CN105002597B - ZnO meso-porous nano fibers - Google Patents
ZnO meso-porous nano fibers Download PDFInfo
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Abstract
ZnO meso-porous nanos fiber disclosed by the invention, the main component of nanofiber are Zn, O and other inevitable impurity elements, and nanofiber has porous structure, and the hole of porous structure is including mesoporous；Wherein main forms of Zn, O element in nanofiber are ZnO, and nanofiber is being circular either ellipse or bandlet shape or subcircular or nearly ellipse or nearly bandlet shape perpendicular to growth axis normal section.The configuration of the present invention is simple is stablized, and convenient for production, quality stability is good, has preferable repeatability, convenient for expanding the scale of production.
Description
Technical field
The present invention relates to a kind of 1-dimention nano fibrous materials, particularly ZnO meso-porous nano fibers.
TS refers to Tea Saponin in the present invention；ZnAc refers to zinc acetate, including water-containing acetic acid zinc or acetic anhydride zinc；It is circular or
Circular or oval or bandlet shape or subcircular or near oval or near flat in the oval either bandlet shape of person
Banding include but not limited to positive round, smooth either rough subcircular, ellipse, it is smooth or it is rough it is near ellipse, it is flat
Flat ribbon, smooth either rough or tortuous squashed structure.
Background technology
The characteristic that is showed due to monodimension nanometer material in photoelectronics, electronics, thermodynamics etc. and in light
The potential application foreground in the fields such as electricity, microelectronic component, environment and biomedicine has received more and more attention.ZnO is
A kind of direct band system semiconductor material with wide forbidden band of important II-V races has suitable energy gap, is 3.37eV under room temperature, compared with
High exciton bind energy, higher than 60meV, cheap price, preferable conduction, heat conductivility and very high chemical stability, this
So that nano ZnO material has broad prospect of application in fields such as semi-conducting material, photoelectric conversion, photocatalysis and sensors.One
Inorganic nano material is tieed up, makes them in necks such as following nano-devices since it is different from the unique physico-chemical performance of block materials
There is huge potential application foreground in domain.There are many kinds of the methods for preparing One-Dimensional ZnO material, and wherein method of electrostatic spinning is in recent years
A kind of method for preparing ZnO nano fiber to grow up.Electrostatic spinning technique starts from the thirties in last century, is risen in last century
The nineties.Since its preparation process is simple, it is of low cost the features such as be increasingly taken seriously, application field is also gradually by weaving
Industry is expanded to fields such as biomedicine, semiconductors.The type of prepared fiber is also developed to inorganic by initial high molecular material
Material and inorganic/organic composite material.Electrospinning ZnO nano fiber large specific surface area itself can prepare longer one-dimentional structure,
Electric spinning polymer/ZnO nano fiber can launch stronger white light, white-light nanometer device be can be applied to, such as LED and FPD
Device.
In addition, one-dimensional mesoporous ZnO material has broadband system, high carrier mobility, high chemical stability and uniqueness
Many excellent physical characteristics such as high-specific surface area, in photocatalysis, biomedicine, photodetection, gas sensor and solar energy
The fields such as battery are widely used.Various appearance structures, the preparation research of one-dimensional mesoporous ZnO nano material of doping system have drawn
Play the close attention of countries in the world researcher.
At present, the preparation research of ZnO meso-porous nanos fibrous material has been achieved great progress, and successfully has developed quiet
Electrical spinning method, hydro-thermal method, template and vapour deposition process.But still it is faced with that preparation process is complicated, material purity is relatively low, compares table
Area is relatively low to wait difficult and challenge.Moreover, the work of ZnO meso-porous nano fibrous materials fine structure regulation and control has not been reported, sternly
The development of ZnO material is constrained again.
The content of the invention
To solve the above problems, ZnO meso-porous nanos fibre structure disclosed by the invention is stablized, have when as photoelectric material
There are good activity and reaction sensitivity, while product purity is high, by adjusting water and ethyl alcohol in electrostatic spinning precursor solution
Content, it is fine to mesoporous banding again from mesoporous cylindrical fiber to mesoporous elliptic cylindrical shape fiber to realize ZnO one-dimensional nano structures
The controllable transformation of dimension, and it is simple for process easy to operate, there is good repeatability.
