CN114106832B - Synthesis method of rare earth doped lanthanum oxyhalide nanocrystals with core-shell structure - Google Patents
Synthesis method of rare earth doped lanthanum oxyhalide nanocrystals with core-shell structure Download PDFInfo
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 49
- 229910052746 lanthanum Inorganic materials 0.000 title claims abstract description 32
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 239000002159 nanocrystal Substances 0.000 title claims abstract description 27
- 239000011258 core-shell material Substances 0.000 title claims abstract description 25
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 24
- 238000001308 synthesis method Methods 0.000 title claims abstract description 12
- -1 rare earth halide salt Chemical class 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 12
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002243 precursor Substances 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 238000004729 solvothermal method Methods 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 24
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 22
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 22
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 22
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 22
- 239000005642 Oleic acid Substances 0.000 claims description 22
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 22
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 7
- 230000002194 synthesizing effect Effects 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 4
- CTLWNUORPLEHQU-UHFFFAOYSA-N O(I)I.[La] Chemical group O(I)I.[La] CTLWNUORPLEHQU-UHFFFAOYSA-N 0.000 claims description 3
- 238000010189 synthetic method Methods 0.000 claims description 3
- 229910016859 Lanthanum iodide Inorganic materials 0.000 claims 2
- OKVQKDALNLHZLB-UHFFFAOYSA-K erbium(3+);triiodide Chemical compound I[Er](I)I OKVQKDALNLHZLB-UHFFFAOYSA-K 0.000 claims 2
- KYKBXWMMXCGRBA-UHFFFAOYSA-K lanthanum(3+);triiodide Chemical group I[La](I)I KYKBXWMMXCGRBA-UHFFFAOYSA-K 0.000 claims 2
- LSSJSIMBIIVSTN-UHFFFAOYSA-K ytterbium(3+);triiodide Chemical compound I[Yb](I)I LSSJSIMBIIVSTN-UHFFFAOYSA-K 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 8
- 238000003786 synthesis reaction Methods 0.000 abstract description 8
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 23
- 239000002105 nanoparticle Substances 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 239000012071 phase Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 238000002189 fluorescence spectrum Methods 0.000 description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000010791 quenching Methods 0.000 description 4
- 230000000171 quenching effect Effects 0.000 description 4
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229910052691 Erbium Inorganic materials 0.000 description 2
- 229910052769 Ytterbium Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 description 1
- 229940107816 ammonium iodide Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012984 biological imaging Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- SORGMJIXNUWMMR-UHFFFAOYSA-N lanthanum(3+);propan-2-olate Chemical compound [La+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SORGMJIXNUWMMR-UHFFFAOYSA-N 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000329 molecular dynamics simulation Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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Abstract
The invention discloses a synthesis method of rare earth doped lanthanum oxyhalide nanocrystals with a core-shell structure, and belongs to the technical field of rare earth luminescent nanomaterial synthesis. The rare earth halide salt is taken as a raw material to obtain a nanocrystalline bare core through solvothermal reaction, lanthanum oxyhalide is taken as a shell precursor solution, the solution is injected into the nanocrystalline bare core, the reaction is carried out for 15min at 300 ℃, then the reaction is carried out for 2-4h at 280-295 ℃, the cooling and the washing are carried out, and then the solution is dispersed in cyclohexane, thus obtaining the rare earth doped lanthanum oxyhalide nanocrystal with a core-shell structure. The method has the advantages of easily obtained raw materials, low cost and low equipment requirement, and the obtained nanocrystals have better morphology, and compared with the existing luminescent materials, the luminescent intensity is obviously enhanced.
Description
Technical Field
The invention belongs to the technical field of rare earth luminescent nano material synthesis, and particularly relates to a synthesis method of rare earth doped lanthanum oxyhalide nanocrystals with a core-shell structure.
Background
The rare earth up-conversion luminescent material has wide application prospect in the fields of anti-counterfeiting, biological imaging, laser and the like. The rare earth luminescent material consists of doped ions and matrix materials. Common matrix materials are typically oxides, fluorides, etc. The oxide generally has better stability, but has higher phonon energy (1000 cm -1 About), the up-conversion luminescent material using an oxide as a matrix is generally low in luminous efficiency. The halide phonon energy is small (300 cm) -1 ) Has higher luminous efficiency, but has poorer stability, is deliquescent and limits the practical application thereof. Compared with the prior artLanthanum halide or lanthanum oxide, ln 3+ The (lanthanoid) -doped lanthanum oxyhalide combines the high chemical/thermal stability of lanthanum oxide with the low phonon energy of lanthanum halide (400 cm) -1 ) The fluorescent material has the advantages of being hopefully a new luminous matrix material, and has great application prospect in the field of anti-counterfeiting.
