CN103361062A - Preparation method of core-shell structured sodium rare-earth fluoride nanocrystals - Google Patents
Preparation method of core-shell structured sodium rare-earth fluoride nanocrystals Download PDFInfo
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Abstract
The invention provides a preparation method of core-shell structured sodium rare-earth fluoride nanocrystals. The method comprises the following steps: mixing rare-earth trifluoroacetate, sodium trifluoroacetate, oleic acid and octadecene to obtain a mixture; reacting the mixture in the protection atmosphere under heating and stirring conditions, and centrifuging after reaction ending to obtain sodium rare-earth fluoride nanocrystals; mixing the sodium rare-earth fluoride nanocrystals with rare-earth trifluoroacetate, sodium trifluoroacetate, oleic acid and octadecene as a core to obtain a mixture; and rapidly reacting the mixture including the core nanocrystals in the protection atmosphere under heating and stirring conditions, and centrifuging after reaction ending to obtain the core-shell structured sodium rare-earth fluoride nanocrystals. The core-shell structured sodium rare-earth fluoride nanocrystals have the advantages of good particle size consistency, controllable core size and shell thickness, and formation of optic/magnetic, magnetic/optic, optic/optic and magnetic/magnetic multifunctional core/shell structures, and can be widely used in the multi-mode biomarker field, the medical diagnosis field, the sensor field, the optical field or magnetic field detection field, and other high-tech fields.
Description
Technical field
The present invention relates to a kind of preparation method of rare earth fluoride sodium nano-crystal with core-shell structure, belong to technical field of inorganic nonmetallic materials and nano-metal-oxide fabricating technology and optomagnetic technical field.
Background technology
Rare earth fluoride sodium (NaREF4, wherein RE is rare earth) is a kind of non-metallic material, has very good optics or magnetic property, such as, the NaYF4 crystal of Yb3+ and Er3+ ion doping can send the visible lights such as red, yellow, and green under the exciting of infrared light; And NaGdF4 has good paramagnetic characteristic.Owing in fields such as biomarker, imaging, demonstration and illuminations huge potential using value being arranged, a lot of scientists have dropped into the announcement that a large amount of man power and materials further investigate the controlled preparation of rare earth fluoride sodium, performance analysis and optomagnetic Mechanism of characters in the world.Research a few years ago, everybody mainly pays attention to pattern, size, degree of crystallinity, and mix isoparametric exploration and the control of this material of rare earth fluoride sodium, to improve the optomagnetic characteristic of rare earth fluoride sodium.Yet through the development in more than 20 years, the limit was arrived in the regulation and control of these parameters.If continue to improve the optomagnetic performance of rare earth fluoride sodium, must the developing new thinking.2007, Chem.Mater.Vol.19,341 (2007) and J.Phys.Chem.C Vol.111,13721 (2007) have early reported the characteristics of luminescence of further improving rare earth fluoride sodium by nucleocapsid structure, such as at luminescence nanocrystalline NaYF4:Yb3+, the non-luminous NaYF4 shell of outside epitaxy one deck of Er3+, it is nanocrystalline that performance test shows that the nanocrystalline luminous intensity with nucleocapsid structure is significantly higher than independent nuclear.Mechanism studies show that, luminescence nanocrystalline NaYF4:Yb3+, and the Er3+ surface has that imperfect lattice (being a large amount of defectives) causes that surface scattering is serious and luminous efficiency is low.Yet after coating the non-luminous NaYF4 shell of one deck, its lattice surface becomes complete, thereby causes energy transfer efficiency between the surface ion obviously to improve and surface scattering decreases.The new page of rare earth fluoride sodium light magnetic property regulation and control has been opened up in the introducing of nucleocapsid structure.
