WO2012162858A1 - Procédés de préparation de nanoparticules fluorescentes dopées avec des terres rares, solution de nanoparticules et système associés - Google Patents

Procédés de préparation de nanoparticules fluorescentes dopées avec des terres rares, solution de nanoparticules et système associés Download PDF

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WO2012162858A1
WO2012162858A1 PCT/CN2011/000936 CN2011000936W WO2012162858A1 WO 2012162858 A1 WO2012162858 A1 WO 2012162858A1 CN 2011000936 W CN2011000936 W CN 2011000936W WO 2012162858 A1 WO2012162858 A1 WO 2012162858A1
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Prior art keywords
rare earth
solution
earth doped
doped fluorescent
microreactor
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PCT/CN2011/000936
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English (en)
Chinese (zh)
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WO2012162858A8 (fr
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付敏
应盈
刘涛
廖建平
马熠龙
弗兰克·劳舍尔
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拜尔技术工程（上海）有限公司
拜尔技术服务有限公司
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Priority to PCT/CN2011/000936 priority Critical patent/WO2012162858A1/fr
Priority to CN201180070655.0A priority patent/CN103502389B/zh
Priority to PCT/EP2012/060258 priority patent/WO2012164024A1/fr
Publication of WO2012162858A1 publication Critical patent/WO2012162858A1/fr
Publication of WO2012162858A8 publication Critical patent/WO2012162858A8/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
    • C09K11/7777—Phosphates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F17/00—Compounds of rare earth metals
    • C01F17/30—Compounds containing rare earth metals and at least one element other than a rare earth metal, oxygen or hydrogen, e.g. La4S3Br6
    • C01F17/36—Compounds containing rare earth metals and at least one element other than a rare earth metal, oxygen or hydrogen, e.g. La4S3Br6 halogen being the only anion, e.g. NaYF4
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
    • C09K11/7772—Halogenides
    • C09K11/7773—Halogenides with alkali or alkaline earth metal
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
    • C09K11/778—Borates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
    • C09K11/7795—Phosphates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C01P2002/54—Solid solutions containing elements as dopants one element only
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer

Definitions

  • the invention relates to a method and system for continuously preparing rare earth doped fluorescent nanoparticles and solutions thereof. Background technique
  • rare earth doped fluorescent nanoparticles are characterized by absorption and luminescence properties that are only related to the particle composition and independent of the size and distribution of the particles themselves.
  • Rare-earth doped fluorescent nanoparticles are widely used in functional films, biomarkers, solar cells, lasers, high-density data storage, submarine communications, large-screen displays, detection, and light-emitting diodes.
  • a commonly used method for preparing rare earth doped fluorescent nanoparticles is a solvent method.
  • the cation source compound and the anion source compound are used as a reaction medium and a surfactant in a high boiling point solvent, and the reaction temperature is usually 200 ° C or more for several hours.
  • Riwotzki et al. use La(NO 3 )*7H 2 O, EuCl 3 , H 2 O as the cation source compound, pity acid as the anion source compound, triethylhexyl phosphate as the organic solvent for controlling crystal growth, adding trisin
  • the amine was a chelate compound, and the CePO 4 :Tb fluorescent nanoparticles were synthesized by reacting at 200 ° C for 16 hours. The fluorescent nanoparticle size is about 5 nm. They also synthesized LaPO 4 :Eu fluorescent nanoparticles by the same method (J. Phys. Chem. B 2000, 104, 2824-2828).
  • US20030032192A1 discloses a method for the synthesis of rare earth doped fluorescent nanoparticles by a solvothermal process based on a batch process. This method combines an anion source compound, a cation source compound, and at least one organic solvent for controlling crystal growth to form a mixed solution, and the reaction is continued at 200 ° C or more for 4 hours or more.
  • the rare earth-doped fluorescent nanoparticles obtained by this method have high crystallinity, monodispersity, small particle size (less than 20 nm), high luminescence intensity, and high product yield. Summary of the invention
  • the present invention provides a method of continuously preparing a rare earth doped fluorescent nanoparticle solution.
  • the method includes the following steps:
  • the mixed solution is allowed to stand in a microreactor at a preset temperature for a predetermined time to obtain the rare earth doped fluorescent nanoparticle solution, wherein the microreactor comprises a micromixing device and a micro a heat exchange device for continuously mixing the mixed solution, the micro heat exchange device for adjusting a temperature of the microreactor to the predetermined temperature.
  • the method further includes the steps of: controlling the microreactor pressure to maintain the rare earth doped fluorescent nanoparticle solution in a liquid phase.
  • the microreactor pressure is from 1 bar to 100 bar, preferably from 1 bar to 30 bar, more preferably from 1 bar to 10 bar.
  • the rare earth doped fluorescent nanoparticles are selected from the group consisting of:
  • Ln represents a lanthanoid element, Y or Sc
  • D represents Ba, Sr or Ca
  • E represents Cu, Ag, Eu, Bi, Al or Au
  • G represents Pr, Tm, Er, Yb or Ho
  • Q represents Gd, Y, Li or K
  • W represents Tb or Dy
  • A is selected from one or more of the following Li, Na, K:, Rb, Mg 5 , Bao. 5 , Cao. 5 and Sr Q . 5; Department element.
  • the rare earth doped fluorescent nanoparticles are preferably selected from the group consisting of: LnPO 4 : Ce: W,
  • the rare earth miscellaneous fluorescent nanoparticles are more preferably one or more of the following:
  • the pre-set temperature of the microreactor is 200 ° C or higher, preferably 250 ° C to 400 ° C, more preferably 250 ° C to 340 ° C.
  • the preset residence time of the mixed solution in the microreactor is 30s ⁇ 7200s, preferably 150s to 3600s, more preferably 600s to 2400s.
