WO2012162858A1 - 一种稀土掺杂荧光纳米粒子及其溶液的制备方法和系统 - Google Patents

一种稀土掺杂荧光纳米粒子及其溶液的制备方法和系统 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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French (fr)
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WO2012162858A8 (zh
Inventor
付敏
应盈
刘涛
廖建平
马熠龙
弗兰克·劳舍尔
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Bayer Technology and Engineering Shanghai Co Ltd
Bayer AG
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Bayer Technology and Engineering Shanghai Co Ltd
Bayer Technology Services GmbH
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Priority to CN201180070655.0A priority Critical patent/CN103502389B/zh
Priority to PCT/CN2011/000936 priority patent/WO2012162858A1/zh
Priority to PCT/EP2012/060258 priority patent/WO2012164024A1/en
Publication of WO2012162858A1 publication Critical patent/WO2012162858A1/zh
Publication of WO2012162858A8 publication Critical patent/WO2012162858A8/zh
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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 materials, e.g. electroluminescent or chemiluminescent
    • C09K11/08—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials
    • C09K11/77—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing rare earth metals
    • C09K11/7766—Luminescent materials, e.g. electroluminescent or chemiluminescent 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 materials, e.g. electroluminescent or chemiluminescent
    • C09K11/08—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials
    • C09K11/77—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing rare earth metals
    • C09K11/7766—Luminescent materials, e.g. electroluminescent or chemiluminescent 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 materials, e.g. electroluminescent or chemiluminescent
    • C09K11/08—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials
    • C09K11/77—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing rare earth metals
    • C09K11/7766—Luminescent materials, e.g. electroluminescent or chemiluminescent 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 materials, e.g. electroluminescent or chemiluminescent
    • C09K11/08—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials
    • C09K11/77—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing rare earth metals
    • C09K11/7783—Luminescent materials, e.g. electroluminescent or chemiluminescent 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

提供了一种稀土掺杂荧光纳米粒子及其溶液的制备方法和系统。所述方法包括如下步骤：混和阳离子源化合物、阴离子源化合物和至少一种用于控制所述稀土掺杂荧光纳米粒子晶体生长的溶剂形成混合溶液；和，使所述混合溶液在微反应器中在预设定温度停留预设定时间，得到所述稀土掺杂荧光纳米粒子溶液，其中，所述微反应器包括一个微混合装置和一个微换热装置。所述微混合装置用于持续混合所述混合溶液，所述微换热装置用于调节所述微反应器的温度至所述预设定温度。所得稀土掺杂荧光纳米粒子尺寸均一、结晶性高且产品质量稳定性高。

Description

一种稀土掺杂荧光纳米粒子及其溶液的制备方法和系统 技术领域
本发明涉及一种连续制备稀土掺杂荧光纳米粒子及其溶液的方法和系统。 背景技术
常用的无机发光纳米材料分为半导体纳米粒子和稀土惨杂荧光纳米粒子 两种。与半导体纳米粒子相比， 稀土掺杂荧光纳米粒子的特点是吸收和发光性 能仅与粒子组分有关， 与粒子本身的大小和分布无关。
稀土掺杂荧光纳米粒子在功能薄膜、 生物标记、 太阳能电池、 激光、 高密 度数据存储、海底通信、大屏幕显示、检测、发光二极管等领域得到广泛的应用。
制备稀土掺杂荧光纳米粒子常用的方法是溶剂法。在溶剂法中， 阳离子源 化合物和阴离子源化合物以高沸点溶剂作为反应介质和表面活性剂，在反应温 度通常是 200°C以上持续反应几个小时。
己有报道描述用溶剂法制备稀土惨杂荧光纳米粒子的工艺。 例如： K.
