CN106847382A - Function coaxial nano cable of photoelectromagnetic photocatalysis four and preparation method thereof - Google Patents
Function coaxial nano cable of photoelectromagnetic photocatalysis four and preparation method thereof Download PDFInfo
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- CN106847382A CN106847382A CN201710090331.2A CN201710090331A CN106847382A CN 106847382 A CN106847382 A CN 106847382A CN 201710090331 A CN201710090331 A CN 201710090331A CN 106847382 A CN106847382 A CN 106847382A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/016—Apparatus or processes specially adapted for manufacturing conductors or cables for manufacturing co-axial cables
Abstract
The present invention relates to function coaxial nano cable of photoelectromagnetic photocatalysis four and preparation method thereof, belong to technical field of nanometer material preparation.The present invention includes four steps：(1) precipitation method prepare the Fe of Coated with Oleic Acid3O4It is nanocrystalline；(2) method of electrostatic spinning combination high-temperature roasting prepares Bi2WO6:Yb3+,Er3+Nanofiber；(3) spinning solution is prepared；(4) [PANI/Fe is prepared3O4/PAN]@[Bi2WO6:Yb3+,Er3+/ PAN] the function coaxial nano cable of photoelectromagnetic photocatalysis four, prepared using coaxial electrostatic spinning technology.Prepared nano-cable has the good function of up-conversion luminescence electroconductive magnetic photocatalysis four simultaneously.The method of the present invention is simple and easy to apply, can produce in batches, and this new nano structural material has broad application prospects.
Description
Technical field
The present invention relates to technical field of nanometer material preparation, the function co-axial nano of photoelectromagnetic photocatalysis four electricity is in particulard relate to
Cable and preparation method thereof.
Background technology
The preparation and property research of one-dimensional nano structure material are one of forward position focus of current material science research field.
Nano-cable (Nanocables) is due to its unique performance, abundant scientific meaning, wide application prospect and in future
The important strategic status occupied in nano structure device, cause the great attention of people in recent years.Coaxial nano cable grinds
Study carefully and be started in the mid-90, develop later within 2000 relatively rapidly, up to the present, people use different synthetic methods,
Different types of material has successfully prepared hundreds of coaxial nano cable, such as：Fe/C、Zn/ZnO、C/C、SiC/C、
SiGaN/SiOxNyAnd Fe-C-BN the and α-Si of three-decker3N4-Si-SiO2Deng.According to nano-cable sandwich layer and sheaths material
Difference, can be divided into following a few classes：Semiconductor-insulator, semiconductor-semiconductor, insulator-insulator, macromolecule-metal, height
Molecule-semiconductor, macromolecule-macromolecule, metal-metal, SEMICONDUCTOR-METAL etc..In past more than ten years, people are original
Prepare and develop many methods for preparing coaxial nano cable on the basis of quasi-one-dimensional nanometer material, such as：Hydro-thermal method, colloidal sol-solidifying
Glue method, based on nanometer collimation method, vapor growth method, template etc..Continue to explore new synthetic technology, continue to develop and improve coaxial
The preparation science of nano-cable, obtains high-quality coaxial nano cable, is still the main side of current coaxial nano cable research
To.
Simple function applications to nanostructures is limited in scope, and difunctional or multi-functional nanometer material range of application is more
Extensively, this kind of material has more characteristic and attraction, therefore, multi-functional nanometer material is paid high attention to by researcher.With nanometer
The development of science and technology, nano material such as has the characteristics of luminescence, photocatalysis property, electric conductivity, magnetic, towards double work(by simple function
Can and multifunctional direction development, such as have magnetic-fluorescence, luminous-photocatalysis, fluorescence-conduction or conduction-magnetic it is difunctional with
And luminous-photocatalysis-the function of conduction-magnetic four, difunctional or four functions can be so realized on a kind of nano structural material,
Development to the science and technology of nano-device, nanometer technology and correlation is significant.For example, magnetic-fluorescent dual-function
Nano composite material is that medical diagnosis on disease and treatment provide a kind of new platform, because their difunctional property makes disease
" it was found that-detection-treatment " is integrally formed.The use of this nano composite material will further improve the efficiency of diagnosis and reduce secondary
Effect, causes the highest attention of researcher.Electromagnetism dual-functional nanometer compound is in thunderstorm activity, electromagnetic shielding, antistatic
The aspect such as coating and sensor has broad application prospects.
Ferroso-ferric oxide Fe3O4It is a kind of important and wide variety of magnetic material.People have used various methods, such as
The method such as the precipitation method, sol-gel process, microemulsion method, hydro-thermal and solvent-thermal method, thermal decomposition method, method of electrostatic spinning is successfully made
It is standby gone out Fe3O4The nano materials such as nanocrystalline, nanometer rods, nano wire, nanometer film, hybrid structure, Core-shell Structure Nanoparticles, skill
Art comparative maturity.Bi2WO6:Yb3+,Er3+With good photocatalysis and Upconversion luminescence, researcher has used various
Method is prepared for Bi2WO6:Yb3+,Er3+Nano material, technology also comparative maturity.Polyaniline PANI is readily synthesized due to it, conductance
The advantages of rate is high good with environmental stability, has become one of focus of conducting polymer area research.People have synthesized
The polyaniline PANI of the one-dimensional nano structures such as nano wire, nanometer rods, nanotube and nanofiber, therefore, using electrically conductive polyaniline
PANI, magnetic Fe3O4Nanocrystalline and Bi2WO6:Yb3+,Er3+Construct with up-conversion luminescence-conduction-function of magnetic-photocatalysis four
1-dimention nano cable material is preferable material.