  • At least one pre-micro heat exchanger is disposed at the front end of the microreactor, and the pre-micro heat exchanger is used to heat the mixed solution.
  • the temperature of the premixed micro heat exchanger for heating the mixed solution may generally be higher than or equal to a preset temperature of the microreactor, for example, 200 ° C or higher, preferably 250 ° C to 400 ° C, more preferably 250 °C ⁇ 360° ( .
  • the residence time of the mixed solution in the pre-microheat exchanger is 9s to 900s, preferably 0.18s to 72s, more preferably 0.9s to 36s.
  • the post micro heat exchanger for cooling the rare earth doped fluorescent nanoparticle solution to a preset temperature generally lower than the microreactor For example, it is 200 ° C or less, preferably 150 ° C or less.
  • the residence time of the rare earth doped fluorescent nanoparticle solution in the post micro heat exchanger is 9s to 900 s, preferably 0.18 s to 72 s, more preferably 0.9 s to 36 s.
  • the mixed solution contains water.
  • the presence of water causes the rare earth miscellaneous fluorescent nanoparticles to be rod-shaped.
  • the water may be derived from an aqueous cationic source compound or directly added water.
  • the rare earth doped fluorescent nanoparticles can be spherical.
  • the rare earth doped fluorescent nanoparticles are metal salt nanoparticles comprising a matrix nanocrystal carrying at least one dopant.
  • the matrix nanocrystals are selected from one or more of the group consisting of phosphates, vanadates, borates, silicates and fluoride salts.
  • the cationic element of the matrix nanocrystal is selected from one or more of the group consisting of ruthenium, osmium main element and rare earth element.
  • the dopant is selected from one or more of the following: lanthanides, lanthanum and cerium. According to one embodiment of the present invention, there is provided a method of continuously preparing rare earth doped fluorescent nanoparticles. The method includes the following steps:
  • the rare earth doped fluorescent nanoparticle solution prepared by any one of the above methods is mixed with a polar solvent to form a suspension; and the suspension is separated to obtain the rare earth doped fluorescent nanoparticles.
  • the polar solvent is selected from one or more of the following: methanol, ethanol, isopropanol, butanol, methyl ethyl ketone and acetone.
  • the present invention provides a system for continuously preparing a rare earth doped fluorescent nanoparticle solution.
  • the system includes:
  • a mixer for mixing a cation source compound, an anion source compound and at least one solvent for controlling crystal growth of the rare earth doped fluorescent nanoparticles to form a mixed solution, a pre-micro heat exchanger for heating The mixed solution,
  • At least one microreactor for allowing the mixed solution to remain at a predetermined temperature for a predetermined time to obtain the rare earth doped fluorescent nanoparticle solution, wherein the microreactor comprises a micromixing device and a micro heat exchange device for continuously mixing the mixed solution, the micro heat exchange device for adjusting a temperature of the micro reactor to the preset temperature,
  • the present invention provides a system for continuously preparing rare earth doped fluorescent nanoparticles.
  • the system includes:
  • a mixer for mixing a cationic source compound, an anion source compound, and at least one solvent for controlling crystal growth of the rare earth miscellaneous fluorescent nanoparticles to form a mixed solution
  • At least one microreactor for allowing the mixed solution to remain at a predetermined temperature for a predetermined time to obtain a rare earth doped fluorescent nanoparticle solution
  • the microreactor comprises a micromixing device and a a micro heat exchange device for continuously mixing the mixed solution, the micro heat exchange device for adjusting a temperature of the micro reactor to the preset temperature
  • a post-micro heat exchanger for cooling the rare earth miscellaneous fluorescent nanoparticle solution
  • a pressure controller for controlling the pressure of the system, and the mixed solution and the rare earth doped fluorescent nanoparticle solution Maintain the liquid phase
  • a mixing device for mixing the rare earth doped fluorescent nanoparticle solution with a polar solvent to form a suspension
  • a separation device for separating the suspension to obtain the rare earth doped fluorescent nanoparticles is 10 ⁇ to 2000 ⁇ , preferably 25 ⁇ to 1000 ⁇ .
  • the microreactor has a specific surface area of not less than 800 l/m, preferably not less than 1000 l/m, further Preferably it is not less than 1200 l/m.
  • the front micro heat exchanger has a specific surface area of not less than 20,000 1 / m, preferably not less than 25,000 1 / m, more preferably not less than 30,000 l / m.
  • the post micro heat exchanger has a specific surface area of not less than 20,000 1 / m, preferably not less than 25,000 1 / m, more preferably not less than 30,000 l / m.
  • the pre-micro heat exchanger and the post micro heat exchanger may be the same or different.
  • the system is equipped with at least one pressure controller for controlling the pressure of the system, the pressure of the system being 1 bar to 100 bar, preferably 1 bar to 30 bar, more preferably 1 bar to 10 bar D
  • the mixer in the system for continuously preparing rare earth doped fluorescent nanoparticles or solutions is a micromixer for mixing two or more fluids.
  • the internal channel size of the micromixer is 10 ⁇ to 2000 ⁇ , preferably 25 ⁇ to 1000 ⁇ .
  • the invention has the following characteristics:
  • the invention adopts a microreactor to realize continuous synthesis of rare earth doped fluorescent nanoparticles and a solution thereof.
  • the microreactor enables precise control of temperature and residence time.
  • the material is uniformly mixed instantaneously in precise proportions, shortening reaction time, no amplification effect, and high product quality repeatability.
  • the present invention prepares fluorescent nanoparticles of different morphologies by changing the cation source and/or controlling the water content in the mixed solution.
  • the microreactor used in the present invention is provided with a micro heat exchange device and a micromixing device.
  • the micro heat exchange device ensures a large specific surface area and has great heat exchange and mixing efficiency; the micro-mixing device increases the lateral disturbance of the mixed solution, thereby effectively reducing the fluid velocity distribution of the mixed solution in the reaction channel, and making the mixed solution
  • the residence time in the microreactor is consistent, thereby ensuring the particle size of the fluorescent nanoparticles.