Riwotzki等采用 La(NO3)*7H2O、 EuCl3，H2O为阳离子源化合物，憐酸为阴离子 源化合物， 三乙基己基磷酸酯为用于控制晶体生长的有机溶剂， 添加三辛胺为 螯合物， 在 200°C下反应 16小时合成 CePO4:Tb荧光纳米粒子。 该荧光纳米粒 子颗粒尺寸约 5nm。 他们还采用相同的方法合成了 LaPO4:Eu荧光纳米粒子 (J. Phys. Chem. B 2000， 104, 2824-2828)。
US20030032192A1 公开了一种基于批次工艺用溶剂热法合成稀土掺杂荧 光纳米粒子的方法。该方法将阴离子源化合物、阳离子源化合物和至少一种用 于控制晶体生长的有机溶剂混合形成混合溶液， 在 200°C以上持续反应 4个小 时以上。此方法得到的稀土掺杂荧光纳米粒子的颗粒结晶度高、 单分散、 颗粒 尺寸小 （低于 20nm)、 发光强度高以及产品收率高。 发明内容
根据本发明的一个实施例， 本发明提供一种连续制备稀土掺杂荧光纳米 粒子溶液的方法。 所述方法包括以下步骤：
混合阳离子源化合物、 阴离子源化合物和至少一种用于控制所述稀土掺 杂荧光纳米粒子晶体生长的溶剂， 形成一个混合溶液， 和 使所述混合溶液在一个微反应器中在一个预设定温度停留一预设定时 间， 得到所述稀土掺杂荧光纳米粒子溶液， 其中， 所述微反应器包括一个微混 合装置和一个微换热装置， 所述微混合装置用于持续混合所述混合溶液， 所述 微换热装置用于调节所述微反应器的温度至所述预设定温度。
所述方法进一步包括步骤： 控制所述微反应器压力， 使所述稀土掺杂荧 光纳米粒子溶液维持液相。
所述微反应器压力为 lbar~100bar， 优选为 lbar~30bar， 更优选为 1 bar〜10bar。
所述稀土掺杂荧光纳米粒子选自下面的一种：
LnPO4: Ce: W、
LnPO4: Eu、
LnVO4: Ce: W、
LnVO4: Eu、
Ln(VO4)x(PO4)y： B (x+y=l , 其中， 0≤x≤l)、
AYF4: G、
AYC14: G、
AYBr4: G、
NaQF4: Yb: B、
NaQCl4: Yb: B、
NaQBr4: Yb: B、
LnBO3： Ce : W、
LnBO3： Eu、
(YGd)BO3: Eu、
DSO4: B、
DSO4: Mn、 和
Zn2(SiO4): Mn;
其中， Ln代表镧系元素、 Y或 Sc; D代表 Ba、 Sr或 Ca; E代表 Cu、 Ag、 Eu、 Bi、 Al或 Au ; G代表 Pr、 Tm、 Er、 Yb或 Ho; Q代表 Gd、 Y、 Li 或 K; W代表 Tb 或 Dy; A选自下面的一种或多种 Li、 Na、 K：、 Rb、 Mg 5、 Bao.5、 Cao.5和 SrQ.5; B代表镧系元素。
所述稀土掺杂荧光纳米粒子优选自下面的一种： LnPO4: Ce: W、
LaPO4: Eu、
YPO4: Ce: W、
YPO4: Eu、
CePO4: Tb、
LnVO4: Ce: W、
LnVO4: Eu、
LiYF4: Yb： G、
NaYF4: Yb： G、
LnBO3: Ce: W、
LnBO3: Eu、 和
(YGd)BO3: Eu; 其中， Ln代表镧系元素、 Y或 Sc; G代表
Ho; W代表 Tb或 Dy。