Existing research is it has been proved that work as dark colour electrically conductive polyaniline PANI and magnetic Fe3O4With mix rare earth luminous chemical combination
Thing directly mixes, and can significantly reduce its illumination effect, therefore to obtain and mix the good illumination effect of rare earth compound, it is necessary to make to mix
Rare earth compound and PANI and Fe3O4Realization is efficiently separated.If by conductive polymer polyanilinc PANI and Fe3O4It is nanocrystalline with
Polyacrylonitrile (PAN) is combined, and constitutes the sandwich layer of nano-cable, then sandwich layer will be difunctional with conduction-magnetic, if rare earth will be mixed
Compound Bi2WO6:Yb3+,Er3+It is compound with PAN, constitute the shell of nano-cable, then shell will be with up-conversion luminescence-photocatalysis
Difunctional, constructed [PANI/Fe3O4/PAN]@[Bi2WO6:Yb3+,Er3+/ PAN] coaxial nano cable, will be with upper conversion
Luminous-conduction-the function of magnetic-photocatalysis four, the material before wherein@is sandwich layer, and the material behind@is shell.It is this coaxial
Nano cable structure can just realize polyaniline PANI and Fe3O4With mix rare earth compound Bi2WO6:Yb3+,Er3+Efficiently separate, from
And the good one-dimensional coaxial nano cable material of four features is obtained, this four new function coaxial nano cable materials will
With important application prospect, the document report of correlation is had not yet to see.
The United States Patent (USP) of Patent No. 1975504 discloses a relevant electrospinning process (electrospinning)
Technical scheme, the method is to prepare a kind of continuous, effective ways of the micro nanometer fiber with macro length, by
Formhals was proposed first in 1934.This method is mainly used to prepare high polymer nanometer fiber, it is characterized in that making powered
Polymer Solution or melt are sprayed by the traction of electrostatic force in electrostatic field by nozzle, invest the receiving screen on opposite, so that real
Existing wire drawing, then, solvent evaporation, or melt cooling at normal temperatures solidifies to normal temperature, obtains micro nanometer fiber.Nearly 10 years
Come, occurred in that in inorfil preparing technical field and prepare inorganic compound such as oxide nanofiber using electrospinning process
Technical scheme, described oxide includes TiO2、ZrO2、Y2O3、Y2O3:RE3+(RE3+=Eu3+、Tb3+、Er3+、Yb3+/Er3+)、
NiO、Co3O4、Mn2O3、Mn3O4、CuO、SiO2、Al2O3、V2O5、ZnO、Nb2O5、MoO3、CeO2、LaMO3(M=Fe, Cr, Mn,
Co、Ni、Al)、Y3Al5O12、La2Zr2O7Deng metal oxide and composite oxide of metal.The single spinning head of the use such as Dong Xiangting,
PAN/Eu (BA) is prepared for using electrostatic spinning technique3Phen recombination luminescences nanofiber [New Chemical Materials, 2008,36
(9),49-52]；Wang Ce etc. is prepared for polyvinylpyrrolidone/ferroso-ferric oxide using single spinning head, using method of electrostatic spinning
Composite nano fiber [SCI, 2006,27 (10), 2002-2004]；Qingbiao Yang, et al are used
Single spinning head, Fe is prepared for using electrostatic spinning technique2O3nanoparticles/Eu(DBM)3(Bath) it is combined difunctional magnetic
Light nanofiber [Journal of Colloid and Interface Science, 2010,350,396-401].By electrostatic
Spining technology is improved, and using coaxial spinning head, spinning solution is injected separately into inner and outer tubes, when increasing direct current
During pressure, the solution in inner and outer pipes is pulled out by electric field force simultaneously, and coaxial nano cable is formed after solidification, and the technology is coaxial quiet
Electrospinning.The technology such as Wang Ce be prepared for silica Polymers Coaxial Nanofibers [SCI,
2005,26(5):985-987]；Dong Xiangting etc. is prepared for TiO using the technology2@SiO2Sub-micron coaxial cable [chemical journal,
2007,65(23):2675-2679]、ZnO@SiO2Coaxial nano cable [Chinese Journal of Inorganic Chemistry, 2010,26 (1), 29-34],
Al2O3/SiO2Coaxial ultra micro cable [silicate journal, 2009,37 (10), 1712-1717]；Han, et al use the technology system
Standby PC (Shell)/PU (Core) composite nano fiber [Polymer composites, 2006,10:381-386].Dong Xiangting
A kind of magneto-optic double-function coaxial nano cable [application for a patent for invention number is prepared for Deng using coaxial electrostatic spinning technology：
201110284141.7].Have no at present and prepare [PANI/Fe using coaxial electrostatic spinning technology3O4/PAN]@[Bi2WO6:Yb3+,
Er3+/ PAN] the function coaxial nano cable of photoelectromagnetic photocatalysis four relevant report.
