CN106466599B - A kind of preparation method of the tungsten trioxide nano fiber of core-shell structure - Google Patents
A kind of preparation method of the tungsten trioxide nano fiber of core-shell structure Download PDFInfo
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- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000002121 nanofiber Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000011258 core-shell material Substances 0.000 title claims abstract description 21
- 239000000835 fiber Substances 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 21
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 21
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 21
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 17
- 239000002243 precursor Substances 0.000 claims abstract description 16
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 12
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract description 3
- 238000001354 calcination Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 abstract description 37
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 abstract description 10
- 229910001930 tungsten oxide Inorganic materials 0.000 abstract description 10
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- 239000002904 solvent Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract description 2
- 230000001681 protective effect Effects 0.000 abstract description 2
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000011257 shell material Substances 0.000 description 8
- 238000009987 spinning Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- 240000008042 Zea mays Species 0.000 description 6
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 6
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 6
- 235000005822 corn Nutrition 0.000 description 6
- 150000002576 ketones Chemical class 0.000 description 6
- 229920006316 polyvinylpyrrolidine Polymers 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001802 infusion Methods 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 2
- 229940012189 methyl orange Drugs 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 150000004040 pyrrolidinones Chemical class 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000013036 cure process Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 230000000192 social effect Effects 0.000 description 1
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- 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
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/342—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electric, magnetic or electromagnetic fields, e.g. for magnetic separation
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- Chemical Kinetics & Catalysis (AREA)
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- Electromagnetism (AREA)
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Abstract
The invention belongs to technical field of nanometer material preparation, specifically disclose a kind of preparation method of the tungsten trioxide nano fiber of core-shell structure, include the following steps: that ammonium metatungstate is dissolved in water by S1., polyvinylpyrrolidone is added, stirs to get precursor solution；S2. precursor solution in S1 is subjected to uniaxial electrostatic spinning, obtains as-spun fibre；S3. the as-spun fibre being prepared in S2 is calcined, obtains tungsten trioxide nano fiber after cooling；Method preparation process provided by the invention is simple, and raw material is easy to get, and using water as solvent, is not necessarily to other additives, environmentally protective；And the tungsten oxide purity being prepared is higher.The present invention prepares nanofiber using uniaxial method of electrostatic spinning, and tungsten oxide diameter obtained is evenly distributed, and major diameter is bigger, pattern is more preferable compared with other preparation methods, controllability is strong, while greatly improving the Photocatalytic Degradation Property of tungstic acid, is easy to implement industrial mass production.
Description
Technical field
The invention belongs to technical field of nanometer material preparation, receive more particularly, to a kind of tungstic acid of core-shell structure
The preparation method of rice fiber.
Background technique
Semiconductor light-catalyst is widely distributed on earth with its stable physicochemical properties, is easy to get, it is cheap and
The advantages that without secondary pollution, has obtained extensive research.Traditional Study on photocatalyst it is most be exactly titanium dioxide
(TiO2) and zinc oxide (ZnO), their greater band gap, the ultraviolet light shorter to wavelength have good response, but due to purple
Outer light only accounts for small part in sunlight so practical application is restricted.
As a member of transition metal oxide, tungsten oxide (WO3) it is a kind of indirect band gap n-type semiconductor, prohibit
Bandwidth is 2.2 ~ 2.8eV, has good absorption for visible light, therefore is a kind of very with the semiconductor light of development potentiality
Catalyst.
Preparation method about nuclear shell structure nano fiber at present, there are commonly following several:
(1) coaxial electrostatic spinning
Coaxial electrostatic spinning uses two coaxial mutually nested capillaries as spray head, internal layer and outer capillary tube it
Between there are certain gaps to guarantee the unimpeded of shell solution.It is in coaxial spinning, the presoma of stratum nucleare and Shell Materials is molten
Liquid is divided in two different syringes, and inside and outside layer liquid flows out post-tensioning and solidifies under the action of high voltage electric field, is obtained
Nuclear shell structure nano fiber.It is a kind of simple effective method that coaxial electrostatic spinning method, which prepares nuclear shell structure nano fiber, still
Theoretical research be not also it is very perfect, equipment requirement is also relatively high, large-scale production difficulty it is larger.