所述稀土惨杂荧光纳米粒子更优选自下面的一种或多种：
LaPO4: Ce: Tb、
LaPO4: Ce: Dy、
LaPO4: Eu、
CePO4: Tb、
YVO4: Ce: Tb、
YVO4: Ce: Dy、
YVO4: Eu、
LiYF4: Yb ： G、
NaYF4: Yb ： G、
LaBO3: Ce： Tb、
YBO3: Ce： Tb、
LaBO3: Eu、 和
YBO3: Eu;
其中， G代表 Pr、 Tm
所述微反应器的预设定温度是 200°C以上， 优选 250°C〜400°C， 更优选 250°C〜340°C。
所述混合溶液在所述微反应器中的预设定停留时间是 30s〜7200s， 优选 150s〜3600s， 更优选 600s〜2400s。
所述微反应器前端设置至少一个前置微换热器， 所述前置微换热器用于 加热所述混合溶液。
所述前置微换热器加热所述混合溶液的温度通常可以高于或等于所述微 反应器的预设定温度， 例如 200°C以上， 优选 250°C〜400°C， 更优选 250°C〜 360° ( 。
所述混合溶液在前置微换热器内的停留时间是 9s~900s， 优选 0.18s~ 72s， 更优选 0.9s~36s。
所述微反应器后端设置至少一个后置微换热器， 所述后置微换热器用于 冷却所述稀土掺杂荧光纳米粒子溶液至通常低于所述微反应器的预设定温度， 例如 200°C以下， 优选 150°C以下。
所述稀土掺杂荧光纳米粒子溶液在后置微换热器内的停留时间是 9s〜900 s， 优选 0.18s~ 72s， 更优选 0.9s~36s。
所述混合溶液包含水。 水的存在使稀土惨杂荧光纳米粒子呈棒状。 所述 水可以来自含水的阳离子源化合物， 也可以是直接加入的水。
当所述混合溶液不含水时， 制得稀土惨杂荧光纳米粒子可以呈球状。 所述稀土掺杂荧光纳米粒子为金属盐纳米粒子，包括一个基质纳米晶体负 载至少一种掺杂剂。
所述基质纳米晶体选自下面的一种或多种： 磷酸盐、 钒酸盐、 硼酸盐、 硅 酸盐和氟化盐。
所述基质纳米晶体的阳离子元素选自下面的一种或多种： ΙΑ、 ΠΑ主族元 素和稀土元素。
所述掺杂剂选自下面的一种或多种： 镧系元素、 钇和钪。 根据本发明的一个实施例， 本发明提供的一种连续制备稀土掺杂荧光纳 米粒子的方法。 所述方法包括以下步骤：
将上述任意一种方法制备的稀土掺杂荧光纳米粒子溶液与一极性溶剂混 合形成一悬浮液； 和， 分离所述悬浮液得到所述稀土掺杂荧光纳米粒子。
所述极性溶剂选自下面的一种或多种： 甲醇、 乙醇、 异丙醇、 丁醇、 甲 乙酮和丙酮。 根据本发明的一个实施例， 本发明提供一种连续制备稀土掺杂荧光纳米 粒子溶液的系统。 所述系统包括：
一个混合器， 用于将阳离子源化合物、 阴离子源化合物和至少一种用于 控制所述稀土掺杂荧光纳米粒子晶体生长的溶剂混合形成一个混合溶液， 一个前置微换热器， 用于加热所述混合溶液，
至少一个微反应器，用于使所述混合溶液在一个预设定温度停留一预设定 时间， 得到所述稀土掺杂荧光纳米粒子溶液， 其中， 所述微反应器包括一个微 混合装置和一个微换热装置， 所述微混合装置用于持续混合所述混合溶液， 所 述微换热装置用于调节所述微反应器的温度至所述预设定温度，
