CN109731613A - A kind of PVDF/ hexagon ZnO nano-wire tunica fibrosa and its preparation method and application - Google Patents
A kind of PVDF/ hexagon ZnO nano-wire tunica fibrosa and its preparation method and application Download PDFInfo
- Publication number
- CN109731613A CN109731613A CN201811645417.8A CN201811645417A CN109731613A CN 109731613 A CN109731613 A CN 109731613A CN 201811645417 A CN201811645417 A CN 201811645417A CN 109731613 A CN109731613 A CN 109731613A
- Authority
- CN
- China
- Prior art keywords
- pvdf
- zno nano
- wire
- preparation
- obtains
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Artificial Filaments (AREA)
- Catalysts (AREA)
Abstract
The present invention provides a kind of PVDF/ hexagon ZnO nano-wire tunica fibrosas and its preparation method and application.The preparation method includes the following steps: that PVDF and zinc acetate are dissolved in organic solvent by (1), and electrostatic spinning forms PVDF/ zinc acetate nano fibrous membrane；(2) the PVDF/ zinc acetate nano fibrous membrane for obtaining step (1) is heat-treated, and obtains PVDF/ZnO nano fibrous membrane；(3) zinc salt and hexamethylenetetramine are dissolved in ammonium hydroxide, obtain growth-promoting media；(4) the PVDF/ZnO nano fibrous membrane that step (2) obtains is placed in the growth-promoting media that step (3) obtains and is reacted, obtain PVDF/ hexagon ZnO nano-wire tunica fibrosa.ZnO nano-wire on PVDF/ hexagon ZnO nano-wire tunica fibrosa provided by the invention is in hexagon, and length thickness is uniform, photocatalysis efficiency with higher.
Description
Technical field
The invention belongs to composite nano materials technical fields, and in particular to a kind of PVDF/ hexagon ZnO nano-wire fiber
Film and its preparation method and application.
Background technique
The structure and property of zinc oxide (ZnO) determine it with the performances such as good conduction, uvioresistant, nano zine oxide material
Material be even more due to having nanoscale microsize, the characteristics such as high surface area and significantly increase itself unique performance, therefore
Extensive research is prepared in nano zinc oxide material.The zinc oxide nano for the different-shape structure that different preparation methods obtain
Rice material is widely used in health care, the fields such as opto-electronic device.
The method for preparing nano zinc oxide material at present is numerous, and with their own characteristics, but generally main method can be divided into gas
Xiang Fa, solid phase method and liquid phase method three categories.
Vapor phase method is exactly to convert gas phase by processes such as distillation, evaporation, decomposition for the crystalline material of quasi- growth, is then led to
It crosses under felicity condition and makes it saturated vapor, form micro-nano material through condensation-crystallization.It is usually used in preparing ZnO nano material
Vapor phase method mainly includes pulsed laser deposition, metal-organic chemical vapor deposition equipment, thermal evaporation, magnetron sputtering and gas phase mould
Plate method etc..
Solid phase method refers to that one of reactant must be the reaction that solid matter is participated in.Common solid phase method mainly includes high energy
Ball-milling method, thermal decomposition method, high-temperature solid phase reaction method and reduction reaction method.
Liquid phase method is the one or more suitable soluble metal salts of selection, is prepared by prepared material composition metering
At solution, make each element in lewis' acid state, a kind of suitable precipitating reagent of reselection, or is grasped with evaporation, distillation, hydrolysis etc.
Make, makes metal ion homogeneous precipitation or crystallize out, it finally will precipitating or exsiccation or heat resolve preparation nano material
Method.The liquid phase method for being usually used in preparing ZnO nano material mainly includes the precipitation method, hydro-thermal method, sol-gel method, solvent heat
Method, liquid phase template and microemulsion method etc..
Certain methods compared to vapor phase method need to complete in harsh conditions such as high temperature and pressure, and hydro-thermal method has reaction temperature
The advantages such as low, the fast, less energy consumption of reaction rate, and technique is relatively simple, easy to operate, yield is high, and product good dispersion, and
The ZnO nano material being orientated, defect is few, crystallinity is high can equally be obtained.Currently, one as materials synthesis and crystal growth
Kind important method, hydro-thermal method are used widely in scientific research.
In addition, electrostatic spinning technique is also a kind of important method that preparation prepares nano zinc oxide material.(the Song such as Song
L,Jiang Q,Du P,et al.A facile synthesis of novel ZnO structures and their
Applications in photocatalysis [J] .Materials Letters, 2014,123:214-216) first pass through it is quiet
PVAc/Zn (the CH of different acetic acid Zn contents is prepared in electrospinning3COO)2Nanofiber, then fiber is calcined to acquisition at 500 DEG C
Graininess, threadiness, dandelion shape, peanut shape and microspheric ZnO nano material, and find dandelion shape ZnO to methylene
The photocatalytic degradation efficiency of base indigo plant is up to 96.2%.Senthamizhan etc. (Senthamizhan A, Balusamy B,
Aytac Z,et al.Grain boundary engineering in electrospun ZnO nanostructures as
Promising photocatalysts [J] .CrystEngComm, 2016,18 (34): 6341-6351.) pass through electrostatic spinning
Zn (Ac) is prepared in method2/ PVA nanofiber, then fiber is calcined to preparation difference under different temperatures (500 DEG C -1000 DEG C)
The growth forms of pattern nano-ZnO, the nanoparticle of discovery composition ZnO change with calcination temperature and are changed, and find 500 DEG C and forge
The ZnO nano particle of burning not only to the photocatalytic degradation efficiency highest of methylene blue, also there is very rhodamine B and p-nitrophenol
Strong degradation capability.
