CN103225121B - Magnetic up-conversion luminescence dual-functional coaxial composite nanofiber and preparation method thereof - Google Patents
Magnetic up-conversion luminescence dual-functional coaxial composite nanofiber and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to magnetic up-conversion luminescence dual-functional coaxial composite nanofiber and preparation method thereof, belong to technical field of nanometer material preparation.The present invention includes four steps: (1) sedimentation method prepare Fe3O4Nanocrystalline；(2) sedimentation method prepare NaYF4:Yb3+,Er3+Nanocrystalline；(3) preparation spinning liquid；(4) [Fe is prepared3O4/PVP][NaYF4:Yb3+,Er3+/ PVP] magnetic up-conversion luminescence dual-functional coaxial composite nanofiber, use coaxial electrostatic spinning technology to prepare, the average diameter of coaxial composite nano fiber is 390nm, a diameter of 130nm of sandwich layer, and shell thickness is 130nm, and length is more than 100 μm.This coaxial composite nano fiber with magneto-optic double-function, novel structure, will have important application prospect.The method of the present invention is simple, can produce in batches, have broad application prospects.
Description
Technical field
The present invention relates to technical field of nanometer material preparation, in particular relate to magnetic up-conversion luminescence dual-functional coaxial composite nanofiber
And preparation method thereof.
Background technology
The preparation of one-dimensional nano structure material and character research are one of forward position focuses of current material science research field.Coaxial multiple
Close nanofiber due to the performance of its uniqueness, abundant scientific meaning, wide application prospect and at following nano structure device
In the important strategic status occupied, cause the great attention of people in recent years.
Up-conversion luminescence process refers to that absorbed sends the process of higher-energy photon compared with energy photons, and up-conversion is had
This special nature having makes it at laser technology, optical fiber communication technology, fibre amplifier, Display Technique and many necks such as false proof
Territory has broad application prospects.Up-conversion generally includes activator, sensitizer and substrate.Erbium ion Er3+Have abundant
Energy level, and partial level lasts a long time, and upper conversion efficiency is the highest, is the activator of the up-conversion that research is more at present.
With Er3+Ion is that the up-conversion of activator generally uses ytterbium ion Yb3+For sensitizer.Rare earth tetrafluoride is rich owing to having
Rich 4f energy level and relatively low phonon energy, be one of the most rare earth ion doped substrate of efficient up-conversion luminescent material.Erbium ytterbium
Double-doped sodium yttrium tetrafluoride NaYF4:Er3+,Yb3+It is a kind of important up-conversion luminescent material, has important and be widely applied.
Magnetic-fluorescent dual-function composite is that medical diagnosis on disease provides a kind of new platform, due to their bi-functional with treatment
Matter makes " the finding-detection-treatment " of disease to be integrally forming.This composite use by improve further diagnosis efficiency and
Reduce side effect, cause the highest attention of researcher.At present, the research of magnetic-fluorescent dual-function composite nano materials has had
More report, such as, Hongxia Peng, et al uses direct precipitation method to be prepared for Fe3O4YVO4:Eu3+Nucleocapsid structure magnetic
Light nanoparticle [Journal of Alloys and Compounds, 2011,509,6930]；Liu Guixia etc. use hydro-thermal method to be prepared for
Fe3O4Gd2O3:Eu3+Nucleocapsid structure magneto-optic composite nanoparticle [chemistry journal, 2011,69 (9), 1081]；A Son, et al uses
Flame atomizing decomposition method is prepared for Fe3O4Gd2O3:Eu3+Nucleocapsid structure magneto-optic nanoparticle [Anal.Biochem., 2007,370,
186].Have no the report of magnetic up-conversion luminescence bifunctional coaxial nanoribbon at present.
Ferroso-ferric oxide Fe3O4It it is a kind of important and wide variety of magnetic material.People have used multiple method, such as precipitation
Method, sol-gel process, microemulsion method, hydro-thermal are successfully prepared with methods such as solvent-thermal method, thermal decomposition method, method of electrostatic spinning
Fe3O4The nano materials such as nanocrystalline, nanometer rods, nano wire, nanometer film, hybrid structure, Core-shell Structure Nanoparticles, skill
Art comparative maturity.NaYF4:Yb3+,Er3+It is a kind of good up-conversion luminescent material, has used the sedimentation method, hydro-thermal method, quiet
Electrical spinning method is prepared for NaYF4:Yb3+,Er3+Nanocrystalline, nanometer rods, nanofiber and nano belt.
