CN105778902A - Preparation method of rare earth hollow nanocrystal - Google Patents
Preparation method of rare earth hollow nanocrystal Download PDFInfo
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- CN105778902A CN105778902A CN201610018783.5A CN201610018783A CN105778902A CN 105778902 A CN105778902 A CN 105778902A CN 201610018783 A CN201610018783 A CN 201610018783A CN 105778902 A CN105778902 A CN 105778902A
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- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
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Abstract
The invention discloses a preparation method of a rare earth hollow nanocrystal, wherein the preparation method comprises the following steps: preparing a rare earth soluble salt aqueous solution of rare earth ions La and Eu; preparing a lithium ion soluble salt aqueous solution; preparing a transparent solution from polyvinylpyrrolidone; dropwise adding the rare earth soluble salt aqueous solution and the lithium ion soluble salt aqueous solution into the obtained solution, to obtain a transparent solution; preparing an NH4F aqueous solution, slowly dropwise adding the NH4F aqueous solution to the obtained solution, to obtain a white colloidal solution; and pouring the obtained colloidal solution into a hydrothermal kettle, centrifuging, putting the obtained white product into a baking oven, and thus obtaining a rare earth hollow nanocrystalline powder. The LaF3:Eu<3+> hollow nanocrystal is formed by using self weight crystallization and localized Ostwald ripening; by doping Li<+> ions, the red luminescence intensity of the nanocrystal is greatly enhanced. The prepared rare earth hollow nanocrystal has the advantages of uniform size, good dispersion, high water solubility and fluorescence intensity and the like, and has highly important research and application significance in the aspects of biological fluorescence imaging, kinetics diagnosis and treatment, photocatalysis and the like.
Description
Technical field
The invention belongs to technical field of inorganic nano-material preparation, the preparation nanocrystalline particularly to a kind of rare earth hollow and the method for Fluorescence Increasing
Background technology
Rare earth mixing with nano is brilliant in recent years preparation and application receive much concern always, especially because this nanocrystalline relatively conventional fluorescent dye and quantum dot have good chemical stability and low toxicity, can as the fluorescent probe of a new generation in various biomedical sectors.Wherein, rare earth porous nano granule is a kind of special nano material, they have higher specific surface area and permeability, can by various hydrophilic molecules, such as some biomacromolecules, organic dyestuff, medicine or photosensitizer etc., be loaded into nanocrystalline in, say, that rare earth hollow is nanocrystalline as the desirable pharmaceutical carrier of one, therefore can have important application prospect in the fields such as biologic medical.
At present, orderly hollow material is usually needs to utilize soft or hard template to go synthesis.But, use template typically cost higher, and building-up process is cumbersome, thus hinders them in the application of biological technical field and development.Therefore, the technology without templated synthesis that research and development hollow is nanocrystalline has very important significance.Additionally, the luminous intensity of rare-earth nano-crystal generally depends on the internal 4f transition between energy level probability of rare earth ion, it is generally relatively low that the feature of rare earth ion electron structure determines its luminous efficiency, particularly rare earth hollow is nanocrystalline, due to its hollow structure, add radiationless transition process, it is likely that make its luminous efficiency reduce further.If nanocrystalline luminous efficiency reduces, in order to increase fluorescence intensity, the doping content of rare earth luminous ion will increase, and so can increase the nanocrystalline toxicity to organism.Therefore, under the premise not increasing rear-earth-doped concentration, how to improve the nanocrystalline fluorescence intensity of rare earth hollow to reduce the toxic effect to organism and also there is important researching value and meaning.
The luminous efficiency of rare-earth nano-crystal is generally relatively low, by the Li that adulterates+Ion improve the rare earth nanocrystalline fluorescence intensity of hollow lanthanum fluoride report but without.The development of material and chemistry subject is had important promotion meaning by the technology without templated synthesis developing hollow nanocrystalline, it addition, strengthen the nanocrystalline fluorescence intensity of this rare earth hollow also the development of material and physics subject can be had positive facilitation.
Summary of the invention
Instant invention overcomes shortcoming of the prior art, provide the preparation method that a kind of rare earth hollow is nanocrystalline, its have without template, simplicity, with low cost and green general-purpose advantage, the nanocrystalline pattern ratio of preparation is more uniform, favorable dispersibility, almost each nano-particle has hollow structure, and has water solublity, additionally fluorescence intensity also effectively improves, and can be applied in biomedical sector as pharmaceutical carrier.