ZnO meso-porous nanos fiber disclosed by the invention, the main component of nanofiber are Zn, O and other inevitable
Impurity element,
Nanofiber has porous structure, and the hole of the porous structure is including mesoporous；
Wherein main forms of Zn, O element in nanofiber are that (ZnO crystalline structures in nano wire are six to ZnO
Square wurtzite structure either cubic sphalerite structure) nanofiber perpendicular to growth axis normal section to be circular or
Oval either bandlet shape or subcircular or nearly ellipse or nearly bandlet shape.
A kind of improvement of ZnO meso-porous nanos fiber disclosed by the invention, nanofiber have porous structure and described porous
The hole of structure is mesoporous.
A kind of improvement of ZnO meso-porous nanos fiber disclosed by the invention has the specific surface of the nanofiber of meso-hole structure
Product is 45-55m2/ g, mesoporous aperture averaging are 3-20nm.
The preparation method of ZnO meso-porous nanos fiber disclosed by the invention, includes the following steps, 1), PVP/ZnAc/TS forerunner
Body spinning solution configures；2) prepared by precursor nano wire；3) prepared by ZnO meso-porous nanos fiber；
Wherein step 2) precursor nano wire is prepared as PVP/ZnAc/TS spinning liquid as precursor through spinning (this place spinning
Not only include carrying out spinning using various spinning-drawing machines, further include spinning solution using other physico-chemical processes into silk, such as lead
Be pulled silk etc.) obtain precursor nano wire；
The precursor nano wire that step 3) ZnO meso-porous nano fibers are prepared as obtaining step 2) is through high-temperature calcination, you can
Obtain ZnO meso-porous nano fibers.
A kind of improvement of the preparation method of ZnO meso-porous nanos fiber disclosed by the invention, in step 2) before PVP/ZnAc/TS
It drives body spinning solution and obtains precursor nano wire through electrostatic spinning, the wherein field strength of electrostatic spinning is less than or equal to 0.8KV/cm.
A kind of improvement of the preparation method of ZnO meso-porous nanos fiber disclosed by the invention, the precursor obtained in step 2)
Nano wire carries out high-temperature calcination again also after drying process, and drying process is dried in the shade for low temperature drying or room temperature.
A kind of improvement of the preparation method of ZnO meso-porous nanos fiber disclosed by the invention, low temperature drying are precursor nanometer
Line carried out at 50-80 DEG C 8-14 it is small when drying process.
A kind of improvement of the preparation method of ZnO meso-porous nanos fiber disclosed by the invention, room temperature are dried in the shade for precursor nanometer
For line when aeration-drying 16-24 is small at ambient temperature, ventilation wind speed is 1-2m/s.
A kind of improvement of the preparation method of ZnO meso-porous nanos fiber disclosed by the invention, in step 1) before PVP/ZnAc/TS
Drive body spinning solution be configured to appropriate PvP being dissolved in ethyl alcohol, stirring at normal temperature obtains transparent and homogeneous solution, then add in zinc acetate,
Deionized water and TS, then heating water bath obtain yellow PVP/ZnAc/TS spinning liquid as precursor.
A kind of improvement of the preparation method of ZnO meso-porous nanos fiber disclosed by the invention, in step 1) before PVP/ZnAc/TS
The mass ratio of ethyl alcohol and water is (3-1) when driving the configuration of body spinning solution：1, wherein water is deionized water or distilled water.Pass through control
The content of water and ethyl alcohol in precursor solution realizes the accurate control of organic precursor monodimension nanometer material structure.
A kind of improvement of the preparation method of ZnO meso-porous nanos fiber disclosed by the invention, in step 1) before PVP/ZnAc/TS
It is dissolved in when driving the configuration of body spinning solution per 1gPVP in 6-9g ethyl alcohol.The PVP/ZnAc/TS presomas that i.e. step 1) counterweight obtains are spun
Often then accordingly contain 6-9g ethyl alcohol containing 1gPVP in silk liquid.
A kind of improvement of the preparation method of ZnO meso-porous nanos fiber disclosed by the invention, in step 1) before PVP/ZnAc/TS
Often containing 1gPVP, then deionized water or distilled water usage amount are 3-6g in spinning solution when driving the configuration of body spinning solution.I.e. step 1) is matched somebody with somebody
Often then accordingly contain 3-6g deionized waters or distilled water containing 1gPVP in the PVP/ZnAc/TS spinning liquid as precursor restored.