The nanoparticle has a large specific surface area, and defects, functional groups, water molecules and the like on the surface of the particle can reduce the intensity of up-converted luminescence, namely surface quenching. The outside of the nano particles is coated with an inert layer (i.e. undoped oxyhalide), which can protect luminescent rare earth ions (especially ions near the surface) in the nuclear structure, avoid non-radiative transition caused by surface defects and collision deactivation of solvent or surface ligand in the colloid dispersing agent, thereby effectively inhibiting surface quenching and enhancing the luminous intensity.
The technology for preparing lanthanum oxyhalide in the prior art comprises a solid phase reaction method, a sol-gel method, a solvothermal method and the like. However, when the high-temperature solid phase method is adopted for preparation, the raw materials are unevenly mixed, the reaction temperature is high, the granularity of the product is large, and the morphology of the particles is uneven; the luminescent performance of the nanocrystals prepared by the sol-gel method is poor; the majority of nanocrystals prepared by a solvothermal method are prepared by taking lanthanum trihaloacetate as a raw material, and tetrabromobutyl ammonium iodide is required to be added when lanthanum oxyiodide is prepared, so that the lanthanum oxyiodide prepared by the method is not pure enough, contains other impurities, and cannot be prepared in a large scale due to the high price of lanthanum isopropoxide.
At present, no report exists about the preparation of core-shell lanthanum oxyhalide nanoparticles.
Disclosure of Invention
In view of the above, the present invention provides a method for synthesizing rare earth doped lanthanum oxyhalide nanocrystals with core-shell structure, which solves the problems existing in the prior art.
In order to achieve the above purpose, the present invention provides the following technical solutions:
a method for synthesizing rare earth doped lanthanum oxyhalide nanocrystals with a core-shell structure comprises the steps of taking rare earth halide salt as a raw material, performing solvothermal reaction to obtain nanocrystalline bare cores, taking lanthanum oxyhalide as a shell precursor solution, injecting the nanocrystalline bare cores, reacting for 15min at 300 ℃, then reacting for 2-4h at 280-295 ℃, cooling, centrifugally washing for 3 times by cyclohexane, centrifugally washing for 3 times by ethanol, and dispersing in cyclohexane to obtain the rare earth doped lanthanum oxyhalide nanocrystals with the core-shell structure.
Further, the rare earth halide salt includes lanthanum halide, ytterbium halide, or erbium halide.
Further, the synthesis method of the rare earth halide salt comprises the following steps: rare earth oxide and halonate are mixed according to a mole ratio of 1: (3-5) mixing, adding deionized water, and heating to remove excessive halogen acid to obtain the rare earth halide salt. The heating temperature is 60-100 ℃.
Further, the synthesis method of the nanocrystalline bare core comprises the following steps: sequentially adding oleic acid and oleylamine (volume ratio is (1-2.5): 13-16)) into the halogenated rare earth salt, heating and stirring until the solution turns color, and vacuumizing the reaction system for 10-20min to remove redundant oxygen and water;
introducing argon, reacting for 45-90min at 300 ℃, cooling to room temperature, centrifuging and washing 3 times with cyclohexane, and washing 3 times with ethanol to obtain the nanocrystalline bare core.
Similarly, oleic acid and rare earth halide salt are completely dissolved and the water is removed, then oleylamine is added, and then the water is removed again, namely the heating temperature is not changed (110-130 ℃) in the whole reaction process, so as to remove all the water. The presence or absence of bubbles and color change are observed to determine. After the oleylamine is added, the reaction system changes from colorless to yellow in the process of removing water, namely, the reaction system starts to enter the next operation.
Further, the volume ratio of oleic acid to oleylamine is 1:6-15.
Further, the heating temperature is 110-130 ℃ and the time is 30min.
The invention also provides an application of the rare earth doped lanthanum oxyhalide nanocrystal with the core-shell structure obtained by the synthesis method as a rare earth up-conversion luminescent material.
The invention also provides a rare earth doped lanthanum oxyhalide nanocrystal with a core-shell structure.