(2) method of electrostatic spinning is blended
It is the method that two or more material is carried out to simple physical mixed spinning, root that method of electrostatic spinning, which is blended,
According to the different physical property of two kinds of materials of nucleocapsid, two kinds of substances of process gradually generate layering as the solvent evaporates, obtain nucleocapsid
Composite construction.But this method is only limited between solvent and solute be uniform mixed system, and waves solvent
Temperature requirement during hair is higher.
(3) infusion process (surface chemistry combination)
Infusion process, also referred to as surface chemistry combine, and are a kind of methods that functional materials are grafted to fiber surface.It makes first
Standby stratum nucleare nanofiber out, then it is modified its surface by immersion or other methods, in conjunction with other upper target bases
Group or substance form shell structurre.This method will affect the draw ratio and its mechanical performance of fiber in the process of implementation,
Combination between nucleocapsid is preferable, but the shell grown is relatively thin.
(4) chemical application method
Chemical application method is a kind of simple physical method, can only be coated in the superficial layer of tunica fibrosa.Although operation
Process is simple, but each fiber in film cannot be made all to be obtain a uniformly coated, and controllability is poor.
To sum up, seeking one kind can be realized large-scale production, and preparation process environmental protection, the tungsten oxide nanometer being prepared are fine
Tieing up growth characteristics, good semiconductor light-catalyst preparation method is the task of top priority.
Summary of the invention
It is an object of the invention to the deficiencies according to tungsten trioxide nano fiber producing processes in the prior art, provide one
The preparation method of the tungsten trioxide nano fiber of kind core-shell structure.
The purpose of the present invention is achieved through the following technical solutions:
The present invention provides a kind of preparation methods of the tungsten trioxide nano fiber of core-shell structure, include the following steps:
S1. ammonium metatungstate is dissolved in water, polyvinylpyrrolidone is added, stirs to get precursor solution；
S2. precursor solution in S1 is subjected to uniaxial electrostatic spinning, obtains as-spun fibre；
S3. the as-spun fibre being prepared in S2 is calcined, obtains core-shell structure tungsten trioxide nano fiber after cooling；
In S1, the solid-to-liquid ratio of ammonium metatungstate and water is (0.2 ~ 0.6): 1；The molecular weight of the polyvinylpyrrolidone is (1
~ 2) × 106；The solid-to-liquid ratio of polyvinylpyrrolidone and water is (0.1 ~ 0.3): 1；
In S2 step electrostatic spinning, voltage is 10 ~ 25KV, and receiving distance is 12cm, and fltting speed is 0.005 ~ 0.1ml/
min。
It is calcined when S3 step is calcined by different parameters, obtains the core-shell structure tungstic acid of different surface morphology after cooling
Nanofiber
The present invention by the way that ammonium metatungstate is dissolved in water, is added polyvinylpyrrolidone, regulates and controls the ratio between each raw material first
Example, obtains precursor solution, then by electrostatic spinning process, the above-mentioned presoma for having preferable electric conductivity and viscosity is molten
As-spun fibre is made in liquid, and after calcining, the core-shell structure tungsten trioxide nano fiber of different surface morphology is prepared.
Electrostatic spinning technique is a kind of method for quickly and easily preparing nanofiber, and manufacturing device is simple, is spun to
This is cheap, can spin that substance classes are various, not only has very big progress in terms of laboratory research, industrialization potential is also very huge
Greatly.Therefore method of electrostatic spinning batch prepare tungsten trioxide nano fiber and be used as photochemical catalyst have very big industrial value and
Social effect.
Preferably, the molecular weight of polyvinylpyrrolidone is 1.3 × 10 in S16.In the present invention effect of PVP be in order to
Ammonium metatungstate cooperation, the two increase viscosity and the electric conductivity of precursor solution under appropriate proportion for electrostatic spinning, while
At the pattern that can also play the role of support holding fiber in flash cure process after fiber.
Relationship of " solid-to-liquid ratio " referred in the present invention between parts by weight and parts by volume, in terms of g/ml.