一个后置微换热器， 用于冷却所述稀土掺杂荧光纳米粒子溶液， 和 一个压力控制器， 用于控制所述系统的压力， 使所述混合溶液和所述稀土 掺杂荧光纳米粒子溶液维持液相。 根据本发明的一个实施例，本发明提供一种连续制备稀土掺杂荧光纳米粒 子的系统。 所述系统包括：
一个混合器， 用于将阳离子源化合物、 阴离子源化合物和至少一种用于控 制所述稀土惨杂荧光纳米粒子晶体生长的溶剂混合形成一个混合溶液，
一个前置微换热器， 用于加热所述混合溶液，
至少一个微反应器，用于使所述混合溶液在一个预设定温度停留一预设定 时间， 得到一稀土掺杂荧光纳米粒子溶液， 其中， 所述微反应器包括一个微混 合装置和一个微换热装置， 所述微混合装置用于持续混合所述混合溶液， 所述 微换热装置用于调节所述微反应器的温度至所述预设定温度，
一个后置微换热器， 用于冷却所述稀土惨杂荧光纳米粒子溶液， 一个压力控制器， 用于控制所述系统的压力， 使所述混合溶液和所述稀土 掺杂荧光纳米粒子溶液维持液相，
一个混合装置，用于将所述稀土掺杂荧光纳米粒子溶液与一极性溶剂混合 形成一悬浮液， 和
一个分离装置， 用于分离所述悬浮液， 得到所述稀土掺杂荧光纳米粒子。 所述微反应器内部通道尺寸是 10μπι~2000μπι， 优选 25μπι~1000μπι。 所述微反应器的比表面积不小于 800 l/m， 优选不小于 1000 l/m， 进一步 优选不小于 1200 l/m。
所述前置微换热器的比表面积不小于 20,000 1/m,优选不小于 25,000 1/m, 更优选不小于 30,000 l/m。
所述后置微换热器的比表面积不小于 20,000 1/m,优选不小于 25,000 1/m, 更优选不小于 30,000 l/m。
所述前置微换热器与后置微换热器可以相同， 也可以不同。
所述系统安装至少一个压力控制器， 所述压力控制器用于控制所述系统 的压力， 所述系统的压力为 1 bar~100bar， 优选 1 bar ~30 bar, 更优选 1 bar~10 barD
所述连续制备稀土掺杂荧光纳米粒子或溶液的系统中的混合器为一微混 合器， 用于混合二股以上流体。所述微混合器内部通道尺寸为 10μπι~2000μιη， 优选 25μπι ~1000μπι。 本发明与现有技术相比具有以下特点- 本发明采用微反应器实现连续合成稀土掺杂荧光纳米粒子及其溶液。 微 反应器能够实现对温度和停留时间的精确控制， 物料以精确比例瞬间均匀混 合， 缩短了反应时间、 无放大效应， 产品质量重复性高。
本发明通过改变阳离子源和 /或控制混合溶液中的水含量， 制备不同形貌 的荧光纳米粒子。
本发明采用的微反应器带有微换热装置和微混合装置。微换热装置保证了 极大的比表面积， 具有极大的换热和混合效率； 微混合装置增加了混合溶液的 横向扰动， 因而有效降低了混合溶液在反应通道内流体速度分布， 使混合溶液 在微反应器内的停留时间是一致的， 从而保证了荧光纳米粒子的颗粒尺寸均 本发明采用的一种控制所述稀土掺杂荧光纳米粒子晶体生长的溶剂属于 耐高温溶剂， 使反应能够在高反应温度下进行。 进一步引入的压力控制器， 使 得反应能够在更高的反应温度下进行，縮短了反应时间并提高了荧光纳米粒子 的结晶性。 附图说明
图 1.根据本发明的一个实施例采用微反应器制备稀土掺杂荧光纳米粒子的工 艺流程示意图。
图 2.根据本发明的一个实施例采用微反应器和后置微换热器制备稀土掺杂荧 光纳米粒子的工艺流程示意图。