The nucleocapsid structure material preparation has become study hotspot both domestic and external at present, and disclosed nucleocapsid structure material preparation method has:
(1) announced the different higher metallic nano crystal of activity for preparing first of the activity of in preparation process, utilizing the different metal ion among the U.S. Patent application US6783569, then carried out replacement(metathesis)reaction with the relatively low metal ion of activity and the virgin metal nanocrystal surface is replaced as another kind of metal prepares nucleocapsid structure.This method is simple and yield rate is high, can only prepare metal/metal nucleocapsid structure or a small amount of metal/non-metal nucleocapsid structure but exist, to problems such as the nonmetal nucleocapsid structure of complexity are helpless; (2) announced the employing crosslinking reaction in Chinese patent application 99117169.1 and formed shell structure in the nuclear nanocrystal surface, this method exists and is only suitable for forming organic or contains the shell of organic chain, and can not prepare the shortcoming such as inorganic shell; (3) document Chem.Mater.Vol.19,341 (2007) etc. have announced directly at rare earth fluoride sodium luminescence nanocrystalline surface epitaxy one deck shell close with nuclear composition, but there be the in uneven thickness of shell in this method and be difficult to the shortcoming such as control.
Summary of the invention
The purpose of this invention is to provide a kind of preparation method of rare earth fluoride sodium nano-crystal with core-shell structure, the method preparation technology is simple, and cost is low, and is workable, and can be mass-produced.
Technical scheme of the present invention is as follows:
A kind of preparation method of rare earth fluoride sodium nano-crystal with core-shell structure, described method comprises the steps:
1) synthetic kernel is nanocrystalline:
A. trifluoracetic acid rare-earth salts and sodium trifluoroacetate are mixed with organic solvent, obtain mixing solutions; Described organic solvent is the mixture of oleic acid and octadecylene, and wherein the volume ratio of oleic acid and octadecylene is 1:9～7:3; The volumetric molar concentration of trifluoracetic acid rare-earth salts is 0.02mol/L～0.1mol/L in the described mixing solutions; The trifluoracetic acid na concn is 0.08mol/L～0.8mol/L;
B. described mixing solutions is reacted under inert protective atmosphere and condition of heating and stirring, temperature of reaction is 290 ℃～340 ℃, and the described reaction times is 15 minutes～3 hours, and centrifugation after having reacted obtains rare earth fluoride sodium nuclear nanocrystalline;
2) synthetic nano-crystal with core-shell structure:
A) rare earth fluoride sodium nuclear is nanocrystalline and trifluoracetic acid rare-earth salts, sodium trifluoroacetate, oleic acid and octadecylene are mixed to get mixture; The volume ratio of oleic acid and octadecylene is 1:9～7:3 in the mixture, and the volumetric molar concentration of trifluoracetic acid rare-earth salts is 0.04mol/L～0.1mol/L; Described trifluoracetic acid na concn is 0.16mol/L～0.8mol/L;
B) will contain the nanocrystalline mixture of rare earth fluoride sodium nuclear reacts under inert protective atmosphere and condition of heating and stirring; temperature of reaction can be 300 ℃～340 ℃; the time of described reaction can be 15 minutes～and 2 hours, centrifugation after having reacted obtains rare earth fluoride sodium nano-crystal with core-shell structure.
The volume ratio of oleic acid and octadecylene is preferably 1:9～5:5 in the described mixing solutions of step 1); The volumetric molar concentration of the described trifluoracetic acid rare-earth salts of described step 1) is preferably 0.02mol/L～0.05mol/L; The volumetric molar concentration of described sodium trifluoroacetate is preferably 0.08mol/L～0.3mol/L.
Technical characterictic of the present invention also is: in step 2) synthetic nano-crystal with core-shell structure in, the mol ratio of described mixture Rare Earth Ion and sodium ion can be 1:2.5～1:8.To contain the nanocrystalline mixture of rare earth fluoride sodium nuclear under inert protective atmosphere and condition of heating and stirring, in NaNO3 and the bath of KNO3 fused salt mixt, react.
Rare earth element in the trifluoracetic acid rare-earth salts of the present invention is any one in 17 kinds of rare earth elements.The particle diameter of the rare earth fluoride sodium nano-crystal with core-shell structure that the method is prepared is 20～130nm, and the particle diameter of nuclear is 12～45nm, and the thickness of shell is 3～42.5nm.