CN 106521678A discloses a kind of preparation method of polymer fiber base ZnO nano-wire fiber, passes through Static Spinning
Silk method is prepared for the nanofiber containing polymer and ZnO precursor, and then heat treatment forms inside and is evenly distributed at low temperature
The nanofiber of ZnO nano particle goes out ZnO nano-wire finally by hydro-thermal method self-assembled growth, forms polymer fiber base ZnO
Nanometer line fiber.But the ZnO nano-wire that this method is formed is in shuttle shape, size thickness is uneven, and the direction of growth is mixed and disorderly, up for
It is further improved.
Summary of the invention
In view of the deficiencies of the prior art, the present invention intends to provide a kind of PVDF/ hexagon ZnO nano-wire
Tunica fibrosa and its preparation method and application.ZnO nano-wire on the PVDF/ hexagon ZnO nano-wire tunica fibrosa is in hexagonal prisms
Shape, and length thickness is uniform, with higher photocatalysis effect height-oriented along the direction perpendicular to PVDF/ZnO nanofiber
Rate.
To achieve this purpose, the present invention adopts the following technical scheme:
In a first aspect, the present invention provides a kind of preparation method of PVDF/ hexagon ZnO nano-wire tunica fibrosa, feature
It is, the preparation method includes the following steps:
(1) by PVDF and Zn (CH3COO)2It is dissolved in organic solvent, obtains electrostatic spinning liquid, formed by electrostatic spinning
PVDF/Zn(CH3COO)2Nano fibrous membrane；
(2) PVDF/Zn (CH for obtaining step (1)3COO)2Nano fibrous membrane is heat-treated 12-36h at 80-140 DEG C,
Obtain PVDF/ZnO nano fibrous membrane；
(3) zinc salt and hexamethylenetetramine are dissolved in ammonium hydroxide, obtain growth-promoting media；
Wherein, the molar ratio of the zinc salt and the hexamethylenetetramine is 1:(1.5-3), in the growth-promoting media zinc salt and
The total mol concentration of hexamethylenetetramine is 0.08-0.15mol/L；
(4) the PVDF/ZnO nano fibrous membrane that step (2) obtains is placed in the growth-promoting media that step (3) obtains, in 105-
It is reacted at 130 DEG C, obtains PVDF/ hexagon ZnO nano-wire tunica fibrosa.
The present invention uses PVDF (Kynoar) and Zn (CH3COO)2(zinc acetate) prepares PVDF/Zn (CH3COO)2It receives
Rice tunica fibrosa, can make Zn (CH under cryogenic3COO)2It is decomposed to form nano-ZnO seed, water is then carried out in growth-promoting media
Thermal response, gradually growth forms ZnO nano-wire on PVDF/ZnO nanofiber.The present invention is by material rate and preparing item
Part optimizes, and the ZnO nano-wire to be formed can be made in hexagon, and length thickness is uniform, and edge is received perpendicular to PVDF/ZnO
The direction of rice fiber is height-oriented, obtained PVDF/ hexagon ZnO nano-wire tunica fibrosa photocatalysis efficiency with higher.
In the present invention, the temperature of heat treatment described in step (2) can be 80 DEG C, 85 DEG C, 90 DEG C, 95 DEG C, 100 DEG C, 105
DEG C, 110 DEG C, 115 DEG C, 120 DEG C, 125 DEG C, 130 DEG C, 135 DEG C or 140 DEG C etc..
The time of heat treatment described in step (2) can be 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h,
21h, 22h, 23h, for 24 hours, 26h, 28h, 30h, 32h or 36h etc..
The molar ratio of zinc salt described in step (3) and the hexamethylenetetramine can be 1:1.5,1:1.6,1:1.8,1:
2,1:2.2,1:2.3,1:2.5,1:2.6,1:2.8 or 1:3 etc..
In growth-promoting media described in step (3) total mol concentration of zinc salt and hexamethylenetetramine can be 0.08mol/L,
0.09mol/L, 0.1mol/L, 0.11mol/L, 0.12mol/L, 0.13mol/L, 0.14mol/L or 0.15mol/L etc..
When growth-promoting media concentration is lower, ZnO nano-wire is in irregular circle in the PVDF/ZnO nano wire tunica fibrosa of preparation
Cone cell hexagonal structure, and length thickness is uneven, the direction of growth is mixed and disorderly, and only grows on the surface layer of tunica fibrosa；Work as growth-promoting media
When excessive concentration, ZnO nano-wire is grown in fiber surface in confusedly adherency in the PVDF/ZnO nano wire tunica fibrosa of preparation,
The amount of ZnO nano-wire is also extremely few, and mixes for linear structure and laminated structure.
