CN103225122A - Magnetic upconversion and luminous bifunctional coaxial nanoribbon and preparation method thereof - Google Patents

Magnetic upconversion and luminous bifunctional coaxial nanoribbon and preparation method thereof Download PDF

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CN103225122A
CN103225122A CN2013100685127A CN201310068512A CN103225122A CN 103225122 A CN103225122 A CN 103225122A CN 2013100685127 A CN2013100685127 A CN 2013100685127A CN 201310068512 A CN201310068512 A CN 201310068512A CN 103225122 A CN103225122 A CN 103225122A
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pmma
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nanocrystalline
nayf
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董相廷
马千里
王进贤
于文生
刘桂霞
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Changchun University of Science and Technology
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Changchun University of Science and Technology
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Abstract

The invention relates to a magnetic upconversion and luminous bifunctional coaxial nanoribbon and a preparation method thereof and belongs to the technical field of nanomaterial preparation. The method comprises the five steps that (1) Fe3O4 nanocrystals are prepared by a precipitation method; (2) NaYF4:Yb<3+>, Er<3+> nanocrystals are prepared by the precipitation method; (3) polymethyl methacrylate (PMMA) is prepared; (4) a spinning solution is prepared; and (5) the [Fe3O4+PMMA]@[NaYF4:Yb<3+>, Er<3+>+PMMA] magnetic upconversion and luminous bifunctional coaxial nanoribbon is prepared by a coaxial electrostatic spinning technology, the coaxial nanoribbon is 10 micrometers in width, 988nm in thickness and greater than 100 micrometers in length, and a core layer is 3 micrometers in width. The magneto-optical bifunctional coaxial nanoribbon in a novel structure is expected to have an important application. The method is simple and practicable, can be used for mass production and has a wide application prospect.

Description

Difunctional co-axial nano band of a kind of magnetic up-conversion luminescence and preparation method thereof
Technical field
The present invention relates to the nano material preparation technical field, relate to difunctional co-axial nano band of a kind of magnetic up-conversion luminescence and preparation method thereof specifically.
Background technology
The preparation of one-dimensional nano structure material and property research are one of forward position focuses of present material science research field.Co-axial nano band Coaxial Nanoribbons is because its particular performances, abundant scientific meaning, wide application prospect and the important strategic status of occupying in following nano structure device have caused people's great attention in recent years.People have developed several methods that prepare the co-axial nano band on the basis of original preparation nanometer band, as: hydro-thermal method, sol-gel process, vapor growth method, template etc.Continue to explore new synthetic technology, constantly develop and improve the preparation science of co-axial nano band, obtain high-quality co-axial nano band, be still the main direction of present co-axial nano band research.
The up-conversion luminescence process is meant that absorbed sends the process of higher-energy photon than energy photons, and this special nature that up-conversion had makes it have broad application prospects in laser technology, optical fiber communication technology, fibre amplifier, Display Technique and numerous areas such as false proof.Up-conversion generally includes activator, sensitizer and matrix.Erbium ion Er 3+Have abundant energy level, and part is longer the life time of the level, last conversion efficiency is very high, is the activator of the more up-conversion of research at present.With Er 3+Ion is that the up-conversion of activator adopts ytterbium ion Yb usually 3+Be sensitizer.The rare earth tetrafluoride is owing to have abundant 4f energy level and lower phonon energy, is one of matrix of at present rare earth ion doped efficient up-conversion luminescent material.The two tetrafluoro yttrium sodium NaYF that mix of erbium ytterbium 4: Er 3+, Yb 3+Be a kind of important up-conversion luminescent material, have important and application widely.
Magnetic-fluorescent dual-function composite provides a kind of new platform for medical diagnosis on disease and treatment, because their difunctional character becomes one " discovery-detection-treatment " of disease.The use of this composite will further improve the efficient of diagnosis and reduce side effect, cause showing great attention to of researcher.At present, the research of magnetic-fluorescent dual-function composite nano materials has had more report, and for example, Hongxia Peng, et al adopt direct precipitation method to prepare Fe 3O 4@YVO 4: Eu 3+Nucleocapsid structure magneto-optic nano particle [Journal of Alloys and Compounds, 2011,509,6930]; Liu Guixia etc. have adopted Hydrothermal Preparation Fe 3O 4@Gd 2O 3: Eu 3+Nucleocapsid structure magneto-optic composite nanoparticle [chemical journal, 2011,69 (9), 1081]; A Son, et al adopt the flame atomizing decomposition method to prepare Fe 3O 4@Gd 2O 3: Eu 3+Nucleocapsid structure magneto-optic nano particle [Anal.Biochem., 2007,370,186].Do not see at present the report of the difunctional co-axial nano band of magnetic up-conversion luminescence.