A kind of improvement of the preparation method of ZnO meso-porous nanos fiber disclosed by the invention, in step 1) before PVP/ZnAc/TS
Often containing 1gPVP, then TS usage amounts are 0.5-0.9g in spinning solution when driving the configuration of body spinning solution.The PVP/ that i.e. step 1) counterweight obtains
Often then accordingly contain 0.5-0.9gTS containing 1gPVP in ZnAc/TS spinning liquid as precursor.
A kind of improvement of the preparation method of ZnO meso-porous nanos fiber disclosed by the invention, step 3) high temperature calcining be
Heat preservation calcining 1-3h at 300-480 DEG C of calcining heat, nano wire heating rate is 2-4 DEG C/min during calcining.
A kind of improvement of the preparation method of ZnO meso-porous nanos fiber disclosed by the invention, in step 1) before PVP/ZnAc/TS
Often containing 1gPVP, then ZnAc usage amounts are 2-4g in spinning solution when driving the configuration of body spinning solution (in terms of zinc acetate dihydrate).That is step 1)
Often containing 1gPVP then accordingly containing 2-4gZnAc (with zinc acetate dihydrate in the PVP/ZnAc/TS spinning liquid as precursor that counterweight obtains
Meter).
A kind of improvement of the preparation method of ZnO meso-porous nanos fiber disclosed by the invention, step 3) high temperature calcining be
It is carried out under air environment.
ZnO meso-porous nanos fiber disclosed by the invention, stable structure, activity is high, and production method can realize high-purity
The precise controlling of high-quality ZnO meso-porous nano fiber morphology structure, and it is simple for process, and production efficiency is high, easy to operate, no dirt
Dye, cost control is good, reproducible.
Description of the drawings
Fig. 1 is to scan electricity under the low resolution multiplying power of the solid-state organic precursor nanofiber obtained by the embodiment of the present invention one
Mirror figure.
Fig. 2 is the solid-state organic precursor nanofiber cross-sectional scans electron microscope obtained by the embodiment of the present invention one.
Fig. 3, which is that the cylindric meso-porous ZnO nanofiber obtained by the embodiment of the present invention one is low, differentiates scanning electron microscope under multiplying power
Figure.
Fig. 4 is the single cylindric meso-porous ZnO nanofiber scanning electron microscope (SEM) photograph obtained by the embodiment of the present invention one.
Fig. 5 is the single cylindric meso-porous ZnO nanofiber cross-sectional scans electron microscope obtained by the embodiment of the present invention one.
Fig. 6 is the cylindric meso-porous ZnO nano-fiber material X-ray diffracting spectrum obtained by the embodiment of the present invention one.
Fig. 7 is to scan electricity under the low resolution multiplying power of the solid-state organic precursor nanofiber obtained by the embodiment of the present invention two
Mirror figure.
Fig. 8 is the solid-state organic precursor nanofiber cross-sectional scans electron microscope obtained by the embodiment of the present invention two.
Fig. 9 is that low differentiate of the elliptic cylindrical shape meso-porous ZnO nanofiber obtained by the embodiment of the present invention two scans electricity under multiplying power
Mirror figure.
Figure 10 is the single elliptic cylindrical shape meso-porous ZnO nanofiber scanning electron microscope (SEM) photograph obtained by the embodiment of the present invention two.
Figure 11 is the single elliptic cylindrical shape meso-porous ZnO nanofiber cross-sectional scans Electronic Speculum obtained by the embodiment of the present invention two
Figure.
Figure 12 is the elliptic cylindrical shape meso-porous ZnO nano-fiber material x-ray diffraction pattern obtained by the embodiment of the present invention two
Spectrum.
Figure 13 is to be scanned under the low resolution multiplying power of the solid-state organic precursor nanofiber obtained by the embodiment of the present invention three
Electron microscope.
Figure 14 is the solid-state organic precursor nanofiber cross-sectional scans electron microscope obtained by the embodiment of the present invention three.
Figure 15, which is that the banding meso-porous ZnO nanofiber obtained by the embodiment of the present invention three is low, differentiates scanning electron microscope under multiplying power
Figure.
Figure 16 is the single banding meso-porous ZnO nanofiber scanning electron microscope (SEM) photograph obtained by the embodiment of the present invention three.
