of 2-3 root zinc oxide nanowire, and 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 hexagon wurtzite crystalline phase, with the zinc oxide nanowire of every root for axle growth of zinc oxide nano post is to form zinc-oxide nano column array, the hexagonal column of face advantage orientation that zinc-oxide nano column grows into (001).Because the ratio of width to height of synthesizing zinc oxide nano-pillar is higher, the surface-area in unit volume can be increased.Gained zinc oxide composite of the present invention can be used for LED, solar cell, photocatalytic surfaces etc. based on ZnO.Zinc oxide composite preparation technology of the present invention is simple.
Accompanying drawing explanation
Fig. 1 is the preparing zinc oxide nanometer film XRD spectra that electrostatic spinning is made up of zinc oxide nanowire after calcining, and wherein deposition of zinc oxide is on gold-plated silicon.
Shape appearance figure under Fig. 2 preparing zinc oxide nanometer film opticmicroscope (1000 times) that to be the first embodiment electrostatic spinning be made up of zinc oxide nanowire after calcining.
Shape appearance figure under Fig. 3 preparing zinc oxide nanometer film SEM (10000 times) that to be the first embodiment electrostatic spinning be made up of zinc oxide nanowire after calcining.
Fig. 4 is the carrier schematic diagram of the present invention second embodiment substrate used.
Fig. 5 is the carrier diagrammatic cross-section of the present invention second embodiment substrate used.
Fig. 6 is the process of carrying out electrostatic spinning on the carrier of the present invention second embodiment substrate used.
Fig. 7 is the state complete electrostatic spinning on the carrier of the present invention second embodiment substrate used after.
Fig. 8 is the process of taking off substrate from the carrier of the present invention second embodiment substrate used.
Fig. 9 be the present invention second embodiment electrostatic spinning calcining before have the pattern of orientation preparing zinc oxide nanometer film under opticmicroscope (1000 times).
Figure 10 is the pattern of preparing zinc oxide nanometer film-zinc-oxide nano column array matrix material under SEM (500 times) that the present invention second embodiment growth of zinc oxide nano post on the preparing zinc oxide nanometer film having orientation obtains.
Figure 11 is the pattern of preparing zinc oxide nanometer film-zinc-oxide nano column array matrix material under SEM (2000 times) that the present invention second embodiment growth of zinc oxide nano post on the preparing zinc oxide nanometer film having orientation obtains.
Figure 12 is the pattern of preparing zinc oxide nanometer film-zinc-oxide nano column array matrix material under SEM (10000 times) that the present invention second embodiment growth of zinc oxide nano post on the preparing zinc oxide nanometer film having orientation obtains.
Embodiment
For fully understanding the object of the present invention, feature and effect, by following concrete embodiment, the present invention is elaborated.
The following detailed description of once the first embodiment of the present invention.
Prepare a method for zinc oxide composite, the method comprises the following steps:
(1) preparing zinc oxide nanometer film electrostatic spinning liquid is prepared
Polyethylene based polymers is joined in solvent, after polyethylene based polymers is dissolved, in liquid, add zinc salt, then mix and obtain electrostatic spinning liquid.Wherein, the weight ratio of polyethylene based polymers and zinc salt is 1-5:0.5-3.Such as, add 1-5g polyethylene based polymers, then in mixing solutions, add zinc salt in every 10ml solvent, the mixing solutions of every 10ml adds 0.5-3g zinc salt.
Described zinc salt can be zinc acetate, zinc nitrate, zinc oxalate and their hydrate.Described solvent can be methylformamide (DMF), ethanol (ethanol) or tetrahydrofuran (THF) (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 are to promote the performance of zinc oxide in particular aspects, and oxide compound can be Al
2o
3or SnO
2, metal can be Ag, Au, Pt or Cu.
(2) electrostatic spinning
Step (1) gained electrostatic spinning liquid is joined in electrostatic spinning apparatus, then electrostatic spinning liquid is expelled in substrate and carries out electrostatic spinning, substrate obtains polyethylene based polymers/zinc salt tunica fibrosa.
