CN105441080A - Method for quickly preparing NaYF:Yb/Er upconversion nano particles having different phases - Google Patents
Method for quickly preparing NaYF:Yb/Er upconversion nano particles having different phases Download PDFInfo
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- CN105441080A CN105441080A CN201510791268.6A CN201510791268A CN105441080A CN 105441080 A CN105441080 A CN 105441080A CN 201510791268 A CN201510791268 A CN 201510791268A CN 105441080 A CN105441080 A CN 105441080A
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Abstract
The invention discloses a method for quickly preparing NaYF:Yb/Er upconversion nano particles having different phases. The method comprises the following steps: dissolving Y(NO3)3, Yb(NO3)3 and Er(NO3)3 in a solvent according to a stoichiometric ratio of 78:20:2 to form a Ln(NO3)3 solution; adding a NaF solution; stirring, adding NH4HF2 to enable the molar ratio of NH3HF2 to Ln(NO3)3 to be (3-6):1; keeping on stirring, and transferring into a hydrothermal reaction kettle, reacting for 3-48 hours at 140-220 DEG C, and naturally cooling to room temperature; and alternately washing the centrifugally separated product with deionized water and absolute ethyl alcohol, and drying to obtain the NaYF:Yb/Er upconversion nano particles, wherein the solvent is ethyl alcohol, propyl alcohol, acetic acid or propionic acid. The preparation is simple to open, easily available in raw materials and high in reaction speed, and the prepared particles have high purity and excellent upconversion luminescence performance.
Description
Technical field
The present invention relates to up-conversion nano material technical field, be specifically related to one and prepare not jljl phase NaYF fast
4: the method for the upper conversion nano particle of Yb/Er.
Background technology
Yttrium fluoride natrium (NaYF
4) be a kind of important upper conversion substrate material, NaYF
4: Yb/Er be generally acknowledge at present there is one of material of the highest up-conversion luminescence efficiency (Inorg.Chem., 2007,46,5404 ?5410), this material has highlighted wide application prospect in laser apparatus, optical communication fibre, 3 D stereo display, infrared acquisition, fluorescence falsification preventing, photovoltaic cell and biomarker etc.
Yttrium fluoride natrium has two kinds of crystal formations, Emission in Cubic and six side's phases, and the performance of six side's phase up-conversions of doping with rare-earth ions is obviously better than the Emission in Cubic of identical doping, as six side phase NaYF
4: the upper shift strength of Yb/Er is than Emission in Cubic NaYF
4: high one to two orders of magnitude of Yb/Er (J.Mater.Chem., 2009,19,3546 ?3553), therefore effective control NaYF
4the optimization of relative its luminescent properties of thing have great importance.
NaYF
4: synthetic method many employings liquid phase method of the upper conversion nano particle of Yb/Er, mainly includes the methods such as machine thermal decomposition method, ionic liquid method, water (solvent) heat.Organic thermal decomposition method generally adopts organo-metallic yttrium salt costly as reactant, react in organic solvent and tensio-active agent are as oleyl amine, oleic acid, temperature of reaction is higher, and need carry out in an inert atmosphere, products therefrom is coated by organic solvent, and aftertreatment comparatively bothers, comparatively large (the J.Am.Chem.Soc. of byproduct of reaction toxicity, 2006,128,6426 – 6436).Therefore, simple method is adopted to control crystal growth to obtain not jljl phase NaYF fast
4: the upper conversion nano particle of Yb/Er, has important using value, and present method is also for preparation in macroscopic quantity up-conversion provides theory and technology support.
Summary of the invention
Main purpose of the present invention is the defect overcoming the existence of existing technology of preparing, provides one to prepare not jljl phase NaYF fast
4: the method for the upper conversion nano particle of Yb/Er, its thing controls by reaction conditions.