Tri-iron tetroxide Fe 3O 4It is a kind of important and magnetic material of extensive use.People have adopted several different methods, have successfully prepared Fe as methods such as the precipitation method, sol-gel process, microemulsion method, hydro-thermal and solvent-thermal method, thermal decomposition method, method of electrostatic spinning 3O 4Nano materials such as nanocrystalline, nanometer rods, nano wire, nanometer film, hybrid structure, nuclear shell structure nano particle, the technology comparative maturity.NaYF 4: Yb 3+, Er 3+Be a kind of good up-conversion luminescent material, adopted the precipitation method, hydro-thermal method, method of electrostatic spinning has prepared NaYF 4: Yb 3+, Er 3+Nanocrystalline, nanometer rods, nanofiber and nanometer band.
Existing research is verified, as black magnetic compound F 17-hydroxy-corticosterone e 3O 4With NaYF 4: Yb 3+, Er 3+Up-conversion luminescent material directly mixes and can significantly reduce its up-conversion luminescence effect, therefore will obtain NaYF 4: Yb 3+, Er 3+Good up-conversion luminescence effect must make NaYF 4: Yb 3+, Er 3+With Fe 3O 4Realize effectively separating and can not directly contact.If with Fe 3O 4Nanocrystallinely be mixed with into the nanometer band with the macromolecule polymetylmethacrylate, as the sandwich layer of co-axial nano band, this sandwich layer will have magnetic, with NaYF 4: Yb 3+, Er 3+Nanocrystalline and the compound nanometer band that is prepared into of PMMA, as the shell of co-axial nano band, this shell will have the up-conversion luminescence characteristic, thereby can make Fe 3O 4Nanocrystalline and NaYF 4: Yb 3+, Er 3+Nanocrystallinely realize effective separation, so just can obtain the difunctional co-axial nano band of well behaved magnetic up-conversion luminescence.
Do not see at present and pass through Fe 3O 4Nanocrystalline and NaYF 4: Yb 3+, Er 3+Nanocrystalline respectively with the macromolecule polymetylmethacrylate, make up [Fe 3O 4+ PMMA] @[NaYF 4: Yb 3+, Er 3++ PMMA] report of magneto-optic double-function co-axial nano band, the material of @ front is a sandwich layer, the material of @ back is a shell, promptly with Fe 3O 4Nanocrystalline+PMMA is a sandwich layer, has magnetic, with NaYF 4: Yb 3+, Er 3+Nanocrystalline+PMMA is a shell, has the up-conversion luminescence characteristic, constitutes the co-axial nano band.This kind has magneto-optic double-function co-axial nano band and has special structure, will have important use in following nano structure device and medical diagnosis treatment.
The patent No. technical scheme of a relevant electrospinning process (electrospinning) that has been 1975504 U.S. Patent Publication, this method is a kind of effective ways that prepare continuous, as to have macro length micro nanometer fiber, is at first proposed in 1934 by Formhals.This method is mainly used to prepare high polymer nanometer fiber, it is characterized in that making charged Polymer Solution or melt in electrostatic field, to be subjected to the traction of electrostatic force and spray by nozzle, invest the receiving screen on opposite, thereby realization wire drawing, then, solvent evaporation at normal temperatures, perhaps melt is cooled to normal temperature and solidifies, and obtains micro nanometer fiber.Over nearly 10 years, occurred adopting electrospinning process to prepare the technical scheme of inorganic compound such as oxidate nano fiber at the inorfil preparing technical field, described oxide comprises TiO 2, ZrO 2, Y 2O 3, Y 2O 3: RE 3+(RE 3+=Eu 3+, Tb 3+, Er 3+, Yb 3+/ Er 3+), NiO, Co 3O 4, Mn 2O 3, Mn 3O 4, CuO, SiO 2, Al 2O 3, V 2O 5, ZnO, Nb 2O 5, MoO 3, CeO 2, LaMO 3(M=Fe, Cr, Mn, Co, Ni, Al), Y 3Al 5O 12, La 2Zr 2O 7Deng metal oxide and composite oxide of metal.The single spinning head of uses such as Dong Xiangting, employing electrostatic spinning technique have prepared PAN/Eu (BA) 3Phen recombination luminescence nanofiber [New Chemical Materials, 2008,36 (9), 49-52]; The single spinning head of uses such as Wang Ce, employing method of electrostatic spinning have prepared polyvinylpyrrolidone/tri-iron tetroxide composite nano fiber [SCI, 2006,27 (10), 2002-2004]; Qingbiao Yang, et