The present invention's electrostatic spinning apparatus used is conventional commercial electrostatic spinning apparatus.Concrete, step (1) gained electrostatic spinning liquid is joined in the liquid dispensing apparatus such as injection needle of electrostatic spinning apparatus, syringe needle be metal as stainless steel, syringe needle is connect high-voltage power supply, receiving end ground connection.Then be 10kV-20kV at voltage, receiving range is under 8cm-20cm condition, with micro pump with driving velocity 0.1ml/hr-1ml/hr, electrostatic spinning liquid is expelled in substrate by jet apparatus and carries out electrostatic spinning, substrate obtains polyethylene based polymers/zinc salt tunica fibrosa.
The present invention does not have particular requirement to substrate, and conventional substrate all can be applied to the present invention, such as gold-plated silicon.
(3) calcine
Calcined together with substrate by step (2) gained polyethylene based polymers/zinc salt fiber membrane, calcination condition is: be warming up to 500-600 DEG C according to the temperature rise rate of 2-10 DEG C/min, calcining at constant temperature 1-6 hour; Then cool to room temperature, obtains preparing zinc oxide nanometer film.
Gained preparing zinc oxide nanometer film is made up of the zinc oxide nanowire of hexagon wurtzite crystalline phase, and the diameter of this zinc oxide nanowire is 200nm-300nm.
It is the preparing zinc oxide nanometer film XRD spectra that this step of a preferred embodiment of the invention is made up of zinc oxide nanowire shown in Fig. 1.ZnO is hexagon wurtzite crystalline phase as seen from Figure 1, and the strongest peak is 001.Fig. 2 is the shape appearance figure under the preparing zinc oxide nanometer film opticmicroscope (1000 times) that is made up of zinc oxide nanowire of this step of preferred embodiment.Fig. 3 is the shape appearance figure under the preparing zinc oxide nanometer film SEM (10000 times) that is made up of zinc oxide nanowire of this step of preferred embodiment.Can find out that preparing zinc oxide nanometer film of the present invention is made up of zinc oxide nanowire by Fig. 2 and Fig. 3.Can find out that nano-pillar is hexagonal column shape by SEM figure, this shows 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 for Seed Layer, in described Seed Layer, growth of zinc oxide nano post is to form zinc oxide nano array, obtains the matrix material of preparing zinc oxide nanometer film-zinc-oxide nano column array.The present invention adopts hydrothermal synthesis 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 water heat transfer nanometic zinc oxide rod array.The concrete described zinc solution containing hydrogen-oxygen is the aqueous solution of zinc acetate, zinc nitrate or zinc oxalate; Hydrogen-oxygen used is sodium hydroxide, ammoniacal liquor, volatile salt or vulkacit H.Joined by zinc salt in the container (sealed bottle or water heating kettle) that deionized water is housed, and then inject portions of de-ionized water, the concentration of zinc salt is that 5 ~ 50mM(mmole often rises).After zinc salt dissolves, add hydrogen-oxygen (as instillation ammoniacal liquor) again mix, then at 80-100 DEG C, (such as baking oven is utilized), step (3) gained preparing zinc oxide nanometer film is placed in the zinc solution containing hydrogen-oxygen, makes zinc-oxide nano column grow 2-12 hour.
This step gained zinc-oxide nano column is the hexagonal column of (001) face advantage orientation, and described hexagonal column cross section maximum width is 200-300nm, and hexagonal column height is 2-3 μm.
Zinc oxide composite is obtained according to aforesaid method, this zinc oxide composite comprises preparing zinc oxide nanometer film and zinc-oxide nano column array, zinc-oxide nano column vertical-growth forms described zinc-oxide nano column array on the surface in the side of described preparing zinc oxide nanometer film, and described zinc-oxide nano column is the hexagonal column of (001) face advantage orientation.Described preparing zinc oxide nanometer film is made up of the zinc oxide nanowire of hexagon wurtzite crystalline phase, and the diameter of described zinc oxide nanowire is 200-300nm, and the thickness of gained zinc oxide composite 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 hexagon wurtzite crystalline phase, growth of zinc oxide nano post is to form zinc-oxide nano column array, the hexagonal column of face advantage orientation that zinc-oxide nano column grows into (001).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, in order to obtain the preparing zinc oxide nanometer film be made up of the zinc-oxide nano line parallel of hexagon wurtzite crystalline phase, have employed the second embodiment.The following detailed description of the second embodiment.