  • the solvent used in the present invention to control the growth of the rare earth doped fluorescent nanoparticle crystal is a high temperature resistant solvent, so that the reaction can be It is carried out at a high reaction temperature. Further introduced pressure controllers allow the reaction to proceed at higher reaction temperatures, shortening the reaction time and increasing the crystallinity of the fluorescent nanoparticles.
  • Figure 1 Work of preparing a rare earth doped fluorescent nanoparticle using a microreactor according to an embodiment of the present invention. Schematic diagram of the art process.
  • Figure 2 Schematic diagram of a process for preparing rare earth doped fluorescent nanoparticles using a microreactor and a post micro heat exchanger according to one embodiment of the present invention.
  • FIG. 3 Schematic diagram of a process for preparing rare earth doped fluorescent nanoparticles using a microreactor, a pre-micro heat exchanger, a microreactor, a post micro heat exchanger, and a pressure controller in accordance with one embodiment of the present invention.
  • Figure 4 Schematic diagram of a process flow for preparing rare earth doped fluorescent nanoparticles in accordance with one embodiment of the present invention.
  • FIG sample obtained in accordance with one embodiment of the present invention the embodiment 18 LaPO 4: Eu phosphor TEM images of nanoparticles.
  • FIG. 14 Transmission electron micrograph of sample 14 CePO 4: Tb fluorescent nanoparticles obtained in accordance with an embodiment of the present invention.
  • the drawings are used to further describe the specific embodiments and methods of the present disclosure, and the accompanying drawings are intended to be illustrative and not restrictive. detailed description The invention is further illustrated below in conjunction with specific embodiments. It is to be understood that the examples are merely illustrative of the invention and are not intended to limit the scope of the invention. In addition, it should be understood that various changes and modifications may be made by those skilled in the art in the scope of the invention.
  • the rare earth doped fluorescent nanoparticle solution is obtained by staying for a predetermined time, wherein the microreactor comprises a micro mixing device and a micro heat exchange device.
  • the microreactor front end is provided with at least one pre-micro heat exchanger, and the mixed solution is heated to above 200 ° C; at the rear end of the micro heat exchanger, at least one post micro heat exchanger is disposed, and the rare earth is The doped fluorescent nanoparticle solution is cooled to below the predetermined temperature.
  • the rare earth doped fluorescent nanoparticle solution is taken out from the microreactor and collected, a polar solvent is added to form a suspension, the suspension is centrifuged to remove the supernatant solution after centrifugation, and the above process is repeated to wash the fluorescent nanoparticles.
  • a purified rare earth doped fluorescent nanoparticle precipitate is obtained, and the rare earth doped fluorescent nanoparticle is obtained by drying the rare earth doped fluorescent nanoparticle precipitate in a vacuum oven for several hours at a certain temperature.
  • 1 is a process flow diagram in accordance with one embodiment of the present invention.
  • the mixed solution is sent to the microreactor 100 via a syringe pump 600 to obtain a rare earth doped fluorescent nanoparticle solution.
  • the cationic precursor solution is sent to the micromixer 400 via the injection pump 600a, and the anionic precursor solution is sent to the micromixer 400 via the syringe pump 600b, and the cationic precursor solution and the anion precursor solution are mixed in the micromixer 400 to form a mixed solution.
  • the mixed solution flows through the microreactor 100 to obtain a rare earth doped fluorescent nanoparticle solution, and the rare earth doped fluorescent nanoparticle solution flows through the post micro heat exchanger 300 to be cooled to room temperature.
  • the cationic precursor solution is sent to the micromixer 400 via a syringe pump 600a, and the anion precursor solution is sent to the micromixer 400 via a syringe pump 600b.
  • the cationic precursor solution and the anion precursor solution are mixed in the micromixer 400 to form a mixed solution.
  • the mixed solution is heated to 200 ° C or higher through a pre-microheat exchanger 200, it enters the micro-reactor 100 to obtain a rare earth-doped fluorescent nano-particle solution, and the rare-earth doped fluorescent nano-particle solution flows through a post-micro heat exchanger.
  • the polar solvent is fed into the system via a syringe pump 600c, and mixed with the cooled rare earth doped fluorescent nanoparticle solution in a micromixer 700 to form a suspension.
  • the rare earth doped fluorescent nanoparticle solution is cooled to 100 ⁇ or less, and it is more preferred to cool the rare earth doped fluorescent nanoparticle solution to 50 ° C or lower.
  • the solvent for controlling the growth of the rare earth miscellaneous fluorescent nanoparticle crystal is selected from one or more of the following: mercapto phosphate, alkyl phosphodiester, alkyl phosphate triester, tridecylphosphine and three Alkyl phosphine oxide.
  • the solvent for controlling the growth of the rare earth doped fluorescent nanoparticle crystals is preferably one or more of the following: Preferred are alkyl phosphate triesters, tridecylphosphines and tridecylphosphine oxides.
  • the solvent for controlling the growth of the rare earth doped fluorescent nanoparticle crystal is more preferably one or more of the following: mercaptophosphoric acid triester is preferably tributyl phosphate, trioctyl phosphate; trialkylphosphine is preferably three Ethylphosphine, tripropylphosphine, tributylphosphine, tri-sec-butylphosphine, tripentylphosphine, trihexylphosphine, trioctylphosphine; trimethylphosphine oxide, triethylphosphine oxide, tripropyl oxygen Phosphine, tributylphosphine oxide, tri-sec-butylphosphine oxide, tripentylphosphine oxide, trihexylphosphine oxide and trioctylphosphine oxide.