al use single spinning head, adopt electrostatic spinning technique to prepare Fe 2O 3Nanoparticles/Eu (DBM) 3(Bath) Composite Double function magneto-optic nanofiber [Journal of Colloid and Interface Science, 2010,350,396-401]; Employing electrostatic spinning techniques such as Dong Xiangting have prepared Fe 3O 4/ 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 Fe 3O 4/ Eu (BA) 3Phen/PMMA composite Nano band [national inventing patent, application number: 201110303031.0].Electrostatic spinning technique is improved, adopt coaxial spinning head, spinning solution is injected into respectively in interior pipe and the outer tube, when adding High Level DC Voltage, spinning solution in the inner and outer pipes is pulled out by electric field force simultaneously, solidifies the back and forms coaxial nano cable, and this technology promptly is a coaxial electrostatic spinning technology.This technology of usefulness such as Wang Ce has prepared silica polymer co-axial nano fiber [SCI, 2005,26 (5): 985-987]; Dong Xiangting etc. utilize this technology to prepare TiO 2@SiO 2Sub-micron coaxial cable [chemical journal, 2007,65 (23): 2675-2679], ZnO@SiO 2Coaxial nano cable [Chinese Journal of Inorganic Chemistry, 2010,26 (1), 29-34] and Al 2O 3/ SiO 2Coaxial ultra micro cable [silicate journal, 2009,37 (10), 1712-1717]; Han, et al adopt this technology to prepare PC (Shell)/PU (Core) composite nano fiber [Polymer Composites, 2006,10:381-386]; This technology of employings such as Dong Xiangting has prepared (Fe 3O 4+ PVP) @[Eu (BA) 3Phen+PVP] magneto-optic double-function coaxial nano cable [national inventing patent, application number: 201110284141.7].At present, do not see and utilize coaxial electrostatic spinning technology preparation [Fe 3O 4+ PMMA] @[NaYF 4: Yb 3+, Er 3++ PMMA] relevant report of the difunctional co-axial nano band of magnetic up-conversion luminescence.
When utilizing electrostatic spinning technique to prepare nano material, the composition of the kind of raw material, the molecular weight of high polymer templates, spinning solution, spinning process parameter all have material impact to the pattern and the size of final products.The present invention adopts coaxial electrostatic spinning technology, with Fe 3O 4Nanocrystalline, polymetylmethacrylate, N, dinethylformamide DMF and chloroform CHCl 3Mixed liquor be the sandwich layer spinning solution, with NaYF 4: Yb 3+, Er 3+Nanocrystalline+PMMA+DMF+CHCl 3Mixed liquor be shell layer spinning solution, the viscosity of control shell and sandwich layer spinning solution is most important, under the process conditions of the best, obtains (the Fe of novel structure 3O 4+ PMMA) @ (NaYF 4: Yb 3+, Er 3++ PMMA) magneto-optic double-function co-axial nano band.
Summary of the invention
In background technology, use single spinning head, adopted electrostatic spinning technique to prepare metal oxide and composite oxide of metal nanofiber, polyvinylpyrrolidone/tri-iron tetroxide composite nano fiber, PAN/Eu (BA) 3Phen recombination luminescence nanofiber, Fe 2O 3Nanoparticles/Eu (DBM) 3(Bath) Composite Double function magneto-optic nanofiber, Fe 3O 4/ Eu (BA) 3Phen/PVP magneto-optic double-function composite nano fiber and magneto-optic double-function Fe 3O 4/ Eu (BA) 3Phen/PMMA composite Nano band.Use coaxial electrostatic spinning technology in the background technology has prepared inorganic matter @ inorganic matter, inorganic matter @ macromolecule and macromolecule @ high molecular nanometer cable and (Fe 3O 4+ PVP) @[Eu (BA) 3Phen+PVP] the magneto-optic double-function coaxial nano cable, employed raw material, template agent, solvent and final objective product are all different with method of the present invention.The present invention uses coaxial electrostatic spinning technology to prepare the [Fe of novel structure 3O 4+ PMMA] @[NaYF 4: Yb 3+, Er 3++ PMMA] the difunctional co-axial nano band of magnetic up-conversion luminescence, with Fe 3O 4Nanocrystalline+PMMA is a sandwich layer, with NaYF 4: Yb 3+, Er 3+Nanocrystalline+PMMA is that shell has constituted the co-axial nano band, and width is 10 μ m, and the sandwich layer width is 3 μ m, and thickness is 988nm, and length is greater than 100 μ m.
