CN106702534A - Preparation method of AZO (Al-doped ZnO) hollow nanofibers - Google Patents
Preparation method of AZO (Al-doped ZnO) hollow nanofibers Download PDFInfo
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- CN106702534A CN106702534A CN201611016415.3A CN201611016415A CN106702534A CN 106702534 A CN106702534 A CN 106702534A CN 201611016415 A CN201611016415 A CN 201611016415A CN 106702534 A CN106702534 A CN 106702534A
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- 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
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- 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
- D01F1/08—Addition of substances to the spinning solution or to the melt for forming hollow filaments
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- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
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Abstract
The invention discloses a preparation method of AZO (Al-doped ZnO) hollow nanofibers. The preparation method comprises the following steps: stirring PVA (polyvinyl acetate) and deionized water at a certain ratio at the constant temperature into a solution A and performing electrostatic spinning, so as to obtain PVA nanofibers; placing the PVA nanofibers into an oven for heat treatment, so as to endow the PVA nanofibers with the feature of hot water resistance; preparing a mixed solution B of zinc salt and aluminum salt at a certain ratio, placing the PVA nanofibers after heat treatment into a 3-mouth flask, soaking the PVA nanofibers with deionized water, stirring the mixture at a low speed, inserting a thermometer into one side of the 3-mouth flask to monitor reaction temperature in real time, dropwise adding the solution A on the other side of the 3-mouth flask, dropwise adding 1-50mol/L alkali liquor to adjust the pH value to 5-10, controlling the pH value of the solution to be constant, taking out AZO@PVA precursor nanofiber membrane after the reaction is ended, spreading the membrane on a polyfluortetraethylene plate for indoor temperature airing, and performing high-temperature calcination, so as to obtain the AZO hollow nanofibers. The AZO hollow nanofibers obtained by the invention are stable in dimension and uniform in shape.
Description
Technical field
The present invention relates to a kind of preparation method of Al-Doped ZnO (AZO) hollow Nano fiber in use, belong to nanofiber technology
Field.
Background technology
Requirement with city and industrial expansion and people to clean living environment is improved constantly, and environmental improvement is subject to
Pressure it is increasing.Nanometer technology can substantially reduce existing heavy pollution sources to environment by providing premium quality product
Destruction, improves environment for human survival quality.The features such as nano material has larger specific surface area and lightweight, as research at present
Focus, has wide in photocatalysis, sensor, air-sensitive detection, battery electrode, capacitor, biological medicine and the field such as bionical
Application prospect and potential value.
Chinese Patent Application No. CN105013462A is disclosed and a kind of is had hollow and mesoporous TiO concurrently2The system of nanofiber
Preparation Method, adds a certain proportion of foaming agent in spinning precursor solution, and composite Nano is prepared by electrostatic spinning process
Fiber, further across high-temperature calcination treatment, obtains the TiO with hollow structure2Nanofiber；Chinese Patent Application No.
CN104451942A disclose one kind with polyacrylonitrile as outer layer, tin metal salt as internal layer, by coaxial spin processes prepare provide
There is the nanofiber of skin-core structure, the hollow Nano fiber in use of carbon coating tin ash is prepared through carbonization, the fibrous material can use
In manufacture ultracapacitor, but such nanofiber is black, is added in tinted material, and its dyeing is restricted.Additionally,
Tin is a heavy metal species, and secondary pollution is easily caused during use；Chinese Patent Application No. CN103334179A is disclosed
A kind of method for preparing hollow structure nanofiber, prepares PVDF nanofibers, using magnetic control by method of electrostatic spinning first
In its surface spraying indium oxide layer, further across high temperature sintering treatment, PVDF is removed sputtering technology under the high temperature conditions,
The indium oxide nanometer fiber with hollow structure is formed, this kind of nanofiber has excellent electric property, but exists former
Material is expensive, and supply is limited, there is requirement higher to magnetron sputtering technique, the problems such as production cost is high.
The present invention prepares the nascent nanofibers of PVA using electrostatic spinning, and the characteristic with heat-proof water is allowed to through Overheating Treatment,
One layer of zinc-aluminium hydroxide film layer is coated in PVA nanofiber surfaces by hydrothermal synthesis method, with reference to high-temperature calcination treatment in fibre
Dimension table face forms the AZO film layers of densification and carbonizes the PVA nanofibers of inside, is received so as to prepare the AZO with hollow structure
Rice fiber.This AZO hollow Nano fiber in use Stability Analysis of Structures, form are uniform, with good photocatalysis performance, in degradation of organic substances
Aspect has certain application prospect.Additionally, AZO is a kind of environment-friendly nano-material, can mitigate in terms of environmental improvement
Pressure.
