CN110241484A - A kind of preparation method and application of ZnO/CNF composite material - Google Patents
A kind of preparation method and application of ZnO/CNF composite material Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 24
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 21
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 21
- 239000002121 nanofiber Substances 0.000 claims abstract description 19
- 238000009987 spinning Methods 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000003751 zinc Chemical class 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 20
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 11
- 239000004246 zinc acetate Substances 0.000 claims description 11
- 230000001699 photocatalysis Effects 0.000 claims description 10
- 238000007146 photocatalysis Methods 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 239000002070 nanowire Substances 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 16
- 239000000463 material Substances 0.000 abstract description 12
- 239000000835 fiber Substances 0.000 abstract description 5
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 3
- 239000002134 carbon nanofiber Substances 0.000 description 68
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 65
- 230000015556 catabolic process Effects 0.000 description 19
- 238000006731 degradation reaction Methods 0.000 description 19
- 238000001354 calcination Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229940043267 rhodamine b Drugs 0.000 description 4
- -1 zinc salt Chemical class 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007850 degeneration Effects 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- FCOUFRZOMZERRM-UHFFFAOYSA-N [O-2].[Zn+2].[C+4].[O-2].[O-2] Chemical compound [O-2].[Zn+2].[C+4].[O-2].[O-2] FCOUFRZOMZERRM-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000002500 effect on skin Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
- D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Chemical Kinetics & Catalysis (AREA)
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- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention belongs to technical field of nanometer material preparation, and in particular to a kind of preparation method and application of ZnO/CNF composite material.The preparation method of the ZnO/CNF composite material includes the following: that (1) polyvinyl alcohol is dissolved in water, forms polyvinyl alcohol water solution；(2) under stirring condition, soluble zinc salt is added in the polyvinyl alcohol water solution, spinning solution is obtained；(3) spinning solution is subjected to electrostatic spinning, it is dry, ZnO/CNF presoma nanofiber is made；(4) by the ZnO/CNF presoma nanofiber, in N2Under conditions of, it is calcined, ZnO/CNF composite material is made.The method of the present invention preparation ZnO/CNF composite material composite performance it is good, ZnO can uniform load on CNF, the uniform and stable property of fiber thickness is good, and have excellent photocatalytic degradation efficiency.
Description
Technical field
The invention belongs to technical field of nanometer material preparation, and in particular to a kind of preparation method of ZnO/CNF composite material
And application.
Background technique
Photocatalytic oxidation is a kind of advanced oxidation technology to grow up in recent decades, it be by specific light source (such as
Ultraviolet light) and catalyst (TiO2, ZnO or CdS etc.) synergy carries out the process of degradation treatment to organic wastewater.With traditional water
Physical method in processing technique based on the separation of pollutant, concentration and phase transfer etc. is compared, and has apparent energy conservation, height
Effect, the advantages that contaminant degradation is thorough.
Currently, light-catalysed material is based on conductor oxidate, but by the higher limitation of operating temperature, and nano junction
Structure material consumes less energy and the advantages such as operation is safer is widely used in photocatalysis due to can reduce operating temperature
Material.
Electrostatic spinning technique is one kind with high-strength electric field by polymer molecule solution or melt jet at superfine fibre
Technology.Electrostatic spinning is the currently the only method that can directly, continuously prepare polymer nanofiber, is preparing nanofiber neck
Domain is widely used, it is considered to be most one of simple effective method has successfully been prepared for not in this way
Same nanofiber.Electrostatic spinning apparatus is mainly made of four parts: DC high-voltage power supply, solution supplying device, spinning appts,
It is grounded reception device.Electrostatic spinning technique has the characteristics of easy to operate, can quickly, largely, continuously to prepare micro nanometer fiber.
At present the most important feature of ZnO/CNF composite material nanometer structural material be exactly there is high specific surface area so that
Catalytic degradation efficiency is higher.ZnO/CNF composite material is able to achieve having complementary functions for various composite materials, widens application field.