This embodiment has the electrostatic spinning step different from above-mentioned first embodiment, also comprises the polyethylene based polymers/zinc salt tunica fibrosa obtaining fiber sprinning ordered arrangement.Before electrostatic spinning, substrate 6 is placed in the accommodating cavity of carrier (as shown in Figure 4 and Figure 5).This carrier comprises the first carrier substrate 1, is arranged on Second support ground 2 and the 3rd carrier substrate 3 of the first carrier substrate one side surface, at the bottom of Second support 2 and the 3rd carrier substrate 3 parallel, spaced-apart arrange.At the bottom of Second support, be provided with the first metal strip 4, first metal strip 4 on 2 arrange along the limit parallel with the 3rd carrier substrate of Second support ground 2.3rd carrier substrate 3 is provided with the second metal strip 5, second metal strip 5 arrange along the limit parallel with Second support ground 2 of the 3rd carrier substrate 3.Second support ground 2 and the first metal strip 4, and form accommodating cavity between the 3rd carrier substrate 3 and the second metal strip 5.
Fig. 6 is the process that this embodiment carries out electrostatic spinning, is ejected in substrate 6 via electrospinning device 7 by electrostatic spinning liquid, forms zinc oxide nanowire 8.Fig. 7 is the state after this embodiment completes electrostatic spinning.Fig. 8 is that this embodiment takes off the process of substrate from carrier.Can find out that preparing zinc oxide nanometer film can be made up of zinc-oxide nano line parallel by Fig. 6-Fig. 8.In this embodiment, every cu μ m preparing zinc oxide nanometer film is on average made up of 2-3 root zinc oxide nanowire, and zinc-oxide nano column is entwined each other.Such as, the total surface area of preparing zinc oxide nanometer film is 4.15 μm
2, in every cu μ m preparing zinc oxide nanometer film, on average have 2.56 zinc oxide nanowires.
When electrostatic spinning, injection head connects positive electricity, and the metal strips for grounding on carrier, thus produce an electric field in-between.And the fiber that can be considered as positively charged of electrostatic spinning itself, to be stressedly under the electric field deposited on the carrier of ground connection.When spinning moves near metal strip, electrically contrary due to both, under the effect of Coulomb force, the two ends of spinning on metal strip, by maximum Coulomb force magnetism, are therefore pullled the two ends of spinning and make it vertical with the direction of metal strip.On the other hand, be different from the part on metal strip, the spinning between metal strip can positively charged.The ordered arrangement strengthened between spinning due to the Coulomb repulsion between spinning.
Described first metal strip and the second metal strip material used are aluminium foil, Copper Foil, aluminium flake or copper sheet; Described first carrier substrate, Second support ground and the 3rd carrier substrate material used are isolation material, such as glass.
Step (1) gained electrostatic spinning liquid is joined in electrostatic spinning apparatus, then electrostatic spinning liquid is ejected in the substrate be placed in the accommodating cavity of carrier and carries out electrostatic spinning, substrate obtains polyethylene based polymers/zinc salt tunica fibrosa.After calcining, gained preparing zinc oxide nanometer film is made up of the zinc-oxide nano line parallel of hexagon wurtzite crystalline phase.In present embodiment, preparing zinc oxide nanometer film has certain orientation, and make the zinc-oxide nano column grown on zinc oxide nanowire more have order, the specific surface area obtained is larger.That is, when with parallel silk for Seed Layer time, because the density of parallel silk is very high, the zinc-oxide nano column of hydrothermal synthesis method synthesis is entwined the zinc oxide carpet making surface become orderly each other.The zinc oxide composite specific surface area of this embodiment is larger.Use this carrier to carry out electrostatic spinning and prepare polyethylene based polymers/zinc salt tunica fibrosa, there is technique simple, repeatability is high, each preparation only need change substrate, polyethylene based polymers/zinc salt tunica fibrosa the order of preparation is high, arranged in parallel through calcining rear oxidation zinc nano wire, make the zinc-oxide nano column grown have larger specific surface area thereon.