图 3.根据本发明的一个实施例采用微反应器、 前置微换热器、 微反应器、 后 置微换热器和压力控制器制备稀土掺杂荧光纳米粒子的工艺流程示意图。
图 4.根据本发明的一个实施例弓 I入极性溶剂制备稀土掺杂荧光纳米粒子的工 艺流程示意图。
图 5. 根据本发明的一个实施例得到的样品 5 CePO4: Tb荧光纳米粒子的透射 电镜照片。
图 6. 根据本发明的一个实施例得到的样品 8 CePO4: Tb荧光纳米粒子的透射 电镜照片。
图 7. 根据本发明的一个实施例得到的样品 12 LaPO4: Eu荧光纳米粒子的透 射电镜照片。
图 8. 根据本发明的一个实施例得到的样品 18 LaPO4: Eu荧光纳米粒子的透 射电镜照片。
图 9. 根据本发明的一个实施例得到的样品 19 LaPO4: Eu荧光纳米粒子的透 射电镜照片。
图 10. 根据本发明的一个实施例得到的样品 20 LaP04: Eu荧光纳米粒子的透 射电镜照片。
图 11. 根据本发明的一个实施例得到的样品 31 NaYF4: Y : Er荧光纳米粒子 的透射电镜照片。
图 12. 根据本发明的实施例得到的 CeP04: Tb荧光纳米粒子的吸收光谱。 图 13. 根据本发明的实施例得到的 LaPO4: Eu稀土掺杂荧光纳米粒子的吸收 光谱。
图 14.根据本发明的实施例得到的样品 14 CePO4:Tb荧光纳米粒子的透射 电镜照片。 所列附图用于进一步描述利用本发明的公开的具体实施例和方法，附图以 及该描述是示例性而非限制性的。 具体实施方式 下面结合具体实施例， 进一步阐述本发明。 应理解， 这些实施例仅用于 说明本发明而不用于限制本发明的范围。此外应理解， 在阅读了本发明讲授的 内容之后， 本领域技术人员可以对本发明作各种改动或修改， 这些等价形式同 样落于本申请所附权利要求书所限定的范围。
混合阳离子源化合物、 阴离子源化合物和至少一种用于控制所述稀土掺 杂荧光纳米粒子晶体生长的溶剂， 形成一个混合溶液， 使所述混合溶液在一个 微反应器中在一个预设定温度停留一预设定时间，得到所述稀土掺杂荧光纳米 粒子溶液， 其中， 所述微反应器包括一个微混合装置和一个微换热装置。 所述 微反应器前端设置至少一个前置微换热器， 将所述混合溶液加热至 200°C以 上； 所述微换热器后端设置至少一个后置微换热器， 将所述稀土掺杂荧光纳米 粒子溶液冷却至所述预设定温度以下。
将上述稀土掺杂荧光纳米粒子溶液从微反应器引出并收集，加入极性溶剂形 成一悬浮液， 将悬浮液离心沉降， 除去离心沉降后的上层溶液， 重复上述过程 对荧光纳米粒子进行洗涤， 得到纯化的稀土掺杂荧光纳米粒子沉淀物， 将稀土 掺杂荧光纳米粒子沉淀物在一定温度下在真空炉内干燥数小时后得到稀土掺 杂荧光纳米粒子。 图 1 是根据本发明的一个实施例的工艺流程图。 混合溶液经注射泵 600 送入微反应器 100反应， 得到稀土掺杂荧光纳米粒子溶液。
图 2 是根据本发明的一个实施例的工艺流程图。 阳离子前驱体溶液经注 射泵 600a送入微混合器 400， 阴离子前驱体溶液经注射泵 600b送入微混合器 400， 阳离子前驱体溶液和阴离子前驱体溶液在微混合器 400中混合形成混合 溶液。混合溶液流经微反应器 100反应得到稀土掺杂荧光纳米粒子溶液， 稀土 掺杂荧光纳米粒子溶液流经后置微换热器 300冷却至室温。