The temperature of reaction described in step (4) can be 105 DEG C, 108 DEG C, 110 DEG C, 112 DEG C, 115 DEG C, 118 DEG C, 120
DEG C, 122 DEG C, 125 DEG C, 128 DEG C or 130 DEG C etc..
As the preferred technical solution of the present invention, the content of PVDF is 8-25wt% in the electrostatic spinning liquid；Such as it can
Be 8.0wt%, 9.5wt%, 11.0wt%, 12.5wt%, 14.0wt%, 15.5wt%, 17.0wt%, 18.5wt%,
20.0wt%, 21.5wt%, 23.0wt% or 25.0wt% etc..
As the preferred technical solution of the present invention, PVDF and Zn (CH in the electrostatic spinning liquid3COO)2Mass ratio be 1:
(0.1-0.5)；Such as can be 1:0.1,1:0.2,1:0.3,1:0.4 or 1:0.5 etc..
After a small amount of zinc acetate is added, concentration and the viscosity of spinning solution are slightly increased, and conductivity dramatically increases, when spinning
The electrostatic force enhancing rate that fluid column is subject to is greater than its surface tension, and the diameter of fiber is gradually reduced；After a large amount of zinc acetates are added,
The concentration of spinning solution is dramatically increased with viscosity, and conductivity is excessive, and spinning solution mutability, at collosol state, spinning process is unstable.
As the preferred technical solution of the present invention, organic solvent described in step (1) is pressed by dimethylformamide and acetone
Mass ratio (6-7): (3-4) (such as 6:4,6.1:3.9,6.2:3.8,6.3:3.7,6.4:3.6,6.5:3.5,6.6:3.4,
6.7:3.3,6.8:3.2,6.9:3.1 or 7:3 etc.) composition.
As the preferred technical solution of the present invention, zinc salt and hexamethylenetetramine rubs in growth-promoting media described in step (3)
You are than being 1:(1.5-3), such as can be 1:1.5,1:1.8,1:2,1:2.3,1:2.5,1:2.8 or 1:3 etc., further preferably
For 1:2.
Preferably, the zinc salt is selected from the combination of one of zinc chloride, zinc nitrate or zinc sulfate or at least two；It is described
Combination is typical but non-limiting example has: the combination of zinc chloride and zinc nitrate, the combination of zinc chloride and zinc sulfate, zinc nitrate and sulphur
The combination etc. of sour zinc.
As the preferred technical solution of the present invention, the concentration of ammonium hydroxide described in step (3) is 1-1.5wt%；Such as it can be with
Be 1wt%, 1.1wt%, 1.15wt%, 1.2wt%, 1.25wt%, 1.3wt%, 1.35wt%, 1.4wt%, 1.45wt% or
1.5wt% etc..
As the preferred technical solution of the present invention, the time of reaction described in step (4) is 3-12h；Such as can be 3h,
4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h or 12h etc..
As the preferred technical solution of the present invention, the preparation method includes the following steps:
(1) by PVDF and Zn (CH3COO)2It is dissolved in organic solvent, obtains electrostatic spinning liquid, formed by electrostatic spinning
PVDF/Zn(CH3COO)2Nano fibrous membrane；
Wherein, the PVDF and Zn (CH3COO)2Mass ratio be 1:(0.1-0.5), in the electrostatic spinning liquid
The content of PVDF is 8-25wt%；
(2) PVDF/Zn (CH for obtaining step (1)3COO)2Nano fibrous membrane is heat-treated 12-36h at 80-140 DEG C,
Obtain PVDF/ZnO nano fibrous membrane；
(3) zinc salt and hexamethylenetetramine are dissolved in the ammonium hydroxide of 1-1.5wt%, obtain growth-promoting media；
Wherein, the molar ratio of the zinc salt and the hexamethylenetetramine is 1:(1.5-3), in the growth-promoting media zinc salt and
The total mol concentration of hexamethylenetetramine is 0.08-0.15mol/L；
(4) the PVDF/ZnO nano fibrous membrane that step (2) obtains is placed in the growth-promoting media that step (3) obtains, in 105-
3-12h is reacted at 130 DEG C, obtains PVDF/ hexagon ZnO nano-wire tunica fibrosa.
Second aspect, the present invention provide a kind of PVDF/ hexagon ZnO nano-wire tunica fibrosa, the PVDF/ hexagon
ZnO nano-wire tunica fibrosa is prepared by the method that first aspect present invention provides.
The third aspect, the present invention provides a kind of purposes of above-mentioned PVDF/ hexagon ZnO nano-wire tunica fibrosa, described
PVDF/ hexagon ZnO nano-wire tunica fibrosa is used for photochemical catalyst or fungicide.
Compared with prior art, the invention has the following advantages:
The present invention can make the ZnO nano-wire to be formed in hexagonal prisms by optimizing to material rate and preparation condition
Shape, and length thickness is uniform, it is height-oriented along the direction perpendicular to PVDF/ZnO nanofiber.Compared with pure ZnO powder, this hair
The PVDF/ hexagon ZnO nano-wire tunica fibrosa of bright offer has higher photocatalysis efficiency.