Object of the present invention is achieved through the following technical solutions:
One prepares not jljl phase NaYF fast
4: the method for the upper conversion nano particle of Yb/Er, first by Y (NO
3)
3, Yb (NO
3)
3with Er (NO
3)
3stoichiometrically 78:20:2 is dissolved in solvent and forms Ln (NO
3)
3solution, adds NaF solution, control NaF and Ln (NO
3)
3mol ratio be 2 ~ 4:1, add NH after stirring
4hF
2, make NH
4hF
2with Ln (NO
3)
3mol ratio be 3 ~ 6:1, continue to stir more than 30min, transfer in hydrothermal reaction kettle, react 3 ~ 48h, naturally cool to room temperature under 140 ~ 220 DEG C of conditions, centrifugation product deionized water and dehydrated alcohol be washing alternately, after drying NaYF
4: the upper conversion nano particle of Yb/Er;
Described solvent is the one in ethanol, propyl alcohol, acetic acid and propionic acid; Described not jljl is α phase and β phase mutually, and use ethanol or propyl alcohol as solvent, after dry, products therefrom is β ?NaYF
4: the upper conversion nano particle of Yb/Er; Use acetic acid or propionic acid as solvent, after dry products therefrom Wei α ?NaYF
4: the upper conversion nano particle of Yb/Er.
For realizing object of the present invention further, described reaction carries out in teflon-lined autoclave.
Preferably, temperature of reaction is 160 ~ 200 DEG C.
Preferably, the number of times that described deionized water and dehydrated alcohol alternately wash is 3 ~ 5 times.
Preferably, described Y (NO
3)
3, Yb (NO
3)
3with Er (NO
3)
3total amount is 0.2 ~ 1.0mmol.
Preferably, the volume of described solvent is 14 ~ 20mL.
Preferably, the concentration of described NaF solution is 0.6 ~ 3.0mol/L.
Preferably, NH is added
4hF
2the time of front stirring is 10 ~ 15min.
Relative to prior art, tool of the present invention has the following advantages and beneficial effect:
(1) the present invention adopts solvent-thermal method to prepare NaYF
4: the upper conversion nano particle of Yb/Er, simple and quick, consume energy low, without the need to tensio-active agent, product postprocessing is simple.
(2) the present invention adopts different solvents can reach control and obtains not jljl phase product, in alcoholic solvent, namely obtain β ?NaYF
4: the upper conversion nano particle of Yb/Er, obtain in acid-soluble dose α ?NaYF
4: the upper conversion nano particle of Yb/Er.
(3) products therefrom particle of the present invention is controlled, good dispersity, has excellent up-conversion luminescence performance.
Accompanying drawing explanation
The NaYF of Fig. 1 prepared by the embodiment of the present invention 1 ~ 4
4: the X-ray diffractogram of the upper conversion nano particle of Yb/Er.
The NaYF of Fig. 2 prepared by the embodiment of the present invention 1
4: the stereoscan photograph of the upper conversion nano particle of Yb/Er.
The NaYF of Fig. 3 prepared by the embodiment of the present invention 1
4: the fluorescence spectrum figure of the upper conversion nano particle of Yb/Er under 980nm laser excitation.
The NaYF of Fig. 4 prepared by the embodiment of the present invention 3
4: the stereoscan photograph of the upper conversion nano particle of Yb/Er.
Embodiment
For better understanding the present invention, below in conjunction with drawings and Examples, the invention will be further described, but the scope of protection of present invention is not limited to the scope of embodiment statement.
Embodiment 1
By the Y (NO of 1.0mmol (total amounts of three kinds of materials)
3)
3, Yb (NO
3)
3with Er (NO
3)
3stoichiometrically 78:20:2 is dissolved in 14mL ethanolic soln, adds the NaF solution of 3.0mmol, after stirring 10min, then adds 0.342gNH
4hF
2, after continuing to stir 30min, transfer in hydrothermal reaction kettle, react 48h, naturally cool to room temperature under 140 DEG C of conditions, centrifugation also replaces washing 3 times with deionized water and dehydrated alcohol, can obtain β ?NaYF after drying
4: the upper conversion nano particle of Yb/Er.
The XRD diffraction peak of product is as shown in curve a in Fig. 1, and as shown in Figure 2, its up-conversion luminescence performance as shown in Figure 3 for pattern.From Fig. 1, curve a can find out, all diffraction peaks Yu β ?NaYF
4standard diffraction peak (JCPDS16 ?0334) corresponding.
Can find out from the SEM photo Fig. 2, product is nano particle, and size is about 100 ~ 200nm.The strongest Up-conversion emission peak of product is positioned at 542nm as can be seen from Figure 3.