The present invention is achieved in that and at first adopts the precipitation method to prepare Fe 3O 4Nanocrystalline and NaYF 4: Yb 3+, Er 3+Nanocrystalline, adopt mass polymerization to prepare polymetylmethacrylate, prepare the shell with certain viscosity and the sandwich layer spinning solution that are used for coaxial electrostatic spinning technology again, the viscosity of control shell and sandwich layer spinning solution is most important.Use coaxial electrostatic spinning technology and carry out electrostatic spinning, under the process conditions of the best, obtain [the Fe of novel structure 3O 4+ PMMA] @[NaYF 4: Yb 3+, Er 3++ PMMA] magneto-optic double-function co-axial nano band, the steps include:
(1) precipitation method prepare Fe 3O 4Nanocrystalline
With 5.4060g FeCl 36H 2O, 2.7800g FeSO 47H 2O, 4.04g NH 4NO 3With the 1.9g molecular weight be that 20000 polyethylene glycol is dissolved in the 100mL deionized water, be heated to 50 ° of C and feed argon gas 30min, slow then dropping ammonia to the pH value of solution is 11, continue logical argon gas 20min and obtain black suspension, after this turbid liquid magnetic separation, wash successively three times with absolute ethyl alcohol and deionized water, product is placed the dry 12h of vacuum drying chamber of 60 ° of C, obtain the Fe that diameter is 8-10nm 3O 4Nanocrystalline;
(2) precipitation method prepare NaYF 4: Yb 3+, Er 3+Nanocrystalline
With 0.8807g Y 2O 3, 0.3940g Yb 2O 3With 0.0382g Er 2O 3Be dissolved in the 50mL concentrated hydrochloric acid and heating evaporation to crystallization; adding 50mL ethylene glycol dissolves crystallization; obtain solution I; in being connected to the 250mL three-necked bottle of reflux; with 5.0388gNaF and 5g molecular weight is that 30,000 polyvinylpyrrolidone is as protective agent; be dissolved in the mixed solvent of 30mL deionized water and 120mL ethylene glycol; obtain solution II; solution II is fed argon gas 30min and is warming up to 180 ° of C; under argon shield, join solution I in the solution II and back flow reaction 3h under 180 ° of C then; obtain white precipitate; with resulting sediment centrifugation; and wash successively 3 times with deionized water and ethanol, product is placed 60 ° of C vacuum drying chamber 12h, obtain the NaYF that diameter is 25-27nm 4: Yb 3+, Er 3+Nanocrystalline;
(3) preparation polymetylmethacrylate
Take by weighing 100g methyl methacrylate MMA and 0.1g dibenzoyl peroxide BPO, join in the 250mL three-necked bottle that has reflux and stir, with solution vigorous stirring and be back to solution certain viscosity is arranged under the temperature of 90-95 ° of C, after its viscosity and glycerine are close, when continuing stirring, stop heating and naturally cool to room temperature, afterwards solution is filled in the test tube, influx height is 5-7cm, 2h is left standstill in perfusion after finishing does not have bubble to invisible spectro solution, test tube is transferred in 50 ° of C drying boxes then and placed 48h, invisible spectro liquid hardening is transparent solid, at last the drying box temperature is increased to 110 ° of C and is incubated 2h, polymerisation is finished, naturally cool to room temperature then, obtain PMMA;
(4) preparation spinning solution
With 2g Fe 3O 4Nanocrystalline being dispersed in the 100ml water that feeds the 30min argon gas and ultrasonic dispersions 20min is heated to 80 ° of C with turbid liquid then under argon shield, and adds 1mL oleic acid, continues reaction 40min then, obtains the Fe of oleic acid coating 3O 4Nanocrystalline, resulting precipitation magnetic is separated, remove water layer and will be deposited in dry 12h in 60 ° of C vacuum drying chambers, and the Fe that resulting oleic acid is coated 3O 4In the nanocrystalline mixed solvent that is dispersed in 9g chloroform and 1g DMF, add 0.4g PMMA then, obtain the sandwich layer spinning solution, 0.2g NaYF 4: Yb 3+, Er 3+In the nanocrystalline mixed solvent that is dispersed in 4.5g chloroform and 0.5g DMF and ultrasonic dispersion 20min, add 0.2g PMMA then, obtain shell layer spinning solution;
(5) preparation [Fe 3O 4+ PMMA] @[NaYF 4: Yb 3+, Er 3++ PMMA] the difunctional co-axial nano band of magnetic up-conversion luminescence
Have section 5mL syringe of flat 12# stainless steel syringe needle as interior spin duct with one, a 10mL syringe that has 1mL plastics lance head is as outer spin duct, interior spin duct with the front end of stainless steel syringe needle be in outer spin duct with the center of plastics lance head, form coaxial spinning head, the sandwich layer spinning solution is joined in the interior spin duct, shell layer spinning solution joins carries out coaxial electrostatic spinning in the outer spin duct, adopt perpendicular spray mode, spinning voltage is 6kV, needle point and collection wire netting spacing 12cm, environment temperature is 20-26 ° of C, and relative humidity is 20%-30%, obtains [Fe 3O 4+ PMMA] @[NaYF 4: Yb 3+, Er 3++ PMMA] the difunctional co-axial nano band of magnetic up-conversion luminescence.