图 3 是根据本发明的一个实施例的工艺流程图。 阳离子前驱体溶液经注 射泵 600a送入微混合器 400， 阴离子前驱体溶液经注射泵 600b送入微混合器 400， 阳离子前驱体溶液和阴离子前驱体溶液在微混合器 400中混合形成混合 溶液。混合溶液经一前置微换热器 200加热至 200°C以上后，进入微反应器 100 反应得到稀土掺杂荧光纳米粒子溶液，稀土掺杂荧光纳米粒子溶液流经一后置 微换热器 300冷却至室温， 在后置微换热器 300后端设置一压力控制器 500， 使所述混合溶液和所述稀土掺杂荧光纳米粒子溶液维持液相。 图 4是根据本发明的一个实施例的工艺流程图。 在图 3所示工艺流程基 础上， 极性溶剂经注射泵 600c送入系统， 与冷却的稀土掺杂荧光纳米粒子溶 液在微混合器 700中混合形成悬浮液。 优选将所述稀土掺杂荧光纳米粒子溶液冷却至 100Ό以下，更优选将所述 稀土掺杂荧光纳米粒子溶液冷却至 50°C以下。
所述用于控制所述稀土惨杂荧光纳米粒子晶体生长的溶剂选自下面的一 种或多种： 垸基磷酸酯、 烷基磷酸二酯、 烷基磷酸三酯、 三垸基膦和三烷基氧 膦。
所述用于控制所述稀土掺杂荧光纳米粒子晶体生长的溶剂优选自下面的 一种或多种： 优选烷基磷酸三酯、 三垸基膦和三垸基氧膦。
所述用于控制所述稀土掺杂荧光纳米粒子晶体生长的溶剂更优选自下面 的一种或多种： 垸基磷酸三酯优选磷酸三丁酯、 磷酸三辛酯； 三烷基膦优选三 乙基膦、 三丙基膦、 三丁基膦、 三仲丁基膦、 三戊基膦、 三己基膦、 三辛基膦； 三垸基氧膦、 三乙基氧膦、 三丙基氧膦、 三丁基氧膦、 三仲丁基氧膦、 三戊基 氧膦、 三己基氧膦和三辛基氧膦。
所述阳离子源化合物选自下面的一种或多种： 氯化盐、 溴化盐、 醋酸盐、 硝酸盐、 氟化盐、 碘化盐、 三氟醋酸盐、 水合氯化盐、 水合溴化盐、 水合醋酸 盐、 水合硝酸盐、 水合氟化盐、 水合碘化盐、 水合三氟醋酸和金属氧化物。
所述阴离子源化合物选自下面的一种或多种： 含有阴离子源的自由酸、 含有阴离子源的自由酸和在反应温度下可以释放阴离子的有机化合物。
所述阴离子源化合物优选自下面的一种或多种： 磷酸、 硼酸、 硫酸、 硅 酸、 氟化纳、 Ln(CF3COO)3 (Ln选自下面的一种或多种： Li、 Na、 K、 Rb、 Mg0.5、 Bao.5、 Cao.5或 Sr 5、 镧系元素、 钇或钪） 、 NaF、 NH4HF2、 NH4F和偏 钒酸钠。
所述混合溶液进一步包含金属螯合物。
所述金属螯合物选自下面的一种或多种： 二己醚、 二苯醚、 二卞醚、 二 辛醚、 二丁醚、 二戊醚、 二庚醚、 二异戊醚、 乙二醇二丁醚、 二乙二醇二丁醚、 十六烷、 十八垸、 二十烷、 十四垸、 二己胺、 三辛胺、 二 （2-乙基己基） 胺和 三 （2-乙基己基） 胺。
所述混合溶液可以由阳离子源化合物、 阴离子源化合物和至少一种用于 控制所述稀土掺杂荧光纳米粒子晶体生长的溶剂直接混合形成；也可以由阳离 子前驱体溶液和阴离子前驱体溶液混合形成。
当混合溶液由阳离子源化合物、 阴离子源化合物和至少一种用于控制所 述稀土掺杂荧光纳米粒子晶体生长的溶剂直接混合形成时，各物质的浓度范围 如下：
阳 离 子源化合 物 的 摩尔 浓度 是 0.001mol/L〜2.5mol/L ， 优选 0.01mol/L~0.7mol/L ， 更优选 0.05mol/L~0.4mol/L。