Set forth the enforcement of method of the present invention below by specific embodiment, one skilled in the art will appreciate that this should not be understood to the restriction to the claims in the present invention scope.
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, and the zinc-oxide nano linear diameter forming preparing zinc oxide nanometer film is 300nm, and zinc-oxide nano column is of a size of diameter 300nm, height 2 μm.
The following describes the preparation method of this matrix material
(1) preparing zinc oxide nanometer film electrostatic spinning liquid is prepared
22.7g polyvinylpyrrolidone (PVP, molecular weight 1.3M) is slowly joined in 10ml methylformamide (DMF), after polyvinylpyrrolidone dissolves, more slowly adds 0.9g zinc acetate, then mix and obtain electrostatic spinning liquid.
(2) electrostatic spinning
Join in injection needle by step (1) gained electrostatic spinning liquid, syringe needle (stainless steel) connects high-voltage power supply, receiving end ground connection.Then be 15kV at voltage, receiving range is under 14cm condition, with micro pump with driving velocity 0.5ml/hr, is expelled to by electrostatic spinning liquid on the gold-plated silicon of substrate and carries out electrostatic spinning, substrate obtains PVP/ zinc salt tunica fibrosa.
(3) calcine
Calcined in High Temperature Furnaces Heating Apparatus together with substrate by step (2) gained fiber membrane, calcination condition is: be warming up to 500 DEG C according to the temperature rise rate of 10 DEG C/min, calcining at constant temperature 1 hour; Then cool to room temperature, obtains 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.ZnO is hexagon wurtzite crystalline phase as seen from Figure 1, and the strongest peak is 001.Fig. 2 is the shape appearance figure under the preparing zinc oxide nanometer film opticmicroscope (1000 times) that is made up of zinc oxide nanowire of this step.Fig. 3 is the shape appearance figure under the preparing zinc oxide nanometer film SEM (10000 times) that is made up of zinc oxide nanowire of this step.Can find out that preparing zinc oxide nanometer film is made up of zinc oxide nanowire by Fig. 2 and Fig. 3.Gained preparing zinc oxide nanometer film is made up of the zinc oxide nanowire of hexagon wurtzite crystalline phase, and the diameter of this zinc oxide nanowire is 300nm.
(4) growth of zinc oxide nano post array
0.238g zinc nitrate is joined in the sealed bottle that 250ml deionized water is housed, and then inject 40ml deionized water, after zinc nitrate dissolves, instill 1ml ammoniacal liquor (weight percent is 25%) again mix, then at 90 DEG C, react 5 hours in an oven, zinc-oxide nano column is grown.
This step gained zinc-oxide nano column is the hexagonal column of (001) face advantage orientation, and described hexagonal column cross section maximum width is 300nm, and hexagonal column 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, and the zinc-oxide nano linear diameter forming preparing zinc oxide nanometer film is 300nm, and zinc-oxide nano column is of a size of diameter 300nm, height 2 μm.The following describes the preparation method of this matrix material
(1) preparing zinc oxide nanometer film electrostatic spinning liquid is prepared
22.7g polyvinylpyrrolidone (PVP, molecular weight 1.3M) is slowly joined in 10ml methylformamide (DMF), after polyvinylpyrrolidone dissolves, more slowly adds 0.9g zinc acetate, then mix and obtain electrostatic spinning liquid.
(2) electrostatic spinning
Join in injection needle by step (1) gained electrostatic spinning liquid, syringe needle (stainless steel) connects high-voltage power supply, receiving end ground connection.Then be 15kV at voltage, receiving range is under 14cm condition, with micro pump with driving velocity 0.5ml/hr, is expelled to by electrostatic spinning liquid on the gold-plated silicon of substrate and carries out electrostatic spinning, substrate obtains PVP/ zinc salt tunica fibrosa.