[the Fe of prepared novel structure in the said process 3O 4+ PMMA] @[NaYF 4: Yb 3+, Er 3++ PMMA] the difunctional co-axial nano band of magnetic up-conversion luminescence, with Fe 3O 4Nanocrystalline+PMMA is a sandwich layer, with NaYF 4: Yb 3+, Er 3+Nanocrystalline+PMMA is that shell has constituted the co-axial nano band, width is 10 μ m, the sandwich layer width is 3 μ m, thickness is 988nm, and length is greater than 100 μ m, and saturation magnetization is 28.37emu/g, with wavelength is that the diode laser of 980nm is as excitation source, obtain peak value and be respectively the last switching emission spectrum that the green glow of 542nm and 654nm and ruddiness bands of a spectrum are formed, this co-axial nano band have good magnetic and up-conversion luminescence difunctional, realized goal of the invention.
Description of drawings
Fig. 1 is Fe 3O 4Nanocrystalline TEM photo;
Fig. 2 is Fe 3O 4Nanocrystalline XRD spectra;
Fig. 3 is NaYF 4: Yb 3+, Er 3+Nanocrystalline TEM photo;
Fig. 4 is NaYF 4: Yb 3+, Er 3+Nanocrystalline XRD spectra;
Fig. 5 is [Fe 3O 4+ PMMA] @[NaYF 4: Yb 3+, Er 3++ PMMA] XRD spectra of the difunctional co-axial nano band of magnetic up-conversion luminescence;
Fig. 6 is [Fe 3O 4+ PMMA] @[NaYF 4: Yb 3+, Er 3++ PMMA] the SEM photo of the difunctional co-axial nano band of magnetic up-conversion luminescence;
Fig. 7 is [Fe 3O 4+ PMMA] @[NaYF 4: Yb 3+, Er 3++ PMMA] optical microscope photograph of the difunctional co-axial nano band of magnetic up-conversion luminescence, the double accompanying drawing that makes an abstract of this figure;
Fig. 8 is [Fe 3O 4+ PMMA] @[NaYF 4: Yb 3+, Er 3++ PMMA] the difunctional co-axial nano band of magnetic up-conversion luminescence when exciting power is 549mW on the switching emission spectrogram;
Fig. 9 is [Fe 3O 4+ PMMA] @[NaYF 4: Yb 3+, Er 3++ PMMA] the difunctional co-axial nano band of magnetic up-conversion luminescence when different exciting power on the switching emission spectrogram;
Figure 10 is [Fe 3O 4+ PMMA] @[NaYF 4: Yb 3+, Er 3++ PMMA] natural logrithm of luminous intensity of the difunctional co-axial nano band of magnetic up-conversion luminescence is with the variation diagram of the natural logrithm of exciting power;
Figure 11 is [Fe 3O 4+ PMMA] @[NaYF 4: Yb 3+, Er 3++ PMMA] the hysteresis curve figure of the difunctional co-axial nano band of magnetic up-conversion luminescence.
The specific embodiment
The yittrium oxide Y that the present invention is selected 2O 3, ytterbium oxide Yb 2O 3With erbium oxide Er 2O 3Purity is 99.99%, N, dinethylformamide DMF, chloroform CHCl 3, Iron(III) chloride hexahydrate, green vitriol, ammonium nitrate, molecular weight are 20000 polyethylene glycol, argon gas, hydrochloric acid, ethylene glycol, oleic acid, sodium fluoride, molecular weight is 30,000 polyvinylpyrrolidone PVP, methyl methacrylate MMA, dibenzoyl peroxide BPO, absolute ethyl alcohol, ammoniacal liquor NH 3H 2O is commercially available analysis net product; The self-control of deionized water laboratory; Used glass apparatus and equipment are instrument and equipments commonly used in the laboratory.