  • the cation source compound is selected from one or more of the following: chloride salt, bromide salt, acetate salt, nitrate salt, fluoride salt, iodide salt, trifluoroacetate salt, hydrated chloride salt, hydrated Bromide, hydrated acetate, hydrated nitrate, hydrated fluoride salt, hydrated iodized salt, hydrated trifluoroacetic acid and metal oxide.
  • the anion source compound is selected from one or more of the following: a free acid containing an anion source, a free acid containing an anion source, and an organic compound capable of releasing an anion at the reaction temperature.
  • the anion source compound is preferably one or more of the following: phosphoric acid, boric acid, sulfuric acid, silicic acid, sodium fluoride, Ln(CF 3 COO) 3 (Ln is selected from one or more of the following: Li, Na , K, Rb, Mg 0 . 5 , Bao. 5 , Cao. 5 or Sr 5 , lanthanides, lanthanum or cerium), NaF, NH 4 HF 2 , NH 4 F and sodium metavanadate.
  • the mixed solution further contains a metal chelate.
  • the metal chelate is selected from one or more of the following: dihexyl ether, diphenyl ether, didecyl ether, dioctyl ether, dibutyl ether, dipentyl ether, diheptyl ether, diisoamyl ether, B Diol dibutyl ether, diethylene glycol dibutyl ether, hexadecane, octadecyl, eicosane, tetradecyl, dihexylamine, trioctylamine, di(2-ethylhexyl)amine and tri 2-ethylhexyl)amine.
  • the mixed solution may be used for a cation source compound, an anion source compound, and at least one
  • the solvent for controlling the growth of the rare earth doped fluorescent nanoparticle crystal is directly mixed; or may be formed by mixing a cationic precursor solution and an anionic precursor solution.
  • the concentration range of each substance is as follows:
  • the molar concentration of the cation-derived compound is 0.001 mol/L to 2.5 mol/L, preferably 0.01 mol/L to 0.7 mol/L, more preferably 0.05 mol/L to 0.4 mol/L.
  • the molar concentration of the anion source compound is from 0.001 mol/L to 2.5 mol/L, preferably from 0.01 mol/L to 0.7 mol/L, more preferably from 0.05 mol/L to 0.4 mol/L.
  • the molar ratio of the anion source compound to the cation source compound is greater than
  • the cation source compound and/or the anion source compound is a solid or viscous liquid at room temperature, it is heated to a liquid in a heatable container at a temperature ranging from room temperature to 200 ° C, preferably room temperature to 100 ° ° ( .
  • the cationic precursor solution comprises a cationic source compound and at least one solvent for controlling crystal growth of the rare earth doped fluorescent nanoparticles;
  • the precursor solution contains an anion source compound and at least one solvent for dispersing the anion source compound.
  • the step of preparing the cationic precursor solution comprises: mixing a solvent comprising a cation source compound and at least one solvent for controlling crystal growth of the rare earth doped fluorescent nanoparticles, and stirring until the cation source compound dissolves.
  • adding a low-boiling polar solvent to help dissolve the cation source compound further optionally adding a metal chelate compound to help dissolve the cation source compound, and replacing the crystallization water in the cation source compound; distilling off the solution in the solution
  • the low boiling point polar solvent, the crystal water in the above solution may be distilled off or may be retained.
  • the cationic precursor When the cationic precursor is a solid or viscous liquid at room temperature, it is heated to a liquid in a heatable container at a temperature ranging from room temperature to 200 ° C, preferably room temperature to 100 ° C.
  • the low boiling polar solvent is selected from one or more of the following: methanol, ethanol, propanol, isobutanol, butanol
  • the step of preparing the anion precursor solution comprises: mixing an anion source compound and at least one solvent for dispersing or dissolving the anion source compound, heating and stirring until a transparent homogeneous solution is formed.
  • the anion precursor is a solid or viscous liquid at room temperature, it is heated to a liquid in a heatable container at a temperature ranging from room temperature to 200 ° C, preferably from room temperature to 100 ° C.
  • the solvent for dispersing the anion source compound is selected from one or more of the following: mercapto phosphate, mercaptophosphoric acid diester, alkyl phosphate triester, tridecylphosphine or trialkylphosphine oxide, two Hexyl ether, diphenyl ether, didecyl ether, dioctyl ether, dibutyl ether, dipentyl ether, diheptyl ether, diisoamyl ether, ethylene glycol dibutyl ether, diethylene glycol dibutyl ether, hexadecane , 18 ⁇ , 20 ⁇ , tetradecane, dihexylamine, trioctylamine, bis(2-ethylhexyl)amine and tris(2-ethylhexyl)amine.
  • the cationic precursor solution and the anionic precursor solution may be mixed by conventional agitation or may be fed into a micromixer by a constant flow pump.
  • the constant current pump may be selected from the group consisting of a HPLC pump, a plug pump, and the like.
  • the concentration range of each substance is as follows:
  • the molar concentration of the cation source compound is 0.001 mol/L to 2.5 mol/L, preferably 0.01 mol/L to 0.7 mol/L, more preferably 0.05 mol/L to 0.4 mol/L.
  • the molar concentration of the anion source compound is from 0.001 mol/L to 2.5 mol/L, preferably from 0.01 mol/L to 0.7 mol/L, more preferably from 0.05 mol/L to 0.4 mol/L.
  • the molar ratio of the anion source compound to the cation source compound is more than 0.5, preferably 0.5 to 10, more preferably 0.8 to 5.
  • the temperature of the mixed solution should be lower than the preset temperature of the microreactor, preferably 200 ° C or lower, more preferably 150 ° C or lower.
  • the rare earth doped nano fluorescent particles prepared by the invention are widely used in the fields of functional films, biomarkers, solar cells, lasers, high-density data storage, submarine communication, large-screen display, detection, and light-emitting diodes.
  • the experimental conditions in which the specific conditions are not specified in the following examples are usually in accordance with conventional conditions, such as a catalyst chemical operation manual, or in accordance with the conditions recommended by the manufacturer.