Quantum size effect, small-size effect, skin effect and the interfacial effect of nano material make it have a series of excellent
The macroeffects such as different electricity, magnetic, light, mechanics and chemistry.Especially in photocatalysis, this challenging field of photoelectric conversion,
Nano semiconductor material more would indicate that its peculiar advantage.Since the photocatalytic effect discovery of semiconductor, people are caused always
Attention, reason be this effect water treatment, organic matter degradation, failure in terms of have important application.
In recent years, people have been devoted to find the material that photolytic activity is good, photocatalysis efficiency is high, inexpensive, especially to sun photaesthesia
Material, so as to using photocatalysis develop new product, expand application range.Groundwork at this stage is dedicated to developing novel
Catalysis material.
There is high-specific surface area to be conducive to come into full contact with light source for ZnO/CNF composite material nanometer structure, to sunlight
It is more sensitive, substantially increase photolytic activity, photocatalysis efficiency.Compared with simple ZnO nano fiber, ZnO/CNF composite active
It is higher and higher to catalytic degradation efficiency.
For the prior art, the article delivered such as Jingbo Mu " High Photocatalytic Activity of
ZnO-Carbon Nanofiber Heteroarchitectures ", PAN is obtained into PAN nanofiber using method of electrostatic spinning,
Then the obtained carbon nano-fiber that is carbonized is carried out, then zinc acetate and carbon nano-fiber are carried out by hydro-thermal reaction by hydro-thermal method and obtained
ZnO/CNFs, this method is complicated for operation, high production cost, and the ZnO being prepared into is covered on carbon nano-fiber surface, is easy to de-
It falls, stability is poor.Article " the Solution blowing of ZnO nanoflake- delivered such as Shaojun Shi
Encapsulated carbon nanofibers as electrodes for supercapacitors ", use purging
Method obtain zinc acetate/PAN, obtain ZnO/CNF after calcining, the method be not easy realize industrialization.
Chinese patent CN108760847A discloses a kind of electrostatic spinning and high temperature cabonization method prepares zinc oxide-carbon Nanowire
The method for tieing up composite material and its modified electrode after this mixes ZnO nano particle with PAN spinning solution, carries out electrostatic spinning,
Then ZnO/PAN nanofiber is obtained；After ZnO/PAN composite nano fiber is carried out calcining carbonization again, it is compound to obtain ZnO/CNF
Material is very easy to reunite due to ZnO nano particle, after being the mixing of PAN spinning solution, disperses it not in spinning solution
Uniformly cause ZnO and CNF composite effect in the ZnO/CNF composite material of preparation bad, it is possible that on carbon nano-fiber
The situation of the not no loading ZnO in part, causes its performance bad.
Summary of the invention
In order to solve the stability and uniformity of ZnO/CNF composite material in the prior art, the present invention provides one kind
The preparation method of ZnO/CNF composite material.The present invention is carried out using spinning solution prepared by soluble zinc salt and polyvinyl alcohol (PVA)
Electrostatic spinning obtains zinc salt/PVA nanofiber, and using calcining, the zinc in zinc salt is oxidized to obtain ZnO, PVA high temperature cabonization
Carbon nano-fiber (CNF) is obtained, finally obtained product ZnO/CNF composite material.
The technical scheme is that proceed as follows:
A kind of preparation method of ZnO/CNF composite material, which comprises the steps of:
(1) polyvinyl alcohol is dissolved in distilled water, forms polyvinyl alcohol water solution；
(2) under stirring condition, soluble zinc salt is added in polyvinyl alcohol water solution obtained by step (1), it is molten to obtain spinning
Liquid；
(3) spinning solution for obtaining step (2) carries out electrostatic spinning, and ZnO/CNF presoma nanometer is made in drying at room temperature
Fiber；
(4) by ZnO/CNF presoma nanofiber obtained by step (3), in logical N2Under conditions of, it is calcined, is made
ZnO/CNF composite material.
Preferably, step (2) soluble zinc salt is one or more of zinc nitrate, zinc chloride and zinc acetate.