The principle of the invention is as follows:
based on thermodynamics and molecular dynamics, controlling the proportion of oleic acid and oleylamine in a solvent, the reaction temperature and the reaction time, preparing nanocrystals with a core-shell structure by a hot injection method, firstly preparing core nanoparticles, then adding a precursor solution of a shell layer, and epitaxially growing the core nanoparticles on the surface of the core nanoparticles without independently forming cores by using the core nanoparticles as seed crystals to finally obtain the rare earth doped oxyhalide nanoparticles with the core-shell structure, wherein the nanoparticles are pure tetragonal phase oxyhalide.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a preparation method of a synthesized rare earth doped lanthanum oxyhalide nanocrystal with simple process, which has the advantages of easily available raw materials, low cost and low equipment requirement, and the obtained nanocrystal has better morphology and obviously enhanced luminous intensity compared with the existing luminescent material.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an X-ray diffraction pattern of a 15Yb/2Er@LaOI nano luminescent material prepared in example 1;
FIG. 2 is a transmission electron microscope image of the LaOI 15Yb/2Er@LaOI nano luminescent material prepared in example 1;
FIG. 3 is a graph of fluorescence spectra obtained by exciting two materials, namely LaOI 15Yb/2Er@LaOI and LaOI 15Yb/2Er prepared in example 1 at 980 nm;
FIG. 4 is an X-ray diffraction pattern of the LaOI 2Er@LaOBr nano luminescent material prepared in example 2;
FIG. 5 is a transmission electron microscope image of the LaOI 2Er@LaOBr nano luminescent material prepared in example 2;
FIG. 6 is a graph of fluorescence spectra obtained by excitation of two materials, laOI:2Er@LaOBr and LaOI:2Er, prepared in example 2, at a wavelength of 1532 nm.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the invention described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present invention. The specification and examples are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
A method for synthesizing rare earth doped lanthanum oxyhalide nanocrystals with a core-shell structure comprises the steps of taking rare earth halide salt as a raw material, performing solvothermal reaction to obtain lanthanum oxyhalide, taking lanthanum oxyhalide as a shell precursor solution, injecting the lanthanum oxyhalide into a nanocrystalline bare core, reacting for 15min at 300 ℃, then reacting for 2-4h at 280-295 ℃, cooling, centrifugally washing for 3 times by cyclohexane, centrifugally washing for 3 times by ethanol, and dispersing in cyclohexane to obtain the rare earth doped lanthanum oxyhalide nanocrystals with the core-shell structure.
The rare earth halide salt includes lanthanum halide, ytterbium halide, or erbium halide.
The synthesis method of the rare earth halide salt comprises the following steps: rare earth oxide and halonate are mixed according to a mole ratio of 1: (3-5) mixing, adding deionized water, and heating to remove excessive halogen acid to obtain the rare earth halide salt. The heating temperature is 60-100 ℃.
The solvothermal reaction specifically comprises the following steps: oleic acid and oleylamine are sequentially added into the halogenated rare earth salt, stirred for 45min at 110-130 ℃ and vacuumized for 15min, so as to obtain lanthanum oxyhalide. The volume ratio of oleic acid to oleylamine is (0.1-0.5): (2-5). After oleic acid and rare earth halide salt are completely dissolved and moisture is removed, oleylamine is added, and then the moisture is removed again, namely the temperature in the whole reaction process is unchanged, so that all the moisture is removed. The presence or absence of bubbles was observed to determine.
The synthesis method of the nanocrystalline bare core comprises the following steps: sequentially adding oleic acid and oleylamine (volume ratio is (1-2.5): 13-16)) into the halogenated rare earth salt, heating and stirring until the solution turns color, and vacuumizing the reaction system for 10-20min to remove redundant oxygen and water;
introducing argon, reacting for 45-90min at 300 ℃, cooling to room temperature, centrifuging and washing 3 times with cyclohexane, and washing 3 times with ethanol to obtain the nanocrystalline bare core.
Similarly, oleic acid and rare earth halide salt are completely dissolved and the water is removed, then oleylamine is added, and then the water is removed again, namely the heating temperature is not changed (110-130 ℃) in the whole reaction process, so as to remove all the water. The presence or absence of bubbles and color change are observed to determine. After the oleylamine is added, the reaction system changes from colorless to yellow in the process of removing water, namely, the reaction system starts to enter the next operation.
The volume ratio of the halogenated rare earth salt to oleic acid to oleylamine is 1:6-15.