Preferably, in S1, the solid-to-liquid ratio of ammonium metatungstate and water is (0.3 ~ 0.5): 1；Polyvinylpyrrolidone and water are consolidated
Liquor ratio is 0.2:1.
Preferably, in S2 step single shaft electrostatic spinning, voltage is 15 ~ 20KV, and receiving distance is 12cm, and fltting speed is
0.002~0.05ml/min。
Preferably, calcination temperature is 500 ~ 550 DEG C in S3, and heating rate is 3 ~ 5 DEG C/min, and heat preservation can obtain for 0.5 hour
The core-shell structure tungsten trioxide nano fiber smooth to surface；Calcination temperature is 550 ~ 650 DEG C, and heating rate is 1 ~ 3 DEG C/min,
And it keeps the temperature 3 hours and the rodlike tungsten trioxide nano fiber of rough surface corn can be obtained.
Compared with prior art, the present invention has the following advantages and beneficial effects:
Method preparation process provided by the invention is simple, and raw material is easy to get, and using water as solvent, is not necessarily to other additives,
It is environmentally protective；And the tungsten oxide purity being prepared is higher.The present invention prepares nanofiber using uniaxial method of electrostatic spinning, is made
Tungsten oxide diameter be evenly distributed, draw ratio is big, and the controllability of pattern is strong, is easy to implement industrial mass production.It improves simultaneously
The Photocatalytic Degradation Property of tungstic acid, actual application prospect are extensive.
Detailed description of the invention
Fig. 1 is preparation process schematic diagram of the present invention.
Fig. 2 is the scanning electron microscope (SEM) of the smooth core-shell structure tungsten oxide nanofibers in surface made from embodiment 1
Figure.
Fig. 3 is the scanning electron microscope (SEM) of the rodlike core-shell structure tungsten oxide nanofibers of corn made from embodiment 4
Figure.
Fig. 4 is the XRD diagram of tungstic acid prepared by embodiment 1 and embodiment 4.
Specific embodiment
Further illustrate the present invention below in conjunction with specific embodiments and the drawings, but embodiment the present invention is not done it is any
The restriction of form.Unless stated otherwise, the present invention uses reagent, method and apparatus is the art conventional reagents, method
And equipment.
Unless stated otherwise, agents useful for same and material of the present invention are commercially available.
Embodiment 1
The commercially available ammonium metatungstate hydrate of 2.5g is dissolved in 5ml deionized water, the polyethylene that molecular weight is 1300000 is added
Pyrrolidones (PVP), additional amount 1g are stirred and are obtained precursor solution after being in homogeneous transparent to solution；Then by uniaxial quiet
Electrical spinning method, voltage 15KV receive distance 12cm, fltting speed 0.01ml/min, obtain white cloth-like as-spun fibre；It will just spin
Fiber is placed in 550 DEG C of calcinings in Muffle furnace, and 5 DEG C/min of heating rate keeps the temperature 30min, and cooled to room temperature obtains nucleocapsid knot
Structure tungsten oxide nanofibers.
Preparation process as shown in Figure 1, the core-shell structure tungsten oxide nanofibers structure being prepared as shown in Fig. 2, from Fig. 2
In as can be seen that the nanofiber be core-shell structure, surface is smooth, and diameter is evenly distributed, and draw ratio is big.
Embodiment 2
2.0g ammonium metatungstate hydrate is dissolved in 5ml deionized water, the polyvinylpyrrolidine that molecular weight is 1300000 is added
Ketone (PVP), additional amount 1g are stirred and are obtained precursor solution after being in homogeneous transparent to solution；Then pass through uniaxial electrostatic spinning
Method, voltage 15KV receive distance 12cm, and fltting speed 0.01ml/min obtains as-spun fibre；As-spun fibre is placed in Muffle furnace
In 500 DEG C of calcinings, 4 DEG C/min of heating rate keeps the temperature 30min, and cooled to room temperature obtains the smooth core-shell structure oxygen in surface
Change tungsten nanofiber.