Figure 17 is the column mesoporous ZnO nano fibre section scanning electron microscope (SEM) photograph of band obtained by the embodiment of the present invention three.
Figure 18 is the banding meso-porous ZnO nano-fiber material X-ray diffracting spectrum obtained by the embodiment of the present invention three.
Specific embodiment
With reference to the accompanying drawings and detailed description, the present invention is furture elucidated, it should be understood that following specific embodiments are only
For illustrating the present invention rather than limiting the scope of the invention.
Dosage in the present invention program following embodiment on ethyl alcohol, ZnAc, deionized water and Tea Saponin is with every
1gPVP is basis of reference.Cylindric either ellipticity or banding to nanofibrous structures description are not limited to include straight
Linear structure or shaped form structure.
Embodiment one
1.0g PVP (polyvinylpyrrolidone) are dissolved in 9g ethyl alcohol, stirring gluing to formation homogeneous transparent under room temperature
Thick liquid.Then add in 2.5g zinc acetate dihydrates (ZnAc), 3g deionized waters (in following embodiment can also with distilled water or
Distilled water is substituted, without influence the present invention program implementation) and 0.6g Tea Saponin (TS).By above-mentioned 60 DEG C of water of mixed liquor
Bath 30 minutes PVP/ZnAc/TS precursor solutions for being formed yellow of heating.After the spinning liquid as precursor configured is stood
In injected plastic needle tubing, and it is horizontally placed on spinning-drawing machine.Metal needle (internal diameter 0.41mm) makees electrospinning wire anode, and wire netting is made
The cathode of material is received, the distance between anode and cathode 18cm carries out electrostatic spinning under 12.5kV high pressures, is prepared
The organic precursor carrying material of high-purity.Then machine precursor tape material is placed in 70 DEG C of constant temperature drying boxes, toasts 8h, obtained
Solid-state organic precursor fiber, as shown in Figure 1 and Figure 2.Finally solid-state organic precursor fiber is placed in crucible, in air gas
Calcining heat is warming up under atmosphere with 3 DEG C/min to be calcined when 480 DEG C of heat preservations 2 are small again, then furnace cooling.Fig. 3, Fig. 4 are
The typical low power and high power stereoscan photograph of the cylindric meso-porous ZnO nanofiber of prepared high-purity show prepared
Material is the nano material of the meso-hole structure of high-purity；Fig. 5 is the cross-sectional scans electron microscope of single meso-porous ZnO nanofiber, into
One step proves the nano material that preparation-obtained material is mesoporous cylindrical-shaped structure；Fig. 6 is its corresponding X-ray diffraction
(XRD) collection of illustrative plates shows the hexagonal wurtzite ZnO that prepared meso-porous nano fibrous material is high-purity, and with good knot
Crystalline substance.
Embodiment two
1.0g PVP are dissolved in 8g ethyl alcohol, the thick liquid of stirring extremely formation homogeneous transparent under room temperature.Then add in
The Tea Saponin (TS) of 2.5g zinc acetate dihydrates (ZnAc), 4g deionized waters and 0.6g.By above-mentioned 60 DEG C of heating water baths 30 of mixed liquor
Minute is formed the PVP/ZnAc/TS precursor solutions of yellow.Injected plastic after the spinning liquid as precursor configured is stood
In needle tubing, and it is horizontally placed on spinning-drawing machine.Metal needle (internal diameter 0.41mm) makees electrospinning wire anode, and wire netting makees reception material
Cathode, the distance between anode and cathode 18cm carries out electrostatic spinning under 12.5kV high pressures, high-purity is prepared
Organic precursor fibrous material.Then machine precursor tape material is placed in 70 DEG C of constant temperature drying boxes, toasts 8h, obtaining solid-state has
Machine precursor fibre material, as shown in Figure 7, Figure 8.Finally solid-state organic precursor is placed in crucible, in air atmosphere with 3
DEG C/min be warming up to calcining heat again 480 DEG C heat preservation 2 it is small when calcined, then furnace cooling.Fig. 9, Figure 10 are prepared
The typical low power of high-purity ZnO nano fibrous material and high power stereoscan photograph, it is high-purity to show prepared material
Meso-porous nano fibrous material；Figure 11 is the cross-sectional scans picture of single ZnO nano fiber, clearly indicates out prepared receive
The section of rice material is ellipse, and it is mesoporous elliptic cylindrical shape nanofiber further to prove the material being prepared.Figure 12 is it
Corresponding X-ray diffraction (XRD) collection of illustrative plates shows the hexagonal wurtzite that prepared meso-porous nano fibrous material is high-purity
ZnO, and with good crystallinity.