阴离子源化合物的摩尔浓度为 0.001mol/L~2.5mol/L， 优选 0.01mol/L~ 0.7mol/L， 更优选 0.05mol/L~0.4mol/L。
所述混合溶液中， 阴离子源化合物相对阳离子源化合物的摩尔比大于
0.5， 优选 0.5~10， 更优选 0.8~5。
当所述阳离子源化合物和 /或阴离子源化合物在室温下为固体或粘稠状液 体时， 需将其在可加热容器内加热为液体， 加热温度范围是室温 ~200°C， 优选 室温〜 100° ( 。
当混合溶液由阳离子前驱体溶液和阴离子前驱体溶液混合形成时， 所述 阳离子前驱体溶液包含阳离子源化合物和至少一种用于控制所述稀土掺杂荧 光纳米粒子晶体生长的溶剂；所述阴离子前驱体溶液包含阴离子源化合物和至 少一种用于分散所述阴离子源化合物的溶剂。
所述阳离子前驱体溶液的制备步骤包括： 将包含阳离子源化合物和至少 一种用于控制稀土掺杂荧光纳米粒子晶体生长的溶剂混合，搅拌至阳离子源化 合物溶解。 可选的加入低沸点极性溶剂， 帮助所述阳离子源化合物溶解； 进一 步可选的加入金属螯合物， 帮助阳离子源化合物溶解， 并置换阳离子源化合物 中的结晶水； 蒸馏除去上述溶液中的低沸点极性溶剂， 上述溶液中的结晶水可 以蒸馏出去， 也可以保留。
当所述阳离子前驱体在室温下为固体或粘稠状液体时， 需将其在可加热 容器内加热为液体， 加热温度范围为室温〜 200°C， 优选室温〜 100°C。
所述低沸点极性溶剂选自下面的一种或多种： 甲醇、 乙醇、 丙醇、 异丁 醇、 丁醇
所述阴离子前驱体溶液的制备步骤包括： 混合阴离子源化合物和至少一 种用于分散或溶解所述阴离子源化合物的溶剂， 加热、搅拌至形成透明的均相 溶液。 所述阴离子前驱体在室温下为固体或粘稠状液体时， 需将其在可加热容 器内加热为液体， 加热温度范围为室温〜 200°C， 优选室温〜 100°C。
所述用于分散所述阴离子源化合物的溶剂选自下面一种或几种： 垸基磷 酸酯、 垸基磷酸二酯、 烷基磷酸三酯、 三垸基膦或三烷基氧膦、 二己醚、 二苯 醚、 二卞醚、 二辛醚、 二丁醚、 二戊醚、 二庚醚、 二异戊醚、 乙二醇二丁醚、 二乙二醇二丁醚、 十六垸、 十八垸、 二十垸、 十四烷、 二己胺、 三辛胺、 二（2- 乙基己基） 胺和三 （2-乙基己基） 胺。
所述阳离子前驱体溶液和阴离子前驱体溶液可以通过传统搅拌混合， 也 可以用恒流泵送入微混合器混合。 所述恒流泵可以选自 HPLC泵、 注塞泵等。
各物质的浓度范围如下：
阳离子前驱体溶液中， 阳离子源化合物的摩尔浓度是 0.001mol/L ~2.5mol/L， 优选 0.01mol/L~0.7mol/L， 更优选 0.05mol/L~0.4mol/L。
阴离子前驱体溶液中， 阴离子源化合物的摩尔浓度为 0.001mol/L ~2.5mol/L, 优选 0.01mol/L~0.7mol/L， 更优选 0.05mol/L~0.4mol/L。
混合溶液中， 阴离子源化合物相对阳离子源化合物的摩尔比大于 0.5， 优 选 0.5~10， 更优选 0.8~5。