  • the front micro heat exchanger is a coaxial micro heat exchanger manufactured by Ehrfeld Mikrotechnik Bayer Technology Services GmbH with a volume of V « 0.3 ml and an area of A * 0.0076 m 2 .
  • the microreactor is a sandwich reactor of Bayer Elfeld Microtech, volume V « 30 ml, area A « 0.03 m 2 .
  • the post-micro heat exchanger is a coaxial micro heat exchanger from Bayer Elfeld Microtechnology, volume V 3 ⁇ 4 0.3 ml, area A * 0.0076 m 2 .
  • the micromixer is a valve micromixer from Bayer Elfeld Microtech or a self-contained T-type micromixer.
  • the microchannel size of the valve micromixer is ⁇ and 210 ⁇ .
  • the pressure controller is selected from Swagelok's pressure-controlled wide or Bayer Elfeld microtechnology pressure controllers.
  • the characterization methods of rare earth doped fluorescent nanoparticles are as follows:
  • the obtained rare earth doped fluorescent nanoparticles were diluted with chloroform and subjected to optical performance tests.
  • the excitation spectrum of the sample was measured using a Specord 40 (Analytik Jena) ultraviolet-visible spectrophotometer, and the same solution was subjected to fluorescence spectroscopy using a Fluorolog 3-22 (HORIBA Jobin Yvon) type spectrophotometer. When the fluorescence spectrum was measured, the excitation wavelength was 277 nm.
  • trioctylphosphine oxide 44 g was mixed, and the mixture was stirred with heating to 80 ° C in a flask until a homogeneous transparent solution was formed.
  • 22.5 mmol of CeCl 3 -7H 2 O and 7.5 mmol of TbCl 3 -6H 2 O were placed in the above vessel, and stirred at 80 ° C until the powder was completely dissolved.
  • the above solution was vacuum distilled at 50 ° C to remove water to form a cationic precursor solution;
  • the cationic precursor solution and the anion precursor solution were mixed with a T-type micromixer by a syringe pump at a certain volume flow rate (see Table 1) to form a mixed solution.
  • the mixed solution flows through the pre-micro heat exchanger, the microreactor, the post-micro heat exchanger and the pressure controller, and obtains a rare earth miscellaneous fluorescent nanoparticle solution by reaction, and the process flow chart is shown in FIG. 3 .
  • the preset temperatures for the pre-micro heat exchangers and microreactors are shown in Table 1.
  • the preset temperature of the post micro heat exchanger is room temperature.
  • the preset residence time of the mixed solution in the microreactor is shown in Table 1.
  • the system pressure is shown in Table 1.
  • the rare earth doped fluorescent nanoparticle solution is taken out from the reaction system and collected, and a mixed solution of methanol and isopropyl alcohol containing 4 times by volume of the rare earth doped fluorescent nanoparticle solution is added (methanol to isopropanol volume ratio is 1:10) Mix to form a suspension.
  • the suspension was centrifuged to remove the supernatant solution after centrifugation and sedimentation to obtain a rare earth doped fluorescent nanoparticle precipitate, and the above washing process was repeated three times to obtain a purified rare earth doped fluorescent nanoparticle precipitate.
  • the rare earth doped fluorescent nanoparticle precipitates were dried in a vacuum oven at 60 ° C for 3 hours to obtain rare earth miscellaneous fluorescent nano fluorescent particles.
  • Table 1 shows the preparation conditions of rare earth doped fluorescent nanoparticles.
  • Figure 12 is an absorption spectrum of a rare earth doped fluorescent nanoparticle sample Y1.
  • trioctylphosphine oxide 44 g was mixed, and the mixture was heated and stirred in a vessel to 80 ° C until a homogeneous transparent solution was formed.
  • 22.5mmol CeCl 3 -7H 2 O and 7.5mmol TbCl 3 -6H 2 O were mixed with the above solution, and vacuum distilled at 50 ° C to remove water to form a cationic precursor solution;
  • the cationic precursor solution and the anion precursor solution were mixed with a T-type micromixer by a syringe pump at a flow rate of a certain volume (see Table 2) to form a mixed solution.
  • the mixed solution flows through the pre-micro heat exchanger, the microreactor, the post micro heat exchanger and the pressure controller in sequence, and a rare earth doped fluorescent nanoparticle solution is obtained through the reaction.
  • the pre-set temperature of the pre-micro heat exchanger and microreactor is 320 °C.
  • the preset temperature of the post micro heat exchanger is room temperature.
  • the preset residence time of the mixed solution in the microreactor is shown in Table 2, and the system pressure is 5 bar.
  • the rare earth doped fluorescent nanoparticle solution is taken out from the reaction system and collected, and a mixture of methanol and isopropyl alcohol (methanol and isopropanol volume ratio of 1:10) containing 4 times of the rare earth doped fluorescent nanoparticle solution is added to form a mixture. suspension.
  • the suspension was centrifuged to remove the supernatant solution after centrifugation to obtain a rare earth doped fluorescent nanoparticle precipitate, and the above washing process was repeated three times to obtain a purified rare earth doped fluorescent nanoparticle precipitate.
  • the rare earth doped fluorescent nanoparticle precipitate was dried in a vacuum oven at 60 ° C for 3 hours. The rare earth doped fluorescent nanoparticles are obtained after time.
  • Table 2 shows the preparation conditions of rare earth doped fluorescent nanoparticles.
  • Figure 5 is a transmission electron micrograph of a rare earth doped fluorescent nanoparticle sample Y5.
  • Figure 12 is an absorption spectrum of rare earth doped fluorescent nanoparticle samples Y4 and Y5.
  • trioctylphosphine oxide 44 g was mixed, and the mixture was heated and stirred in a vessel to 80 ° C until a homogeneous transparent solution was formed.