Detailed description of the invention
Fig. 1 is PVDF/Zn (CH in embodiment 13COO)2The SEM photograph of nano fibrous membrane；
Fig. 2 is the SEM photograph of PVDF/ZnO nano fibrous membrane in embodiment 1；
Fig. 3 is the SEM photograph for the PVDF/ hexagon ZnO nano-wire tunica fibrosa that embodiment 1 provides；
Fig. 4 is the SEM photograph of the ZnO nano-wire on the PVDF/ hexagon ZnO nano-wire tunica fibrosa that embodiment 1 provides；
Fig. 5 is PVDF/Zn (CH in comparative example 13COO)2The SEM photograph of nano fibrous membrane；
Fig. 6 is PVDF/Zn (CH in comparative example 23COO)2The SEM photograph of nano fibrous membrane；
Fig. 7 is PVDF/Zn (CH in embodiment 23COO)2The SEM photograph of nano fibrous membrane；
Fig. 8 is PVDF/Zn (CH in embodiment 33COO)2The SEM photograph of nano fibrous membrane；
Fig. 9 is PVDF/Zn (CH in comparative example 33COO)2The SEM photograph of nano fibrous membrane；
Figure 10 is the SEM photograph of PVDF/ZnO nano fibrous membrane in comparative example 4；
Figure 11 is the SEM photograph of PVDF/ZnO nano fibrous membrane in embodiment 4；
Figure 12 is the SEM photograph of PVDF/ZnO nano fibrous membrane in comparative example 5；
Figure 13 is that the SEM of the ZnO nano-wire on the PVDF/ hexagon ZnO nano-wire tunica fibrosa that embodiment 5 provides shines
Piece；
Figure 14 is that the SEM of the ZnO nano-wire on the PVDF/ hexagon ZnO nano-wire tunica fibrosa that embodiment 6 provides shines
Piece；
Figure 15 is that the SEM of the ZnO nano-wire on the PVDF/ hexagon ZnO nano-wire tunica fibrosa that embodiment 7 provides shines
Piece；
Figure 16 is that the SEM of the ZnO nano-wire on the PVDF/ hexagon ZnO nano-wire tunica fibrosa that comparative example 6 obtains shines
Piece；
Figure 17 is that the SEM of the ZnO nano-wire on the PVDF/ hexagon ZnO nano-wire tunica fibrosa that embodiment 8 provides shines
Piece；
Figure 18 is that the SEM of the ZnO nano-wire on the PVDF/ hexagon ZnO nano-wire tunica fibrosa that embodiment 9 provides shines
Piece；
Figure 19 is that the SEM of the ZnO nano-wire on the PVDF/ hexagon ZnO nano-wire tunica fibrosa that comparative example 7 obtains shines
Piece；
Figure 20 is the SEM photograph of the ZnO nano-wire on the PVDF/ZnO nano wire tunica fibrosa that embodiment 10 obtains；
Figure 21 is that the SEM of the ZnO nano-wire on the PVDF/ hexagon ZnO nano-wire tunica fibrosa that embodiment 11 provides shines
Piece；
Figure 22 is photocatalytic degradation of the PVDF/ hexagon ZnO nano-wire tunica fibrosa that provides of embodiment 1 to rhodamine B
Efficiency chart.
Specific embodiment
To further illustrate the technical scheme of the present invention below with reference to the accompanying drawings and specific embodiments.Art technology
Personnel understand the present invention it will be clearly understood that the specific embodiment is only to aid in, and should not be regarded as a specific limitation of the invention.
Embodiment 1
The present embodiment provides a kind of PVDF/ hexagon ZnO nano-wire tunica fibrosa, preparation method is as follows:
(1) by PVDF and Zn (CH3COO)2It is dissolved in the in the mixed solvent of dimethylformamide and acetone (mass ratio 7:3), is obtained
To electrostatic spinning liquid, setting spinning voltage is 15kV, and the distance of receiver board to spinning end is 12cm, is formed by electrostatic spinning
PVDF/Zn(CH3COO)2Nano fibrous membrane；
Wherein, PVDF and Zn (CH3COO)2Mass ratio be 1:0.3, the content of PVDF is 10wt% in electrostatic spinning liquid；
(2) PVDF/Zn (CH for obtaining step (1)3COO)2Nano fibrous membrane is heat-treated for 24 hours at 140 DEG C, is obtained
PVDF/ZnO nano fibrous membrane；
(3) zinc chloride and hexamethylenetetramine are dissolved in the ammonium hydroxide of 1.25wt%, obtain growth-promoting media；
Wherein, the molar ratio of zinc chloride and hexamethylenetetramine is 1:2；Zinc chloride and hexamethylenetetramine in growth-promoting media
Total mol concentration is 0.1mol/L；
(4) the PVDF/ZnO nano fibrous membrane that step (2) obtains is placed in the growth-promoting media that step (3) obtains, at 105 DEG C
Lower growth response 3h obtains PVDF/ hexagon ZnO nano-wire tunica fibrosa.