Embodiment is with 5.4060g FeCl 36H 2O, 2.7800g FeSO 47H 2O, 4.04g NH 4NO 3With the 1.9g molecular weight be that 20000 polyethylene glycol is dissolved in the 100mL deionized water, be heated to 50 ° of C and feed argon gas 30min, slow then dropping ammonia to the pH value of solution is 11, continue logical argon gas 20min and obtain black suspension, after this turbid liquid magnetic separation, wash successively three times with absolute ethyl alcohol and deionized water, product is placed the dry 12h of vacuum drying chamber of 60 ° of C, obtain tri-iron tetroxide Fe 3O 4Nanocrystalline, prepared Fe 3O 4Nanocrystalline diameter is 8-10nm, sees shown in Figure 1; Prepared Fe 3O 4Nanocrystalline have good crystallinity, the d value of its diffraction maximum and relative intensity and a Fe 3O 4The listed d value of PDF standard card (74-0748) consistent with relative intensity, belong to cubic system, see shown in Figure 2; With 0.8807g Y 2O 3, 0.3940g Yb 2O 3With 0.0382g Er 2O 3Be dissolved in the 50mL concentrated hydrochloric acid and heating evaporation to crystallization; adding 50mL ethylene glycol dissolves crystallization; obtain solution I; in being connected to the 250mL three-necked bottle of reflux; with 5.0388g NaF and 5g molecular weight is that 30,000 polyvinylpyrrolidone is as protective agent; be dissolved in the mixed solvent of 30mL deionized water and 120mL ethylene glycol; obtain solution II; solution II is fed argon gas 30min and is warming up to 180 ° of C; under argon shield, join solution I in the solution II and back flow reaction 3h under 180 ° of C then; obtain white precipitate; with resulting sediment centrifugation; and wash successively 3 times with deionized water and ethanol, product is placed 60 ° of C vacuum drying chamber 12h, obtain NaYF 4: Yb 3+, Er 3+Nanocrystalline, prepared NaYF 4: Yb 3+, Er 3+Nanocrystalline diameter is 25-27nm, as shown in Figure 3; Prepared NaYF 4: Yb 3+, Er 3+Nanocrystalline have good crystallinity, the d value of its diffraction maximum and relative intensity and a NaYF 4The listed d value of PDF standard card (06-0342) consistent with relative intensity, belong to cubic system, show the NaYF that is synthesized 4: Yb 3+, Er 3+Nanocrystalline is cubic system, sees shown in Figure 4; Take by weighing 100g methyl methacrylate MMA and 0.1g dibenzoyl peroxide BPO, join in the 250mL three-necked bottle that has reflux and stir, with solution vigorous stirring and be back to solution certain viscosity is arranged under the temperature of 90-95 ° of C, after its viscosity and glycerine are close, when continuing stirring, stop heating and naturally cool to room temperature, afterwards solution is filled in the test tube, influx height is 5-7cm, 2h is left standstill in perfusion after finishing does not have bubble to invisible spectro solution, test tube is transferred in 50 ° of C drying boxes then and placed 48h, invisible spectro liquid hardening is transparent solid, at last the drying box temperature is increased to 110 ° of C and is incubated 2h, polymerisation is finished, naturally cool to room temperature then, obtain PMMA; With 2g Fe 3O 4Nanocrystalline being dispersed in the 100ml water that feeds the 30min argon gas and ultrasonic dispersions 20min is heated to 80 ° of C with turbid liquid then under argon shield, and adds 1mL oleic acid, continues reaction 40min then, obtains the Fe of oleic acid coating 3O 4Nanocrystalline, resulting precipitation magnetic is separated, remove water layer and will be deposited in dry 12h in 60 ° of C vacuum drying chambers, and the Fe that resulting oleic acid is coated 3O 4In the nanocrystalline mixed solvent that is dispersed in 9g chloroform and 1g DMF, add 0.4g PMMA then, obtain the sandwich layer spinning solution, 0.2g NaYF 4-: Yb 3+, Er 3+In the nanocrystalline mixed solvent that is dispersed in 4.5g chloroform and 0.5g DMF and ultrasonic dispersion 20min, add 0.2g PMMA then, obtain shell layer spinning solution; Have section 5mL syringe of flat 12# stainless steel syringe needle as interior spin duct with one, a 