Existing research is it has been proved that work as black magnetic compound Fe3O4With NaYF4:Yb3+,Er3+Up-conversion luminescent material is direct
Mixing can significantly reduce its up-conversion luminescence effect, NaYF to be obtained4:Yb3+,Er3+Good up-conversion luminescence effect, must
NaYF must be made4:Yb3+,Er3+With Fe3O4Realization efficiently separates and can not directly contact.If by Fe3O4Nanocrystalline and high score
Sub-polyvinylpyrrolidone PVP is prepared by mixing into nanofiber, and as the sandwich layer of coaxial composite nano fiber, this sandwich layer will tool
It is magnetic, by NaYF4:Yb3+,Er3+Nanocrystalline being combined with PVP is prepared as nanofiber, as coaxial composite nano fiber
Shell, this shell will have Upconversion luminescence, such that it is able to make Fe3O4Nanocrystalline and NaYF4:Yb3+,Er3+Nanocrystalline
Achieve and efficiently separate, so can be obtained by magnetic up-conversion luminescence dual-functional coaxial composite nanofiber of good performance.
Have no at present and pass through Fe3O4Nanocrystalline and NaYF4:Yb3+,Er3+Nanocrystalline respectively with high-molecular polythene ketopyrrolidine PVP,
Build [Fe3O4/PVP][NaYF4:Yb3+,Er3+/ PVP] report of magnetic up-conversion luminescence dual-functional coaxial composite nanofiber,
Material above is sandwich layer, and material below is shell, i.e. with Fe3O4Nanocrystalline+PVP is sandwich layer, has magnetic, with
NaYF4:Yb3+,Er3+Nanocrystalline+PVP is shell, has Upconversion luminescence, constitutes coaxial composite nano fiber.This kind
There is magnetic up-conversion luminescence dual-functional coaxial composite nanofiber there is special structure, will be following nano structure device and doctor
Treat in diagnoses and treatment and there is important application prospect.
The United States Patent (USP) of Patent No. 1975504 discloses a technical scheme about electrospinning process (electrospinning),
The method is to prepare continuous print, have a kind of effective ways of the micro nanometer fiber of macro length, by Formhals in 1934
First propose.This method is mainly used to prepare high polymer nanometer fiber, it is characterized in that making charged macromolecular solution or melt exist
Electrostatic field is sprayed by nozzle by the traction of electrostatic force, invests the receiving screen on opposite, thus realize wire drawing, then, at room temperature
Lower solvent evaporates, or melt cooling solidifies to room temperature, obtains micro nanometer fiber.Over nearly 10 years, prepare skill at inorfil
Art field occurs in that the technical scheme using electrospinning process to prepare inorganic compound such as oxide nanofiber, described oxidation
Thing 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.Dong Xiangting etc. make
With single spinning head, electrostatic spinning technique is used to be prepared for PAN/Eu (BA)3Phen recombination luminescence nanofiber [New Chemical Materials,
2008,36(9),49-52]；Wang Ce etc. use single spinning head, use method of electrostatic spinning to be prepared for polyvinylpyrrolidone/tetra-oxidation
Three-iron composite nano fiber [SCI, 2006,27 (10), 2002-2004]；Qingbiao Yang, et al uses single
Individual spinning head, employing electrostatic spinning technique are prepared for Fe2O3nanoparticles/Eu(DBM)3(Bath) Composite Double function magneto-optic nanometer
Fiber [Journal of Colloid and Interface Science, 2010,350,396-401]；Dong Xiangting etc. use electrostatic spinning technique
It is prepared for Fe3O4/Eu(BA)3Phen/PVP magneto-optic double-function composite nano fiber [Journal of Nanoparticle Research,
2012,14 (10): 1203-1209] and magneto-optic double-function Fe3O4/Eu(BA)3Phen/PMMA composite Nano band [national inventing patent,