Preferably, stirring described in step (2) carries out at being 60~80 DEG C in temperature.
Preferably, the soluble zinc salt is with Zn2+The molar ratio of meter and polyvinyl alcohol is 200~500:1.
Preferably, the condition of electrostatic spinning described in step (3) are as follows: voltage be 10~30kV, 0.5~1.5mL/h of flow velocity,
Receiving distance is 15~30cm.
Preferably, 250~1000 DEG C of temperature of step (4) described calcining, time are 6.5~11.5h.
It is another object of the present invention to provide the ZnO/CNF composite materials of the preparation method preparation described in one kind in light
Application in catalytic field.
Beneficial effects of the present invention:
(1) present invention carries out electrostatic spinning using spinning solution prepared by soluble zinc salt and polyvinyl alcohol (PVA), can make
Soluble zinc salt and PVA can be uniformly mixed, being conducive to ZnO that subsequent calcination obtains and CNF can combine closely, and ZnO
The preferable ZnO/CNF composite material of composite performance can be obtained, compared with the existing technology Jingbo Mu with uniform load on CNF
Etc. " the High Photocatalytic Activity of ZnO-Carbon Nanofiber delivered
Heteroarchitectures " first electrostatic spinning synthesis CNF and publication CN108760847A directly carried out with ZnO it is compound
The easy to reunite and inorganic material of existing inorganic material (CNF, ZnO) and the compatibility of organic material (PAN), the degree of cross linking are not
High and caducous problem, the above-mentioned technical problem of preparation method effective solution of the invention, is had good stability
ZnO/CNF composite material.
(2) ZnO/CNF composite material prepared by the present invention, due to ZnO can uniform load on the surface CNF so that ZnO/
CNF composite material, with the active site of more light-catalyzed reaction, improves the degradation of light-catalyzed reaction in photocatalytic degradation
Effect.
(3) production process continuous-stable of the present invention, technology controlling and process is simple, preparation ZnO/CNF composite fiber thickness
Uniformly, stable product quality is good；The present invention is easily industrialized, and it is simple to be conducive to technical controlling.
Detailed description of the invention
Fig. 1 is the XRD diagram of ZnO/CNF presoma nanofiber made from embodiment 1；
Fig. 2 is the SEM figure of ZnO/CNF presoma nanofiber made from embodiment 1；
Fig. 3 is the XRD diagram of ZnO/CNF composite material made from embodiment 1；
Fig. 4 is the SEM figure of ZnO/CNF composite material made from embodiment 1；
Fig. 5 is degradation rate curve graph of the ZnO/CNF composite material to rhodamine B solution；
Fig. 6 is effect tendency figure of the ZnO/CNF composite material to degradation rate of different dosages.
Specific embodiment
The contents of the present invention will be described further below, the content of present invention is not limited only to the interior of following each embodiments
Hold, the purpose invented equally also may be implemented in the combination of one of them or several specific embodiments.
One, the preparation of ZnO/CNF composite material
Embodiment 1
(1) polyvinyl alcohol (average molecular weight 145000) for weighing 3.0152g is dissolved in 30mL distilled water, is stirred evenly
Obtain polyvinyl alcohol water solution.
(2) it weighs 1.2390g zinc acetate to pour into polyvinyl alcohol water solution obtained by step (2), the 3h time is stirred at 80 DEG C,
Obtain spinning solution；
(3) spinning solution that step (2) obtains is placed in syringe, is 15kV in electrostatic spinning voltage, flow velocity is
0.8mL/h and reception distance carry out electrostatic spinning under conditions of being 16cm, a night are dried at room temperature for, before ZnO/CNF is made
Drive body nanofiber.