When preparing nano material using electrostatic spinning technique, the species of raw material, the molecular weight of high polymer templates, spinning solution
The structure of composition, spinning process parameter and spinning head the pattern and size of final products are all had a major impact.In the present invention,
Bi prepared by electrostatic spinning technique2WO6:Yb3+,Er3+Nanofiber and polyacrylonitrile (PAN) are added to N,N-dimethylformamide
In DMF, an electrostatic spinning liquid with certain viscosity is configured to, shell layer spinning solution is constituted, by the Fe of Coated with Oleic Acid3O4Nanometer
Crystalline substance, PAN, aniline, camphorsulfonic acid, ammonium persulfate, DMF mixing, after aniline polymerization into another spinning solution of composition after polyaniline, structure
Into sandwich layer spinning solution, control the viscosity of spinning solution most important.Using coaxial electrostatic spinning technology, in optimal process conditions
Under, prepare [PANI/Fe3O4/PAN]@[Bi2WO6:Yb3+,Er3+/ PAN] the function coaxial nano cable of photoelectromagnetic photocatalysis four.
The content of the invention
Single spinning head has been used in the introduction, metal oxide has been prepared for using electrostatic spinning technique and metal is multiple
Close oxide nanofiber, polyvinylpyrrolidone/ferroso-ferric oxide composite nano fiber, PAN/Eu (BA)3The compound hairs of phen
Light nanofiber and Fe2O3nanoparticles/Eu(DBM)3(Bath) it is combined difunctional magneto-optic nanofiber.In background technology
Use coaxial electrostatic spinning technology be prepared for inorganic matter@inorganic matters, inorganic matter@macromolecules, macromolecule@high molecular nanometer cables
With magneto-optic double-function coaxial nano cable.Raw material, template, solvent and the final target product for being used all with it is of the invention
Method is different.In order to increase a kind of new multifunctional coaxial nano-cable material in coaxial nano cable Material Field,
We have invented [PANI/Fe3O4/PAN]@[Bi2WO6:Yb3+,Er3+/ PAN] the function coaxial nano cable of photoelectromagnetic photocatalysis four.
The present invention is achieved in that the Fe for preparing Coated with Oleic Acid using the precipitation method first3O4It is nanocrystalline, using electrostatic
Spining technology combination high-temperature calcination process prepares Bi2WO6:Yb3+,Er3+Up-conversion luminescence photocatalysis dual-functional nanometer fiber, will
Bi2WO6:Yb3+,Er3+Nanofiber and polyacrylonitrile (PAN) are added in DMF DMF, and being configured to one has
The electrostatic spinning liquid of certain viscosity, referred to as shell layer spinning solution, by the Fe of Coated with Oleic Acid3O4Nanocrystalline, aniline, camphorsulfonic acid, PAN,
DMF and ammonium persulfate mixing constitute another spinning solution, wherein aniline polymerization into polyaniline PANI, referred to as sandwich layer spinning solution；Control
The viscosity of shell processed and sandwich layer spinning solution is most important, and electrostatic spinning is carried out using coaxial electrostatic spinning technology, in optimal work
Under the conditions of skill, the novel [PANI/Fe of structure is obtained3O4/PAN]@[Bi2WO6:Yb3+,Er3+/ PAN] function of photoelectromagnetic photocatalysis four
Coaxial nano cable.Its step is：
(1) precipitation method prepare the Fe of Coated with Oleic Acid3O4It is nanocrystalline
By 5.4060g FeCl3·6H2O, 2.7800g FeSO4·7H2O, 4.04g NH4NO3It is with 1.9000g molecular weight
20000 polyethylene glycol is dissolved in 100mL deionized waters, is heated to 50 DEG C and is passed through argon gas 30min, is then slowly added dropwise ammoniacal liquor
PH value to solution is 11, continues logical argon gas 20min and obtains black suspension, by this suspension Magneto separate after, use absolute ethyl alcohol
Washed successively with deionized water three times, product is placed in 60 DEG C of vacuum drying chamber and dries 12h, obtain a diameter of 8-10nm's
Fe3O4It is nanocrystalline；Take the Fe prepared by 1.5000g3O4It is nanocrystalline to be dispersed in the 100mL deionized waters for being passed through 30min argon gas
And ultrasonic disperse 20min, solution is then heated to 80 DEG C under argon gas protection, and 1.5mL oleic acid is added, then proceed to reaction
40min, Magneto separate is carried out by resulting precipitation, is removed water layer and will be deposited in 60 DEG C of vacuum drying chambers and dries 6h, is obtained
The Fe of Coated with Oleic Acid3O4It is nanocrystalline；
(2) method of electrostatic spinning combination high-temperature roasting prepares Bi2WO6:Yb3+,Er3+Nanofiber
Weigh 0.0194g Yb2O3With 0.0095g Er2O3It is dissolved in appropriate concentrated nitric acid and evaporative crystallization, obtains dilute
Native nitrate mixture, after adding 5mL deionized water dissolvings, adds 0.6085g (NH4)10W12O41With 1.0087g citric acids, in
110 DEG C of stirring evaporations form gel, and 2.3285g Bi (NO are added after being cooled to room temperature3)3·5H2O and 23.4960g N, N- bis-