(3) calcine
Calcined in High Temperature Furnaces Heating Apparatus together with substrate by step (2) gained fiber membrane, calcination condition is: be warming up to 600 DEG C according to the temperature rise rate of 5 DEG C/min, calcining at constant temperature 2 hours; Then cool to room temperature, obtains preparing zinc oxide nanometer film.
Detect via XRD and can find out that preparing zinc oxide nanometer film is made up of zinc oxide nanowire.Gained preparing zinc oxide nanometer film is made up of the zinc oxide nanowire of hexagon wurtzite crystalline phase, and the diameter of this zinc oxide nanowire is 300nm.
(4) growth of zinc oxide nano post array
0.238g zinc nitrate is joined in the sealed bottle that 250ml deionized water is housed, and then inject 40ml deionized water, after zinc nitrate dissolves, instill 1ml ammoniacal liquor (weight percent 28%) again mix, then at 90 DEG C, react 5 hours in an oven, zinc-oxide nano column is grown.
This step gained zinc-oxide nano column is the hexagonal column of (001) face advantage orientation, and described hexagonal column cross section maximum width is 300nm, and hexagonal column height is 2 μm.
Comparative example 1
This comparative example gained thickness of composite material is 1.5 μm, and the zinc-oxide nano linear diameter forming preparing zinc oxide nanometer film is 120nm, and zinc-oxide nano column is of a size of diameter 120nm, height 0.8 μm.The following describes the preparation method of this matrix material
(1) preparing zinc oxide nanometer film electrostatic spinning liquid is prepared
22.7g polyvinylpyrrolidone (PVP, molecular weight 1.3M) is slowly joined in 10ml methylformamide (DMF), after polyvinylpyrrolidone dissolves, more slowly adds 0.9g zinc acetate, then mix and obtain electrostatic spinning liquid.
(2) electrostatic spinning
Join in injection needle by step (1) gained electrostatic spinning liquid, syringe needle (stainless steel) connects high-voltage power supply, receiving end ground connection.Then be 15kV at voltage, receiving range is under 14cm condition, with micro pump with driving velocity 0.5ml/hr, is expelled to by electrostatic spinning liquid on the gold-plated silicon of substrate and carries out electrostatic spinning, substrate obtains PVP/ zinc salt tunica fibrosa.
(3) calcine
Calcined in High Temperature Furnaces Heating Apparatus together with substrate by step (2) gained fiber membrane, calcination condition is: be warming up to 450 DEG C according to the temperature rise rate of 2 DEG C/min, calcining at constant temperature 3 hours; Then cool to room temperature, obtains preparing zinc oxide nanometer film.
(4) growth of zinc oxide nano post array
0.238g zinc nitrate is joined in the sealed bottle that 250ml deionized water is housed, and then inject 40ml deionized water, after zinc nitrate dissolves, instill 1ml ammoniacal liquor (weight percent 28%) again mix, then at 90 DEG C, react 5 hours in an oven, zinc-oxide nano column is grown.
In this comparative example ZnO/PVP composite cellulosic membrane, PVP incomplete combustion, spinning may still have the existence of PVP, causes the zinc oxide crystallite grain in spinning cannot assemble and grow up, reduces the crystallinity of zinc oxide.Cause the density of the zinc-oxide nano column grown to decline thereon, crystal column is less, crystal face preferred orientation change etc.
Comparative example 2
This comparative example gained thickness of composite material is 1.3 μm, and the zinc-oxide nano linear diameter forming preparing zinc oxide nanometer film is 150nm, and zinc-oxide nano column is of a size of 150nm, height 1 μm.The following describes the preparation method of this matrix material
(1) preparing zinc oxide nanometer film electrostatic spinning liquid is prepared
22.7g polyvinylpyrrolidone (PVP, molecular weight 1.3M) is slowly joined in 10ml methylformamide (DMF), after polyvinylpyrrolidone dissolves, more slowly adds 0.9g zinc acetate, then mix and obtain electrostatic spinning liquid.