Embodiment 3
2.0g ammonium metatungstate hydrate is dissolved in 5ml deionized water, the polyvinylpyrrolidine that molecular weight is 1300000 is added
Ketone (PVP), additional amount 1g are stirred and are obtained precursor solution after being in homogeneous transparent to solution；Then pass through uniaxial electrostatic spinning
Method, voltage 15KV receive distance 12cm, and fltting speed 0.05ml/min obtains as-spun fibre；As-spun fibre is placed in Muffle furnace
In 550 DEG C of calcinings, 5 DEG C/min of heating rate keeps the temperature 30min, and cooled to room temperature obtains the smooth core-shell structure oxygen in surface
Change tungsten nanofiber.
Embodiment 4
The commercially available ammonium metatungstate hydrate of 2.0g is dissolved in 5ml deionized water, the polyethylene that molecular weight is 1300000 is added
Pyrrolidones (PVP), additional amount 1g are stirred and are obtained precursor solution after being in homogeneous transparent to solution；Then by uniaxial quiet
Electrical spinning method, voltage 18KV receive distance 12cm, fltting speed 0.005ml/min, obtain white cloth-like as-spun fibre；It will be first
It spins fiber and is placed in 600 DEG C of calcinings in Muffle furnace, 2 DEG C/min of heating rate keeps the temperature 3 hours, and cooled to room temperature obtains corn
Rodlike tungsten trioxide nano fiber.
The tungsten trioxide nano fibre structure being prepared is as shown in figure 3, from figure 3, it can be seen that the Nanowire dimension table
Face is made of the little crystal grain within many 100nm, and there is the axis for being similar to corn ear at nanofiber center, is the rodlike core of corn
Shell structure, diameter are evenly distributed, and draw ratio is big.
XRD test is carried out to the tungsten trioxide nano fiber of different-shape made from embodiment 1 and embodiment 4, as a result such as
Shown in Fig. 4.Peak of the angle of diffraction at 23.1,23.5,24.3,26.5,28.9,33.2,34.1 and 41.9 ° is belonging respectively in Fig. 4
Monoclinic form tungsten oxide (002), (020), (200), (120), (112), (022), the diffraction of (202) and (222) crystal face can be with
The product for finding out preparation is all tungstic acid, and crystallinity is good.
Embodiment 5
1.5g ammonium metatungstate hydrate is dissolved in 5ml deionized water, the polyvinylpyrrolidine that molecular weight is 1300000 is added
Ketone (PVP), additional amount 1g are stirred and are obtained precursor solution after being in homogeneous transparent to solution；Then pass through uniaxial electrostatic spinning
Method, voltage 20KV receive distance 12cm, and fltting speed 0.02ml/min obtains as-spun fibre；As-spun fibre is placed in Muffle furnace
In 650 DEG C calcining, 1 DEG C/min of heating rate, keep the temperature 3 hours, cooled to room temperature obtains the rodlike tungsten trioxide nano of corn
Fiber.
Comparative example 1
5.0g ammonium metatungstate hydrate is dissolved in 5ml deionized water, the polyvinylpyrrolidine that molecular weight is 1300000 is added
Ketone (PVP), additional amount 0.5g are stirred and are obtained precursor solution after being in homogeneous transparent to solution；Then pass through uniaxial Static Spinning
Silk method, voltage 20KV receive distance 12cm, and fltting speed 0.01ml/min obtains as-spun fibre；As-spun fibre is placed in Muffle
500 DEG C of calcinings in furnace, 5 DEG C/min of heating rate keep the temperature 30min, cooled to room temperature, obtained tungsten trioxide nano fiber
Diameter is unevenly distributed, and adhesion phenomenon is extremely serious between fiber.
Comparative example 2
3.0g ammonium metatungstate hydrate is dissolved in 5ml deionized water, the polyvinylpyrrolidine that molecular weight is 1300000 is added
Ketone (PVP), additional amount 2.5g are stirred and are obtained precursor solution after being in homogeneous transparent to solution；Then pass through uniaxial Static Spinning
Silk method, voltage 20KV receive distance 12cm, and fltting speed 0.01ml/min obtains as-spun fibre；As-spun fibre is placed in Muffle
600 DEG C of calcinings in furnace, 5 DEG C/min of heating rate keep the temperature 30min, cooled to room temperature, obtained tungsten trioxide nano fiber
Diameter is unevenly distributed, and be easy to appear during the spinning process syringe needle blocking etc. influence conventional efficient the case where.