The present invention compared with prior art has the following advantages and the technique effect of high-lighting:
1. preparation method's provided by the invention reaction system is simple, and thermolysis gets final product to get required nano-crystal with core-shell structure in oleic acid/octadecylene solvent.2. preparation method's provided by the invention reaction times short, be a kind of quick preparation method.3. preparation method's provided by the invention technique is simple and easy to operate, and key step is with regard to two steps: the first step is dissolved in oleic acid/octadecylene solvent first synthetic kernel with trifluoroacetate nanocrystalline; Second step will be examined nanocrystalline and trifluoroacetate is dissolved in synthetic nano-crystal with core-shell structure in oleic acid/octadecylene solvent together.4. the particle diameter consistence of the nucleocapsid structure rare earth fluoride natrium nanocrystalline of the present invention's preparation is very good.5. the nuclear size of the nucleocapsid structure rare earth fluoride natrium nanocrystalline of the present invention's preparation all can be regulated and control with thickness of the shell.6. the present invention can realize the large-scale preparation of nucleocapsid structure rare earth fluoride natrium nanocrystalline.7. synthetic product its endorse and think luminous or magneticsubstance, and shell also can be luminous or magneticsubstance, multi-functional optomagnetic material can be formed, multimode biomarker, medical diagnosis, sensor, light field or magnetic field detection and other high-tech area can be widely used in.
Description of drawings
Fig. 1 is the nanocrystalline TEM figure of embodiment 1 gained nuclear.
Fig. 2 is the TEM figure of embodiment 1 gained nano-crystal with core-shell structure.
Fig. 3 is the nanocrystalline TEM figure of embodiment 2 gained nuclear.
Fig. 4 is the TEM figure of embodiment 2 gained nano-crystal with core-shell structure.
Fig. 5 is the nanocrystalline TEM figure of embodiment 3 gained nuclear.
Fig. 6 is the TEM figure of embodiment 3 gained nano-crystal with core-shell structure.
Fig. 7 is the nanocrystalline TEM figure of embodiment 4 gained nuclear.
Fig. 8 is the TEM figure of embodiment 4 gained nano-crystal with core-shell structure.
Fig. 9 is the nanocrystalline TEM figure of embodiment 5 gained nuclear.
Figure 10 is the TEM figure of embodiment 5 gained nano-crystal with core-shell structure.
Embodiment
The preparation method of a kind of rare earth fluoride sodium nano-crystal with core-shell structure provided by the invention, it specifically comprises the steps:
1) synthetic kernel is nanocrystalline:
First trifluoracetic acid rare-earth salts and sodium trifluoroacetate are mixed with organic solvent, obtain mixing solutions; Described organic solvent is the mixture of oleic acid and octadecylene, and wherein the volume ratio of oleic acid and octadecylene is 1:9～7:3, is preferably 1:9～5:5; The volumetric molar concentration of trifluoracetic acid rare-earth salts is 0.02mol/L～0.1mol/L in the described mixing solutions, is preferably 0.02mol/L～0.05mol/L; The trifluoracetic acid na concn is 0.08mol/L～0.8mol/L, is preferably 0.08mol/L～0.3mol/L;
Described mixing solutions is reacted under inert protective atmosphere and condition of heating and stirring, and temperature of reaction is 290 ℃～340 ℃, and the described reaction times is 15 minutes～3 hours, and centrifugation after having reacted obtains rare earth fluoride sodium nuclear nanocrystalline.
2) synthetic nano-crystal with core-shell structure:
Be mixed to get mixture with trifluoracetic acid rare-earth salts, sodium trifluoroacetate, oleic acid and octadecylene with rare earth fluoride sodium nuclear is nanocrystalline; The volume ratio of oleic acid and octadecylene is 1:9～7:3 in the mixture, and the volumetric molar concentration of trifluoracetic acid rare-earth salts is 0.04mol/L～0.1mol/L; Described trifluoracetic acid na concn is 0.16mol/L～0.8mol/L; The mol ratio of mixture Rare Earth Ion and sodium ion can be 1:2.5～1:8.Then will contain the nanocrystalline mixture of rare earth fluoride sodium nuclear and react under inert protective atmosphere and condition of heating and stirring, temperature of reaction can be 300 ℃～340 ℃, and the time of reaction can be 15 minutes～and 2 hours; Also can under inert protective atmosphere and condition of heating and stirring, in NaNO3 and the bath of KNO3 fused salt mixt, react; Centrifugation after having reacted obtains rare earth fluoride sodium nano-crystal with core-shell structure.