Embodiment three
1.0g PVP are dissolved in 6g ethyl alcohol, the thick liquid of stirring extremely formation homogeneous transparent under room temperature.Then add in
The Tea Saponin (TS) of 2.5g zinc acetate dihydrates (ZnAc), 6g deionized waters and 0.6g.By above-mentioned 60 DEG C of heating water baths 30 of mixed liquor
Minute is formed the PVP/ZnAc/TS precursor solutions of yellow.Injected plastic after the spinning liquid as precursor configured is stood
In needle tubing, and it is horizontally placed on spinning-drawing machine.Metal needle (internal diameter 0.41mm) makees electrospinning wire anode, and wire netting makees reception material
Cathode, the distance between anode and cathode 18cm carries out electrostatic spinning under 12.5kV high pressures, high-purity is prepared
Organic precursor fiber.Then machine precursor fibre is placed in 70 DEG C of constant temperature drying boxes, toasts 8h, obtain solid-state organosilane precursor
Body fibrous material, as shown in Figure 13, Figure 14.Finally solid-state organic precursor is placed in crucible, in air atmosphere with 3 DEG C/
Min is warming up to calcining heat and is calcined again when 480 DEG C of heat preservations 2 are small, then furnace cooling.Figure 15, Figure 16 are shown as made
The typical low power of standby ZnO nano fibrous material and high power stereoscan photograph, it is meso-hole structure ZnO to show prepared material
Nano-fiber material；Figure 17 is the cross-sectional scans photo of single ZnO nano fiber, clearly indicates out prepared nano material
Rectangular cross-section, further prove the material being prepared be mesoporous banding nanofiber.Figure 18 is its corresponding X-ray
Diffraction (XRD) collection of illustrative plates shows the hexagonal wurtzite ZnO that prepared meso-porous nano fibrous material is high-purity, and with good
Crystallinity.
The present invention proposes a kind of foaming auxiliary electrostatic spining technology, by regulating and controlling containing for second alcohol and water in precursor solution
Amount reaches the precise controlling of ZnO meso-porous nano fibrous material structures.In view of traditional Electrospinning prepares the extensive of fibrous material
Property and versatility, in conjunction with the embodiments one, the result of embodiment two and embodiment three understand that the method for the present invention is only needed by regulating and controlling water
With the content of ethyl alcohol, when the introduction volume of ethyl alcohol is 9g, (i.e. alcohol water quality is than 3 for 3g for water content:1) when, can prepare cylindric
ZnO meso-porous nano fibrous materials；When the introduction volume of ethyl alcohol is 8g, (i.e. alcohol water quality is than 2 for 4g for water content:1) when, can prepare
Go out the ZnO meso-porous nano fibrous materials of elliptic cylindrical shape；When the introduction volume of ethyl alcohol is 6g, (i.e. alcohol water quality is than 1 for 6g for water content:
1) when, the ZnO meso-porous nano fibrous materials of banding can be prepared.
Embodiment 4
1.0g PVP are dissolved in about 7g ethyl alcohol, the thick liquid of stirring extremely formation homogeneous transparent under room temperature.Then plus
Enter 2g zinc acetate dihydrates (ZnAc), (alcohol water is than 2.12 for about 3.3g distilled waters:And the Tea Saponin of 0.5g (TS) 1).By above-mentioned mixing
The PVP/ZnAc/TS precursor solutions that 50 DEG C of liquid heating water bath 40 minutes is formed yellow.The presoma spinning that will have been configured
After liquid is stood in injected plastic needle tubing, and it is horizontally placed on spinning-drawing machine.Metal needle (internal diameter 0.41mm) makees electrospinning wire anode,
Wire netting is made to receive the cathode of material, and the distance between anode and cathode 15.625cm carries out electrostatic under 12.5kV high pressures
The organic precursor fiber of high-purity is prepared in spinning.Then machine precursor fibre is placed in 50 DEG C of constant temperature drying boxes, dried
Roasting 9h, obtains solid-state organic precursor fibrous material.Finally solid-state organic precursor is placed in crucible, in air atmosphere with
3.5 DEG C/min is warming up to calcining heat and is calcined again when 450 DEG C of heat preservations 1 are small, then furnace cooling.After testing, receive
Rice fiber possesses meso-hole structure, while is the ZnO meso-porous nano fibrous materials of elliptic cylindrical shape, and zinc oxide is brilliant in nano wire after testing
Type is cubic sphalerite structure.
