CN102660806B - Method for preparing europium-doped LiYF4 nanofiber - Google Patents
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- CN102660806B CN102660806B CN201210044388.6A CN201210044388A CN102660806B CN 102660806 B CN102660806 B CN 102660806B CN 201210044388 A CN201210044388 A CN 201210044388A CN 102660806 B CN102660806 B CN 102660806B
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Abstract
The invention relates to a method for preparing europium-doped LiYF4 nanofiber, belonging to the field of nano material preparing technology. The method comprises the four steps of: (1) preparing a spinning solution; (2) preparing a PVP/metal nitrate composite fiber by adopting an electrostatic spinning technology; (3) preparing mixed oxide nanofiber; (4) and preparing LiYF4:3%Eu<3+> nanofiber, wherein the red luminous LiYF4:3%Eu<3+> nanofiber is prepared by adopting a double-crucible method to carry out a fluoridization treatment on the mixed oxide nanofiber by ammonium bifluoride. The prepared LiYF4:3%Eu<3+> nanofiber has a good crystallinity, with a diameter of 152.9 nm plus or minus 19.9 nm and a length being larger than 50 mum. The LiYF4:3%Eu<3+> nanofiber is a novel red luminous material, which has an important application value. The preparation method provided by the invention is simple and easy to implement, which is suitable for mass production and has a broad application prospect.
Description
Technical field
The present invention relates to nano material preparation research field, relate to specifically a kind of preparation method who mixes europium tetrafluoro yttrium lithium nanofiber.
Background technology
Nanofiber refers to the filamentary material of bidimensional in nanoscale on the three dimensions yardstick of material, and radial dimension is nanometer scale conventionally, and length is larger.Because the radial dimension of nanofiber is little of nanometer scale, demonstrate series of characteristics, the most outstanding is that specific area is large, thereby its surface can increase with active, and then produce small-size effect, surface or interfacial effect, quantum size effect, macro quanta tunnel effect etc., and therefore show the specificity of a series of chemistry, physics (heat, light, sound, electricity, magnetic etc.) aspect.In the prior art, there is the method for much preparing nanofiber, the method for for example reeling off raw silk from cocoons, template synthetic method, split-phase method and self-assembly method etc.In addition, also has arc evaporation, laser high temperature inustion, compound pyrolysismethod.These three kinds of methods are in fact all at high temperature to make after compound (or simple substance) evaporation, make nanofiber or nanotube through pyrolysis (or directly condensation), from essence, all belong to compound steam sedimentation.
Rare earth tetrafluoride, owing to having abundant 4f energy level and lower phonon energy, is one of current efficient rare-earth ion doping luminous host.Mix europium tetrafluoro yttrium lithium LiYF
4: Eu
3+be a kind of important red illuminating material, there is important application prospect.Adopt the methods such as the precipitation method, sol-gel process, microemulsion method, presoma pyrolysismethod, hydro-thermal and solvent-thermal method, polyalcohol method, higher boiling ligand solvent method, prepared LiYF
4: Eu
3+the nano materials such as nanocrystalline, nanometer rods, sheet, cube is nanocrystalline, hexahedron is nanocrystalline, octahedra nanocrystalline, hollow tubular structures, nano wire, spindle.Mix europium tetrafluoro yttrium lithium LiYF
4: Eu
3+nanofiber is a kind of novel red illuminating material, will obtain important application in fields such as luminous and demonstration, false proof, medical science detection, biomarker, solar cell, chemistry and biology sensor, nano-devices, has broad application prospects.At present, have no and mix europium tetrafluoro yttrium lithium LiYF
4: Eu
3+the report of nanofiber.
The patent No. is that 1975504 United States Patent (USP) discloses a technical scheme about electrospinning process (electrospinning), the method is to prepare a kind of effective ways of continuous, to have macro length micro nanometer fiber, is 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, are subject to the traction of electrostatic force and are sprayed by nozzle, invest the receiving screen on opposite, thereby realize wire drawing, then, solvent evaporation at normal temperatures, or melt cooling solidifies to normal temperature, obtains micro nanometer fiber.Over nearly 10 years, occurred adopting electrospinning process to prepare inorganic compound as the technical scheme of oxidate nano fiber at 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 employing electrostatic spinning techniques such as Wang Jinxian have been prepared rare earth fluoride/rare earth oxyfluoride composite nano fibre (Chinese invention patent, grant number: ZL200810050959.0); The employing electrostatic spinning techniques such as Dong Xiangting have been prepared and have been mixed europium Y
7o
6f
9nanofiber (Chinese invention patent, grant number: ZL201010550196.3); The employing electrostatic spinning techniques such as Wang Jinxian have been prepared trifluorides nanofiber (Chinese invention patent, grant number: ZL201010107993.4); Wang Ce etc. adopt electrostatic spinning technique to pass through R (CF
3cO
2)
3/ PVP (R=Eu, Ho) composite nano fiber is heat-treated, and has synthesized ROF (R=Eu, Ho) nanofiber (J.Nanosci.Nanotechnol., 2009,9 (2): 1522-1525).Electrospinning process can continuous production big L/D ratio micrometer fibers or nanofiber.Have no at present adopt electrostatic spinning technique combine with fluorination technology prepare LiYF
4: Eu
3+the report of emitting red light nanofiber.