Followingly enumerate several specific embodiments, in order to further understand preparation process of the present invention.Employed experimental technique is ordinary method if no special instructions among the embodiment.Used material, reagent etc. if no special instructions, all can obtain from commercial channels among the embodiment.
Rare earth element in the rare-earth salts of trifluoracetic acid described in the present invention is any one in 17 kinds of rare earth elements, wherein rare-earth Gd, Nd, Sm and Yb are more suitable for for the preparation of magnetic core or shell, and rare earth La, Lu, Y, Yb, Er, Ho, Tm, Dy, Eu and Tb are more suitable for for the preparation of luminous nucleon or shell.
The preparation of embodiment 1, rare earth fluoride sodium nano-crystal with core-shell structure
Examine nanocrystalline preparation: 0.95 mmole Gadolinium Trifluoroacetate, 0.05 mmole trifluoracetic acid erbium and 2 mmole sodium trifluoroacetates are mixed in two mouthfuls of flasks with 5 milliliters of oleic acid and 45 milliliters of octadecylenes; Two mouthfuls of flasks that fill mixture are vacuumized, then stirred 40 minutes to get transparent homogeneous solution at 110 ℃; Introduce in nitrogen to the two mouthful flask, brushed solution approximately 10 minutes, during to keep temperature be 110 ℃; Change nitrogen gas stream into argon gas stream, and two mouthfuls of flasks that reaction soln will be housed change fast during 290 ℃ NaNO3 and KNO3 fused salt mixt bathe over to, reacted 3 hours; After having reacted, centrifugation namely gets the fluorine gadolinium natrium nanocrystalline (NaGdF4:Er3+) that erbium mixes.
The growth of shell: with above-mentioned preparation nanocrystalline as nuclear nanocrystalline, in two mouthfuls of flasks, mix with 2.5 milliliters of oleic acid and 22.5 milliliters of octadecylenes with 1 mmole Gadolinium Trifluoroacetate and 4 mmole sodium trifluoroacetates; Two mouthfuls of flasks that fill mixture are vacuumized, then stirred 40 minutes to get transparent homogeneous solution at 110 ℃; Introduce in nitrogen to the two mouthful flask, brushed solution approximately 10 minutes, during to keep temperature be 100 ℃; Change nitrogen gas stream into argon gas stream, and two mouthfuls of flasks that reaction soln will be housed change fast during 300 ℃ NaNO3 and KNO3 fused salt mixt bathe over to, reacted 2 hours; After having reacted, centrifugation namely gets nano-crystal with core-shell structure (NaGdF4:Er3+/NaGdF4 nuclear/shell).
The TEM of the above-mentioned nuclear for preparing and nano-crystal with core-shell structure schemes respectively as depicted in figs. 1 and 2, and by this Fig. 1 as can be known, the nuclear of preparation is nanocrystalline to be disc-shaped, and diameter is 45 nanometers; The nano-crystal with core-shell structure of preparation is hexagonal plate, and diameter is 130 nanometers.
The preparation of embodiment 2, rare earth fluoride sodium nano-crystal with core-shell structure
Examine nanocrystalline preparation: 0.95 mmole Gadolinium Trifluoroacetate, 0.05 mmole trifluoracetic acid erbium and 2.5 mmole sodium trifluoroacetates are mixed in two mouthfuls of flasks with 10 milliliters of oleic acid and 10 milliliters of octadecylenes; Two mouthfuls of flasks that fill mixture are vacuumized, then stirred 40 minutes to get transparent homogeneous solution at 100 ℃; Introduce in nitrogen to the two mouthful flask, brushed solution approximately 10 minutes, during to keep temperature be 100 ℃; Change nitrogen gas stream into argon gas stream, and two mouthfuls of flasks that reaction soln will be housed change fast during 320 ℃ NaNO3/KNO3 fused salt mixt bathes over to, reacted 50 minutes; After having reacted, centrifugation namely gets the fluorine gadolinium natrium nanocrystalline (NaGdF4:Er3+) that erbium mixes.