The heating temperature is 110-130 ℃ and the heating time is 30min.
The synthesis method of the rare earth halide salt comprises the following steps: rare earth oxide and halogen acid are mixed according to a mole ratio of 1: (3-5) mixing, adding 20-40mL of deionized water, transferring the mixture into a flask, heating the flask to 60-100 ℃ to remove excessive halogen acid, and then adding water to fix the volume to obtain the rare earth halide salt.
The rare earth halide salts used in the invention all adopt the above synthetic methods.
Example 1 Synthesis of LaOI 15Yb/2Er@LaOI
Step A, synthesizing LaOI 15Yb/2Er bare core
1) LaI with a volume of 1.38mL was taken 3 (0.2M) solution, 0.875mL of YbI 3 (0.2M) solution, 0.117mL ErI 3 (0.2M) solution was added to a 50mL two-necked round bottom flask followed by 1mL Oleic Acid (OA) and the water was removed at 120 ℃;
2) Adding 14mL of Oleylamine (OM) into the step 1), removing water in the oil phase at 120 ℃ through stirring, and maintaining for 80min until the color of the solution changes from colorless to yellow;
3) Vacuumizing the reaction system in the step 2) for 15min, and removing oxygen and water vapor in the system; argon is introduced, the temperature is raised to 300 ℃, and the reaction is carried out for 45min, so as to obtain the LaOI 15Yb/2Er bare core;
and (B) step (B): synthesis of LaOI Shell precursor solution
LaI with a volume of 0.83mL was taken 3 Removing water from the solution at 120 ℃ for 5min, adding 0.1mL of Oleic Acid (OA) and then continuously removing water, adding 3mL of Oleylamine (OM), stirring and removing water for 45min, vacuumizing for 15min to obtain LaOI shell precursor solution, and keeping vacuum heating for later use;
step C: synthesis of LaOI 15Yb/2Er@LaOI core-shell nanoparticles
1) B, injecting the LaOI shell precursor solution synthesized in the step B into the LaOI 15Yb/2Er bare core system obtained in the step A by using an injector, keeping the temperature of 300 ℃ for continuous reaction for 15min, then adjusting the temperature to 285 ℃ for reaction for 3h, and cooling to room temperature;
2) Washing the reaction product of the step 1) with cyclohexane and ethanol for 3 times respectively, and centrifuging for 3-4min under the condition of the rotating speed of 7830 r/min;
3) Dispersing the centrifugal product in the step 2) in 4mL of cyclohexane to obtain the LaOI 15Yb/2Er@LaOI core-shell nanoparticle.
FIG. 1 is an X-ray diffraction pattern of a 15Yb/2Er@LaOI nano luminescent material prepared in the present example, and it can be seen from the figure that the nanocrystals prepared in the present example have a pure tetragonal phase crystal structure.
FIG. 2 is a transmission electron microscope image of the LaOI 15Yb/2Er@LaOI nano luminescent material prepared by the embodiment, and the graph shows that the nano crystal prepared by the embodiment has good morphology, uniform particle morphology and size distribution of 100-150nm.
FIG. 3 is a graph showing fluorescence spectra of two materials, namely LaOI 15Yb/2Er@LaOI and LaOI, prepared in this example under excitation at 980 nm. As can be seen from the graph, the LaOI 15Yb/2Er@LaOI nano particle with the core-shell structure prepared by the method has obviously enhanced fluorescence performance compared with the LaOI 15Yb/2Er material, because the LaOI shell layer can effectively prevent the surface quenching of the luminescent nano particle.