Application number: 201110303031.0；Optical Materials,2013,35(3),526-530].Electrostatic spinning technique is improved,
Use coaxial spinning head, spinning liquid is injected separately in inner and outer tubes, the spinning when adding High Level DC Voltage, in inner and outer pipes
Liquid is pulled out by electric field force simultaneously, forms coaxial nano cable or coaxial composite nano fiber after solidification, and this technology is i.e. coaxial
Electrostatic spinning technique.Wang Ce etc. with this technology be prepared for silica polymer Coaxial Nanofibers [SCI,
2005,26(5):985-987]；Dong Xiangting etc. utilize this technology to be prepared for TiO2SiO2Submicron coaxial cable [chemistry journal,
2007,65(23):2675-2679]、ZnOSiO2Coaxial nano cable [Chinese Journal of Inorganic Chemistry, 2010,26 (1), 29-34] and
Al2O3/SiO2Coaxial ultra micro cable [silicate journal, 2009,37 (10), 1712-1717]；Han, et al uses this technology to be prepared for
PC (Shell)/PU (Core) composite nano fiber [Polymer Composites, 2006,10:381-386]；Dong Xiangting etc. use this skill
Art is prepared for (Fe3O4+PVP)[Eu(BA)3Phen+PVP] magneto-optic double-function coaxial nano cable [national inventing patent, application
Number: 201110284141.7].At present, have no and utilize coaxial electrostatic spinning technology to prepare
[Fe3O4/PVP][NaYF4:Yb3+,Er3+/ PVP] relevant report of magnetic up-conversion luminescence dual-functional coaxial composite nanofiber.
When utilizing electrostatic spinning technique to prepare nano material, the kind of raw material, the molecular weight of high polymer templates, the group of spinning liquid
Become, pattern and the size of final products are all had a major impact by spinning process parameter.The present invention uses coaxial electrostatic spinning technology,
With Fe3O4Nanocrystalline, PVP and chloroform CHCl3Mixed liquor be sandwich layer spinning liquid, with NaYF4:Yb3+,Er3+Nanocrystalline, PVP
Being shell layer spinning solution with the mixed liquor of DMF DMF, the viscosity controlling shell and sandwich layer spinning liquid is most important,
Under optimal process conditions, it is thus achieved that [the Fe of novel structure3O4/PVP][NaYF4:Yb3+,Er3+/ PVP] magnetic up-conversion luminescence
Dual-functional coaxial composite nanofiber.
Summary of the invention
Employ single spinning head in the introduction, use electrostatic spinning technique to be prepared for metal-oxide and metal composite oxidation
Thing nanofiber, polyvinylpyrrolidone/ferroso-ferric oxide composite nano fiber, PAN/Eu (BA)3Phen recombination luminescence Nanowire
Dimension, Fe2O3nanoparticles/Eu(DBM)3(Bath) Composite Double function magneto-optic nanofiber, Fe3O4/Eu(BA)3phen/PVP
Magneto-optic double-function composite nano fiber and magneto-optic double-function Fe3O4/Eu(BA)3Phen/PMMA composite Nano band.In background technology
Use coaxial electrostatic spinning technology be prepared for inorganic matter inorganic matter, inorganic matter macromolecule and macromolecule high molecular nanometer electricity
Cable and (Fe3O4+PVP)[Eu(BA)3Phen+PVP] magneto-optic double-function coaxial nano cable, the raw material used, template,
Solvent is all different from the method for the present invention with final target product.It is new that the present invention uses coaxial electrostatic spinning technology to be prepared for structure
[the Fe of grain husk3O4/PVP][NaYF4:Yb3+,Er3+/ PVP] magnetic up-conversion luminescence dual-functional coaxial composite nanofiber, with Fe3O4
Nanocrystalline+PVP is sandwich layer, with NaYF4:Yb3+,Er3+Nanocrystalline+PVP is that shell constitutes coaxial composite nano fiber, averagely
A diameter of 390nm, length is more than 100 μm, the rough injustice in surface, has projection.