The growth of shell: with above-mentioned preparation nanocrystalline as nuclear nanocrystalline, in two mouthfuls of flasks, mix with 5 milliliters of oleic acid and 5 milliliters of octadecylenes with 1 mmole trifluoracetic acid yttrium and 8 mmole sodium trifluoroacetates; Two mouthfuls of flasks that fill mixture are vacuumized, then stirred 40 minutes to get transparent homogeneous solution at 110 ℃; Introduce in nitrogen to the two mouthful flask, brushed solution approximately 10 minutes, during to keep temperature be 100 ℃; Then this reaction soln is changed over to fast during 340 ℃ NaNO3/KNO3 fused salt mixt bathes, reacted 15 minutes; After having reacted, centrifugation namely gets nano-crystal with core-shell structure (NaGdF4:Er3+/NaYF4 nuclear/shell).
The TEM of the above-mentioned nuclear for preparing and nano-crystal with core-shell structure schemes respectively as shown in Figure 3 and Figure 4, and by this Fig. 3 as can be known, the nuclear of preparation is nanocrystalline to be the hexagonal column, and diameter is 19 nanometers, and length is 29 nanometers; The nano-crystal with core-shell structure of preparation also is the hexagonal column as shown in Figure 4, and diameter is 27 nanometers, and length is 35 nanometers.
The preparation of embodiment 3, rare earth fluoride sodium nano-crystal with core-shell structure
Examine nanocrystalline preparation: 0.95 mmole Gadolinium Trifluoroacetate, 0.05 mmole trifluoracetic acid erbium and 2.5 mmole sodium trifluoroacetates are mixed in two mouthfuls of flasks with 8 milliliters of oleic acid and 8 milliliters of octadecylenes; Two mouthfuls of flasks that fill mixture are vacuumized, then stirred 40 minutes to get transparent homogeneous solution at 100 ℃; Introduce in nitrogen to the two mouthful flask, brushed solution approximately 10 minutes, during to keep temperature be 100 ℃; Change nitrogen gas stream into argon gas stream, and two mouthfuls of flasks that reaction soln will be housed change fast during 310 ℃ NaNO3 and KNO3 fused salt mixt bathe over to, reacted 50 minutes; After having reacted, centrifugation namely gets the fluorine gadolinium natrium nanocrystalline (NaGdF4:Er3+) that erbium mixes.
The growth of shell: with above-mentioned preparation nanocrystalline as nuclear nanocrystalline, in two mouthfuls of flasks, mix with 5 milliliters of oleic acid and 5 milliliters of octadecylenes with 1 mmole trifluoracetic acid yttrium and 8 mmole sodium trifluoroacetates; Two mouthfuls of flasks that fill mixture are vacuumized, then stirred 40 minutes to get transparent homogeneous solution at 110 ℃; Introduce in nitrogen to the two mouthful flask, brushed solution approximately 10 minutes, during to keep temperature be 100 ℃; Then this reaction soln is changed over to fast during 320 ℃ NaNO3/KNO3 fused salt mixt bathes, reacted 30 minutes; After having reacted, centrifugation namely gets nano-crystal with core-shell structure (NaGdF4:Er3+/NaYF4 nuclear/shell).
The TEM of the above-mentioned nuclear for preparing and nano-crystal with core-shell structure schemes respectively as shown in Figure 5 and Figure 6,, as shown in Figure 5, the nuclear of preparation is nanocrystalline to be spherical, mean diameter is 10 nanometers; The nano-crystal with core-shell structure of preparation also is spherical as shown in Figure 6, and mean diameter is 18 nanometers.