As can be seen from the present embodiment, the present invention adopts solvent-thermal method to prepare NaYF
4: the upper conversion nano particle of Yb/Er, simple and quick, consume energy low, without the need to tensio-active agent, product postprocessing is simple.Products therefrom particle of the present invention is controlled, good dispersity, has excellent up-conversion luminescence performance.
Embodiment 2
By the Y (NO of 0.2mmol
3)
3, Yb (NO
3)
3with Er (NO
3)
3stoichiometrically 78:20:2 is dissolved in 14mL propanol solution, adds the NaF solution of 0.6mmol, after stirring 10min, then adds 0.068gNH
4hF
2, after continuing to stir 30min, transfer in hydrothermal reaction kettle, react 24h, naturally cool to room temperature under 180 DEG C of conditions, centrifugation also replaces washing 3 times with deionized water and dehydrated alcohol, can obtain β ?NaYF after drying
4: the upper conversion nano particle of Yb/Er.
The XRD diffraction peak of product is as shown in curve b in Fig. 1.From Fig. 1, curve b can find out, all diffraction peaks Yu β ?NaYF
4standard diffraction peak (JCPDS16 ?0334) corresponding.
Embodiment 3
By the Y (NO of 0.5mmol
3)
3, Yb (NO
3)
3with Er (NO
3)
3stoichiometrically 78:20:2 is dissolved in 14mL acetic acid solution, adds the NaF solution of 1.5mmol, after stirring 10min, then adds 0.171gNH
4hF
2, after continuing to stir 30min, transfer in hydrothermal reaction kettle, react 24h, naturally cool to room temperature under 180 DEG C of conditions, centrifugation also replaces washing 3 times with deionized water and dehydrated alcohol, can obtain α ?NaYF after drying
4: the upper conversion nano particle of Yb/Er.
The XRD diffraction peak of product is as shown in curve c in Fig. 1, and pattern as shown in Figure 4.From Fig. 1, curve c can find out, all diffraction peaks Yu α ?NaYF
4standard diffraction peak (JCPDS77 ?2042) corresponding.Can find out from the SEM photo Fig. 4, product is nano particle, and size is about 100 ~ 150nm.
Embodiment 4
By the Y (NO of 1.0mmol
3)
3, Yb (NO
3)
3with Er (NO
3)
3stoichiometrically 78:20:2 is dissolved in 14mL propionic acid solution, adds the NaF solution of 2.0mmol, after stirring 10min, then adds 0.141gNH
4hF
2, after continuing to stir 30min, transfer in hydrothermal reaction kettle, react 3h, naturally cool to room temperature under 220 DEG C of conditions, centrifugation also replaces washing 3 times with deionized water and dehydrated alcohol, can obtain α ?NaYF after drying
4: the upper conversion nano particle of Yb/Er.
The XRD diffraction peak of product is as shown in curve d in Fig. 1.From Fig. 1, curve d can find out, all diffraction peaks Yu α ?NaYF
4standard diffraction peak (JCPDS77 ?2042) corresponding.
The present invention adopts the hot legal system of simple solvent for NaYF
4: the upper conversion nano particle of Yb/Er, synthesis temperature is low compared with high temperature solid-state method and organic thermal decomposition method, and power consumption is few, pollute few, reaction process without the need to tensio-active agent, without the need to carrying out special processing to product, and be that solvent can control to obtain not jljl phase product, simple and fast by alcohol and carboxylic acid.
Above-described embodiment can be found out, the present invention can obtain the product of not jljl phase fast by the regulation and control of different solvents; Obtain in alcoholic solvent β ?NaYF
4: the upper conversion nano particle of Yb/Er, obtain in acid-soluble dose α ?NaYF
4: the upper conversion nano particle of Yb/Er.