The content of the invention
Goal of the invention：It is former it is an object of the invention to provide a kind of preparation method of environmentally friendly AZO hollow Nano fiber in use
Material wide material sources, low production cost, preparation method is simple, for the production of its industrialization provides certain Research foundation.This
Outward, AZO is a kind of lurid metal oxide, and being added to the compound prepared in macromolecular material can carry out dyeing treatment,
Expand application field.
Technical scheme：A kind of preparation method of Al-Doped ZnO (AZO) hollow Nano fiber in use, the method includes following step
Suddenly：
(1) a certain amount of PVA dissolvings are weighed in deionized water, a certain proportion of acid solution is added and is placed on magnetic agitation
Sufficiently stirring is carried out on device and forms mixed solution A, placed it in by electrostatic spinning on spinning-drawing machine, obtain PVA nanofibers；
The mol ratio of water and PVA is 1~8：1, solidify 10~20cm of distance, 12~48h of spinning time.
(2) PVA nanofibers are peeled from aluminium-foil paper, heat treatment 0.5 is carried out under the conditions of being placed on 150~250 DEG C
~4h, makes it have the characteristic of heat-proof water.
(3) a certain amount of zinc salt and aluminium salt dissolving are weighed in deionized water, mixed solution B is obtained；Aluminium in mixed solution B
The mol ratio of salt and zinc salt is 1~40:100.
(4) will be placed in there-necked flask through the PVA nanofibers of Overheating Treatment and infiltrated with deionized water, low speed is stirred
Mix, the side insertion thermometer monitoring reaction temperature of there-necked flask, after solution temperature rises to 40~80 DEG C and keeps constant,
Opposite side is added dropwise over mixed solution B, while appropriate 1~10mol/L aqueous slkalis and 1~10mol/L acid solutions is added dropwise, it is molten
The pH value of liquid is 5~10, and titration time is 20~60min, 1~12h of reaction time.
(5) after reaction terminates, PVA@AZO presoma nano fibrous membranes are taken out, is laid in polyfluortetraethylene plate upper chamber
Temperature is dried, then carries out 300~800 DEG C of high-temperature calcinations 1~10h for the treatment of, obtains described AZO hollow Nano fiber in use.
In step (1), the acid solution is the one kind in hydrochloric acid, nitric acid, carbonic acid, acetic acid.
In step (3), the zinc salt is the one kind in zinc sulfate, zinc chloride, zinc acetate and zinc nitrate.
In step (3), the aluminium salt is the one kind in aluminum sulfate, aluminium chloride, aluminum nitrate and aluminum acetate.
In step (4), the alkali lye is the one kind in NaOH, ammoniacal liquor, urea, sodium carbonate, potassium hydroxide.
In step (4), the acid solution is the one kind in hydrochloric acid, nitric acid, acetic acid, sulfuric acid.
Compared with prior art, it is an advantage of the invention that：
(1) AZO nano materials raw material sources are extensively, with low cost, are a kind of new environment-friendly nano-materials.
(2) AZO hollow Nano fiber in use form is uniform, size is controllable, preparation process is simple, easily realizes producing in enormous quantities.
Brief description of the drawings
Fig. 1 is the SEM figures of the AZO hollow Nano fiber in use of the embodiment of the present invention 1；
Fig. 2 is the SEM figures of the AZO hollow Nano fiber in use of the embodiment of the present invention 2；
Fig. 3 is the SEM figures of the AZO hollow Nano fiber in use of the embodiment of the present invention 3；
Specific embodiment
With reference to specific drawings and Examples, the invention will be further described.
Embodiment 1：A kind of preparation method of AZO hollow Nano fiber in use, comprises the following steps：
(1) a certain amount of PVA dissolvings are weighed in deionized water, a certain proportion of acid solution is added and is placed on magnetic agitation
Sufficiently stirring is carried out on device and forms mixed solution A, placed it in by electrostatic spinning on spinning-drawing machine, obtain PVA nanofibers；
The mol ratio of water and PVA is 1：1, solidify apart from 20cm, spinning time 12h.
(2) PVA nanofibers are peeled from aluminium-foil paper, heat treatment 5h is carried out under the conditions of being placed on 100 DEG C, have it
There is the characteristic of heat-proof water.
(3) by zinc salt and aluminium salt dissolving in deionized water, mixed solution B is obtained；Zinc salt and aluminium salt in mixed solution B
Mol ratio is 1:100；
(4) will be placed in there-necked flask through the PVA nanofibers of Overheating Treatment and infiltrated with deionized water, low speed is stirred
Mix, in the side insertion thermometer monitoring reaction temperature of there-necked flask, after solution temperature rises to 40 DEG C and keeps constant, another
Side is added dropwise over mixed solution B, while appropriate 10mol/L aqueous slkalis and 1mol/L acid solutions, the pH value of solution is added dropwise
It is 5, titration time is 20min, reaction time 1h.