Comparative example 3
3.0g ammonium metatungstate hydrate is dissolved in 5ml deionized water, the polyvinylpyrrolidine that molecular weight is 1300000 is added
Ketone (PVP), additional amount 2.5g are stirred and are obtained precursor solution after being in homogeneous transparent to solution；Then pass through uniaxial Static Spinning
Silk method, voltage 30KV receive distance 12cm, and fltting speed 0.05ml/min obtains as-spun fibre；As-spun fibre is placed in Muffle
550 DEG C of calcinings in furnace, 3 DEG C/min of heating rate keep the temperature 3 hours, cooled to room temperature, obtained tungsten trioxide nano fiber
Diameter is unevenly distributed, and thin only tens nanometers and not have core-shell structure, thick has reached several hundred nanometers.
Embodiment 6
Photocatalytic Degradation Property verifying to methyl orange:
Verification method: the methyl orange solution that 150ml concentration is 10mg/L is added into reactor, takes 50mg embodiment 1 ~ 5
Tungsten trioxide nano fiber obtained puts into wherein (and comparing with commercially available tungsten trioxide photocatalyst) dark reaction respectively
Reach adsorption equilibrium after 30min, then irradiated under 300W xenon lamp, every 30min takes a sample, then with UV-vis spectroscopy light
The absorbance of degree meter measurement solution simultaneously calculates degradation rate.Table 1 is after using each sample to react 2 hours as photochemical catalyst respectively
The degradation rate of methyl orange.
The catalyst degradation rate being prepared in 1 embodiment 1 ~ 5 of table
| Embodiment number | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | It is commercially available |
| Degradation rate (%) | 25 | 28 | 26 | 27 | 30 | 20 |
Claims (7)
1. a kind of preparation method of core-shell structure tungsten trioxide nano fiber, which comprises the steps of:
S1. ammonium metatungstate is dissolved in water, polyvinylpyrrolidone is added, stirs to get precursor solution；
S2. precursor solution in S1 is subjected to uniaxial electrostatic spinning, obtains as-spun fibre；
S3. the as-spun fibre being prepared in S2 is calcined, core-shell structure tungsten trioxide nano fiber after cooling；
In S1, the solid-to-liquid ratio of ammonium metatungstate and water is (0.2 ~ 0.6): 1；The molecular weight of the polyvinylpyrrolidone is (1 ~ 2)
×106；The solid-to-liquid ratio of polyvinylpyrrolidone and water is (0.1 ~ 0.3): 1；
In S2 step electrostatic spinning, voltage is 10 ~ 25KV, and receiving distance is 12cm, and fltting speed is 0.005 ~ 0.1ml/min；
Wherein, ratio of the solid-to-liquid ratio between parts by weight and parts by volume, in terms of g/mL.
2. preparation method according to claim 1, which is characterized in that the molecular weight of polyvinylpyrrolidone is 1.3 in S1
×106。
3. preparation method according to claim 1, which is characterized in that in S1, the solid-to-liquid ratio of ammonium metatungstate and water be (0.3 ~
0.6): 1；The solid-to-liquid ratio of polyvinylpyrrolidone and water is 0.2:1.
4. preparation method according to claim 1, which is characterized in that in S2 step single shaft electrostatic spinning, voltage be 15 ~
20KV, receiving distance is 12cm, and fltting speed is 0.002 ~ 0.05ml/min.
5. preparation method according to claim 1, which is characterized in that calcination temperature is 500 ~ 550 DEG C in S3, heating rate
For 1 ~ 5 DEG C/min, and keep the temperature 0.5 hour.
6. the core-shell structure tungsten trioxide nano fiber that a kind of any preparation method of claim 1 to 5 is prepared.
7. core-shell structure tungsten trioxide nano fiber as claimed in claim 6 is preparing the application in photochemical catalyst.
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