Using scanning electron microscope (SEM) respectively to PVDF/Zn (CH obtained in embodiment 13COO)2Nanofiber
The surface topography of film, PVDF/ZnO nano fibrous membrane and PVDF/ hexagon ZnO nano-wire tunica fibrosa is characterized.As a result it shows
Show:
PVDF/Zn(CH3COO)2The average diameter of nanofiber is 366nm (Fig. 1)；PVDF/ZnO nanofiber surface is raw
At a large amount of ZnO seed grains, the average diameter of PVDF/ZnO nanofiber is 284nm (Fig. 2)；PVDF/ hexagon ZnO receives
Ectonexine fiber surface, which is grown, in rice noodles tunica fibrosa has ZnO nano-wire (Fig. 3), and the ZnO nano-wire is in hexa-prism, thickness
Uniformly, compound with regular structure, the degree of orientation (Fig. 4) with higher.
Embodiment 2-3 and comparative example 1-3
Difference with embodiment 1 is only that the content of PVDF is different in electrostatic spinning liquid in step (1), table 1 specific as follows
It is shown:
The content table of PVDF in 1 electrostatic spinning liquid of table
| Comparative example 1 | Comparative example 2 | Embodiment 2 | Embodiment 3 | Comparative example 3 |
| 3wt% | 6wt% | 8wt% | 20wt% | 27wt% |
Using SEM respectively to PVDF/Zn (CH obtained in embodiment 2-3 and comparative example 1-33COO)2Nano fibrous membrane
Surface topography is characterized.As the result is shown:
PVDF/Zn (CH obtained in comparative example 1 and comparative example 23COO)2Nano fibrous membrane has a large amount of irregular beading knot
Structure fiber (Fig. 5 and Fig. 6), this is mainly due to the too low viscosity for leading to spinning solution of concentration of dope and surface tension are smaller,
Electrostatic force suffered by fluid column is much larger than its surface tension during electrostatic spinning, therefore fluid column in a very short period of time can not be fast
Speed, which stretches, takes out thin and is directly pulled off and flies out to form irregular shuttle shape bead structure；
Be capable of forming the relatively smooth fiber of even thickness and surface under the conditions of embodiment 2 and embodiment 3, bead structure compared with
Few, average fibre diameter is respectively 265nm (Fig. 7) and 446nm (Fig. 8)；
Since the viscosity of spinning solution and surface tension are excessive in comparative example 3, electrostatic force is caused to be not enough to overcome the table of fluid column
For face tension to cause spinning process unstable, fluid column slenderizing disorder leads to single fiber plucked and rough surface,
Average fibre diameter is 832nm (Fig. 9).
Embodiment 4 and comparative example 4-5
Difference with embodiment 1 is only that the temperature being heat-treated in step (2) is different, shown in table 2 specific as follows:
2 heat treatment temperature table of table
| Comparative example 4 | Embodiment 4 | Comparative example 5 |
| 60℃ | 80℃ | 160℃ |
Using SEM respectively to the surface topography of PVDF/ZnO nano fibrous membrane obtained in embodiment 4 and comparative example 4-5 into
Row characterization.As the result is shown:
The PVDF/ZnO nanofiber surface formed under the conditions of comparative example 4 is smooth, and average diameter is 371nm (Figure 10), table
Bright 60 DEG C of heat treatment there is not influence to the ingredient in fiber appearance structure and fiber substantially；
The PVDF/ZnO nanofiber surface formed under the conditions of embodiment 4 is coarse, there is the particulate matter of a large amount of size unevenness, fine
The average diameter of dimension is 362nm (Figure 11), shows Zn (CH3COO)2It is gradually converted into ZnO seed grain；
For comparative example 5 since heat treatment temperature is excessively high, the PVDF/ZnO nanofiber surface of formation starts fusing deformation, fiber
Appearance structure start destroy (Figure 12).
Embodiment 5-7
Difference with embodiment 1 is only that zinc chloride is different from the molar ratio of hexamethylenetetramine in step (3), specifically
It is as shown in table 3 below:
The molar ratio table of 3 zinc chloride of table and hexamethylenetetramine
| Embodiment 5 | Embodiment 6 | Embodiment 7 |
| 1:3 | 1:2.5 | 1:1.5 |
The surface topography of the obtained tunica fibrosa of embodiment 5-7 is characterized respectively using SEM.As the result is shown:
The ZnO nano-wire on PVDF/ZnO nano wire tunica fibrosa that embodiment 5-7 is obtained is in hexagon, but embodiment 5
It is uneven with ZnO nano-wire thickness in embodiment 6, and (Figure 13 and Figure 14) is cross-linked with each other between nano wire；ZnO receives in embodiment 7
For rice noodles in the hexagon of rule, length thickness is more uniform, but the direction of growth is mixed and disorderly (Figure 15).