Embodiment 5
1.0g PVP are dissolved in about 7.5g ethyl alcohol, the thick liquid of stirring extremely formation homogeneous transparent under room temperature.Then
3.5g zinc acetate dihydrates (ZnAc) are added in, (alcohol water is than 1.5 for about 5g distilled waters:And the Tea Saponin of 0.7g (TS) 1).By above-mentioned mixing
The PVP/ZnAc/TS precursor solutions that 55 DEG C of liquid heating water bath 50 minutes is formed yellow.The presoma spinning that will have been configured
After liquid is stood in injected plastic needle tubing, and it is horizontally placed on spinning-drawing machine.Metal needle (internal diameter 0.41mm) makees electrospinning wire anode,
Wire netting is made to receive the cathode of material, and the distance between anode and cathode 16cm carries out electrostatic spinning under 12.5kV high pressures,
The organic precursor fiber of high-purity is prepared.Then machine precursor fibre is placed in 60 DEG C of constant temperature drying boxes, toasted
10h obtains solid-state organic precursor fibrous material.Finally solid-state organic precursor is placed in crucible, in air atmosphere with
3.3 DEG C/min is warming up to calcining heat and is calcined again when 440 DEG C of heat preservations 2.8 are small, then furnace cooling.After testing,
Nanofiber possesses meso-hole structure, while is the ZnO meso-porous nano fibers of more flat elliptic cylindrical shape (having both banded structure)
Material, zinc oxide crystal form is cubic sphalerite structure in nano wire after testing.
Embodiment 6
1.0g PVP are dissolved in about 8.5g ethyl alcohol, the thick liquid of stirring extremely formation homogeneous transparent under room temperature.Then
4g zinc acetate dihydrates (ZnAc) are added in, (alcohol water is than 1.6 for about 5.3g deionized waters:And the Tea Saponin of 0.9g (TS) 1).It will be above-mentioned mixed
Close the PVP/ZnAc/TS precursor solutions that 60 DEG C of liquid heating water bath 40 minutes is formed yellow.The presoma configured is spun
After silk liquid is stood in injected plastic needle tubing, and it is horizontally placed on spinning-drawing machine.Metal needle (internal diameter 0.41mm) makees Electrospun sun
Pole, wire netting are made to receive the cathode of material, and the distance between anode and cathode 17cm carries out Static Spinning under 12.5kV high pressures
The organic precursor fiber of high-purity is prepared in silk.Then machine precursor fibre is placed in 80 DEG C of constant temperature drying boxes, toasted
8.5h obtains solid-state organic precursor fibrous material.Finally solid-state organic precursor is placed in crucible, in air atmosphere with
2.3 DEG C/min is warming up to calcining heat and is calcined again when 400 DEG C of heat preservations 2 are small, then furnace cooling.After testing, receive
Rice fiber possesses meso-hole structure, while is the ZnO meso-porous nano fibrous materials of flat elliptic cylindrical shape.
Embodiment 7
1.0g PVP are dissolved in about 6.6g ethyl alcohol, the thick liquid of stirring extremely formation homogeneous transparent under room temperature.Then
2.7g zinc acetate dihydrates (ZnAc) are added in, (alcohol water is than 1.94 for about 3.4g deionized waters:And the Tea Saponin of 0.8g (TS) 1).It will be upper
State the PVP/ZnAc/TS precursor solutions that 70 DEG C of mixed liquor heating water bath 60 minutes is formed yellow.The forerunner that will have been configured
After body spinning solution is stood in injected plastic needle tubing, and it is horizontally placed on spinning-drawing machine.Metal needle (internal diameter 0.41mm) makees electrospinning
Wire anode, wire netting are made to receive the cathode of material, and the distance between anode and cathode 18cm is carried out quiet under 12.5kV high pressures
The organic precursor fiber of high-purity is prepared in Electrospun.Then machine precursor fibre is placed in 55 DEG C of constant temperature drying boxes,
14h is toasted, obtains solid-state organic precursor fibrous material.Finally solid-state organic precursor is placed in crucible, in air atmosphere
Under with 4 DEG C/min be warming up to calcining heat again 420 DEG C heat preservation 2.5 it is small when calcined, then furnace cooling.Through inspection
It surveys, nanofiber possesses meso-hole structure, while is the ZnO meso-porous nano fibrous materials of nearly elliptic cylindrical shape.