  • the cationic precursor solution and the anion precursor solution were preheated to 60 ° C, they were mixed by a syringe pumping T-type micromixer at a certain volume flow rate (see Table 3) to form a mixed solution.
  • the mixed solution flows through the pre-micro heat exchanger, the microreactor, the post-micro heat exchanger and the pressure controller, and the rare earth doped fluorescent nanoparticle solution is obtained through the reaction.
  • the pre-set temperature of the pre-micro heat exchanger and microreactor is 320 °C.
  • the preset temperature of the post micro heat exchanger is room temperature.
  • the preset residence time of the mixed solution in the microreactor is shown in Table 3, and the system pressure is 4 bar.
  • the rare earth doped fluorescent nanoparticle solution is taken out from the reaction system and collected, and a mixture of methanol and isopropyl alcohol (methanol and isopropanol volume ratio of 1:10) containing 4 times of the rare earth doped fluorescent nanoparticle solution is added to form a mixture. suspension.
  • the suspension was centrifuged to remove the supernatant solution after centrifugation to obtain a rare earth doped fluorescent nanoparticle precipitate.
  • the above washing process was repeated 3 times to obtain a purified rare earth doped fluorescent nanoparticle precipitate, and the rare earth doped fluorescent nanoparticle precipitate was dried in a vacuum oven at 60 ° C for 3 hours to obtain rare earth doped fluorescent nanoparticles.
  • Table 3 shows the preparation conditions of rare earth doped fluorescent nanoparticles.
  • Figure 7 is a transmission electron micrograph of a rare earth doped fluorescent nanoparticle sample Y8.
  • Figure 12 is an absorption spectrum of rare earth doped fluorescent nanoparticle samples Y7 and Y9. Preparation conditions of CePO 4 : Tb fluorescent nanoparticles
  • trioctylphosphine oxide 60 g was mixed, and the mixture was heated and stirred in a vessel to 80 Torr until a homogeneous transparent solution was formed.
  • 40 mmol of LaCl 3 -7H 2 O and 2 mmol of EuCl 3 were mixed with the above solution, and vacuum distilled at 50 ° C to remove water to form a cationic precursor solution;
  • the cationic precursor solution and the anion precursor solution were mixed with a T-type micromixer by a syringe pump at a certain volume flow rate (see Table 4) to form a mixed solution.
  • the mixed solution sequentially flows through the pre-micro heat exchanger, the micro-reactor and the post-micro heat exchanger, and a rare earth miscellaneous fluorescent nanoparticle solution is obtained through the reaction.
  • the preset temperatures of the pre-micro heat exchanger and microreactor are shown in Table 4.
  • the preset temperature of the rear micro heat exchanger is room temperature.
  • the preset residence time of the mixed solution in the microreactor is shown in Table 4.
  • the rare earth doped fluorescent nanoparticle solution is taken out from the reaction system and collected, and a mixture of methanol and isopropyl alcohol (methanol and isopropanol volume ratio of 1:10) containing 4 times of the rare earth doped fluorescent nanoparticle solution is added to form a mixture. suspension.
  • the suspension was centrifuged to remove the supernatant solution after centrifugation to obtain a rare earth doped fluorescent nanoparticle precipitate, and the above washing process was repeated three times to obtain a purified rare earth doped fluorescent nanoparticle precipitate.
  • the rare earth doped fluorescent nanoparticles were dried in a vacuum oven at 60 ° C for 3 hours to obtain rare earth doped fluorescent nanoparticles. Table 4 shows the preparation conditions of rare earth doped fluorescent nanoparticles.
  • Figure 7 is a transmission electron micrograph of a rare earth doped fluorescent nanoparticle sample Y12.
  • Figure 13 is an absorption spectrum of rare earth doped fluorescent nanoparticle samples Y10, Y1 1.
  • Table 4 Preparation conditions of LaPO 4 : Eu fluorescent nanoparticles
  • the rare earth doped fluorescent nanoparticle solution is taken out from the reaction system and collected, and a mixture of methanol and isopropyl alcohol (methanol and isopropanol volume ratio of 1:10) containing 4 times of the rare earth doped fluorescent nanoparticle solution is added to form a mixture. suspension.
  • the suspension was centrifuged to remove the supernatant solution after centrifugation to obtain a rare earth doped fluorescent nanoparticle precipitate, and the above washing process was repeated three times to obtain a purified rare earth doped fluorescent nanoparticle precipitate.
  • the rare earth doped fluorescent nanoparticles were dried in a vacuum oven at 60 ° C for 3 hours to obtain rare earth doped fluorescent nanoparticles.
  • Table 5 shows the preparation conditions of rare earth doped fluorescent nanoparticles.
  • Table 5 Preparation conditions of LaPO 4 : Eu fluorescent nanoparticles
  • the cationic precursor solution and the anion precursor solution were preheated to 60 Torr, they were mixed by a syringe pumping T-type micromixer at a certain volume flow rate (see Table 6) to form a mixed solution.
  • the mixed solution flows through a microreactor and a post micro heat exchanger, and is reacted at 300 ° C to obtain a rare earth doped fluorescent nanoparticle solution.
  • the preset temperature of the post micro heat exchanger is room temperature.
  • the preset residence time of the mixed solution in the microreactor is shown in Table 6.
  • the rare earth doped fluorescent nanoparticle solution is taken out from the reaction system and collected, and a mixture of methanol and isopropyl alcohol (methanol and isopropanol volume ratio of 1:10) containing 4 times of the rare earth doped fluorescent nanoparticle solution is added to form a mixture. suspension.
  • the suspension was centrifuged to remove the supernatant solution after centrifugation to obtain a rare earth doped fluorescent nanoparticle precipitate, and the above washing process was repeated three times to obtain a purified rare earth doped fluorescent nanoparticle precipitate.