NMF DMF, adds the polyvinylpyrrolidone PVP that 2.9431g molecular weight is 1300000, stirs 4h and static 4h
Afterwards, the flaxen spinning solution of homogeneous transparent is formed, spinning solution is injected into a 5mL with 1mL plastic spray gun heads and is injected
In device, the positive pole of high-voltage DC power supply is connected with copper wire electrode in syringe, with copper cash by the ground wire wiring of high-voltage DC power supply
Post is connected and is grounded with reception device wire netting, and lance head is in 15 ° of angles with horizontal direction, and lance head is with the distance of wire netting
15cm, spinning voltage is 13kV, and environment temperature is 20-25 DEG C, and relative humidity is 40%-50%, is carried out after electrostatic spinning in iron
PVP/Bi (NO are collected on silk screen3)3/(NH4)10W12O41Nanofiber, the PVP/Bi (NO that will be obtained3)3/(NH4)10W12O41Receive
Rice fiber is put into crucible, then crucible is put into temperature programming stove, and 300 DEG C, insulation are warming up to the heating rate of 1 DEG C/min
Half an hour, then 500 DEG C are warming up to the heating rate of 2 DEG C/min, after insulation 1h, natural cooling obtains Bi after being down to room temperature2WO6:
Yb3+,Er3+Nanofiber；
(3) spinning solution is prepared
Weigh the Bi described in 0.36g2WO6:Yb3+,Er3+Nanofiber, adds 6.0g DMF and ultrasound 20min, adds
0.6g molecular weight is 86000 polyacrylonitrile (PAN), and 2h is stirred at 70 DEG C, and shell layer spinning solution is obtained after cooling；By 0.6g oleic acid
The Fe of cladding3O4Nanocrystalline to be added in 4.0g DMF solvents and ultrasound 20min, adding that 0.6g molecular weight is 86000 poly- third
Alkene nitrile PAN, in 2h is stirred at 70 DEG C, is cooled to aniline ANI and 0.5238g the camphorsulfonic acid CSA of addition 0.42g after room temperature, room
The lower magnetic agitation 2h of temperature, 1.0291g ammonium persulfates APS is dissolved in 2.0g DMF, magnetic agitation 2h, by this two parts of solution in ice
1h is placed in water-bath, afterwards mixes this two parts of solution in ice-water bath, after magnetic agitation 3h, mixed liquor is put into 5 DEG C of ice
24h is refrigerated in case, sandwich layer spinning solution is obtained；
(4) [PANI/Fe is prepared3O4/PAN]@[Bi2WO6:Yb3+,Er3+/ PAN] the function co-axial nano of photoelectromagnetic photocatalysis four
Cable
Using coaxial electrostatic spinning technology, the 8# stainless steels after the composition of coaxial spinning head uses interior spinning head for truncated are noted
Pin is penetrated, outer spinning head is the plastic spray gun head of 1mL, fixed after two spinning heads are packaged, and the shell layer spinning solution that will be prepared adds
Enter in the syringe being connected with outer spinning head, sandwich layer spinning solution be added in the syringe being connected with interior spinning head,
The gap of the inside and outside spinning head of regulation is smoothly flowed out with ensureing shell layer spinning solution, using perpendicular spray mode, coaxial spinning head and horizontal plane
Vertically, regulation DC voltage be 15kV, spinning head to receiving screen wire netting solidification distance be 10cm, 20-25 DEG C of indoor temperature,
Relative humidity is 40%-50%, with the volatilization of solvent, the i.e. available [PANI/Fe on receiving screen wire netting3O4/PAN]@
[Bi2WO6:Yb3+,Er3+/ PAN] the function coaxial nano cable of photoelectromagnetic photocatalysis four.
Novel [the PANI/Fe of structure prepared in said process3O4/PAN]@[Bi2WO6:Yb3+,Er3+/ PAN] photoelectricity
Magneto-optic is catalyzed four function coaxial nano cables, with the conductive and difunctional PANI/Fe of magnetic3O4/ PAN is sandwich layer, to have
Up-conversion luminescence and the difunctional Bi of photocatalysis2WO6:Yb3+,Er3+/ PAN is shell, constitutes coaxial nano cable, cable
Average diameter is about 600nm, and sandwich layer diameter is about 200nm, and shell thickness is about 200nm, and length is more than 500 μm；980nm's
Diode laser is excited down, [PANI/Fe3O4/PAN]@[Bi2WO6:Yb3+,Er3+/ PAN] function of photoelectromagnetic photocatalysis four is coaxial
Nano-cable launch main peak positioned at 528nm and 543nm Green band and 655nm emitting red light band, transmitting it is glimmering
Light color is green；[PANI/Fe3O4/PAN]@[Bi2WO6:Yb3+,Er3+/ PAN] the function co-axial nano of photoelectromagnetic photocatalysis four electricity
The average conductivity of cable is 3.86 × 10-3S·cm-1；Saturation magnetization is 8.404emu/g；It is the ultraviolet of 365nm in wavelength
After light irradiation 300min, [PANI/Fe3O4/PAN]@[Bi2WO6:Yb3+,Er3+/ PAN] the function co-axial nano of photoelectromagnetic photocatalysis four
Cable reaches 92.64% to the photocatalytic activity of rhodamine B, and prepared coaxial nano cable has good photoelectricity magneto-optic
Four functions are catalyzed, goal of the invention is realized.