(4) ZnO/CNF presoma nanofiber obtained by step (3) is placed in porcelain boat, in logical N2Under conditions of, from room temperature
600 DEG C are gradually heated to, 10.5h is calcined, sample ZnO/CNF composite material is made.
The XRD diagram of ZnO/CNF presoma nanofiber prepared by the present embodiment is as shown in Figure 1, it can be seen that without spy
It levies peak to occur, the product ZnO/CNF presoma nanofiber before illustrating calcining is unbodied state；Its SEM schemes such as Fig. 2 institute
Show, it can be seen from the figure that ZnO/CNF presoma nanofiber surface is Non-smooth surface tubulose.
The XRD diagram of ZnO/CNF composite material prepared by the present embodiment is fig. 3, it is shown that by calcining carbonization
Product afterwards has phase at 24.6 °, 31.6 °, 34.2 °, 47.3 °, 56.6 °, 62.9 °, 67.9 °, 68.9 °, 77.1 °, 89.5 °
The diffraction maximum answered illustrates that the present embodiment is successfully prepared ZnO/CNF composite material；Its SEM figure is as shown in figure 4, can be with from figure
Find out, the ZnO/CNF composite material surface obtained after calcining carbonization is smooth tubulose.
Embodiment 2
The present embodiment is unlike the first embodiment: the zinc acetate in step (2) changes zinc nitrate, polyethylene in step (1) into
Zinc nitrate in pure and mild step (2) is added according to the amount that molar ratio is 1:400, and electrostatic spinning voltage is changed to 20kV in step (3),
Other are the same as embodiment 1.
Embodiment 3
The present embodiment is unlike the first embodiment: the zinc acetate in step (2) changes zinc nitrate, polyethylene in step (1) into
Zinc nitrate in pure and mild step (2) is added according to the amount that molar ratio is 1:200, and electrostatic spinning flow velocity is changed in step (3)
1.0mL/h, the calcination time in step (4) are 7h.Other are the same as embodiment 1.
Embodiment 4
The present embodiment is unlike the first embodiment: the zinc acetate in step (2) changes zinc nitrate, polyethylene in step (1) into
Zinc nitrate in pure and mild step (2) is added according to the amount that molar ratio is 1:450, and electrostatic spinning flow velocity is changed in step (3)
1.2mL/h, the calcination time in step (4) are 8h.Other are the same as embodiment 1.
Embodiment 5
The present embodiment is unlike the first embodiment: the zinc acetate in step (2) changes zinc nitrate, Static Spinning in step (3) into
The reception distance of silk is 15cm, and the temperature heated in step (4) is changed to 700 DEG C.Other are the same as embodiment 1.
Embodiment 6
The present embodiment is unlike the first embodiment: the zinc acetate in step (2) changes zinc nitrate, Static Spinning in step (3) into
It is 15cm that silk, which receives distance, and the temperature heated in step (4) is changed to 750 DEG C.Other are the same as embodiment 1.
Embodiment 7
The present embodiment is unlike the first embodiment: electrostatic spinning voltage is 20kV in step (3), and receiving distance is 20cm,
The temperature heated in step (4) is changed to 800 DEG C.Other are the same as embodiment 1.
Embodiment 8
The present embodiment is unlike the first embodiment: electrostatic spinning voltage is 15kV in step (3), and receiving distance is 25cm,
The temperature heated in step (4) is changed to 900 DEG C.Other are the same as embodiment 1.
Embodiment 9
The present embodiment is unlike the first embodiment: electrostatic spinning voltage is 15kV in step (3), and receiving distance is 20cm,
The temperature heated in step (4) is 1000 DEG C.Other are the same as embodiment 1.
Embodiment 10
The present embodiment is unlike the first embodiment: electrostatic spinning voltage is 15kV in step (3), and receiving distance is 25cm,
The temperature heated in step (4) is 1000 DEG C.Other are the same as embodiment 1.
Comparative example 1
Zinc acetate in embodiment 1 is replaced with into ZnO nano particle, other with embodiment 1, obtain sample ZnO/CNF
Composite material.