(5) after reaction terminates, PVA@AZO presoma nano fibrous membranes are taken out, is laid in polyfluortetraethylene plate upper chamber
Temperature is dried, then carries out 800 DEG C of high-temperature calcination treatment 1h, obtains described AZO hollow Nano fiber in use.The hollow nanometers of AZO for obtaining
The SEM figures of fiber are as shown in Figure 1.
Embodiment 2：A kind of preparation method of AZO hollow Nano fiber in use, comprises the following steps：
(1) a certain amount of PVA dissolvings are weighed in deionized water, a certain proportion of acid solution is added and is placed on magnetic agitation
Sufficiently stirring is carried out on device and forms mixed solution A, placed it in by electrostatic spinning on spinning-drawing machine, obtain PVA nanofibers；
The mol ratio of water and PVA is 4：1, solidify apart from 15cm, spinning time 36h.
(2) PVA nanofibers are peeled from aluminium-foil paper, heat treatment 10h is carried out under the conditions of being placed on 150 DEG C, make it
Characteristic with heat-proof water.
(3) by zinc salt and aluminium salt dissolving in deionized water, mixed solution B is obtained；Zinc salt and aluminium salt in mixed solution B
Mol ratio is 20:100；
(4) will be placed in there-necked flask through the PVA nanofibers of Overheating Treatment and infiltrated with deionized water, low speed is stirred
Mix, in the side insertion thermometer monitoring reaction temperature of there-necked flask, after solution temperature rises to 60 DEG C and keeps constant, another
Side is added dropwise over mixed solution B, while appropriate 5mol/L aqueous slkalis and 5mol/L acid solutions is added dropwise, the pH value of solution is
5~10, titration time is 30min, reaction time 6h.
(5) after reaction terminates, PVA@AZO presoma nano fibrous membranes are taken out, is laid in polyfluortetraethylene plate upper chamber
Temperature is dried, then carries out 500 DEG C of high-temperature calcination treatment 6h, obtains described AZO hollow Nano fiber in use.The hollow nanometers of AZO for obtaining
The SEM figures of fiber are as shown in Figure 2.
Embodiment 3：A kind of preparation method of AZO hollow Nano fiber in use, comprises the following steps：
(1) a certain amount of PVA dissolvings are weighed in deionized water, a certain proportion of acid solution is added and is placed on magnetic agitation
Sufficiently stirring is carried out on device and forms mixed solution A, placed it in by electrostatic spinning on spinning-drawing machine, obtain PVA nanofibers；
The mol ratio of water and PVA is 8：1, solidify apart from 10cm, spinning time 48h.
(2) PVA nanofibers are peeled from aluminium-foil paper, heat treatment 20h is carried out under the conditions of being placed on 300 DEG C, make it
Characteristic with heat-proof water.
(3) by zinc salt and aluminium salt dissolving in deionized water, mixed solution B is obtained；Zinc salt and aluminium salt in mixed solution B
Mol ratio is 40:100；
(4) will be placed in there-necked flask through the PVA nanofibers of Overheating Treatment and infiltrated with deionized water, low speed is stirred
Mix, in the side insertion thermometer monitoring reaction temperature of there-necked flask, after solution temperature rises to 80 DEG C and keeps constant, another
Side is added dropwise over mixed solution B, while appropriate 1mol/L aqueous slkalis and 10mol/L acid solutions, the pH value of solution is added dropwise
It is 10, titration time is 60min, reaction time 12h.
(5) after reaction terminates, PVA@AZO presoma nano fibrous membranes are taken out, is laid in polyfluortetraethylene plate upper chamber
Temperature is dried, then carries out 300 DEG C of high-temperature calcination treatment 10h, obtains described AZO hollow Nano fiber in use.The hollow nanometers of AZO for obtaining
The SEM figures of fiber are as shown in Figure 3.
Embodiment described above only expresses several embodiments of the invention, and its description is more specific and detailed, but simultaneously
Therefore the limitation to the scope of the claims of the present invention can not be interpreted as.It should be pointed out that for one of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to guarantor of the invention
Shield scope.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (6)
1. a kind of preparation method of Al-Doped ZnO (AZO) hollow Nano fiber in use, mainly includes preparation, the PVA of PVA nanofibers
The cladding of nanofiber, the part of synthesis three composition of AZO hollow Nano fiber in use, preparation method and step are as follows：
(1) a certain amount of PVA dissolvings are weighed in deionized water, a certain proportion of acid solution is added and is placed on magnetic stirring apparatus
Carry out sufficiently stirring and form mixed solution A, place it in by electrostatic spinning on spinning-drawing machine, obtain PVA nanofibers；Water and
The mol ratio of PVA is 1~8：1, solidify 10~20cm of distance, 12~48h of spinning time.