The preparation of embodiment 4, rare earth fluoride sodium nano-crystal with core-shell structure
Examine nanocrystalline preparation: 0.95 mmole Gadolinium Trifluoroacetate, 0.05 mmole trifluoracetic acid erbium and 2.5 mmole sodium trifluoroacetates are mixed in two mouthfuls of flasks with 10 milliliters of oleic acid and 10 milliliters of octadecylenes; Two mouthfuls of flasks that fill mixture are vacuumized, then stirred 40 minutes to get transparent homogeneous solution at 100 ℃; Introduce in nitrogen to the two mouthful flask, brushed solution approximately 10 minutes, during to keep temperature be 100 ℃; Change nitrogen gas stream into argon gas stream, and two mouthfuls of flasks that reaction soln will be housed change fast during 305 ℃ NaNO3/KNO3 fused salt mixt bathes over to, reacted 65 minutes; After having reacted, centrifugation namely gets the fluorine gadolinium natrium nanocrystalline (NaGdF4:Er3+) that erbium mixes.
The growth of shell: with above-mentioned preparation nanocrystalline as nuclear nanocrystalline, in two mouthfuls of flasks, mix with 5 milliliters of oleic acid and 5 milliliters of octadecylenes with 1 mmole trifluoracetic acid yttrium and 8 mmole sodium trifluoroacetates; Two mouthfuls of flasks that fill mixture are vacuumized, then stirred 40 minutes to get transparent homogeneous solution at 110 ℃; Introduce in nitrogen to the two mouthful flask, brushed solution approximately 10 minutes, during to keep temperature be 100 ℃; Then this reaction soln is changed over to fast during 330 ℃ NaNO3/KNO3 fused salt mixt bathes, reacted 25 minutes; After having reacted, centrifugation namely gets nano-crystal with core-shell structure (NaGdF4:Er3+/NaYF4 nuclear/shell).
The TEM of the above-mentioned nuclear for preparing and nano-crystal with core-shell structure schemes respectively as shown in Figure 7 and Figure 8, and as shown in Figure 7, the nuclear of preparation is nanocrystalline to be spherical, and mean diameter is 8 nanometers; The nano-crystal with core-shell structure of preparation also is spherical as shown in Figure 8, and mean diameter is 20 nanometers.
The preparation of embodiment 5, rare earth fluoride sodium nano-crystal with core-shell structure
Examine nanocrystalline preparation: 0.95 mmole Gadolinium Trifluoroacetate, 0.05 mmole trifluoracetic acid erbium and 6 mmole sodium trifluoroacetates are mixed in two mouthfuls of flasks with 7 milliliters of oleic acid and 3 milliliters of octadecylenes; Two mouthfuls of flasks that fill mixture are vacuumized, then stirred 40 minutes to get transparent homogeneous solution at 120 ℃; Introduce in nitrogen to the two mouthful flask, brushed solution approximately 10 minutes, during to keep temperature be 120 ℃; Change nitrogen gas stream into argon gas stream, and two mouthfuls of flasks that reaction soln will be housed change fast during 300 ℃ NaNO3/KNO3 fused salt mixt bathes over to, reacted 2 hours; After having reacted, centrifugation namely gets the fluorine gadolinium natrium nanocrystalline (NaGdF4:Er3+) that erbium mixes.
The growth of shell: with above-mentioned preparation nanocrystalline as nuclear nanocrystalline, in two mouthfuls of flasks, mix with 7 liters of oleic acid and 3 liters of octadecylenes with 1 mmole trifluoracetic acid yttrium and 6 mmole sodium trifluoroacetates; Two mouthfuls of flasks that fill mixture are vacuumized, then mixed 40 minutes to get transparent homogeneous solution at 120 ℃; Introduce in nitrogen to the two mouthful flask, brushed solution approximately 10 minutes, during to keep temperature be 120 ℃; Change nitrogen gas stream into argon gas stream, and two mouthfuls of flasks that reaction soln will be housed change fast during 330 ℃ NaNO3/KNO3 fused salt mixt bathes over to, reacted 20 minutes; After having reacted, centrifugation namely gets nano-crystal with core-shell structure (NaGdF4:Er3+/NaYF4).
The TEM of the above-mentioned nuclear for preparing and nano-crystal with core-shell structure schemes respectively as shown in Figure 9 and Figure 10, and as shown in Figure 9, the nuclear of preparation is nanocrystalline to be spherical, and diameter is 12 nanometers; The nano-crystal with core-shell structure of preparation also is spherical as shown in Figure 10, and diameter is 20 nanometers.