Example 2 Synthesis of LaOI:2Er@LaOBr
Step A, synthesizing LaOI 2Er bare core
1) LaI with a volume of 1.63mL was taken 3 (0.2M) solution, 0.117mL ErI 3 (0.2M) solution was added to a 50mL two-necked round bottom flask followed by 1mL Oleic Acid (OA) and the water was removed at 120 ℃;
2) Adding 14mL of Oleylamine (OM) into the step 1), removing water in the oil phase at 120 ℃ through stirring, and keeping for 60min until the color of the solution changes from colorless to yellow;
3) Vacuumizing the reaction system after the water removal in the step 2) for 10-20min, and removing oxygen and water vapor in the system; argon is introduced, the temperature is raised to 300 ℃, and the reaction is carried out for 45min, so as to obtain LaOI 2Er bare core;
and (B) step (B): synthesis of LaOBr Shell precursor solution
LaI with a volume of 0.83mL was taken 3 (0.2M) solution, dewatering at 110 ℃ for 5min, adding 0.1mL of Oleic Acid (OA) and then continuously dewatering, adding 3mL of Oleylamine (OM), stirring and dewatering for 45min, vacuumizing for 15min to obtain LaOI shell precursor solution, and keeping vacuum heating for later use;
step C: synthesis of LaOI 2Er@LaOBr core-shell nanoparticles
1) B, injecting the LaOBr shell precursor solution synthesized in the step B into the LaOI 2Er bare core solution system obtained in the step A by using an injector, keeping the temperature of 300 ℃ for continuous reaction for 15min, then adjusting the temperature to 290 ℃ for reaction for 3h, and cooling to room temperature;
2) And (3) centrifuging and washing the reaction product obtained in the step (1) by using 4mL of cyclohexane and 8mL of ethanol for 3 times respectively, and centrifuging for 3-4min under the condition of the rotating speed of 7830r/min to finally obtain the LaOI:2Er@LaOBr nanocrystalline.
FIG. 4 is an X-ray diffraction pattern of the LaOI:2Er@LaOBr nano luminescent material prepared in the present example, and it can be seen from the figure that the nano crystal prepared in the present example has a pure tetragonal phase crystal structure.
FIG. 5 is a transmission electron microscope image of the LaOI:2Er@LaOBr nano luminescent material prepared in the embodiment, and as can be seen from the image, the nano crystal prepared in the embodiment has good morphology, uniform particle morphology and size distribution of 90-150nm.
FIG. 6 is a graph of fluorescence spectra obtained by excitation of two materials LaOI:2Er@LaOBr and LaOI:2Er prepared in this example at a wavelength of 1532 nm. As can be seen from the graph, the LaOI:2Er@LaOBr nano particle with the core-shell structure prepared by the method has obviously enhanced fluorescence performance compared with the LaOI:2Er material, because the LaOBr shell layer can effectively prevent the surface quenching of the luminescent nano particle.
The invention discovers that the pure oxyhalide nanocrystalline product can be obtained by controlling the ratio of oleic acid and oleylamine in the solvent, the reaction temperature and the reaction time. Too much oleic acid or low reaction temperature cannot produce a product, and too much oleylamine or high reaction temperature can produce an oxide. The core-shell structure prepared by epitaxial growth can greatly improve the luminous intensity of oxyhalide nanocrystals.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the particular embodiments disclosed, but on the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.
Claims (4)
1. A method for synthesizing rare earth doped lanthanum oxyhalide nanocrystals with a core-shell structure is characterized in that rare earth halide salt is taken as a raw material to obtain nanocrystalline bare cores through solvothermal reaction, lanthanum oxyhalide is taken as a shell precursor solution, the nanocrystalline bare cores are injected into the nanocrystalline bare cores to react for 15min at 300 ℃, then the nanocrystalline bare cores react for 2-4h at 280-295 ℃, and then the nanocrystalline bare cores are cooled, washed and then dispersed in cyclohexane, so that the rare earth doped lanthanum oxyhalide nanocrystals with the core-shell structure are obtained;
the lanthanum oxyhalide is lanthanum oxyiodide;
the synthesis method of the nanocrystalline bare core comprises the following steps: sequentially adding oleic acid and oleylamine into the halogenated rare earth salt, heating and stirring until the solution changes color, and then vacuumizing the reaction system; introducing argon, reacting at 300 ℃ for 45-90min, cooling to room temperature, and centrifugally washing to obtain nanocrystalline bare cores;
the volume ratio of the oleic acid to the oleylamine is 1:6-15;
the heating temperature is 110-130 ℃ and the heating time is 30min;
the rare earth halide salt is lanthanum iodide and erbium iodide or lanthanum iodide, erbium iodide and ytterbium iodide.
2. The synthetic method according to claim 1, wherein the synthetic method of the rare earth halide salt comprises: rare earth oxide and halonate are mixed according to a mole ratio of 1: (3-5) mixing, adding deionized water, and heating to remove excessive halogen acid to obtain the rare earth halide salt.
3. A rare earth doped lanthanum oxyhalide nanocrystal having a core-shell structure obtained by the synthesis method of any one of claims 1-2.
4. Use of rare earth doped lanthanum oxyhalide nanocrystals with core-shell structure as recited in claim 3 as rare earth up-conversion luminescent materials.
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