Brief description of the drawings
Fig. 1 is [PANI/Fe3O4/PAN]@[Bi2WO6:Yb3+,Er3+/ PAN] the function co-axial nano of photoelectromagnetic photocatalysis four electricity
The XRD spectra of cable；
Fig. 2 is [PANI/Fe3O4/PAN]@[Bi2WO6:Yb3+,Er3+/ PAN] the function co-axial nano of photoelectromagnetic photocatalysis four electricity
The SEM photograph of cable；
Fig. 3 is [PANI/Fe3O4/PAN]@[Bi2WO6:Yb3+,Er3+/ PAN] the function co-axial nano of photoelectromagnetic photocatalysis four electricity
The EDS line analysis figures of cable；
Fig. 4 is [PANI/Fe3O4/PAN]@[Bi2WO6:Yb3+,Er3+/ PAN] the function co-axial nano of photoelectromagnetic photocatalysis four electricity
The TEM photos of cable, the figure also serves as Figure of abstract；
Fig. 5 is [PANI/Fe3O4/PAN]@[Bi2WO6:Yb3+,Er3+/ PAN] the function co-axial nano of photoelectromagnetic photocatalysis four electricity
The Up-conversion emission spectrogram of cable；
Fig. 6 is [PANI/Fe3O4/PAN]@[Bi2WO6:Yb3+,Er3+/ PAN] the function co-axial nano of photoelectromagnetic photocatalysis four electricity
The chromaticity coordinates figure of cable；
Fig. 7 is [PANI/Fe3O4/PAN]@[Bi2WO6:Yb3+,Er3+/ PAN] the function co-axial nano of photoelectromagnetic photocatalysis four electricity
The hysteresis curve figure of cable；
Fig. 8 is [PANI/Fe3O4/PAN]@[Bi2WO6:Yb3+,Er3+/ PAN] the function co-axial nano of photoelectromagnetic photocatalysis four electricity
The degradation rate curve map of the ultraviolet catalytic rhodamine B degradation of cable.
Specific embodiment
Ytterbium oxide Yb selected by the present invention2O3With erbium oxide Er2O3Purity be 99.99%, ammonium tungstate (NH4)10W12O41, citric acid, Bi (NO3)3·5H2O, DMF DMF, Iron(III) chloride hexahydrate, seven hydrated sulfuric acids are sub-
Iron, ammonium nitrate, molecular weight is 20000 polyethylene glycol, and nitric acid, molecular weight is 1300000 polyvinylpyrrolidone PVP, point
Son amount is 86000 polyacrylonitrile (PAN), and absolute ethyl alcohol, ammoniacal liquor, aniline, camphorsulfonic acid, ammonium persulfate, oleic acid, argon gas is city
Sell analysis net product；Make by oneself in deionized water laboratory；Glass apparatus and equipment used is the instrument commonly used in laboratory and sets
It is standby.
Embodiment：By 5.4060g FeCl3·6H2O, 2.7800g FeSO4·7H2O, 4.04g NH4NO3And 1.9000g
Molecular weight is that 20000 polyethylene glycol is dissolved in 100mL deionized waters, is heated to 50 DEG C and is passed through argon gas 30min, then slowly
It is 11 that ammoniacal liquor to the pH value of solution is added dropwise, and continues logical argon gas 20min and obtains black suspension, after this suspension Magneto separate, is used
Absolute ethyl alcohol and deionized water are washed three times successively, product is placed in 60 DEG C of vacuum drying chamber and dries 12h, obtain a diameter of
The Fe of 8-10nm3O4It is nanocrystalline；Take the Fe prepared by 1.5000g3O4Nanocrystalline being dispersed in has been passed through the 100mL of 30min argon gas
In ionized water and ultrasonic disperse 20min, solution is then heated to 80 DEG C under argon gas protection, and adds 1.5mL oleic acid, then
Continue to react 40min, resulting precipitation is carried out into Magneto separate, remove water layer and drying in 60 DEG C of vacuum drying chambers will be deposited in
6h, obtains the Fe of Coated with Oleic Acid3O4It is nanocrystalline；Weigh 0.0194g Yb2O3With 0.0095g Er2O3It is dissolved in appropriate concentrated nitric acid
In and evaporative crystallization, obtain rare earth nitrades mixture, after adding 5mL deionized water dissolvings, add 0.6085g (NH4)10W12O41With 1.0087g citric acids, stir evaporation in 110 DEG C and form gel, 2.3285g Bi are added after being cooled to room temperature
(NO3)3·5H2O and 23.4960g DMF DMF, add the poly- second that 2.9431g molecular weight is 1300000
Alkene pyrrolidone PVP, after stirring 4h and static 4h, forms the flaxen spinning solution of homogeneous transparent, and spinning solution is injected into one
In 5mL syringes of the branch with 1mL plastic spray gun heads, the positive pole of high-voltage DC power supply is connected with copper wire electrode in syringe, uses
The earth terminal of high-voltage DC power supply is connected and is grounded by copper cash with reception device wire netting, and lance head is in horizontal direction
15 ° of angles, lance head is 15cm with the distance of wire netting, and spinning voltage is 13kV, and environment temperature is 20-25 DEG C, and relative humidity is
40%-50%, PVP/Bi (NO are collected into after carrying out electrostatic spinning on wire netting3)3/(NH4)10W12O41Nanofiber, will
PVP/Bi (the NO for arriving3)3/(NH4)10W12O41Nanofiber is put into crucible, then crucible is put into temperature programming stove, with 1 DEG C/