  • the rare earth doped fluorescent nanoparticles were dried in a vacuum oven at 60 ° C for 3 hours to obtain rare earth doped fluorescent nanoparticles. Table 6 shows the preparation conditions of rare earth doped fluorescent nanoparticles.
  • LaPO 4 Eu fluorescent nanoparticles were redispersed in a chloroform solution for characterization.
  • Figures 8, 9, and 10 are transmission electron micrographs of rare earth doped fluorescent nanoparticles, respectively, Y18, ⁇ 19, and ⁇ 20.
  • Table 6 Preparation conditions of LaPO 4 : Eu fluorescent nanoparticles
  • the cationic precursor solution and the anion precursor solution were preheated to 60 ° C, and then mixed with a T-type micromixer by a syringe pump at a volume flow rate of 1 ml/min to form a mixed solution.
  • the mixed solution flows through the microreactor and the post micro heat exchanger, and is reacted at 300 ° C to obtain a rare earth doped fluorescent nanoparticle solution.
  • the preset temperature of the post micro heat exchanger is room temperature.
  • the preset residence time of the mixed solution in the microreactor is 15 min 0
  • the rare earth doped fluorescent nanoparticle solution is taken out from the reaction system and collected, and a mixture of methanol and isopropyl alcohol (methanol and isopropanol volume ratio of 1:10) containing 4 times of the rare earth doped fluorescent nanoparticle solution is added to form a mixture. suspension.
  • the suspension was centrifuged to remove the supernatant solution after centrifugation to obtain a rare earth doped fluorescent nanoparticle precipitate, and the above washing process was repeated three times to obtain a purified rare earth doped fluorescent nanoparticle precipitate.
  • the rare earth doped fluorescent nanoparticles were dried in a vacuum oven at 60 ° C for 3 hours to obtain rare earth doped fluorescent nanoparticles.
  • Example 8 Preparation of CePO 4 : Tb fluorescent nanoparticles
  • the cationic precursor solution and the anion precursor solution were mixed with a T-type micromixer by a syringe pump at a certain volume flow rate (see Table 7) to form a mixed solution.
  • the mixed solution flows through the microreactor and the post micro heat exchanger, and is reacted at 320 ° C to obtain a rare earth doped fluorescent nanoparticle solution.
  • the preset temperature of the post micro heat exchanger is room temperature, and the preset residence time of the mixed solution in the microreactor is shown in Table 7.
  • the rare earth doped fluorescent nanoparticle solution is taken out from the reaction system and collected, and a mixture of methanol and isopropyl alcohol (methanol and isopropanol volume ratio of 1:10) containing 4 times of the rare earth doped fluorescent nanoparticle solution is added to form a mixture. suspension.
  • the suspension was centrifuged to remove the supernatant solution after centrifugation and sedimentation to obtain a precipitate of the rare earth conjugated fluorescent nanoparticles, and the above washing process was repeated three times to obtain a purified rare earth doped fluorescent nanoparticle precipitate.
  • the rare earth doped fluorescent nanoparticles were dried in a vacuum oven at 60 ° C for 4 hours to obtain rare earth doped fluorescent nanoparticles. Table 7 shows the preparation conditions of rare earth doped fluorescent nanoparticles.
  • the cationic precursor solution and the anion precursor solution were mixed with a T-type micromixer by a syringe pump at a certain volume flow rate (see Table 8) to form a mixed solution.
  • Mixed solution Flowing through the microreactor and the post micro heat exchanger, the rare earth doped fluorescent nanoparticle solution is obtained by reacting at a preset temperature of the micro heat exchanger (see Table 8).
  • the preset temperature of the post micro heat exchanger is room temperature, and the preset residence time of the mixed solution in the microreactor is shown in Table 8.
  • the rare earth doped fluorescent nanoparticle solution is taken out from the reaction system and collected, and a mixture of methanol and isopropyl alcohol (methanol and isopropanol volume ratio of 1:10) containing 4 times of the rare earth doped fluorescent nanoparticle solution is added to form a mixture. suspension.
  • the suspension was centrifuged to remove the supernatant solution after centrifugation and sedimentation to obtain a rare earth doped fluorescent nanoparticle precipitate, and the above washing process was repeated 4 times to obtain a purified rare earth doped fluorescent nanoparticle precipitate.
  • the rare earth doped fluorescent nanoparticles were dried in a vacuum oven at 60 ° C for 4 hours to obtain rare earth doped fluorescent nanoparticles. Table 8 shows the preparation conditions of rare earth doped fluorescent nanoparticles.
  • the cationic precursor solution and the anion precursor solution were mixed with a T-type micromixer by a syringe pump at a flow rate of 0.5 ml/min and 0.5 ml/min, respectively, to form a mixed solution.
  • the mixed solution flows through a pre-micro heat exchanger, a microreactor, a post micro heat exchanger and a pressure controller, and a rare earth doped fluorescent nanoparticle solution is obtained through the reaction.
  • the pre-set temperatures of the pre-micro heat exchanger, microreactor and post-micro heat exchanger are 320 ° C, 300 ° C and 30 ° C.
  • the preset residence time of the mixed solution in the microreactor was 30 min.
  • the system pressure is 3 bar.
  • a mixed solution of methanol and isopropanol (methanol to isopropanol volume ratio of 1:10) was mixed with a rare earth doped fluorescent nanoparticle solution in a valve micromixer by a HPLC pump at a volume flow rate of 4 ml/min to form a suspension.
  • the suspension was centrifuged to remove the supernatant solution after centrifugation to obtain a rare earth doped fluorescent nanoparticle precipitate.
  • the above washing process was repeated 3 times to obtain a purified rare earth doped fluorescent nanoparticle precipitate, and the rare earth doped fluorescent nanoparticle precipitate was dried in a vacuum oven at 60 ° C for 4 hours to obtain a rod-like rare earth doped fluorescent nano fluorescent particle.