The present invention is achieved in that and prepares Fe initially with the sedimentation method3O4Nanocrystalline and NaYF4:Yb3+,Er3+Nanocrystalline, then
Prepare the shell with certain viscosity for coaxial electrostatic spinning technology and sandwich layer spinning liquid, control shell and sandwich layer spinning liquid
Viscosity most important.Application coaxial electrostatic spinning technology carries out electrostatic spinning, under optimal process conditions, it is thus achieved that structure is new
[the Fe of grain husk3O4/PVP][NaYF4:Yb3+,Er3+/ PVP] magnetic up-conversion luminescence dual-functional coaxial composite nanofiber, its step
For:
(1) sedimentation method prepare Fe3O4Nanocrystalline
By 5.4060g FeCl3·6H2O, 2.7800g FeSO4·7H2O, 4.04g NH4NO3It is 20000 with 1.9g molecular weight
Polyethylene Glycol is dissolved in 100mL deionized water, is heated to 50 DEG C and is passed through argon 30min, is then slowly added dropwise ammonia to molten
The pH value of liquid is 11, continues logical argon 20min and obtains black suspension, after this suspension Magneto separate, with dehydrated alcohol and
Deionized water washs three times successively, is placed in by product in the vacuum drying oven of 60 DEG C and is dried 12h, obtains a diameter of 8-10nm's
Fe3O4Nanocrystalline；
(2) sedimentation method prepare NaYF4:Yb3+,Er3+Nanocrystalline
By 0.8807g Y2O3, 0.3940g Yb2O3With 0.0382g Er2O3It is dissolved in 50mL concentrated hydrochloric acid and heating evaporation is to crystallization,
Add 50mL ethylene glycol crystallization to be dissolved, obtain solution I, in the 250mL three-necked bottle being connected to reflux, by 5.0388g
NaF and 5g molecular weight be the polyvinylpyrrolidone of 30,000 as protective agent, be dissolved into 30mL deionized water and 120mL second
In the mixed solvent of glycol, obtain solution II, solution II is passed through argon 30min and is warming up to 180 DEG C, then protect at argon
Protect lower solution I being joined in solution II and back flow reaction 3h at 180 DEG C, obtain white precipitate, by obtained precipitate
Centrifugation, and wash successively 3 times with deionized water and ethanol, product is placed in 12h in 60 DEG C of vacuum drying ovens, obtains straight
Footpath is the NaYF of 25-27nm4:Yb3+,Er3+Nanocrystalline；
(3) preparation spinning liquid
By 3g Fe3O4Nanocrystalline being dispersed in is passed through in the 100ml water of 30min argon and ultrasonic disperse 20min, then will be outstanding
Turbid liquid is heated to 80 DEG C under argon shield, and adds 2mL oleic acid, then proceedes to react 40min, obtains Coated with Oleic Acid
Fe3O4Nanocrystalline, by obtained precipitation Magneto separate, remove water layer and dry 12h will be deposited in 60 DEG C of vacuum drying ovens,
Fe by obtained Coated with Oleic Acid3O4Nanocrystalline be dispersed in 3g chloroform, be subsequently adding 0.5g molecular weight be 90000 poly-
Vinylpyrrolidone PVP, obtains sandwich layer spinning liquid, by 0.5g NaYF4:Yb3+,Er3+Nanocrystalline it is dispersed in 3.3g DMF also
Ultrasonic disperse 20min, is subsequently adding the PVP that 0.5g molecular weight is 90000, obtains shell layer spinning solution；
(4) [Fe is prepared3O4/PVP][NaYF4:Yb3+,Er3+/ PVP] magnetic up-conversion luminescence dual-functional coaxial composite nanofiber
Using a 5mL syringe with truncated 7# rustless steel syringe needle as interior spin duct, one stainless with truncated 14#
The 10mL syringe of draw point head, as outer spin duct, forms coaxial spinning head, is joined by sandwich layer spinning liquid in interior spin duct,
Shell layer spinning solution joins and carries out coaxial electrostatic spinning in outer spin duct, uses perpendicular spray mode, and spinning voltage is 13kV, needle point with
Collecting wire gauze spacing 12cm, ambient temperature is 20 DEG C-26 DEG C, and relative humidity is 20%-30%, obtains
[Fe3O4/PVP][NaYF4:Yb3+,Er3+/ PVP] magnetic up-conversion luminescence dual-functional coaxial composite nanofiber.