The heating rate of min is warming up to 300 DEG C, is incubated half an hour, then is warming up to 500 DEG C with the heating rate of 2 DEG C/min, is incubated 1h
Afterwards, natural cooling obtains Bi after being down to room temperature2WO6:Yb3+,Er3+Nanofiber；Weigh the Bi described in 0.36g2WO6:Yb3+,Er3+
Nanofiber, adds 6.0g DMF and ultrasound 20min, the polyacrylonitrile (PAN) that 0.6g molecular weight is 86000 is added, at 70 DEG C
Lower stirring 2h, obtains shell layer spinning solution after cooling；By the Fe of 0.6g Coated with Oleic Acid3O4It is nanocrystalline to be added in 4.0g DMF solvents
And ultrasound 20min, the polyacrylonitrile (PAN) that 0.6g molecular weight is 86000 is added, in stirring 2h at 70 DEG C, after being cooled to room temperature
Aniline ANI and 0.5238g the camphorsulfonic acid CSA of 0.42g is added, at room temperature magnetic agitation 2h, by 1.0291g ammonium persulfates APS
It is dissolved in 2.0g DMF, magnetic agitation 2h, this two parts of solution is placed into 1h in ice-water bath, afterwards by this two parts of solution in frozen water
Mix in bath, after magnetic agitation 3h, mixed liquor is put into 5 DEG C of refrigerator and refrigerates 24h, obtain sandwich layer spinning solution；Using coaxial
Electrostatic spinning technique, the composition of coaxial spinning head use interior spinning head for truncated after 8# stainless steel injection needles, outer spinning head is
The plastic spray gun head of 1mL, fixed after two spinning heads are packaged, the shell layer spinning solution that will be prepared is added to and outer spinning head phase
In the syringe of connection, sandwich layer spinning solution is added in the syringe being connected with interior spinning head, the inside and outside spinning head of regulation
Gap is smoothly flowed out with ensureing shell layer spinning solution, and using perpendicular spray mode, coaxial spinning head and horizontal plane adjust DC voltage
It is 15kV, the solidification distance of spinning head to receiving screen wire netting is 10cm, and 20-25 DEG C of indoor temperature, relative humidity is 40%-
50%, with the volatilization of solvent, the i.e. available [PANI/Fe on receiving screen wire netting3O4/PAN]@[Bi2WO6:Yb3+,Er3+/
PAN] the function coaxial nano cable of photoelectromagnetic photocatalysis four.Described [PANI/Fe3O4/PAN]@[Bi2WO6:Yb3+,Er3+/PAN]
Contain Emission in Cubic Fe in the function coaxial nano cable of photoelectromagnetic photocatalysis four3O4The Bi of nanocrystalline and rhombic system2WO6:Yb3+,
Er3+, as shown in Figure 1；Described [PANI/Fe3O4/PAN]@[Bi2WO6:Yb3+,Er3+/ PAN] function of photoelectromagnetic photocatalysis four is same
The average diameter that axle nano-cable has good fiber morphology, cable is about 600nm, and length is more than 500 μm, as shown in Figure 2；
Described [PANI/Fe3O4/PAN]@[Bi2WO6:Yb3+,Er3+/ PAN] in the function coaxial nano cable of photoelectromagnetic photocatalysis four, gather
Aniline PANI and Fe3O4Positioned at the sandwich layer of cable, Bi2WO6:Yb3+,Er3+Positioned at the shell of cable, the electricity of core-shell structure is formd
Cable, as shown in Figure 3；Described [PANI/Fe3O4/PAN]@[Bi2WO6:Yb3+,Er3+/ PAN] function of photoelectromagnetic photocatalysis four is coaxial
The average diameter of nano-cable is about 600nm, and sandwich layer diameter is about 200nm, and shell thickness is about 200nm, as shown in Figure 4；
The diode laser of 980nm is excited down, [PANI/Fe3O4/PAN]@[Bi2WO6:Yb3+,Er3+/ PAN] photoelectromagnetic photocatalysis four
Function coaxial nano cable launches main peak positioned at the Green band of 528nm and 543nm and the emitting red light band of 655nm,
Correspond respectively to Er3+Ion2H11/2→4I15/2With4S3/2→4I15/2And4F9/2→4I15/2Transition is launched, as shown in Figure 5；Institute
[the PANI/Fe for stating3O4/PAN]@[Bi2WO6:Yb3+,Er3+/ PAN] the function coaxial nano cable of photoelectromagnetic photocatalysis four is in 980nm
Diode laser excite down, the fluorescence color of transmitting is green, and chromaticity coordinates is (0.258,0.712), as shown in Figure 6；Institute
[the PANI/Fe for stating3O4/PAN]@[Bi2WO6:Yb3+,Er3+/ PAN] the function coaxial nano cable of photoelectromagnetic photocatalysis four have compared with
Strong magnetic, saturation magnetization is 8.404emu/g, as shown in Figure 7；[PANI/Fe is measured using Hall effect tester3O4/
PAN]@[Bi2WO6:Yb3+,Er3+/ PAN] the function coaxial nano cable of photoelectromagnetic photocatalysis four average conductivity for 3.86 ×
10-3S·cm-1；In the case where wavelength is 365nm ultraviolet lights, [PANI/Fe3O4/PAN]@[Bi2WO6:Yb3+,Er3+/ PAN] photoelectricity
Magneto-optic is catalyzed four function coaxial nano cables good photocatalytic Degradation to rhodamine B, when degradation time is 300min
When, the degradation rate to rhodamine B reaches 92.64%, as shown in Figure 8.