In order to solve above-mentioned technical problem, the present invention is achieved by the following technical solutions:
The preparation method that a kind of rare earth hollow is nanocrystalline, comprises the following steps:
A, configuration rare earth ion La and Eu rare earth soluble salt aqueous solution, rare earth ion concentration is 0.05-0.25mol/L；Configuration lithium ion soluble salt aqueous solution, concentration is 0.05-0.1mol/L；
B, it is the polyvinylpyrrolidone of 10000-30000 by 0.3-0.6g molecular weight, joins in the mixed solution of 10mL water and 15mL ethanol, stir 10-20 minute, obtain clear solution；
C, the described rare earth soluble salt aqueous solution configured by step a and described lithium ion soluble salt aqueous solution are added drop-wise in step b gained solution, stir 20-30 minute, obtain clear solution；
D, configuration NH4F aqueous solution, concentration is 1mol/L, is slowly added drop-wise to by the solution configured in step c gained solution, obtains white gum solution, stirs 20-30 minute；
E, step d gained colloidal solution is poured in water heating kettle, 190 degree are reacted 3-6 hour, are cooled to room temperature, deionized water wash 3-5 time, when 3000-9000rpm/min centrifugal 3-10 minute, gained white product was put in baking oven 60-80 DEG C and dry within 12 hours, is namely obtained rare earth hollow manocrystalline powders.
Further, described rare earth soluble salt is rare earth nitrate, and described lithium ion soluble salt is lithium nitrate
Compared with prior art, the invention has the beneficial effects as follows:
The preparation method that a kind of rare earth hollow of the present invention is nanocrystalline, adopts simple without one pot of hydro-thermal reaction of template, utilizes and form LaF from the Ostwald ripening of recrystallization drawn game territory3: Eu3+Hollow is nanocrystalline, by the certain density Li that adulterates+Ion, nanocrystalline red light-emitting intensity is greatly enhanced.The method cost is low, easy, nontoxic, it is adaptable to the preparation of other rare earth hollow nano luminescent materials and Fluorescence Increasing.Adopt rare earth hollow that this method prepares nanocrystalline to have that size is homogeneous, good dispersion, have water solublity and fluorescence intensity high, hole all nanocrystalline inner high-visible, the about 5-10nm of magnitude range.The rare-earth nano-crystal of this hollow structure is a kind of desirably pharmaceutical carrier, can be built into novel functional material with other chemical substance compounds, all have very important research and application value in bioluminescence imaging, kinetics diagnosis and treatment and photocatalysis etc..
Accompanying drawing explanation
Accompanying drawing is used for providing a further understanding of the present invention, is used for together with embodiments of the present invention explaining the present invention, is not intended that limitation of the present invention, in the accompanying drawings:
Fig. 1 is the X-ray diffractogram of the rare earth hollow lanthanum trifluoride luminescence nanocrystalline of embodiment 1 preparation；
Fig. 2 is the transmission electron microscope photo of the rare earth hollow lanthanum trifluoride luminescence nanocrystalline of embodiment 1 preparation；
Fig. 3 be embodiment 2 preparation mix Li+The transmission electron microscope photo of the rare earth hollow lanthanum trifluoride luminescence nanocrystalline of ion；
Fig. 4 is the fluorescence spectrum figure of the rare earth hollow lanthanum trifluoride luminescence nanocrystalline of embodiment 1 preparation；
Fig. 5 is the Fourier infrared absorption collection of illustrative plates of the rare earth hollow lanthanum trifluoride luminescence nanocrystalline of embodiment 1 preparation；
Detailed description of the invention
Below in conjunction with accompanying drawing, the preferred embodiments of the present invention are illustrated, it will be appreciated that preferred embodiment described herein is merely to illustrate and explains the present invention, is not intended to limit the present invention.