[the Fe of novel structure prepared in said process3O4/PVP][NaYF4:Yb3+,Er3+/ PVP] magnetic up-conversion luminescence pair
The coaxial composite nano fiber of function, average diameter is 390nm, a diameter of 130nm of sandwich layer, and shell thickness is 130nm, length
More than 100 μm, the rough injustice in surface, there is projection, saturation magnetization is 25.43emu/g, with two poles that wavelength is 980nm
Pipe laser instrument, as excitation source, obtains peak value and is respectively green glow and the upper conversion of HONGGUANG bands of a spectrum composition of 544nm and 655nm
Emission spectrum, this coaxial composite nano fiber has good magnetic and up-conversion luminescence is difunctional, it is achieved that goal of the invention.
Accompanying drawing explanation
Fig. 1 is Fe3O4Nanocrystalline TEM photo；
Fig. 2 is Fe3O4Nanocrystalline XRD spectra；
Fig. 3 is NaYF4:Yb3+,Er3+Nanocrystalline TEM photo；
Fig. 4 is NaYF4:Yb3+,Er3+Nanocrystalline XRD spectra；
Fig. 5 is [Fe3O4/PVP][NaYF4:Yb3+,Er3+/ PVP] XRD of magnetic up-conversion luminescence dual-functional coaxial composite nanofiber
Spectrogram；
Fig. 6 is [Fe3O4/PVP][NaYF4:Yb3+,Er3+/ PVP] SEM of magnetic up-conversion luminescence dual-functional coaxial composite nanofiber
Photo, this figure also serves as Figure of abstract；
Fig. 7 is [Fe3O4/PVP][NaYF4:Yb3+,Er3+/ PVP] TEM of magnetic up-conversion luminescence dual-functional coaxial composite nanofiber
Photo；
Fig. 8 is [Fe3O4/PVP][NaYF4:Yb3+,Er3+/ PVP] magnetic up-conversion luminescence dual-functional coaxial composite nanofiber exciting
Power is Up-conversion emission spectrogram during 300mW；
Fig. 9 is [Fe3O4/PVP][NaYF4:Yb3+,Er3+/ PVP] magnetic up-conversion luminescence dual-functional coaxial composite nanofiber is in difference
Up-conversion emission spectrogram during exciting power；
Figure 10 is [Fe3O4/PVP][NaYF4:Yb3+,Er3+/ PVP] luminescence of magnetic up-conversion luminescence dual-functional coaxial composite nanofiber
The natural logrithm of intensity is with the variation diagram of the natural logrithm of exciting power；
Figure 11 is [Fe3O4/PVP][NaYF4:Yb3+,Er3+/ PVP] magnetic hysteresis of magnetic up-conversion luminescence dual-functional coaxial composite nanofiber
Loop line figure.
Detailed description of the invention
Yittrium oxide Y selected by the present invention2O3, ytterbium oxide Yb2O3With Erbia Er2O3Purity is 99.99%, N, N-dimethyl
Methanamide DMF, chloroform CHCl3, Iron(III) chloride hexahydrate, green vitriol, ammonium nitrate, molecular weight is 20000
Polyethylene Glycol, argon, hydrochloric acid, ethylene glycol, oleic acid, sodium fluoride, molecular weight is the polyvinylpyrrolidone PVP of 30,000 and 90,000,
Dehydrated alcohol, ammonia NH3·H2O is commercially available analytical pure product；Deionized water laboratory is made by oneself；Glass apparatus used and setting
Standby is instrument and equipment conventional in laboratory.