Certainly, the present invention can also have other various embodiments, ripe in the case of without departing substantially from spirit of the invention and its essence
Know those skilled in the art and work as and various corresponding changes and deformation, but these corresponding changes and change can be made according to the present invention
Shape should all belong to the protection domain of appended claims of the invention.
Claims (2)
1. the function coaxial nano cable of photoelectromagnetic photocatalysis four, it is characterised in that with the conductive and difunctional PANI/ of magnetic
Fe3O4/ PAN is sandwich layer, with the difunctional Bi of up-conversion luminescence and photocatalysis2WO6:Yb3+,Er3+/ PAN is shell, is constituted
[PANI/Fe3O4/PAN]@[Bi2WO6:Yb3+,Er3+/ PAN] coaxial nano cable, coaxial nano cable have simultaneously it is upper conversion hair
Light-conduction-four kinds of magnetic-photocatalysis function, the average diameter of coaxial nano cable is about 600nm, and sandwich layer diameter is about
200nm, shell thickness is about 200nm, and length is more than 500 μm.
2. a kind of preparation method of the function coaxial nano cable of photoelectromagnetic photocatalysis as claimed in claim 1 four, its feature exists
In using coaxial electrostatic spinning technology, it is [PANI/Fe to prepare product3O4/PAN]@[Bi2WO6:Yb3+,Er3+/ PAN] photoelectromagnetic
The function coaxial nano cable of photocatalysis four, its step is：
(1) precipitation method prepare the Fe of Coated with Oleic Acid3O4It is nanocrystalline
By 5.4060g FeCl3·6H2O, 2.7800g FeSO4·7H2O, 4.04g NH4NO3It is with 1.9000g molecular weight
20000 polyethylene glycol is dissolved in 100mL deionized waters, is heated to 50 DEG C and is passed through argon gas 30min, is then slowly added dropwise ammoniacal liquor
PH value to solution is 11, continues logical argon gas 20min and obtains black suspension, by this suspension Magneto separate after, use absolute ethyl alcohol
Washed successively with deionized water three times, product is placed in 60 DEG C of vacuum drying chamber and dries 12h, obtain a diameter of 8-10nm's
Fe3O4It is nanocrystalline；Take the Fe prepared by 1.5000g3O4It is nanocrystalline to be dispersed in the 100mL deionized waters for being passed through 30min argon gas
And ultrasonic disperse 20min, solution is then heated to 80 DEG C under argon gas protection, and 1.5mL oleic acid is added, then proceed to reaction
40min, Magneto separate is carried out by resulting precipitation, is removed water layer and will be deposited in 60 DEG C of vacuum drying chambers and dries 6h, is obtained
The Fe of Coated with Oleic Acid3O4It is nanocrystalline；
(2) method of electrostatic spinning combination high-temperature roasting prepares Bi2WO6:Yb3+,Er3+Nanofiber
Weigh 0.0194g Yb2O3With 0.0095g Er2O3It is dissolved in appropriate concentrated nitric acid and evaporative crystallization, obtains rare earth nitric acid
Salt mixture, after adding 5mL deionized water dissolvings, adds 0.6085g (NH4)10W12O41With 1.0087g citric acids, in 110 DEG C
Stirring evaporation forms gel, and 2.3285g Bi (NO are added after being cooled to room temperature3)3·5H2O and 23.4960g N, N- dimethyl methyls
Acid amides DMF, adds the polyvinylpyrrolidone PVP that 2.9431g molecular weight is 1300000, after stirring 4h and static 4h, is formed
The flaxen spinning solution of homogeneous transparent, spinning solution is injected in a 5mL syringe with 1mL plastic spray gun heads, high
The positive pole of dc source is pressed to be connected with copper wire electrode in syringe, with copper cash is by the earth terminal of high-voltage DC power supply and receives
Device wire netting is connected and is grounded, and lance head is in 15 ° of angles with horizontal direction, and lance head is 15cm, spinning with the distance of wire netting
Voltage is 13kV, and environment temperature is 20-25 DEG C, and relative humidity is 40%-50%, is carried out after electrostatic spinning in iron wire online collection
To PVP/Bi (NO3)3/(NH4)10W12O41Nanofiber, the PVP/Bi (NO that will be obtained3)3/(NH4)10W12O41Nanofiber is put into