Embodiment 1:
The preparation of rare earth hollow lanthanum trifluoride luminescence nanocrystalline, specifically comprises the following steps that
1,6.25mmol lanthana and 1.25mmol europium oxide powder is weighed respectively with electronic balance, each it is dissolved in concentrated nitric acid, after heating is completely dissolved, vapor away remaining nitric acid, proceed to after adding suitable quantity of water in 50ml volumetric flask, be configured to the lanthanum nitrate aqueous solution of 0.25mol/L and the europium nitrate aqueous solution of 0.05mol/L；
2, it is the polyvinylpyrrolidone of 30000 by 0.375g molecular weight, joins in the mixed solution of 10mL water and 15mL ethanol, stir 10 minutes, obtain clear solution；
3,3.8mL Lanthanum (III) nitrate step 1 configured and 1mL europium nitrate aqueous solution are slowly added drop-wise in step 2 gained solution, stir 20 minutes, obtain clear solution；
4, the NH of 0.05mol is weighed with electronic balance4F is dissolved in 50mL water, is configured to the NH that concentration is 1mol/L4F aqueous solution, takes the solution configured 3mL and is slowly added drop-wise in step 3 gained solution, and obtains white gum solution, stirs 30 minutes；
5, step 4 gained colloidal solution is poured in water heating kettle, 190 degree are reacted 3 hours, are cooled to room temperature, deionized water wash 3 times, when 4000rpm/min centrifugal 5 minutes, gained white product was put in baking oven 60 DEG C and dry within 12 hours, is namely obtained rare earth hollow lanthanum trifluoride manocrystalline powders.
Prepare the nanocrystalline well-crystallized of lanthanum trifluoride, it does not have dephasign, be uniformly dispersed, Average Particle Diameters is about 25nm, hollow structure be distributed in each nanocrystalline in, aperture diameter is approximately 5-10nm.Its X-ray diffractogram, transmission electron microscope photo, fluorescence emission spectra figure and Fourier infrared absorption collection of illustrative plates respectively as shown in Figure 1, Figure 2, shown in Fig. 4 and Fig. 5, Fourier infrared absorption collection of illustrative plates illustrates that nanocrystal surface is with one layer of hydrophilic molecules polyvinylpyrrolidone.
Embodiment 2:
Mix Li+The preparation of the rare earth hollow lanthanum trifluoride luminescence nanocrystalline of ion, specifically comprises the following steps that
1,6.25mmol lanthana and 1.25mmol europium oxide powder is weighed respectively with electronic balance, each it is dissolved in concentrated nitric acid, after heating is completely dissolved, vapor away remaining nitric acid, proceed to after adding suitable quantity of water in 50ml volumetric flask, be configured to the lanthanum nitrate aqueous solution of 0.25mol/L and the europium nitrate aqueous solution of 0.05mol/L；
2, weigh the lithium nitrate of 2.5mol with electronic balance, be dissolved in 50mL water, be configured to the lithium nitrate aqueous solution of 0.05mol/L.
3, it is the polyvinylpyrrolidone of 30000 by 0.375g molecular weight, joins in the mixed solution of 10mL water and 15mL ethanol, stir 10 minutes, obtain clear solution；
The mixed aqueous solution of the 3.8mL Lanthanum (III) nitrate, 1mL europium nitrate and the 1mL lithium nitrate that 4, step 1 and 2 have been configured slowly is added drop-wise in step 3 gained solution, stirs 20 minutes, obtains clear solution；
5, the NH of 0.05mol is weighed with electronic balance4F is dissolved in 50mL water, is configured to the NH that concentration is 1mol/L4F aqueous solution, takes the solution configured 3mL and is slowly added drop-wise in step 4 gained solution, and obtains white gum solution, stirs 30 minutes；
6, pouring in water heating kettle by step 4 gained colloidal solution, 190 degree are reacted 3 hours, are cooled to room temperature, deionized water wash 3 times, are centrifuged 5 minutes when 4000rpm/min, and gained white product is put into 60 DEG C of dry namely obtaining for 12 hours in baking oven and mixed Li+The rare earth hollow lanthanum trifluoride manocrystalline powders of ion.
What prepare mixes Li+The nanocrystalline well-crystallized of lanthanum trifluoride of ion, it does not have dephasign, is uniformly dispersed, and Average Particle Diameters is about 25nm, hollow structure be distributed in each nanocrystalline in, aperture diameter is approximately 5-10nm.Fig. 3 be embodiment 2 preparation mix Li+The transmission electron microscope photo of the rare earth hollow lanthanum trifluoride luminescence nanocrystalline of ion, Fourier infrared absorption collection of illustrative plates illustrates that nanocrystal surface is with one layer of hydrophilic molecules polyvinylpyrrolidone, and fluorescence spectrum figure illustrates to mix Li+Fluorescence intensity nanocrystalline after ion is greatly enhanced.