Embodiment is by 5.4060g FeCl3·6H2O, 2.7800g FeSO4·7H2O, 4.04g NH4NO3It is 20000 with 1.9g molecular weight
Polyethylene Glycol be dissolved in 100mL deionized water, be heated to 50 DEG C and be passed through argon 30min, being then slowly added dropwise ammonia extremely
The pH value of solution is 11, continues logical argon 20min and obtains black suspension, after this suspension Magneto separate, uses dehydrated alcohol
Wash successively with deionized water three times, product is placed in the vacuum drying oven of 60 DEG C and is dried 12h, obtain ferroso-ferric oxide Fe3O4
Nanocrystalline, prepared Fe3O4Nanocrystalline a diameter of 8-10nm, as shown in Figure 1；Prepared Fe3O4Nanocrystalline have
Good crystallinity, the d value of its diffraction maximum and relative intensity and Fe3O4The d value listed by PDF standard card (74-0748) and
Relative intensity is consistent, belongs to cubic system, as shown in Figure 2；By 0.8807g Y2O3, 0.3940g Yb2O3With 0.0382g Er2O3
It is dissolved in 50mL concentrated hydrochloric acid and heating evaporation is to crystallization, add 50mL ethylene glycol and crystallization is dissolved, obtain solution I, be connected to
In the 250mL three-necked bottle of reflux, using 5.0388g NaF and polyvinylpyrrolidone that 5g molecular weight is 30,000 as protection
Agent, is dissolved in the mixed solvent of 30mL deionized water and 120mL ethylene glycol, obtains solution II, solution II is passed through argon
Gas 30min is also warming up to 180 DEG C, then solution I is joined in solution II under argon shield and refluxes anti-at 180 DEG C
Answer 3h, obtain white precipitate, by obtained precipitate centrifugation, and wash successively 3 times with deionized water and ethanol, will
Product is placed in 12h in 60 DEG C of vacuum drying ovens, obtains NaYF4:Yb3+,Er3+Nanocrystalline, prepared NaYF4:Yb3+,Er3+
Nanocrystalline a diameter of 25-27nm, as shown in Figure 3；Prepared NaYF4:Yb3+,Er3+Nanocrystalline have good crystallinity,
The d value of its diffraction maximum and relative intensity and NaYF4The d value listed by PDF standard card (06-0342) consistent with relative intensity,
Belong to cubic system, show synthesized NaYF4:Yb3+,Er3+Nanocrystalline for cubic system, as shown in Figure 4；By 3g Fe3O4
Nanocrystalline being dispersed in is passed through in the 100ml water of 30min argon and ultrasonic disperse 20min, then by solution under argon shield
It is heated to 80 DEG C, and adds 2mL oleic acid, then proceed to react 40min, obtain the Fe of Coated with Oleic Acid3O4Nanocrystalline, by institute
The precipitation Magneto separate obtained, removes water layer and will be deposited in 60 DEG C of vacuum drying ovens dry 12h, by obtained Coated with Oleic Acid
Fe3O4Nanocrystalline it is dispersed in 3g chloroform, is subsequently adding the polyvinylpyrrolidone PVP that 0.5g molecular weight is 90000,
Obtain sandwich layer spinning liquid, by 0.5g NaYF4:Yb3+,Er3+The nanocrystalline also ultrasonic disperse 20min that is dispersed in 3.3g DMF, so
Rear addition 0.5g molecular weight is the PVP of 90000, obtains shell layer spinning solution；With one with truncated 7# rustless steel syringe needle
5mL syringe as interior spin duct, a 10mL syringe with truncated 14# rustless steel syringe needle as outer spin duct,
Forming coaxial spinning head, joined by sandwich layer spinning liquid in interior spin duct, shell layer spinning solution joins and carries out in outer spin duct coaxially
Electrostatic spinning, uses perpendicular spray mode, and spinning voltage is 13kV, and needle point and collection wire gauze spacing 12cm, ambient temperature is
20 DEG C-26 DEG C, relative humidity is 20%-30%, obtains [Fe3O4/PVP][NaYF4:Yb3+,Er3+/ PVP] magnetic up-conversion luminescence
Dual-functional coaxial composite nanofiber.Prepared [Fe3O4/PVP][NaYF4:Yb3+,Er3+/ PVP] magnetic up-conversion luminescence pair
The coaxial composite nano fiber of function has obvious Fe3O4And NaYF4:Yb3+,Er3+Nanocrystalline diffraction maximum, shows prepared