  • Fig. 14 is a transmission electron micrograph of the rare earth doped fluorescent nanoparticles obtained in the present example.
  • Example 11 Preparation of NaYF 4 : Yb: Er Fluorescent Nanoparticles
  • the solution was pumped into a T-type micromixer by high performance liquid chromatography at a volume flow rate (see Table 9) to form a mixed solution.
  • the mixed solution flows through the pre-micro heat exchanger, the microreactor and the post-micro heat exchanger to obtain a rare earth doped fluorescent nanoparticle solution.
  • the preset temperatures of the pre-micro heat exchanger and microreactor are shown in Table 9.
  • the preset temperature of the post micro heat exchanger is room temperature.
  • the pre-set residence time of the mixed solution in the microreactor is 15 min.
  • the rare earth miscellaneous fluorescent nanoparticle solution is taken out from the reaction system and collected, and 4 times the volume of the mixed solution of methanol and cyclohexane containing the rare earth doped fluorescent nanoparticle solution is added.
  • the mixed solution is sequentially passed through a pre-micro heat exchanger and a micro-reactor at a flow rate of 1 ml/min at a normal temperature to obtain a rare earth miscellaneous fluorescent nanoparticle solution.
  • the pre-set micro heat exchanger has a preset temperature of 340 °C and the microreactor has a preset temperature of 300 °C.
  • the preset residence time of the mixed solution in the microreactor was 30 min.
  • the rare earth doped fluorescent nanoparticle solution is taken out from the reaction system and collected. After natural cooling, a mixed solution of methanol and isopropanol containing 4 times the volume of the rare earth doped fluorescent nanoparticle solution is added (the ratio of methanol to isopropanol is 1). : 10) Mix to form a suspension. The suspension was centrifuged to remove the supernatant solution after centrifugation to obtain a rare earth doped fluorescent nanoparticle precipitate. The above washing process was repeated 4 times to obtain a purified rare earth doped fluorescent nanoparticle precipitate. The rare earth doped fluorescent nanoparticles were dried in a vacuum oven at 60 ° C for 4 hours to obtain rare earth doped fluorescent nanoparticles.
  • Example 13 Preparation of LaBO 3 : Ce: Dy Fluorescent Nanoparticles
  • trioctyl phosphate 45 ml of trioctyl phosphate and 125 ml of diphenyl ether, and the mixture was heated and stirred in a flask to 50 ° C until the powder was completely dissolved.
  • Water and methanol in the above solution were removed by vacuum distillation at 50 ° C; 40 mmol of phosphoric acid, 30 ml of dihexyl ether and 42 ml of trihexylamine were added to the above solution, and stirred until a homogeneous solution was formed.
  • the mixed solution is sequentially passed through a pre-micro heat exchanger, a microreactor and a pressure controller at a flow rate of 5 ml/min at a normal temperature to obtain a rare earth doped fluorescent nanoparticle solution.
  • the pre-set temperature of the pre-micro heat exchanger is 340 ° C
  • the pre-set temperature of the micro-reactor is 300 ° C
  • the system pressure is 5 bar.
  • the preset residence time of the mixed solution in the microreactor was 6 min.
  • the rare earth doped fluorescent nanoparticle solution is taken out from the reaction system and collected.
  • the mixed solution is preheated to 60 ° C, and sequentially flows through a pre-micro heat exchanger, a microreactor, a post micro heat exchanger and a pressure controller at a flow rate of 1 ml/min to obtain a rare earth doped fluorescent nanoparticle. Solution.
  • the pre-set temperatures of the front micro heat exchanger, microreactor and post micro heat exchanger are 300 ° C, 280 ° C and 25 ° C, respectively, and the system pressure is 5 bar.
  • the pre-set residence time of the mixed solution in the microreactor was 30 min.
  • a mixed solution of methanol and isopropanol (methanol to isopropanol volume ratio of 1:10) was mixed with a rare earth doped fluorescent nanoparticle solution in a broad micromixer by a high performance liquid chromatography pump at a volume flow rate of 4 rnl/min. suspension.
  • the suspension was centrifuged to remove the supernatant solution after centrifugation to obtain a rare earth doped fluorescent nanoparticle precipitate.
  • the above washing process was repeated 3 times to obtain a purified rare earth doped fluorescent nanoparticle precipitate, and the rare earth doped fluorescent nanoparticle precipitate was dried in a vacuum oven at 60 ° C for 3 hours to obtain a rod-like rare earth doped fluorescent nano fluorescent particle.
  • Fig. 14 is a transmission electron micrograph of the rare earth doped fluorescent nanoparticles obtained in the present example.

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Abstract

L'invention concerne des procédés de préparation de nanoparticules fluorescentes dopées avec des terres rares, ainsi qu'une solution de particules et un système associés. Les procédés selon l'invention consistent : à mélanger des composés sources de cations, des composés sources d'anions et au moins un solvant pour réguler la croissance cristalline des nanoparticules fluorescentes dopées avec des terres rares afin d'obtenir une solution de mélange; et à maintenir cette solution de mélange dans un micro-réacteur à une température prédéterminée pendant une durée prédéterminée afin d'obtenir la solution de nanoparticules fluorescentes dopées avec des terres rares, le micro-réacteur comprenant un micro-dispositif de mélange et un micro-échangeur de chaleur. Le micro-dispositif de mélange sert à mélanger de façon continue la solution de mélange et le micro-échangeur de chaleur sert à régler la température du micro-réacteur à la température prédéterminée. Les nanoparticules fluorescentes dopées avec des terres rares présentent une taille uniforme, une cristallinité élevée et une stabilité élevée de qualité de produit.
PCT/CN2011/000936 2011-06-03 2011-06-03 Procédés de préparation de nanoparticules fluorescentes dopées avec des terres rares, solution de nanoparticules et système associés WO2012162858A1 (fr)

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