Claims (7)
1. the preparation method of a rare earth fluoride sodium nano-crystal with core-shell structure, described method comprises the steps:
1) synthetic kernel is nanocrystalline:
A. trifluoracetic acid rare-earth salts and sodium trifluoroacetate are mixed with organic solvent, obtain mixing solutions; Described organic solvent is the mixture of oleic acid and octadecylene, and wherein the volume ratio of oleic acid and octadecylene is 1:9～7:3; The volumetric molar concentration of trifluoracetic acid rare-earth salts is 0.02mol/L～0.1mol/L in the described mixing solutions; The trifluoracetic acid na concn is 0.08mol/L～0.8mol/L;
B. described mixing solutions is reacted under inert protective atmosphere and condition of heating and stirring, temperature of reaction is 290 ℃～340 ℃, and the described reaction times is 15 minutes～3 hours, and centrifugation after having reacted obtains rare earth fluoride sodium nuclear nanocrystalline;
2) synthetic nano-crystal with core-shell structure:
A) rare earth fluoride sodium nuclear is nanocrystalline and trifluoracetic acid rare-earth salts, sodium trifluoroacetate, oleic acid and octadecylene are mixed to get mixture; The volume ratio of oleic acid and octadecylene is 1:9～7:3 in the mixture, and the volumetric molar concentration of trifluoracetic acid rare-earth salts is 0.04mol/L～0.1mol/L; Described trifluoracetic acid na concn is 0.16mol/L～0.8mol/L;
B) will contain the nanocrystalline mixture of rare earth fluoride sodium nuclear reacts under inert protective atmosphere and condition of heating and stirring; temperature of reaction can be 300 ℃～340 ℃; the time of described reaction can be 15 minutes～and 2 hours, centrifugation after having reacted obtains rare earth fluoride sodium nano-crystal with core-shell structure.
2. the preparation method of a kind of rare earth fluoride sodium nano-crystal with core-shell structure according to claim 1, it is characterized in that: the volume ratio of oleic acid and octadecylene is 1:9～5:5 in the described mixing solutions of step 1).
3. the preparation method of a kind of rare earth fluoride sodium nano-crystal with core-shell structure according to claim 1, it is characterized in that: the volumetric molar concentration of the described trifluoracetic acid rare-earth salts of described step 1) is 0.02mol/L～0.05mol/L; The volumetric molar concentration of described sodium trifluoroacetate is 0.08mol/L～0.3mol/L.
4. the preparation method of a kind of rare earth fluoride sodium nano-crystal with core-shell structure according to claim 1 is characterized in that: step 2) described in the mol ratio of mixture Rare Earth Ion and sodium ion can be 1:2.5～1:8.
5. according to the preparation method of claim 1,2,3 or 4 described a kind of rare earth fluoride sodium nano-crystal with core-shell structure; it is characterized in that: in step 2) synthetic nano-crystal with core-shell structure in; to contain the nanocrystalline mixture of rare earth fluoride sodium nuclear under inert protective atmosphere and condition of heating and stirring, in NaNO3 and the bath of KNO3 fused salt mixt, react.
6. according to the preparation method of a kind of rare earth fluoride sodium nano-crystal with core-shell structure claimed in claim 1, it is characterized in that: the particle diameter of the rare earth fluoride sodium nano-crystal with core-shell structure of described method preparation is 20～130nm, the particle diameter of nuclear is 12～45nm, and the thickness of shell is 3～42.5nm.
7. the preparation method of a kind of rare earth fluoride sodium nano-crystal with core-shell structure according to claim 1, it is characterized in that: the rare earth element in the described trifluoracetic acid rare-earth salts is any one in 17 kinds of rare earth elements.
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| CN104498038A (en) * | 2014-12-25 | 2015-04-08 | 哈尔滨工程大学 | Rare-earth up-conversion luminescent core-shell nano-luminescence material and preparation method thereof |
| WO2022261967A1 (en) * | 2021-06-18 | 2022-12-22 | 深圳先进技术研究院 | Rare earth core-shell nanomaterial and preparation method therefor |
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