10mL syringe that has 1mL plastics lance head is as outer spin duct, interior spin duct with the front end of stainless steel syringe needle be in outer spin duct with the center of plastics lance head, form coaxial spinning head, the sandwich layer spinning solution is joined in the interior spin duct, shell layer spinning solution joins carries out coaxial electrostatic spinning in the outer spin duct, adopt perpendicular spray mode, spinning voltage is 6kV, needle point and collection wire netting spacing 12cm, environment temperature is 20-26 ° of C, and relative humidity is 20%-30%, obtains [Fe 3O 4+ PMMA] @[NaYF 4: Yb 3+, Er 3++ PMMA] the difunctional co-axial nano band of magnetic up-conversion luminescence.Prepared [Fe 3O 4+ PMMA] @[NaYF 4: Yb 3+, Er 3++ PMMA] the difunctional co-axial nano band of magnetic up-conversion luminescence has tangible Fe 3O 4And NaYF 4: Yb 3+, Er 3+Nanocrystalline diffraction maximum shows that prepared co-axial nano band contains Fe 3O 4And NaYF 4-: Yb 3+, Er 3+Nanocrystalline, see shown in Figure 5; Prepared [Fe 3O 4+ PMMA] @[NaYF 4: Yb 3+, Er 3++ PMMA] the difunctional co-axial nano band of magnetic up-conversion luminescence has banded pattern, and thickness is 988nm, sees shown in Figure 6; Prepared [Fe 3O 4+ PMMA] @[NaYF 4: Yb 3+, Er 3++ PMMA] the difunctional co-axial nano band of magnetic up-conversion luminescence has co-axial nano band pattern, and width is 10 μ m, and the sandwich layer width is 3 μ m, and length is seen shown in Figure 7 greater than 100 μ m; With wavelength be 980nm, power be the diode laser of 549mW as excitation source, obtain [Fe 3O 4+ PMMA] @[NaYF 4: Yb 3+, Er 3++ PMMA] the last switching emission spectrum of the difunctional co-axial nano band of magnetic up-conversion luminescence, the bands of a spectrum that are respectively 542nm and 654nm by peak value are formed, wherein the corresponding Er of the green emission at 542nm place 3+Ion 4S 3/2→ 4I 15/2Transition emission, and the corresponding Er of the red emission at 654nm place 3+Ion 4F 9/2→ 4I 15/2The transition emission is seen shown in Figure 8; [Fe 3O 4+ PMMA] @[NaYF 4: Yb 3+, Er 3++ PMMA] the last switching emission spectrum of the difunctional co-axial nano band of magnetic up-conversion luminescence strengthens along with the increase of the exciting power of diode laser, sees shown in Figure 9; [Fe 3O 4+ PMMA] @[NaYF 4: Yb 3+, Er 3++ PMMA] green emission in the last switching emission spectrum of the difunctional co-axial nano band of magnetic up-conversion luminescence 4S 3/2→ 4I 15/2Transition and red emission 4F 9/2→ 4I 15/2The natural logrithm lnI of the up-conversion luminescence intensity of transition obtains two straight lines, wherein to the natural logrithm lnP mapping of the exciting power of diode laser 4S 3/2→ 4I 15/2Transition and 4F 9/2→ 4I 15/2The slope n of transition is respectively 1.096 and 1.251, shows green emission 4S 3/2→ 4I 15/2And red emission 4F 9/2→ 4I 15/2Be biphotonic process, see shown in Figure 10; Prepared [Fe 3O 4+ PMMA] @[NaYF 4: Yb 3+, Er 3++ PMMA] the difunctional co-axial nano band of magnetic up-conversion luminescence has stronger magnetic, and its hysteresis curve is seen shown in Figure 11, and saturation magnetization is 28.37emu/g.
Certainly; the present invention also can have other various embodiments; under the situation that does not deviate from spirit of the present invention and essence thereof; those of ordinary skill in the art work as can make various corresponding changes and distortion according to the present invention, but these corresponding changes and distortion all should belong to the protection domain of the appended claim of the present invention.

Claims (2)

1. the difunctional co-axial nano band of magnetic up-conversion luminescence is characterized in that the nanometer carrying material presents the co-axial nano band structure, have magnetic and up-conversion luminescence is difunctional, the width of co-axial nano band is 10 μ m, and the sandwich layer width is 3 μ m, thickness is 988nm, and length is greater than 100 μ m.