Last it is noted that these are only the preferred embodiments of the present invention; it is not limited to the present invention; although the present invention being described in detail with reference to embodiment; for a person skilled in the art; technical scheme described in foregoing embodiments still can be modified by it; or wherein portion of techniques feature is carried out equivalent replacement; but all within the spirit and principles in the present invention; any amendment of being made, equivalent replacement, improvement etc., should be included within protection scope of the present invention.
Claims (2)
1. the preparation method that a rare earth hollow is nanocrystalline, it is characterised in that comprise the following steps:
A, configuration rare earth ion La and Eu rare earth soluble salt aqueous solution, rare earth ion concentration is 0.05-0.25mol/L；Configuration lithium ion soluble salt aqueous solution, concentration is 0.05-0.1mol/L；
B, it is the polyvinylpyrrolidone of 10000-30000 by 0.3-0.6g molecular weight, joins in the mixed solution of 10mL water and 15mL ethanol, stir 10-20 minute, obtain clear solution；
C, the described rare earth soluble salt aqueous solution configured by step a and described lithium ion soluble salt aqueous solution are slowly added drop-wise in step b gained solution, stir 20-30 minute, obtain clear solution；
D, configuration NH4F aqueous solution, concentration is 1mol/L, is added drop-wise to by the solution configured in step c gained solution, obtains white gum solution, stirs 20-30 minute；
E, step d gained colloidal solution is poured in water heating kettle, 190 degree are reacted 3-6 hour, are cooled to room temperature, deionized water wash 3-5 time, when 3000-9000rpm/min centrifugal 3-10 minute, gained white product was put in baking oven 60-80 DEG C and dry within 12 hours, is namely obtained rare earth hollow manocrystalline powders.
2. the preparation method that a kind of rare earth hollow is nanocrystalline according to claim 1, it is characterised in that described rare earth soluble salt is rare earth nitrate, described lithium ion soluble salt is lithium nitrate.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106520115A (en) * | 2016-08-31 | 2017-03-22 | 佛山科学技术学院 | Water-soluble rare earth porous nano-crystal preparation method |
| CN108085003A (en) * | 2018-01-25 | 2018-05-29 | 重庆文理学院 | A kind of LaF3:Eu3+Nano-particle fluorescence body and preparation method thereof |
| CN108456525A (en) * | 2018-05-11 | 2018-08-28 | 重庆文理学院 | A kind of preparation method of europium doping yttrium fluoride nano-particle fluorescence body |
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| CN102093892A (en) * | 2011-03-01 | 2011-06-15 | 上海大学 | Method for preparing rare earth doped lanthanum fluoride luminous hollow nano powder by using multi-element solvothermal method |
| CN102786816A (en) * | 2012-08-22 | 2012-11-21 | 北京化工大学 | Preparation method of water-soluble rare earth luminous nanocrystallines with functionalized surfaces |
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2016
- 2016-01-12 CN CN201610018783.5A patent/CN105778902A/en active Pending
Patent Citations (2)
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| CN102093892A (en) * | 2011-03-01 | 2011-06-15 | 上海大学 | Method for preparing rare earth doped lanthanum fluoride luminous hollow nano powder by using multi-element solvothermal method |
| CN102786816A (en) * | 2012-08-22 | 2012-11-21 | 北京化工大学 | Preparation method of water-soluble rare earth luminous nanocrystallines with functionalized surfaces |
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| TING FAN ET AL.: "Enhanced 1.5μm and green upconversion emissions in Y2O3:Er3+ nanoparticles codoped with Li+ ions", 《OPTICS COMMUNICATIONS》 * |
| 刘阳: "稀土氟化物复合纳米微粒的制备及光学性能研究", 《中国优秀硕士学位论文全文数据库》 * |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106520115A (en) * | 2016-08-31 | 2017-03-22 | 佛山科学技术学院 | Water-soluble rare earth porous nano-crystal preparation method |
| CN108085003A (en) * | 2018-01-25 | 2018-05-29 | 重庆文理学院 | A kind of LaF3:Eu3+Nano-particle fluorescence body and preparation method thereof |
| CN108085003B (en) * | 2018-01-25 | 2021-05-18 | 重庆文理学院 | LaF3:Eu3+Nanoparticle phosphor and method for preparing the same |
| CN108456525A (en) * | 2018-05-11 | 2018-08-28 | 重庆文理学院 | A kind of preparation method of europium doping yttrium fluoride nano-particle fluorescence body |
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Application publication date: 20160720 |