Two, catalysis degeneration experiment
The ZnO/CNF composite material that embodiment 1 and comparative example 1 are obtained is tested applied to photocatalytic degradation, by embodiment 1
It is 20mg/L's that the ZnO/CNF composite material of ZnO/CNF composite material and comparative example 1 preparation of preparation, which is separately added into 50mL concentration,
In rhodamine B (RB) solution, it is denoted as example 1 group and 1 group of comparative example respectively, then sets one group of blank group, for any catalysis is not added
Agent stirs 30 minutes under conditions of unglazed, it is anti-then to carry out catalytic degradation under the irradiation apart from the ultraviolet light that liquid level is 15cm
It answers, while carrying out electromagnetic agitation, all reactions carry out at room temperature.Using UV-2802PCS type spectrophotometric determination sample
Light absorption value A, initial concentration C0, the concentration of sample is C, and degradation rate is D%=[(C0-C)/C0] × 100%.With light
Be abscissa according to the time, degradation rate as shown in figure 5, with light application time gradually extension, degradation rate is gradually increased.From figure
5 can be seen that the catalytic effect of ZnO/CNF composite material prepared by embodiment 1 compared with ZnO/CNF composite wood prepared by comparative example 1
The catalytic efficiency of material wants high, it may be possible to which the load on CNF of ZnO is not in the ZnO/CNF composite material prepared due to comparative example 1
Uniformly, to influence the catalytic effect of ZnO, and the composite performance of ZnO/CNF composite material prepared by the embodiment of the present invention 1 compares
Good, ZnO is uniformly dispersed, to have preferable catalytic effect, 60min degradation rate reaches 88.9%.Blank group be not catalyzed
Under conditions of agent, degradation rate is lower, and almost unchanged.
2~10 gained ZnO/CNF composite material of embodiment also imitate by the authenticated catalysis degeneration experiment to rhodamine B, degradation
Rate is suitable with the degradation efficiency of 1 gained ZnO/CNF composite material of embodiment, and the degradation rate of 60min is between 88~92%, experiment
Process repeats no more.
Fixed rhodamine mass concentration is 20mg/L, changes the dosage of ZnO/CNF composite material prepared by embodiment 1,
Influence of the ZnO/CNF composite material of different dosages to degradation rate is as shown in Figure 6, it can be seen that ZnO/CNF composite material
When dosage is 1g/L, degradation rate reaches highest.
Claims (7)
1. a kind of preparation method of ZnO/CNF composite material, which comprises the steps of:
(1) polyvinyl alcohol is dissolved in distilled water, forms polyvinyl alcohol water solution；
(2) under stirring condition, soluble zinc salt is added in polyvinyl alcohol water solution obtained by step (1), spinning solution is obtained；
(3) spinning solution for obtaining step (2) carries out electrostatic spinning, and ZnO/CNF presoma Nanowire is made in drying at room temperature
Dimension；
(4) by ZnO/CNF presoma nanofiber obtained by step (3), in logical N2Under conditions of, it is calcined, ZnO/CNF is made
Composite material.
2. a kind of preparation method of ZnO/CNF composite material according to claim 1, which is characterized in that step (2) is described can
Soluble zinc salt is one or more of zinc nitrate, zinc chloride and zinc acetate.
3. a kind of preparation method of ZnO/CNF composite material according to claim 1, which is characterized in that described in step (2)
Stirring carries out at being 60~80 DEG C in temperature.
4. a kind of preparation method of ZnO/CNF composite material according to claim 1, which is characterized in that the soluble Zn
Salt is with Zn2+The molar ratio of meter and polyvinyl alcohol is 200~500:1.
5. a kind of preparation method of ZnO/CNF composite material according to claim 1, which is characterized in that described in step (3)
The condition of electrostatic spinning are as follows: voltage is 10~30kV, 0.5~1.5mL/h of flow velocity, and receiving distance is 15~30cm.
6. a kind of preparation method of ZnO/CNF composite material according to claim 1, which is characterized in that step (4) is described to forge
250~1000 DEG C of the temperature of burning, time are 6.5~11.5h.
7. the ZnO/CNF composite material of described in any item preparation method preparations is in photocatalysis field according to claim 1~6
Application.
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