(2) PVA nanofibers are peeled from aluminium-foil paper, 0.5~4h of heat treatment are carried out under the conditions of being placed on 150~250 DEG C,
Make it have the characteristic of heat-proof water.
(3) a certain amount of zinc salt and aluminium salt dissolving are weighed in deionized water, mixed solution B is obtained；In mixed solution B aluminium salt and
The mol ratio of zinc salt is 1~40:100.
(4) will be placed in there-necked flask through the PVA nanofibers of Overheating Treatment and infiltrated with deionized water, stirring at low speed, three
The side insertion thermometer monitoring reaction temperature of mouth flask, after solution temperature rises to 40~80 DEG C and keeps constant, another
Side is added dropwise over mixed solution B, while appropriate 1~10mol/L aqueous slkalis and 1~10mol/L acid solutions is added dropwise, solution
PH value is 5~10, and titration time is 20~60min, 1~12h of reaction time.
(5) after reaction terminates, PVA AZO presoma nano fibrous membranes are taken out, is laid in room temperature on polyfluortetraethylene plate and dried in the air
It is dry, then 300~800 DEG C of high-temperature calcinations 1~10h for the treatment of are carried out, obtain described AZO hollow Nano fiber in use.
2. the preparation method of AZO hollow Nano fiber in use as claimed in claim 1, it is characterized in that：In step (1), the acid is molten
Liquid is the one kind in hydrochloric acid, acetic acid.
3. a kind of preparation method of Al-Doped ZnO (AZO) hollow Nano fiber in use as claimed in claim 1, it is characterized in that：Step
Suddenly in (3), the zinc salt is the one kind in zinc sulfate, zinc chloride, zinc acetate and zinc nitrate.
4. a kind of preparation method of Al-Doped ZnO (AZO) hollow Nano fiber in use as claimed in claim 1, it is characterized in that：Step
Suddenly in (3), the aluminium salt is the one kind in aluminum sulfate, aluminium chloride, aluminum nitrate and aluminum acetate.
5. a kind of preparation method of Al-Doped ZnO (AZO) hollow Nano fiber in use as claimed in claim 1, it is characterized in that：Step
Suddenly in (4), the alkali lye is the one kind in NaOH, ammoniacal liquor, potassium hydroxide.
6. a kind of preparation method of Al-Doped ZnO (AZO) hollow Nano fiber in use as claimed in claim 1, it is characterized in that：Step
Suddenly in (4), the acid solution is the one kind in hydrochloric acid, nitric acid, acetic acid, sulfuric acid.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201611016415.3A CN106702534A (en) | 2016-11-18 | 2016-11-18 | Preparation method of AZO (Al-doped ZnO) hollow nanofibers |
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| CN201611016415.3A CN106702534A (en) | 2016-11-18 | 2016-11-18 | Preparation method of AZO (Al-doped ZnO) hollow nanofibers |
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Cited By (1)
| 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 |
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| CN101396652A (en) * | 2008-10-23 | 2009-04-01 | 福建师范大学 | Preparation method of zinc oxide nano fiber catalyst used in ester exchange reaction |
| CN102531038A (en) * | 2012-02-23 | 2012-07-04 | 华东理工大学 | Light color rodlike ZAO (Zinc Aluminium Oxide) conductive powder and preparation method thereof |
| CN104020260A (en) * | 2014-06-18 | 2014-09-03 | 清华大学 | NiO and Al-doped ZnO heterogeneous nano structure as well as preparation method and application |
| CN104707559A (en) * | 2015-02-26 | 2015-06-17 | 三峡大学 | Aluminum ion doped zinc oxide adsorbent (AZO) as well as preparation method and application thereof |
-
2016
- 2016-11-18 CN CN201611016415.3A patent/CN106702534A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101396652A (en) * | 2008-10-23 | 2009-04-01 | 福建师范大学 | Preparation method of zinc oxide nano fiber catalyst used in ester exchange reaction |
| CN102531038A (en) * | 2012-02-23 | 2012-07-04 | 华东理工大学 | Light color rodlike ZAO (Zinc Aluminium Oxide) conductive powder and preparation method thereof |
| CN104020260A (en) * | 2014-06-18 | 2014-09-03 | 清华大学 | NiO and Al-doped ZnO heterogeneous nano structure as well as preparation method and application |
| CN104707559A (en) * | 2015-02-26 | 2015-06-17 | 三峡大学 | Aluminum ion doped zinc oxide adsorbent (AZO) as well as preparation method and application thereof |
Non-Patent Citations (1)
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| 王新月 等: ""α-Fe2O3中空磁性纳米纤维的制备研究"", 《功能材料》 * |
Cited By (2)
| 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 |
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