2. the preparation method of the difunctional co-axial nano band of magnetic up-conversion luminescence as claimed in claim 1 is characterized in that, uses coaxial electrostatic spinning technology, adopts coaxial spinning head, and polymetylmethacrylate is a high polymer templates, and the preparation product is [Fe 3O 4+ PMMA] @[NaYF 4: Yb 3+, Er 3++ PMMA] the difunctional co-axial nano band of magnetic up-conversion luminescence, the steps include:
(1) precipitation method prepare Fe 3O 4Nanocrystalline
With 5.4060g FeCl 36H 2O, 2.7800g FeSO 47H 2O, 4.04g NH 4NO 3With the 1.9g molecular weight be that 20000 polyethylene glycol is dissolved in the 100mL deionized water, be heated to 50 ° of C and feed argon gas 30min, slow then dropping ammonia to the pH value of solution is 11, continue logical argon gas 20min and obtain black suspension, after this turbid liquid magnetic separation, wash successively three times with absolute ethyl alcohol and deionized water, product is placed the dry 12h of vacuum drying chamber of 60 ° of C, obtain the Fe that diameter is 8-10nm 3O 4Nanocrystalline;
(2) precipitation method prepare NaYF 4: Yb 3+, Er 3+Nanocrystalline
With 0.8807g Y 2O 3, 0.3940g Yb 2O 3With 0.0382g Er 2O 3Be dissolved in the 50mL concentrated hydrochloric acid and heating evaporation to crystallization; adding 50mL ethylene glycol dissolves crystallization; obtain solution I; in being connected to the 250mL three-necked bottle of reflux; with 5.0388gNaF and 5g molecular weight is that 30,000 polyvinylpyrrolidone is as protective agent; be dissolved in the mixed solvent of 30mL deionized water and 120mL ethylene glycol; obtain solution II; solution II is fed argon gas 30min and is warming up to 180 ° of C; under argon shield, join solution I in the solution II and back flow reaction 3h under 180 ° of C then; obtain white precipitate; with resulting sediment centrifugation; and wash successively 3 times with deionized water and ethanol, product is placed 60 ° of C vacuum drying chamber 12h, obtain the NaYF that diameter is 25-27nm 4: Yb 3+, Er 3+Nanocrystalline;
(3) preparation polymetylmethacrylate
Take by weighing 100g methyl methacrylate MMA and 0.1g dibenzoyl peroxide BPO, join in the 250mL three-necked bottle that has reflux and stir, with solution vigorous stirring and be back to solution certain viscosity is arranged under the temperature of 90-95 ° of C, after its viscosity and glycerine are close, when continuing stirring, stop heating and naturally cool to room temperature, afterwards solution is filled in the test tube, influx height is 5-7cm, 2h is left standstill in perfusion after finishing does not have bubble to invisible spectro solution, test tube is transferred in 50 ° of C drying boxes then and placed 48h, invisible spectro liquid hardening is transparent solid, at last the drying box temperature is increased to 110 ° of C and is incubated 2h, polymerisation is finished, naturally cool to room temperature then, obtain PMMA;
(4) preparation spinning solution
With 2g Fe 3O 4Nanocrystalline being dispersed in the 100ml water that feeds the 30min argon gas and ultrasonic dispersions 20min is heated to 80 ° of C with turbid liquid then under argon shield, and adds 1mL oleic acid, continues reaction 40min then, obtains the Fe of oleic acid coating 3O 4Nanocrystalline, resulting precipitation magnetic is separated, remove water layer and will be deposited in dry 12h in 60 ° of C vacuum drying chambers, and the Fe that resulting oleic acid is coated 3O 4In the nanocrystalline mixed solvent that is dispersed in 9g chloroform and 1g DMF, add 0.4g PMMA then, obtain the sandwich layer spinning solution, 0.2g NaYF 4: Yb 3+, Er 3+In the nanocrystalline mixed solvent that is dispersed in 4.5g chloroform and 0.5g DMF and ultrasonic dispersion 20min, add 0.2g PMMA then, obtain shell layer spinning solution;
(5) preparation [Fe 3O 4+ PMMA] @[NaYF 4: Yb 3+, Er 3++ PMMA] the difunctional co-axial nano band of magnetic up-conversion luminescence
Have section 5mL syringe of flat 12# stainless steel syringe needle as interior spin duct with one, a 10mL syringe that has 1mL plastics lance head is as outer spin duct, interior spin duct with the front end of stainless steel syringe needle be in outer spin duct with the center of plastics lance head, form coaxial spinning head, the sandwich layer spinning solution is joined in the interior spin duct, shell layer spinning solution joins carries out coaxial electrostatic spinning in the outer spin duct, adopt perpendicular spray mode, spinning voltage is 6kV, needle point and collection wire netting spacing 12cm, environment temperature is 20-26 ° of C, and relative humidity is 20%-30%, obtains [Fe 3O 4+ PMMA] @[NaYF 4: Yb 3+, Er 3++ PMMA] the difunctional co-axial nano band of magnetic up-conversion luminescence, width is 10 μ m, the sandwich layer width is 3 μ m, thickness is 988nm, length is greater than 100 μ m, and saturation magnetization is 28.37emu/g, is that the diode laser of 980nm is as excitation source with wavelength, obtain peak value and be respectively the green glow of 542nm and 654nm and the last switching emission spectrum that the ruddiness bands of a spectrum are formed, this co-axial nano band has magnetic and up-conversion luminescence is difunctional.
CN2013100685127A 2013-03-05 2013-03-05 Magnetic upconversion and luminous bifunctional coaxial nanoribbon and preparation method thereof Pending CN103225122A (en)

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