In crucible, then crucible is put into temperature programming stove, 300 DEG C are warming up to the heating rate of 1 DEG C/min, be incubated half an hour, then
500 DEG C are warming up to the heating rate of 2 DEG C/min, after insulation 1h, natural cooling obtains Bi after being down to room temperature2WO6:Yb3+,Er3+
Nanofiber；
(3) spinning solution is prepared
Weigh the Bi described in 0.36g2WO6:Yb3+,Er3+Nanofiber, adds 6.0g DMF and ultrasound 20min, adds 0.6g
Molecular weight is 86000 polyacrylonitrile (PAN), and 2h is stirred at 70 DEG C, and shell layer spinning solution is obtained after cooling；By 0.6g Coated with Oleic Acid
Fe3O4It is nanocrystalline to be added in 4.0g DMF solvents and ultrasound 20min, add the polyacrylonitrile that 0.6g molecular weight is 86000
PAN, in 2h is stirred at 70 DEG C, is cooled to aniline ANI and 0.5238g the camphorsulfonic acid CSA of addition 0.42g after room temperature, at room temperature
Magnetic agitation 2h, 1.0291g ammonium persulfates APS is dissolved in 2.0g DMF, magnetic agitation 2h, by this two parts of solution in ice-water bath
Middle placement 1h, afterwards mixes this two parts of solution in ice-water bath, after magnetic agitation 3h, mixed liquor is put into 5 DEG C of refrigerator
Refrigeration 24h, obtains sandwich layer spinning solution；
(4) [PANI/Fe is prepared3O4/PAN]@[Bi2WO6:Yb3+,Er3+/ PAN] the function coaxial nano cable of photoelectromagnetic photocatalysis four
Using coaxial electrostatic spinning technology, the 8# stainless steels after the composition of coaxial spinning head uses interior spinning head for truncated are injected
Pin, outer spinning head is the plastic spray gun head of 1mL, fixed after two spinning heads are packaged, and the shell layer spinning solution that will be prepared is added
To in the syringe being connected with outer spinning head, sandwich layer spinning solution is added in the syringe being connected with interior spinning head, adjusted
The gap of the inside and outside spinning head of section is smoothly flowed out with ensureing shell layer spinning solution, and using perpendicular spray mode, coaxial spinning head hangs down with horizontal plane
Directly, regulation DC voltage is 15kV, and the solidification distance of spinning head to receiving screen wire netting is 10cm, 20-25 DEG C of indoor temperature, phase
It is 40%-50% to humidity, with the volatilization of solvent, the i.e. available [PANI/Fe on receiving screen wire netting3O4/PAN]@
[Bi2WO6:Yb3+,Er3+/ PAN] the function coaxial nano cable of photoelectromagnetic photocatalysis four, the average diameter of cable is about 600nm, core
Layer diameter is about 200nm, and shell thickness is about 200nm, and length is more than 500 μm；In the case where the diode laser of 980nm is excited,
[PANI/Fe3O4/PAN]@[Bi2WO6:Yb3+,Er3+/ PAN] the function coaxial nano cable of photoelectromagnetic photocatalysis four launches main peak
Positioned at the Green band and the emitting red light band of 655nm of 528nm and 543nm, the fluorescence color of transmitting is green；[PANI/
Fe3O4/PAN]@[Bi2WO6:Yb3+,Er3+/ PAN] average conductivity of the function coaxial nano cable of photoelectromagnetic photocatalysis four is
3.86×10-3S·cm-1；Saturation magnetization is 8.404emu/g；After wavelength is for the ultraviolet light 300min of 365nm,
[PANI/Fe3O4/PAN]@[Bi2WO6:Yb3+,Er3+/ PAN] the function coaxial nano cable of photoelectromagnetic photocatalysis four is to rhodamine B
Photocatalytic activity reaches 92.64%, and prepared coaxial nano cable has the good function of photoelectromagnetic photocatalysis four.
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| CN109957857A (en) * | 2017-12-14 | 2019-07-02 | 吉林建筑大学 | One kind can Magneto separate photocatalysis coaxial nanoribbon and its preparation process |
| CN113355771A (en) * | 2021-06-09 | 2021-09-07 | 上海理工大学 | Two-dimensional solid carbon dot light-emitting film and preparation method thereof |
| CN114737317A (en) * | 2022-04-20 | 2022-07-12 | 国家纳米科学中心 | Nanofiber composite membrane and method for reinforcing ferrous object |
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Application publication date: 20170613 |