(2) electrostatic spinning
Join in injection needle by step (1) gained electrostatic spinning liquid, syringe needle (stainless steel) connects high-voltage power supply, receiving end ground connection.Then be 15kV at voltage, receiving range is under 14cm condition, with micro pump with driving velocity 0.5ml/hr, is expelled to by electrostatic spinning liquid on the gold-plated silicon of substrate and carries out electrostatic spinning, substrate obtains PVP/ zinc salt tunica fibrosa.
(3) calcine
Calcined in High Temperature Furnaces Heating Apparatus together with substrate by step (2) gained tunica fibrosa, calcination condition is: be warming up to 650 DEG C according to the temperature rise rate of 2 DEG C/min, calcining at constant temperature 3 hours; Then cool to room temperature, obtains preparing zinc oxide nanometer film.
(4) growth of zinc oxide nano post array
0.238g zinc nitrate is joined in the sealed bottle that 250ml deionized water is housed, and then inject 40ml deionized water, after zinc nitrate dissolves, instill 1ml ammoniacal liquor (weight percent 28%) again mix, then at 90 DEG C, react 5 hours in an oven, zinc-oxide nano column is grown.
This comparative example is greater than the preparing zinc oxide nanometer film of 600 DEG C of calcining gained, and zinc oxide grain becomes large, and the ZnO nano post grown thereon under the condition of identical hydrothermal method is comparatively large, 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, and zinc-oxide nano film thickness is 200nm, and zinc-oxide nano column is of a size of diameter 200nm, height 2 μm.The following describes the preparation method of this matrix material
(1) preparing zinc oxide nanometer film electrostatic spinning liquid is prepared
22.7g polyvinylpyrrolidone (PVP, molecular weight 1.3M) is slowly joined in 10ml methylformamide (DMF), after polyvinylpyrrolidone dissolves, more slowly adds 0.9g zinc acetate, then mix and obtain electrostatic spinning liquid.
(2) electrostatic spinning
Join in injection needle by step (1) gained electrostatic spinning liquid, syringe needle (stainless steel) connects high-voltage power supply, receiving end ground connection.Silicon gold-plated for substrate is placed in the accommodating cavity of carrier as shown in Figure 4 and Figure 5.
Be 15kV at voltage, receiving range is under 14cm condition, with micro pump with driving velocity 0.5ml/hr, is expelled to by electrostatic spinning liquid on the gold-plated silicon of substrate and carries out electrostatic spinning, substrate obtains PVP/ zinc salt tunica fibrosa.Fig. 9 has the pattern of orientation preparing zinc oxide nanometer film under opticmicroscope (1000 times).
(3) calcine
Calcined in High Temperature Furnaces Heating Apparatus together with substrate by step (2) gained tunica fibrosa, calcination condition is: be warming up to 500 DEG C according to the temperature rise rate of 10 DEG C/min, calcining at constant temperature 1 hour; Then cool to room temperature, obtains preparing zinc oxide nanometer film.
Gained preparing zinc oxide nanometer film is made up of the zinc-oxide nano line parallel of hexagon wurtzite crystalline phase, and the diameter of this zinc oxide nanowire is 200nm.
(4) growth of zinc oxide nano post array
0.238g zinc nitrate is joined in the sealed bottle that 250ml deionized water is housed, and then inject 40ml deionized water, after zinc nitrate dissolves, instill 1ml ammoniacal liquor (weight percent 28%) again mix, then at 90 DEG C, react 5 hours in an oven, zinc-oxide nano column is grown.
This step gained zinc-oxide nano column is the hexagonal column of (001) face advantage orientation, and described hexagonal column cross section maximum width is 200nm.Hexagonal column height is 2 μm.Figure 10 is the pattern of preparing zinc oxide nanometer film-zinc-oxide nano column array matrix material under SEM (500 times) that this embodiment growth of zinc oxide nano post on the preparing zinc oxide nanometer film having orientation obtains.Figure 11 is the pattern of preparing zinc oxide nanometer film-zinc-oxide nano column array matrix material under SEM (2000 times) that this embodiment growth of zinc oxide nano post on the preparing zinc oxide nanometer film having orientation obtains.Figure 12 is the pattern of preparing zinc oxide nanometer film-zinc-oxide nano column array matrix material under SEM (10000 times) that this embodiment growth of zinc oxide nano post on the preparing zinc oxide nanometer film having orientation obtains.