Embodiment 8-9 and comparative example 6
Difference with embodiment 1 is only that the total moles of zinc chloride and hexamethylenetetramine are dense in growth-promoting media in step (3)
Degree is different, shown in table 4 specific as follows:
The total mol concentration table of 4 zinc chloride of table and hexamethylenetetramine
| Comparative example 6 | Embodiment 8 | Embodiment 9 |
| 0.05mol/L | 0.08mol/L | 0.15mol/L |
The surface topography of the obtained tunica fibrosa of embodiment 8-9 and comparative example 6 is characterized respectively using SEM.
As the result is shown:
The ZnO nano-wire on PVDF/ZnO nano wire tunica fibrosa that comparative example 6 obtains is in hexagon and steeple type, and square
To mixed and disorderly (Figure 16)；
The ZnO nano-wire on PVDF/ZnO nano wire tunica fibrosa that embodiment 8 obtains is in shaped flat, and length thickness is not
, the direction of growth is mixed and disorderly (Figure 17)；
The ZnO nano-wire formed on the tunica fibrosa that embodiment 9 obtains is thicker, and arranges close (Figure 18).
Embodiment 10-11 and comparative example 7
Difference with embodiment 1 is only that the growth response temperature in step (4) is different, shown in table 5 specific as follows:
5 growth response thermometer of table
| Comparative example 7 | Embodiment 10 | Embodiment 11 |
| 90℃ | 110℃ | 130℃ |
Using SEM respectively to the surface topography of the obtained PVDF/ZnO nano wire tunica fibrosa of embodiment 10-11 and comparative example 7
It is characterized.As the result is shown:
Reaction temperature in comparative example 7 is insufficient, the ZnO nano-wire shape point on obtained PVDF/ZnO nano wire tunica fibrosa
Carefully, direction is mixed and disorderly, and without all coverings PVDF/ZnO nano fibrous membrane (Figure 19)；
Hexagon of the ZnO nano-wire on PVDF/ZnO nano wire tunica fibrosa that embodiment 10-11 is obtained in rule, shape
The otherness of looks structure is smaller, and the degree of orientation is higher (Figure 20 and Figure 21)；
Photocatalysis performance test:
The PVDF/ hexagon ZnO nano-wire tunica fibrosa that the embodiment 1 of different quality (1g, 2g and 3g) provides is weighed, is put
Enter that total volume is 30mL, concentration is in the rhodamine B solution of 10mg/L, is first placed in 1h at dark and carries out at adsorption/desorption balance
Reason, then (20W, 254nm) carries out photocatalytic degradation experiment under ultraviolet light irradiation, and using blank sample and 1g ZnO powder as
Control.Take supernatant liquor every 30min, with ultraviolet-visible spectrophotometer rhodamine B maximum absorption wavelength (554nm)
The absorbance of lower measurement sample, as a result as shown in figure 22.
As can be seen from Figure 22, after 3.5h under ultraviolet light, the rhodamine B self-degradation of any substance is not added
About 12%, content is respectively photocatalysis of the PVDF/ hexagon ZnO nano-wire tunica fibrosa of 1g, 2g and 3g to rhodamine B
Degradation is respectively 53%, 79% and 95%, and catalytic rate is sequentially increased.This shows that the zinc oxide content as catalyst is got over
Height is bigger to the catalytic degradation efficiency of rhodamine B.And the pure ZnO of 1g is about 47% to the photocatalytic degradation of rhodamine B, it is very bright
It shows it and PVDF/ hexagon ZnO nano-wire tunica fibrosa is slightly below to the catalytic degradation efficiency of rhodamine B.This may be due to ZnO
Powder is easy to be deposited on bottom during staticaccelerator adsorption degradation in the solution, and the highly oriented hexagonal prisms being grown on tunica fibrosa
Shape ZnO nano-wire effectively increases light-catalysed receiving area, therefore improves it and imitate to the photocatalytic degradation of rhodamine B
Rate.
The Applicant declares that the foregoing is merely a specific embodiment of the invention, but protection scope of the present invention not office
It is limited to this, it should be clear to those skilled in the art, any to belong to those skilled in the art and take off in the present invention
In the technical scope of dew, any changes or substitutions that can be easily thought of, and all of which fall within the scope of protection and disclosure of the present invention.
Claims (10)
1. a kind of preparation method of PVDF/ hexagon ZnO nano-wire tunica fibrosa, which is characterized in that the preparation method includes
Following steps:
(1) by PVDF and Zn (CH3COO)2It is dissolved in organic solvent, obtains electrostatic spinning liquid, PVDF/ is formed by electrostatic spinning
Zn(CH3COO)2Nano fibrous membrane；
(2) PVDF/Zn (CH for obtaining step (1)3COO)2Nano fibrous membrane is heat-treated 12-36h at 80-140 DEG C, obtains
PVDF/ZnO nano fibrous membrane；
(3) zinc salt and hexamethylenetetramine are dissolved in ammonium hydroxide, obtain growth-promoting media；
Wherein, the molar ratio of the zinc salt and the hexamethylenetetramine is 1:(1.5-3), zinc salt and six times in the growth-promoting media
The total mol concentration of tetramine is 0.08-0.15mol/L；
(4) the PVDF/ZnO nano fibrous membrane that step (2) obtains is placed in the growth-promoting media that step (3) obtains, at 105-130 DEG C
Lower reaction obtains PVDF/ hexagon ZnO nano-wire tunica fibrosa.