While 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 and Technology for Heating Processing pattern and the size to final products has material impact.The present invention first adopts electrostatic spinning technique, with a hydronium(ion) oxidation lithium LiOHH
2o, yittrium oxide Y
2o
3with europium oxide Eu
2o
3for raw material, with evaporating after nitric acid dissolve, obtain lithium nitrate LiNO
3, yttrium nitrate Y (NO
3)
3with europium nitrate Eu (NO
3)
3mixed crystal, adds solvent DMF DMF and high polymer templates polyvinylpyrrolidone PVP, obtains carrying out electrostatic spinning after spinning solution, under best experiment condition, prepares PVP/[LiNO
3+ Y (NO
3)
3+ Eu (NO
3)
3] pristine fibre, it is heat-treated in air, obtain mixed oxide nanoparticle fiber, adopt double crucible method, with ammonium acid fluoride NH
4hF
2fluoridize for fluorization agent, prepared the LiYF of novel structure pure phase
4: Eu
3+emitting red light nanofiber.
Summary of the invention
In the various methods of preparing nanofiber in background technology, the shortcoming of the method for reeling off raw silk from cocoons is that solution viscosity is required to too harshness; The shortcoming of template synthetic method is to prepare the continuous fibers that root root separates; Split-phase method and self-assembly method production efficiency are all lower; And compound steam sedimentation is due to the demand to high temperature, so process conditions are difficult to control, and nanofiber major diameter prepared by above-mentioned several method is than little.Use electrostatic spinning technique in background technology has been prepared metal oxide, composite oxide of metal nanofiber, rare earth fluoride/rare earth oxyfluoride composite nano fibre, has been mixed europium Y
7o
6f
9nanofiber, trifluorides nanofiber and ROF (R=Eu, Ho) nanofiber.Prior art adopts the methods such as the precipitation method, sol-gel process, microemulsion method, presoma pyrolysismethod, hydro-thermal and solvent-thermal method, polyalcohol method, higher boiling ligand solvent method, has prepared LiYF
4: Eu
3+the nano materials such as nanocrystalline, nanometer rods, sheet, cube is nanocrystalline, hexahedron is nanocrystalline, octahedra nanocrystalline, hollow tubular structures, nano wire, spindle.For a kind of novel red luminous nano fibre material is provided in nanofiber field, we combine electrostatic spinning technique with fluorination technology, invented LiYF
4: Eu
3+the preparation method of emitting red light nanofiber.