The present invention adopts method of electrostatic spinning-calcine to generate preparing zinc oxide nanometer film in substrate, and this preparing zinc oxide nanometer film is made up of the zinc oxide nanowire of hexagon wurtzite crystalline phase, can be unordered also can be parallel.Then at preparing zinc oxide nanometer film on the surface with every root zinc oxide nanowire for axle growth of zinc oxide nano post is to form zinc-oxide nano column array, this zinc-oxide nano column is the hexagonal column in (001) face advantage orientation.Because the ratio of width to height of the zinc-oxide nano column (hexagonal column) of synthesis is higher, the specific surface area in zinc-oxide nano column array unit volume can be increased.Gained zinc oxide of the present invention may be used for LED, solar cell or photocatalytic surfaces etc.
Claims (24)
1. prepare a method for zinc oxide composite, the method comprises the following steps:
(1) preparing zinc oxide nanometer film electrostatic spinning liquid is prepared
Polyethylene based polymers is joined in solvent, after polyethylene based polymers is dissolved, in liquid, add zinc salt, then mix and obtain electrostatic spinning liquid; Wherein, the weight ratio of polyethylene based polymers and zinc salt is 1-5:0.5-3;
(2) electrostatic spinning
Step (1) gained electrostatic spinning liquid is joined in electrostatic spinning apparatus, then electrostatic spinning liquid is expelled in substrate and carries out electrostatic spinning, substrate obtains polyethylene based polymers/zinc salt tunica fibrosa;
(3) calcine
Calcined together with substrate by step (2) gained polyethylene based polymers/zinc salt tunica fibrosa, calcination condition is: be warming up to 500-600 DEG C according to the temperature rise rate of 2-10 DEG C/min, calcining at constant temperature 1-6 hour; Then cool to room temperature, obtains preparing zinc oxide nanometer film, and described preparing zinc oxide nanometer film is made up of the zinc oxide nanowire of hexagon wurtzite crystalline phase; And
(4) growth of zinc oxide nano post array
With step (3) gained preparing zinc oxide nanometer film for Seed Layer, in described Seed Layer with every root zinc oxide nanowire for axle, growth of zinc oxide nano post, to form zinc-oxide nano column array, obtains the matrix material of preparing zinc oxide nanometer film-zinc-oxide nano column array.
2. the method preparing zinc oxide composite according to claim 1, is characterized in that, in step (1), described zinc salt is zinc acetate, zinc nitrate, zinc oxalate and their hydrate; Described solvent is methylformamide DMF, ethanol ethanol or tetrahydrofuran THF; Described polyethylene based polymers is PVAC polyvinylalcohol or polyvinylpyrrolidone PVP.
3. the method preparing zinc oxide composite according to claim 1 and 2, is characterized in that, in step (1), doping oxide or metal in electrostatic spinning liquid, oxide compound is Al
2o
3or SnO
2, metal is Ag, Au, Pt or Cu.
4. the method preparing zinc oxide composite according to any one of claim 1-3, it is characterized in that, in step (2), be 10kV-20kV at voltage, receiving range is 8cm-20cm, under driving velocity 0.1ml/hr-1ml/hr condition, electrostatic spinning liquid is expelled in substrate and carries out electrostatic spinning.
5. the method preparing zinc oxide composite according to claim 4, is characterized in that, the spinning time is 30 seconds to 10 minutes.
6. the method preparing zinc oxide composite according to any one of claim 1-5, is characterized in that, in step (3), the diameter of described zinc oxide nanowire is 200nm-300nm.
7. the method preparing zinc oxide composite according to any one of claim 1-6, it is characterized in that, in step (4), adopt hydrothermal synthesis method or microwave heating method, containing in the zinc solution of hydrogen-oxygen, with every root zinc oxide nanowire for axle growth of zinc oxide nano post is to form zinc-oxide nano column array.