2. preparation method according to claim 1, which is characterized in that the content of PVDF is 8- in the electrostatic spinning liquid
25wt%.
3. preparation method according to claim 1 or 2, which is characterized in that PVDF and Zn in the electrostatic spinning liquid
(CH3COO)2Mass ratio be 1:(0.1-0.5).
4. preparation method according to claim 1-3, which is characterized in that organic solvent described in step (1) by
Dimethylformamide and acetone (6-7) in mass ratio: (3-4) composition.
5. preparation method according to claim 1-4, which is characterized in that zinc in growth-promoting media described in step (3)
The molar ratio of salt and hexamethylenetetramine is 1:(1.5-3)；
Preferably, the zinc salt is selected from the combination of one of zinc chloride, zinc nitrate or zinc sulfate or at least two.
6. preparation method described in -5 according to claim 1, which is characterized in that the concentration of ammonium hydroxide described in step (3) is 1-
1.5wt%.
7. preparation method according to claim 1-6, which is characterized in that the time of reaction described in step (4)
For 3-12h.
8. preparation method according to claim 1-7, which is characterized in that the preparation method includes following step
It is rapid:
(1) by PVDF and Zn (CH3COO)2It is dissolved in organic solvent, obtains electrostatic spinning liquid, PVDF/ is formed by electrostatic spinning
Zn(CH3COO)2Nano fibrous membrane；
Wherein, the PVDF and Zn (CH3COO)2Mass ratio be 1:(0.1-0.5), PVDF in the electrostatic spinning liquid
Content is 8-25wt%；
(2) PVDF/Zn (CH for obtaining step (1)3COO)2Nano fibrous membrane is heat-treated 12-36h at 80-140 DEG C, obtains
PVDF/ZnO nano fibrous membrane；
(3) zinc salt and hexamethylenetetramine are dissolved in the ammonium hydroxide of 1-1.5wt%, obtain growth-promoting media；
Wherein, the molar ratio of the zinc salt and the hexamethylenetetramine is 1:(1.5-3), zinc salt and six times in the growth-promoting media
The total mol concentration of tetramine is 0.08-0.15mol/L；
(4) the PVDF/ZnO nano fibrous membrane that step (2) obtains is placed in the growth-promoting media that step (3) obtains, at 105-130 DEG C
Lower reaction 3-12h obtains PVDF/ hexagon ZnO nano-wire tunica fibrosa.
9. a kind of PVDF/ hexagon ZnO nano-wire tunica fibrosa, which is characterized in that the PVDF/ hexagon ZnO nano-wire
Tunica fibrosa is prepared by the described in any item methods of claim 1-8.
10. a kind of purposes of PVDF/ hexagon ZnO nano-wire tunica fibrosa as claimed in claim 9, which is characterized in that institute
PVDF/ hexagon ZnO nano-wire tunica fibrosa is stated for photochemical catalyst or fungicide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811645417.8A CN109731613A (en) | 2018-12-29 | 2018-12-29 | A kind of PVDF/ hexagon ZnO nano-wire tunica fibrosa and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811645417.8A CN109731613A (en) | 2018-12-29 | 2018-12-29 | A kind of PVDF/ hexagon ZnO nano-wire tunica fibrosa and its preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109731613A true CN109731613A (en) | 2019-05-10 |
Family
ID=66362678
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811645417.8A Pending CN109731613A (en) | 2018-12-29 | 2018-12-29 | A kind of PVDF/ hexagon ZnO nano-wire tunica fibrosa and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109731613A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112046112A (en) * | 2020-08-28 | 2020-12-08 | 南方医科大学 | Intelligent material with electrostriction as well as preparation method and application thereof |
| CN113042027A (en) * | 2021-03-31 | 2021-06-29 | 苏州大学 | Preparation method of ZnO/CQDs composite nanofiber membrane |
| CN113654577A (en) * | 2021-07-14 | 2021-11-16 | 西南交通大学 | ZnO/PVDF nanofiber flexible piezoelectric sensor with multistage core-shell structure and preparation method thereof |
| CN113877442A (en) * | 2021-11-04 | 2022-01-04 | 阿克菲姆膜材(嘉兴)有限公司 | Supported PTFE hollow fiber membrane with catalytic function and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103474610A (en) * | 2013-09-29 | 2013-12-25 | 天津工业大学 | Method for preparing composite lithium-ion battery separator through electrostatic spinning/electrostatic spraying |
| US20150182652A1 (en) * | 2013-12-31 | 2015-07-02 | Industry-Academic Cooperation Foundation, Yonsei University | Self-powered piezoelectric structure and method of manufacturing the same |
| CN106521678A (en) * | 2016-11-01 | 2017-03-22 | 华南协同创新研究院 | Preparation method of polymer fiber-based ZnO nanowire fiber |
| CN107237043A (en) * | 2017-06-23 | 2017-10-10 | 苏州大学 | Load the preparation method of the tunica fibrosa of oriented zinc oxide nanometer rods |
-
2018