Coaxial composite nano fiber contains Fe3O4And NaYF4:Yb3+,Er3+Nanocrystalline, as shown in Figure 5；Prepared
[Fe3O4/PVP][NaYF4:Yb3+,Er3+/ PVP] magnetic up-conversion luminescence dual-functional coaxial composite nanofiber, there is fiber shape
Looks, average diameter is 390nm, and length is more than 100 μm, the rough injustice in surface, has projection, as shown in Figure 6；Prepared
[Fe3O4/PVP][NaYF4:Yb3+,Er3+/ PVP] sandwich layer of magnetic up-conversion luminescence dual-functional coaxial composite nanofiber is a diameter of
130nm, shell thickness is 130nm, as shown in Figure 7；With wavelength be 980nm, power be the diode laser of 300mW
As excitation source, obtain [Fe3O4/PVP][NaYF4:Yb3+,Er3+/ PVP] magnetic up-conversion luminescence is difunctional coaxial compound receives
The Up-conversion emission spectrum of rice fiber, is made up of the bands of a spectrum of peak value respectively 544nm and 655nm, wherein green at 544nm
Light emission correspondence Er3+Ion4S3/2→4I15/2Transition is launched, and red emission correspondence Er at 655nm3+Ion4F9/2→4I15/2Transition is launched, as shown in Figure 8；[Fe3O4/PVP][NaYF4:Yb3+,Er3+/ PVP] the double merit of magnetic up-conversion luminescence
The Up-conversion emission spectrum of the coaxial composite nano fiber of energy strengthens along with the increase of the exciting power of diode laser, sees Fig. 9
Shown in；[Fe3O4/PVP][NaYF4:Yb3+,Er3+/ PVP] magnetic up-conversion luminescence dual-functional coaxial composite nanofiber upper turn
Change the green emission in emission spectrum4S3/2→4I15/2Transition and red emission4F9/2→4I15/2The Up-conversion Intensity of transition from
So natural logrithm lnP of the exciting power of diode laser is mapped by logarithm lnI, obtains two straight lines, wherein4S3/2→4I15/2
Transition and4F9/2→4I15/2The slope n of transition is respectively 3.288 and 3.400, shows green emission4S3/2→4I15/2And red emission4F9/2→4I15/2It is three-photon processes, as shown in Figure 10；Prepared [Fe3O4/PVP][NaYF4:Yb3+,Er3+/ PVP] magnetic
Property up-conversion luminescence dual-functional coaxial composite nanofiber has stronger magnetic, and saturation magnetization is 25.43emu/g, sees figure
Shown in 11.
Certainly, the present invention also can have other various embodiments, in the case of without departing substantially from present invention spirit and essence thereof, is familiar with this
The technical staff in field is when making various corresponding change and deformation according to the present invention, but these change accordingly and deformation is all answered
Belong to the protection domain of appended claims of the invention.
Claims (1)
1. a magnetic up-conversion luminescence dual-functional coaxial composite nanofiber, it is characterised in that nano-fiber material presents coaxial multiple
Closing nanofibrous structures, have magnetic and up-conversion luminescence is difunctional, the average diameter of coaxial composite nano fiber is 390nm,
The a diameter of 130nm of sandwich layer, shell thickness is 130nm, and length is more than 100 μm, the rough injustice in surface, has projection；Described
The preparation method of magnetic up-conversion luminescence dual-functional coaxial composite nanofiber, uses coaxial electrostatic spinning technology, uses coaxial spinning head,
Molecular weight be the polyvinylpyrrolidone PVP of 90000 as the high polymer templates in spinning liquid, preparing product is
[Fe3O4/PVP][NaYF4:Yb3+,Er3+/ PVP] magnetic up-conversion luminescence dual-functional coaxial composite nanofiber, the steps include:
(1) sedimentation method prepare Fe3O4Nanocrystalline
By 5.4060g FeCl3·6H2O, 2.7800g FeSO4·7H2O, 4.04g NH4NO3It is 20000 with 1.9g molecular weight
Polyethylene Glycol is dissolved in 100mL deionized water, is heated to 50 DEG C and is passed through argon 30min, is then slowly added dropwise ammonia to molten