Claims (8)
1. prepare not jljl phase NaYF fast for one kind
4: the method for the upper conversion nano particle of Yb/Er, is characterized in that: first by Y (NO
3)
3, Yb (NO
3)
3with Er (NO
3)
3stoichiometrically 78:20:2 is dissolved in solvent and forms Ln (NO
3)
3solution, adds NaF solution, control NaF and Ln (NO
3)
3mol ratio be 2 ~ 4:1, add NH after stirring
4hF
2, make NH
4hF
2with Ln (NO
3)
3mol ratio be 3 ~ 6:1, continue to stir more than 30min, transfer in hydrothermal reaction kettle, react 3 ~ 48h, naturally cool to room temperature under 140 ~ 220 DEG C of conditions, centrifugation product deionized water and dehydrated alcohol be washing alternately, after drying NaYF
4: the upper conversion nano particle of Yb/Er;
Described solvent is the one in ethanol, propyl alcohol, acetic acid and propionic acid; Described not jljl is α phase and β phase mutually, and use ethanol or propyl alcohol as solvent, after dry, products therefrom is β ?NaYF
4: the upper conversion nano particle of Yb/Er; Use acetic acid or propionic acid as solvent, after dry products therefrom Wei α ?NaYF
4: the upper conversion nano particle of Yb/Er.
2. quick preparation according to claim 1 not jljl phase NaYF
4: the method for the upper conversion nano particle of Yb/Er, is characterized in that, described reaction carries out in teflon-lined autoclave.
3. quick preparation according to claim 1 not jljl phase NaYF
4: the method for the upper conversion nano particle of Yb/Er, is characterized in that, temperature of reaction is 160 ~ 200 DEG C.
4. quick preparation according to claim 1 not jljl phase NaYF
4: the method for the upper conversion nano particle of Yb/Er, is characterized in that, the number of times that described deionized water and dehydrated alcohol alternately wash is 3 ~ 5 times.
5. quick preparation according to claim 1 not jljl phase NaYF
4: the method for the upper conversion nano particle of Yb/Er, is characterized in that, described Y (NO
3)
3, Yb (NO
3)
3with Er (NO
3)
3total amount is 0.2 ~ 1.0mmol.
6. quick preparation according to claim 5 not jljl phase NaYF
4: the method for the upper conversion nano particle of Yb/Er, is characterized in that, the volume of described solvent is 14 ~ 20mL.
7. quick preparation according to claim 1 not jljl phase NaYF
4: the method for the upper conversion nano particle of Yb/Er, is characterized in that, the concentration of described NaF solution is 0.6 ~ 3.0mol/L.
8. quick preparation according to claim 1 not jljl phase NaYF
4: the method for the upper conversion nano particle of Yb/Er, is characterized in that, add NH
4hF
2the time of front stirring is 10 ~ 15min.
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Cited By (3)
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---|---|---|---|---|
CN109534889A (en) * | 2018-10-26 | 2019-03-29 | 华南农业大学 | A kind of sodium yttrium tetrafluoride nano particle is improving the purposes in plant root/shoot ratio |
CN110278860A (en) * | 2019-06-11 | 2019-09-27 | 华南农业大学 | A kind of nanometer of blade surface promoting photosynthesis of plant turns light technology |
CN115572596A (en) * | 2022-06-24 | 2023-01-06 | 中山大学 | Up-conversion nanoparticle group for detecting biomarkers through two channels and preparation method and application thereof |
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2015
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CN102888222A (en) * | 2011-07-20 | 2013-01-23 | 上海纳米技术及应用国家工程研究中心有限公司 | Solvothermal preparation method of yellow luminous nanometer upconversion material |
CN104830340A (en) * | 2015-05-11 | 2015-08-12 | 武汉大学深圳研究院 | Method for synthesizing water-soluble hexagonal-phase yttrium sodium fluoride micro-crystal by solvothermal liquid-phase process and water-soluble yttrium sodium fluoride micro-crystal |
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JING-HUI ZENG 等: "Synthesis and upconversion luminescence of hexagonal-phase NaYF4:Yb,Er3+ phosphors of controlled size and morphology", 《ADVANCED MATERIALS》 * |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109534889A (en) * | 2018-10-26 | 2019-03-29 | 华南农业大学 | A kind of sodium yttrium tetrafluoride nano particle is improving the purposes in plant root/shoot ratio |
CN110278860A (en) * | 2019-06-11 | 2019-09-27 | 华南农业大学 | A kind of nanometer of blade surface promoting photosynthesis of plant turns light technology |
CN110278860B (en) * | 2019-06-11 | 2021-08-24 | 华南农业大学 | Leaf surface nano light conversion technology for promoting plant photosynthesis |
CN115572596A (en) * | 2022-06-24 | 2023-01-06 | 中山大学 | Up-conversion nanoparticle group for detecting biomarkers through two channels and preparation method and application thereof |
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Application publication date: 20160330 |