- 2018-12-29 CN CN201811645417.8A patent/CN109731613A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103474610A (en) * | 2013-09-29 | 2013-12-25 | 天津工业大学 | Method for preparing composite lithium-ion battery separator through electrostatic spinning/electrostatic spraying |
| US20150182652A1 (en) * | 2013-12-31 | 2015-07-02 | Industry-Academic Cooperation Foundation, Yonsei University | Self-powered piezoelectric structure and method of manufacturing the same |
| CN106521678A (en) * | 2016-11-01 | 2017-03-22 | 华南协同创新研究院 | Preparation method of polymer fiber-based ZnO nanowire fiber |
| CN107237043A (en) * | 2017-06-23 | 2017-10-10 | 苏州大学 | Load the preparation method of the tunica fibrosa of oriented zinc oxide nanometer rods |
Non-Patent Citations (1)
| Title |
|---|
| 陈柔羲: "新型气泡静电纺丝技术及自清洁纳米纤维膜的制备", 《中国博士学位论文全文数据库工程科技I辑》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112046112A (en) * | 2020-08-28 | 2020-12-08 | 南方医科大学 | Intelligent material with electrostriction as well as preparation method and application thereof |
| CN112046112B (en) * | 2020-08-28 | 2021-08-24 | 南方医科大学 | Intelligent material with electrostriction as well as preparation method and application thereof |
| CN113042027A (en) * | 2021-03-31 | 2021-06-29 | 苏州大学 | Preparation method of ZnO/CQDs composite nanofiber membrane |
| CN113654577A (en) * | 2021-07-14 | 2021-11-16 | 西南交通大学 | ZnO/PVDF nanofiber flexible piezoelectric sensor with multistage core-shell structure and preparation method thereof |
| CN113877442A (en) * | 2021-11-04 | 2022-01-04 | 阿克菲姆膜材(嘉兴)有限公司 | Supported PTFE hollow fiber membrane with catalytic function and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109731613A (en) | A kind of PVDF/ hexagon ZnO nano-wire tunica fibrosa and its preparation method and application | |
| Das et al. | Influence of surface morphology on photocatalytic performance of zinc oxide: A review | |
| CN105731535B (en) | A kind of preparation method of Zinc oxide/titanium dioxide composite nano materials | |
| Huang et al. | Low temperature synthesis and photocatalytic properties of highly oriented ZnO/TiO2− xNy coupled photocatalysts | |
| Luo et al. | Self-assembly of single-crystal ZnO nanorod arrays on flexible activated carbon fibers substrates and the superior photocatalytic degradation activity | |
| Duo et al. | One-step hydrothermal synthesis of ZnO microflowers and their composition-/hollow nanorod-dependent wettability and photocatalytic property | |
| Wang et al. | Open porous BiVO4 nanomaterials: Electronspinning fabrication and enhanced visible light photocatalytic activity | |
| CN103359773A (en) | Preparation method of zinc oxide nanorod | |
| CN108914250A (en) | The preparation method of poly- acetyl acetone titanium precursors colloidal sol spinning solution, titanium oxide continuous fiber and nanofiber | |
| Zuo et al. | Application of microcrystalline cellulose to fabricate ZnO with enhanced photocatalytic activity | |
| CN101880054A (en) | Method for preparing hollow zinc oxide microspheres | |
| CN110672672A (en) | Zn–In2O3Preparation method and application of porous nanofiber gas-sensitive material | |
| CN111744503A (en) | Z-shaped heterojunction MoS2/Bi2WO6Composite photocatalyst and preparation method and application thereof | |
| CN108855033A (en) | The method for preparing porous nano-sheet three-dimensional zinc oxide catalysis material as template using shaddock endothelium | |
| Xu et al. | Batch preparation of CuO/ZnO-loaded nanofiber membranes for photocatalytic degradation of organic dyes | |
| Preda et al. | Zinc oxide electroless deposition on electrospun PMMA fiber mats | |
| Fang et al. | Preparation, characterization and photocatalytic performance of heterostructured CuO–ZnO-loaded composite nanofiber membranes | |
| Sun et al. | Controllable hydrothermal synthesis, growth mechanism, and properties of ZnO three-dimensional structures | |
| CN101045552A (en) | Surface chemical preparation method of cadmium sulfide semiconductor nanoparticle | |
| CN109382088B (en) | SnO2/α～Bi2O3/β～Bi2O3Composite material and preparation method thereof | |
| Zhao et al. | Fabrication and photocatalytic performance of one-dimensional Ag3PO4 sensitized SrTiO3 nanowire | |
| Liu et al. | Fabrication and photocatalytic properties of flexible BiOI/SiO2 hybrid membrane by electrospinning method | |
| CN108525662B (en) | Truncated cube Ag2O modified TiO2Preparation and application of hollow nanofiber photocatalyst | |
| CN102070178A (en) | Method for preparing yttrium oxide micro-nano-materials based on hydrothermal technology regulation and control | |
| CN1843935A (en) | A tetrapod-like nanorod of zinc oxide, its preparation method and apparatus |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190510 |