The present invention is achieved in that the spinning solution with certain viscosity of first preparing for electrostatic spinning, and application electrostatic spinning technique carries out electrostatic spinning, under best experiment condition, prepares PVP/[LiNO
3+ Y (NO
3)
3+ Eu (NO
3)
3] composite fibre, it is heat-treated in air, obtained mixed oxide nanoparticle fiber, adopt double crucible method, with ammonium acid fluoride NH
4hF
2fluoridize for fluorization agent, prepared the LiYF of novel structure pure phase
4: Eu
3+emitting red light nanofiber.In the present invention, the mole percent of the europium ion of doping is 3%, is labeled as LiYF
4: 3%Eu
3+, i.e. that the present invention is prepared is LiYF
4: 3%Eu
3+emitting red light nanofiber.The steps include:
(1) preparation spinning solution
That lithium source, He You source, yttrium source are used is a hydronium(ion) oxidation lithium LiOHH
2o, yittrium oxide Y
2o
3with europium oxide Eu
2o
3, high polymer templates adopts polyvinylpyrrolidone PVP, and molecular weight is 1300000, and adopting DMF DMF is solvent, takes an a certain amount of hydronium(ion) oxidation lithium LiOHH
2o, yittrium oxide Y
2o
3with europium oxide Eu
2o
3, wherein Li
+, Y
3+and Eu
3+mol ratio be 100: 97: 3, the mole percent of europium ion is 3%, uses nitric acid HNO
3after dissolving, evaporation, obtains LiNO
3, Y (NO
3)
3and Eu (NO
3)
3mixed crystal, add appropriate N, dinethylformamide DMF solvent and polyvinylpyrrolidone PVP, stir 6h in room temperature lower magnetic force, and standing 4h, forming spinning solution, the mass percent of the each part of this spinning solution is: nitrate content 5%, PVP content 13%, solvent DMF content 82%;
(2) prepare PVP/[LiNO
3+ Y (NO
3)
3+ Eu (NO
3)
3] composite fibre
The spinning solution preparing is added in the liquid storage pipe of device for spinning, carry out electrostatic spinning, shower nozzle internal diameter 0.7mm, the angle of adjusting shower nozzle and horizontal plane is 15 °, applies the DC voltage of 12kV, solidifies apart from 18cm, 20～25 ℃ of room temperatures, relative humidity is 55%～75%, obtains PVP/[LiNO
3+ Y (NO
3)
3+ Eu (NO
3)
3] composite fibre;
(3) prepare mixed oxide nanoparticle fiber
By described PVP/[LiNO
3+ Y (NO
3)
3+ Eu (NO
3)
3] composite fibre is put in temperature programmed control stove and heat-treats, heating rate is 1 ℃/min, at 600 ℃ of constant temperature 4h, then is cooled to 200 ℃ with the speed of 1 ℃/min, naturally cools to room temperature afterwards with body of heater, obtains mixed oxide nanoparticle fiber;
(4) prepare LiYF
4: 3%Eu
3+nanofiber
Fluorination reagent uses ammonium acid fluoride NH
4hF
2adopt double crucible method, ammonium acid fluoride is put into monkey, cover carbon-point above, described mixed oxide nanoparticle fiber is placed on above carbon-point, monkey is put into larger crucible, between interior outer crucible, add excessive ammonium acid fluoride, on outer crucible, add that crucible lid puts into tube furnace, be warming up to 280 ℃ of insulation 2h with the heating rate of 2 ℃/min, then be warmed up to 500 ℃ of insulation 3h, be finally cooled to 200 ℃ with the rate of temperature fall of 1 ℃/min, naturally cool to room temperature with body of heater afterwards, obtain LiYF
4: 3%Eu
3+emitting red light nanofiber, diameter is 152.9 ± 19.9nm, length is greater than 50 μ m.
At the LiYF described in said process
4: 3%Eu
3+emitting red light nanofiber has good crystallinity, and diameter is 152.9 ± 19.9nm, and length is greater than 50 μ m, has realized goal of the invention.
Accompanying drawing explanation
Fig. 1 is LiYF
4: 3%Eu
3+the XRD spectra of nanofiber;
Fig. 2 is LiYF
4: 3%Eu
3+the SEM photo of nanofiber, this figure doubles as Figure of abstract;
Fig. 3 is LiYF
4: 3%Eu
3+the diameter distribution histogram of nanofiber;
Fig. 4 is LiYF
4: 3%Eu
3+the EDS spectrogram of nanofiber;
Fig. 5 is LiYF
4: 3%Eu
3+the exciting light spectrogram of nanofiber;
Fig. 6 is LiYF
4: 3%Eu
3+the utilizing emitted light spectrogram of nanofiber.
The specific embodiment
The yittrium oxide Y that the present invention is selected
2o
3with europium oxide Eu
2o
3purity be 99.99%, polyvinylpyrrolidone PVP, molecular weight 1300000, DMF DMF, carbon-point, a hydronium(ion) oxidation lithium LiOHH
2o, ammonium acid fluoride NH
4hF
2with nitric acid HNO
3be commercially available analysis net product; Glass apparatus, crucible and equipment used is instrument and equipment conventional in laboratory.