8. the method preparing zinc oxide composite according to claim 7, is characterized in that, the described zinc solution containing hydrogen-oxygen is the aqueous solution of zinc acetate, zinc nitrate or zinc oxalate; Hydrogen-oxygen used is sodium hydroxide, ammoniacal liquor, volatile salt or vulkacit H.
9. the method preparing zinc oxide composite according to claim 8, it is characterized in that, in step (4), described hydrothermal synthesis method is: at 80-100 DEG C, containing in the zinc solution of hydrogen-oxygen, with every root zinc oxide nanowire for axle growth of zinc oxide nano post 2-12 hour.
10. the method preparing zinc oxide composite according to any one of claim 1-9, it is characterized in that, in step (4), described zinc-oxide nano column is the hexagonal column of (001) face advantage orientation, described hexagonal column cross section maximum width is 200nm-300nm, and hexagonal column height is 2-3 μm.
11. methods preparing zinc oxide composite according to any one of claim 1-10, it is characterized in that, the thickness of described zinc oxide composite is 5-8 μm.
12. methods preparing zinc oxide composite according to claim 1, is characterized in that, in step (2), the method also comprises the polyethylene based polymers/zinc salt tunica fibrosa obtaining fiber sprinning ordered arrangement.
13. methods preparing zinc oxide composite according to claim 12, is characterized in that, before electrostatic spinning, substrate are placed in the accommodating cavity of carrier; Wherein, this carrier comprises the first carrier substrate, be arranged on Second support ground and the 3rd carrier substrate of the first carrier substrate one side surface, Second support ground and the 3rd carrier substrate parallel, spaced-apart are arranged, Second support ground is provided with the first metal strip, 3rd carrier substrate is provided with the second metal strip, and the first metal strip and the second metal strip be arranged in parallel; Second support ground and the first metal strip, and form accommodating cavity between the 3rd carrier substrate and the second metal strip.
14. methods preparing zinc oxide composite according to claim 13, is characterized in that, described first metal strip and the second metal strip material used are aluminium foil, Copper Foil, aluminium flake or copper sheet; Described first carrier substrate, Second support ground and the 3rd carrier substrate material used are insulating material.
15. methods preparing zinc oxide composite according to claim 13 or 14, it is characterized in that, described preparing zinc oxide nanometer film is made up of the zinc-oxide nano line parallel of hexagon wurtzite crystalline phase.
16. methods preparing zinc oxide composite according to claim 15, is characterized in that, every cu μ m preparing zinc oxide nanometer film is on average made up of 2-3 root zinc oxide nanowire, and zinc-oxide nano column is entwined each other.
17. 1 kinds of zinc oxide composites, adopt the method described in any one of claim 1-16 to make.
18. 1 kinds of zinc oxide composites, is characterized in that, comprise 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 hexagon wurtzite crystalline phase, zinc-oxide nano column with every root zinc oxide nanowire for axle grows, form described zinc-oxide nano column array, described zinc-oxide nano column is the hexagonal column of (001) face advantage orientation.
19. zinc oxide composites according to claim 18, is characterized in that, described hexagonal column cross section maximum width is 200-300nm, and hexagonal column height is 2-3 μm.
20. zinc oxide composites according to claim 18 or 19, it is characterized in that, the diameter of described zinc oxide nanowire is 200-300nm.
21. zinc oxide composites according to any one of claim 18-20, is characterized in that, described preparing zinc oxide nanometer film is made via calcining electrostatic spinning polyethylene based polymers/zinc salt tunica fibrosa.
22. zinc oxide composites according to any one of claim 18-21, it is characterized in that, the thickness of described zinc oxide composite is 5-8 μm.
23. zinc oxide composites according to claim 18, is characterized in that, described preparing zinc oxide nanometer film is made up of the zinc-oxide nano line parallel of hexagon wurtzite crystalline phase.
24. zinc oxide composites according to claim 23, is characterized in that, every cu μ m preparing zinc oxide nanometer film is on average made up of 2-3 root zinc oxide nanowire, and zinc-oxide nano column is entwined each other.
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| CN113353969A (en) * | 2021-06-29 | 2021-09-07 | 科迈特新材料有限公司 | Preparation method of high-activity nano zinc oxide |
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