Embodiment 8
1.0g PVP are dissolved in about 8.2g ethyl alcohol, the thick liquid of stirring extremely formation homogeneous transparent under room temperature.Then
3.8g zinc acetate dihydrates (ZnAc) are added in, (alcohol water is than 2.34 for about 3.5g deionized waters:And the Tea Saponin of 0.75g (TS) 1).It will be upper
State the PVP/ZnAc/TS precursor solutions that 65 DEG C of mixed liquor heating water bath 50 minutes is formed yellow.The forerunner that will have been configured
After body spinning solution is stood in injected plastic needle tubing, and it is horizontally placed on spinning-drawing machine.Metal needle (internal diameter 0.41mm) makees electrospinning
Wire anode, wire netting are made to receive the cathode of material, and the distance between anode and cathode 20cm is carried out quiet under 12.5kV high pressures
The organic precursor fiber of high-purity is prepared in Electrospun.Then machine precursor fibre is placed in 75 DEG C of constant temperature drying boxes,
13h is toasted, obtains solid-state organic precursor fibrous material.Finally solid-state organic precursor is placed in crucible, in air atmosphere
Under with 2 DEG C/min be warming up to calcining heat again 390 DEG C heat preservation 3 it is small when calcined, then furnace cooling.After testing,
Nanofiber possesses meso-hole structure, while is nearly columned ZnO meso-porous nanos fibrous material.
In above-described embodiment 1-8, during electrostatic spinning, the spacing of anode and cathode can also be 19cm, 19.5cm,
20.5cm、21cm、21.5cm、22cm、22.5cm、23cm、23.5cm、23.5cm、24cm、24.5cm、25cm.Simultaneous oxidation zinc
Crystal form do not influence the implementation of technical solution of the present invention, while also the protection domain of the present invention program is not limited to the corresponding tool
In body embodiment.
In above-described embodiment and its alternative, during electrostatic spinning, the baking that precursor fibre is placed in constant temperature drying box
Dry temperature can also be 52 DEG C, 56 DEG C, 58 DEG C, 63 DEG C, 66 DEG C, 69 DEG C, 71 DEG C, 73 DEG C, 76 DEG C, 77 DEG C, 78 DEG C.Drying time
Can also be 8.2h, 9.6h, 8.8h, 10.3h, 10.6h, 11.9h, 12.1h, 12.3h, 12.6h, 13.7h, 13.4h.
In above-described embodiment and its alternative, when precursor nano wire is through high-temperature calcination, calcining heat can also be 392
℃、300℃、310℃、320℃、330℃、340℃、350℃、360℃、370℃、377℃、478℃.Calcination time can be with
For 1.2h, 1.6h, 1.8h, 1.4h, 2.6h, 2.9h, 2.1h, 2.3h, 2.6h, 2.7h, 2.4h.
In above-described embodiment and its alternative, when precursor nano wire is through high-temperature calcination, calcination environment can also be hydrogen
Atmosphere either carbon monoxide atmosphere or oxygen atmosphere or other atmosphere of inert gases including helium, nitrogen.
This place embodiment is in place of the claimed non-limit of technical scope midrange and in embodiment technology
The new technical solution formed is replaced on an equal basis to single or multiple technical characteristics in scheme, equally all the present invention claims
In the range of protection；Simultaneously the present invention program it is all enumerate or unrequited embodiment in, in the same embodiment each
Parameter is merely representative of an example of its technical solution, and between parameters and there is no stringent cooperation and qualified relation,
Except special declaration.
The technical means disclosed in the embodiments of the present invention is not limited to the technical means disclosed in the above technical means, and is further included
Formed technical solution is combined by more than technical characteristic.The above is the specific embodiment of the present invention, should be referred to
Go out, for those skilled in the art, without departing from the principle of the present invention, can also make several
Improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.