Embodiment: take an a certain amount of hydronium(ion) oxidation lithium LiOHH
2o, yittrium oxide Y
2o
3with europium oxide Eu
2o
3, wherein Li
+, Y
3+and Eu
3+mol ratio be 100: 97: 3, the mole percent of europium ion is 3%, uses nitric acid HNO
3after dissolving, evaporation, obtains LiNO
3, Y (NO
3)
3and Eu (NO
3)
3mixed crystal, add appropriate N, dinethylformamide DMF solvent and polyvinylpyrrolidone PVP, stir 6h in room temperature lower magnetic force, and standing 4h, forming spinning solution, the mass percent of the each part of this spinning solution is: nitrate content 5%, PVP content 13%, solvent DMF content 82%; The spinning solution preparing is added in the liquid storage pipe of device for spinning, carry out electrostatic spinning, shower nozzle internal diameter 0.7mm, the angle of adjusting shower nozzle and horizontal plane is 15 °, applies the DC voltage of 12kV, solidifies apart from 18cm, 20～25 ℃ of room temperatures, relative humidity is 55%～75%, obtains PVP/[LiNO
3+ Y (NO
3)
3+ Eu (NO
3)
3] composite fibre; By described PVP/[LiNO
3+ Y (NO
3)
3+ Eu (NO
3)
3] composite fibre is put in temperature programmed control stove and heat-treats, heating rate is 1 ℃/min, at 600 ℃ of constant temperature 4h, then is cooled to 200 ℃ with the speed of 1 ℃/min, naturally cools to room temperature afterwards with body of heater, obtains mixed oxide nanoparticle fiber; Fluorination reagent uses ammonium acid fluoride NH
4hF
2adopt double crucible method, ammonium acid fluoride is put into monkey, cover carbon-point above, described mixed oxide nanoparticle fiber is placed on above carbon-point, monkey is put into larger crucible, between interior outer crucible, add excessive ammonium acid fluoride, on outer crucible, add that crucible lid puts into tube furnace, be warming up to 280 ℃ of insulation 2h with the heating rate of 2 ℃/min, then be warmed up to 500 ℃ of insulation 3h, be finally cooled to 200 ℃ with the rate of temperature fall of 1 ℃/min, naturally cool to room temperature with body of heater afterwards, obtain LiYF
4: 3%Eu
3+nanofiber.Described LiYF
4: 3%Eu
3+nanofiber, has good crystallinity, the d value of its diffraction maximum and relative intensity and LiYF
4the listed d value of PDF standard card (77-0816) consistent with relative intensity, belong to tetragonal crystal system, space group is I41/a, as shown in Figure 1.Described LiYF
4: 3%Eu
3+the diameter of nanofiber is even, is fibrous, and length is greater than 50 μ m, as shown in Figure 2.By Shapiro-Wilk method to LiYF
4: 3%Eu
3+the diameter of nanofiber carries out normal distribution-test, under 95% confidence level, and LiYF
4: 3%Eu
3+the diameter of nanofiber distributes and belongs to normal distribution, and diameter is 152.9 ± 19.9nm, as shown in Figure 3.LiYF
4: 3%Eu
3+nanofiber forms (the Au conductive layer of plated surface when Au derives from SEM sample preparation, Li element can not detect by EDS spectrum) by Y, F and Eu element, as shown in Figure 4.In the time that monitoring wavelength is 591nm, LiYF
4: 3%Eu
3+the strongest excitation peak of nanofiber is positioned at 394nm place, corresponding to Eu
3+'s
7f
0→
5l
6transition, as shown in Figure 5.Under the ultraviolet excitation of 394nm, LiYF
4: 3%Eu
3+nanofiber is launched main peak and is positioned at the bright red of 591nm and 614nm, corresponding to Eu
3+ion
5d
0→
7f
1with
5d
0→
7f
2transition, as shown in Figure 6.
Certainly; the present invention also can have other various embodiments; in the situation that not deviating from spirit of the present invention and essence thereof; those of ordinary skill in the art are when making according to the present invention various corresponding changes and distortion, but these corresponding changes and distortion all should belong to the protection domain of the appended claim of the present invention.