The pH value of liquid is 11, continues logical argon 20min and obtains black suspension, after this suspension Magneto separate, with dehydrated alcohol and
Deionized water washs three times successively, is placed in by product in the vacuum drying oven of 60 DEG C and is dried 12h, obtains a diameter of 8-10nm's
Fe3O4Nanocrystalline；
(2) sedimentation method prepare NaYF4:Yb3+,Er3+Nanocrystalline
By 0.8807g Y2O3, 0.3940g Yb2O3With 0.0382g Er2O3It is dissolved in 50mL concentrated hydrochloric acid and heating evaporation is to crystallization,
Add 50mL ethylene glycol crystallization to be dissolved, obtain solution I, in the 250mL three-necked bottle being connected to reflux, by 5.0388g
NaF and 5g molecular weight be the polyvinylpyrrolidone of 30,000 as protective agent, be dissolved into 30mL deionized water and 120mL second
In the mixed solvent of glycol, obtain solution II, solution II is passed through argon 30min and is warming up to 180 DEG C, then protect at argon
Protect lower solution I being joined in solution II and back flow reaction 3h at 180 DEG C, obtain white precipitate, by obtained precipitate
Centrifugation, and wash successively 3 times with deionized water and ethanol, product is placed in 12h in 60 DEG C of vacuum drying ovens, obtains straight
Footpath is the NaYF of 25-27nm4:Yb3+,Er3+Nanocrystalline；
(3) preparation spinning liquid
By 3g Fe3O4Nanocrystalline being dispersed in is passed through in the 100ml water of 30min argon and ultrasonic disperse 20min, then will be outstanding
Turbid liquid is heated to 80 DEG C under argon shield, and adds 2mL oleic acid, then proceedes to react 40min, obtains Coated with Oleic Acid
Fe3O4Nanocrystalline, by obtained precipitation Magneto separate, remove water layer and dry 12h will be deposited in 60 DEG C of vacuum drying ovens,
Fe by obtained Coated with Oleic Acid3O4Nanocrystalline it is dispersed in 3g chloroform, is subsequently adding 0.5g polyvinylpyrrolidone PVP,
Obtain sandwich layer spinning liquid, by 0.5g NaYF4:Yb3+,Er3+The nanocrystalline also ultrasonic disperse 20min that is dispersed in 3.3g DMF, so
Rear addition 0.5g PVP, obtains shell layer spinning solution；
(4) [Fe is prepared3O4/PVP][NaYF4:Yb3+,Er3+/ PVP] magnetic up-conversion luminescence dual-functional coaxial composite nanofiber
Using a 5mL syringe with truncated 7# rustless steel syringe needle as interior spin duct, one stainless with truncated 14#
The 10mL syringe of draw point head, as outer spin duct, forms coaxial spinning head, is joined by sandwich layer spinning liquid in interior spin duct,
Shell layer spinning solution joins and carries out coaxial electrostatic spinning in outer spin duct, uses perpendicular spray mode, and spinning voltage is 13kV, needle point with
Collecting wire gauze spacing 12cm, ambient temperature is 20 DEG C-26 DEG C, and relative humidity is 20%-30%, obtains
[Fe3O4/PVP][NaYF4:Yb3+,Er3+/ PVP] magnetic up-conversion luminescence dual-functional coaxial composite nanofiber, average diameter is
390nm, a diameter of 130nm of sandwich layer, shell thickness is 130nm, and length is more than 100 μm, and saturation magnetization is 25.43emu/g,
With the diode laser that wavelength is 980nm as excitation source, obtain peak value be respectively 544nm and 655nm green glow and
The Up-conversion emission spectrum of HONGGUANG bands of a spectrum composition, this coaxial composite nano fiber has magnetic and up-conversion luminescence is difunctional.
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| CN105295892A (en) * | 2015-11-24 | 2016-02-03 | 西南民族大学 | Preparation method of core-shell structured magnetic up-conversion luminescence bifunctional nano-particles |
| CN106427114B (en) * | 2016-08-30 | 2018-10-23 | 长春理工大学 | Magnetic multicolor luminous difunctional two layers of composite nano-fiber membrane and preparation method thereof |
| 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 |
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