Claims (9)
1.ZnO meso-porous nano fibers, it is characterised in that：The main component of nanofiber is Zn, O and other inevitable
Impurity element,
The nanofiber has porous structure, and the hole of the porous structure is including mesoporous；
Wherein main forms of Zn, O element in nanofiber are ZnO, and the nanofiber is perpendicular to growth method of principal axes
It is circular either ellipse or bandlet shape or subcircular or nearly ellipse or nearly bandlet shape to section；
The preparation method of the ZnO meso-porous nanos fiber, includes the following steps, 1), PVP/ZnAc/TS spinning liquid as precursor matches somebody with somebody
It puts；2) prepared by precursor nano wire；3) prepared by ZnO meso-porous nanos fiber；
Wherein step 2) precursor nano wire is prepared as PVP/ZnAc/TS spinning liquid as precursor obtaining precursor nanometer through spinning
Line；
The precursor nano wire that step 3) ZnO meso-porous nano fibers are prepared as obtaining step 2) is through high-temperature calcination, you can obtains
ZnO meso-porous nano fibers.
2. ZnO meso-porous nanos fiber according to claim 1, it is characterised in that：The nanofiber has porous structure
And the hole of the porous structure is mesoporous.
3. ZnO meso-porous nanos fiber according to claim 1 or 2, it is characterised in that：The nanometer with meso-hole structure
The specific surface area of fiber is 45-55m2/ g, mesoporous aperture averaging are 3-20nm.
4. ZnO meso-porous nanos fiber according to claim 1, it is characterised in that：In the step 2) before PVP/ZnAc/TS
It drives body spinning solution and obtains precursor nano wire through electrostatic spinning, the wherein field strength of electrostatic spinning is less than or equal to 0.8KV/cm.
5. ZnO meso-porous nanos fiber according to claim 1, it is characterised in that：In the step 1) before PVP/ZnAc/TS
Drive body spinning solution be configured to appropriate PV P being dissolved in ethyl alcohol, stirring at normal temperature obtains transparent and homogeneous solution, then add in zinc acetate,
Deionized water and TS, then heating water bath obtain yellow PVP/ZnAc/TS spinning liquid as precursor.
6. ZnO meso-porous nanos fiber according to claim 5, it is characterised in that：In the step 1) before PVP/ZnAc/TS
Ethyl alcohol and the mass ratio of deionized water are (3-1) when driving the configuration of body spinning solution：1.
7. ZnO meso-porous nanos fiber according to claim 5 or 6, it is characterised in that：PVP/ZnAc/ in the step 1)
It is dissolved in when TS spinning liquid as precursor configures per 1gPVP in 6-9g ethyl alcohol.
8. ZnO meso-porous nanos fiber according to claim 5 or 6, it is characterised in that：PVP/ZnAc/ in the step 1)
Often containing 1gPVP, then deionized water usage amount is 3-6g in spinning solution when TS spinning liquid as precursor configures.
9. ZnO meso-porous nanos fiber according to claim 1, it is characterised in that：Step 3) high temperature calcining be
Heat preservation calcining 1-3h at 300-480 DEG C of calcining heat, nano wire heating rate is 2-4 DEG C/min during calcining.
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| CN101362649A (en) * | 2008-07-01 | 2009-02-11 | 北京师范大学 | Method for preparing electro spinning mesoporous zircite fiber film |
| CN102051702A (en) * | 2010-12-03 | 2011-05-11 | 华东理工大学 | Mesoporous silicon oxide particle/degradable polymer nano composite fiber, preparation method and application thereof |
| CN104404653A (en) * | 2014-11-25 | 2015-03-11 | 宁波工程学院 | General preparation method of full-mesopore nano-fiber material |
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| CN101362649A (en) * | 2008-07-01 | 2009-02-11 | 北京师范大学 | Method for preparing electro spinning mesoporous zircite fiber film |
| CN102051702A (en) * | 2010-12-03 | 2011-05-11 | 华东理工大学 | Mesoporous silicon oxide particle/degradable polymer nano composite fiber, preparation method and application thereof |
| CN104404653A (en) * | 2014-11-25 | 2015-03-11 | 宁波工程学院 | General preparation method of full-mesopore nano-fiber material |
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