Claims (1)
1. mix the preparation method of europium tetrafluoro yttrium lithium nanofiber for one kind, it is characterized in that, the method that adopts electrostatic spinning technique to combine with fluorination technology, using the polyvinylpyrrolidone PVP of molecular weight Mr=1300000 is high polymer templates, adopt N, dinethylformamide DMF is solvent, and fluorination reagent uses ammonium acid fluoride NH
4hF
2, preparing product is europium ion-doped tetrafluoro yttrium lithium LiYF
4: Eu
3+nanofiber, the steps include:
(1) preparation spinning solution
That lithium source, He You source, yttrium source are used is a hydronium(ion) oxidation lithium LiOHH
2o, yittrium oxide Y
2o
3with europium oxide Eu
2o
3, high polymer templates adopts polyvinylpyrrolidone PVP, and adopting DMF DMF is solvent, takes an a certain amount of hydronium(ion) oxidation lithium LiOHH
2o, yittrium oxide Y
2o
3with europium oxide Eu
2o
3, wherein Li
+, Y
3+and Eu
3+mol ratio be 100: 97: 3, the mole percent of europium ion is 3%, uses nitric acid HNO
3after dissolving, evaporation, obtains LiNO
3, Y (NO
3)
3and Eu (NO
3)
3mixed crystal, add appropriate N, dinethylformamide DMF solvent and polyvinylpyrrolidone PVP, stir 6h in room temperature lower magnetic force, and standing 4h, forming spinning solution, the mass percent of the each part of this spinning solution is: nitrate content 5%, PVP content 13%, solvent DMF content 82%;
(2) prepare PVP/[LiNO
3+ Y (NO
3)
3+ Eu (NO
3)
3] composite fibre
The spinning solution preparing is added in the liquid storage pipe of device for spinning, carry out electrostatic spinning, shower nozzle internal diameter 0.7mm, the angle of adjusting shower nozzle and horizontal plane is 15 °, applies the DC voltage of 12kV, solidifies apart from 18cm, 20～25 ℃ of room temperatures, relative humidity is 55%～75%, obtains PVP/[LiNO
3+ Y (NO
3)
3+ Eu (NO
3)
3] composite fibre;
(3) prepare mixed oxide nanoparticle fiber
By described PVP/[LiNO
3+ Y (NO
3)
3+ Eu (NO
3)
3] composite fibre is put in temperature programmed control stove and heat-treats, heating rate is 1 ℃/min, at 600 ℃ of constant temperature 4h, then is cooled to 200 ℃ with the speed of 1 ℃/min, naturally cools to room temperature afterwards with body of heater, obtains mixed oxide nanoparticle fiber;
(4) prepare LiYF
4: 3%Eu
3+nanofiber
Fluorination reagent uses ammonium acid fluoride NH
4hF
2adopt double crucible method, ammonium acid fluoride is put into monkey, cover carbon-point above, described mixed oxide nanoparticle fiber is placed on above carbon-point, monkey is put into larger crucible, between interior outer crucible, add excessive ammonium acid fluoride, on outer crucible, add that crucible lid puts into tube furnace, be warming up to 280 ℃ of insulation 2h with the heating rate of 2 ℃/min, then be warmed up to 500 ℃ of insulation 3h, be finally cooled to 200 ℃ with the rate of temperature fall of 1 ℃/min, naturally cool to room temperature with body of heater afterwards, obtain LiYF
4: 3%Eu
3+emitting red light nanofiber, the mole percent of the europium ion of doping is 3%, and diameter is 152.9 ± 19.9nm, and length is greater than 50 μ m.
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|---|---|---|---|
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|---|---|---|---|---|
| CN102031591A (en) * | 2010-11-19 | 2011-04-27 | 长春理工大学 | Europium-doped Y7O6F9 nano fiber and preparation method thereof |
| CN102031586A (en) * | 2010-11-19 | 2011-04-27 | 长春理工大学 | Method for preparing europium-doped yttrium fluoride nano fiber/polymer composite nano fiber |
| CN102041583A (en) * | 2010-11-19 | 2011-05-04 | 长春理工大学 | Method for preparing europium and fluorine-doped yttrium oxide nanofibres |
| CN102061172A (en) * | 2010-11-19 | 2011-05-18 | 长春理工大学 | Europium (Eu) ion doped Y7O6F9 nanobelt and preparation method thereof |
| CN102306775A (en) * | 2011-08-29 | 2012-01-04 | 长春理工大学 | Lithium iron phosphate nanobelt serving as cathode material of lithium ion battery and preparation method of lithium iron phosphate nanobelt |
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| JP2008057072A (en) * | 2006-08-31 | 2008-03-13 | Teijin Ltd | Rare earth metal element-containing crystalline metal oxide fiber and method for producing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102031591A (en) * | 2010-11-19 | 2011-04-27 | 长春理工大学 | Europium-doped Y7O6F9 nano fiber and preparation method thereof |
| CN102031586A (en) * | 2010-11-19 | 2011-04-27 | 长春理工大学 | Method for preparing europium-doped yttrium fluoride nano fiber/polymer composite nano fiber |
| CN102041583A (en) * | 2010-11-19 | 2011-05-04 | 长春理工大学 | Method for preparing europium and fluorine-doped yttrium oxide nanofibres |
| CN102061172A (en) * | 2010-11-19 | 2011-05-18 | 长春理工大学 | Europium (Eu) ion doped Y7O6F9 nanobelt and preparation method thereof |
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