所述混合溶液温度应低于微反应器的预设定温度， 优选 200°C以下， 更优 选 150°C以下。 本发明制备得到的稀土掺杂纳米荧光粒子在功能薄膜、生物标记、太阳能 电池、 激光、 高密度数据存储、 海底通信、 大屏幕显示、 检测、 发光二极管等领 域得到广泛的应用。 下列实施例中未注明具体条件的实验方法， 通常按照常规条件， 如催化 剂化学操作手册， 或按照制造厂商所建议的条件。
前置微换热器是拜耳埃尔费尔德微技术公司 （Ehrfeld Mikrotechnik Bayer Technology Services GmbH ) 生产的同轴微换热器， 体积 V « 0.3 ml, 面积 A * 0.0076 m2。
微反应器是拜耳埃尔费尔德微技术公司的夹层式反应器， 体积 V « 30 ml, 面积 A « 0.03 m2。
后置微换热器是拜耳埃尔费尔德微技术公司的同轴微换热器， 体积 V ¾ 0.3 ml, 面积 A * 0.0076 m2。
微混合器为拜耳埃尔费尔德微技术公司的阀式微混合器或自制的 T型微 混合器。 阀式微混合器的微通道尺寸为长 ΙΟΟΟμιη, 宽 210μπι。
压力控制器选自世伟洛克的压力控制阔或拜耳埃尔费尔德微技术公司的 压力控制器。 稀土掺杂荧光纳米粒子的表征方法如下：
1) 紫外可见激发光谱与荧光光谱
对获得的稀土掺杂荧光纳米粒子用氯仿稀释后进行光学性能测试。 采用 Specord 40 (Analytik Jena)型紫外 -可见分光光度计测试样品的激发光谱， 对相 同的溶液采用 Fluorolog 3-22 (HORIBA Jobin Yvon)型荧光分光光度计进行荧 光光谱测试。 测量荧光光谱时， 激发波长为 277nm。
2)透射电镜 （TEM)
将铜网浸渍于清洗后的稀土惨杂荧光纳米粒子甲苯溶液中， 自然风干后采用 CM 20 (Philips) 型场发射透射电镜获得样品的透射电镜照片。 实施例 1 : CePO4: Tb荧光纳米粒子的制备
混合 44g 三辛基氧膦和 48ml 三辛基膦， 将混合物在烧瓶内加热搅拌至 80°C直至形成均相透明溶液。将 22.5mmol CeCl3-7H2O和 7.5mmol TbCl3-6H2O加入 上述容器内， 在 80°C下搅拌直至粉末完全溶解。 在 50°C下真空蒸馏上述溶液以除 去水分， 形成阳离子前驱体溶液；
混合 36mmol磷酸、 36ml三辛胺、 45ml 3, 3，-二甲基二苯醚和 40ml三辛基膦， 将混合物在另一容器内， 在常温下搅拌直至形成均相的阴离子前驱体溶液；
将阳离子前驱体溶液和阴离子前驱体溶液分别预热至 60°C后，分别在一定体积 流速（见表 1 )下用注射泵送入 T型微混合器混合形成混合溶液。所述混合溶液依 次流经前置微换热器、 微反应器、 后置微换热器和压力控制器， 经反应得到稀土 惨杂荧光纳米粒子溶液， 工艺流程图见图 3。前置微换热器和微反应器的预设定温 度见表 1。后置微换热器的预设定温度为室温。混合溶液在微反应器内的预设定停 留时间见表 1， 系统压力见表 1。
将稀土掺杂荧光纳米粒子溶液从反应系统引出并收集， 加入含有稀土掺杂荧光 纳米粒子溶液 4倍体积的甲醇和异丙醇混合溶液 （甲醇与异丙醇体积比为 1 : 10) 混合形成悬浮液。将悬浮液离心沉降， 除去离心沉降后的上层溶液得到稀土掺杂荧 光纳米粒子沉淀物， 重复上述洗涤过程 3 次， 得到纯化的稀土掺杂荧光纳米粒子 沉淀物。 将稀土掺杂荧光纳米粒子沉淀物在 60°C下在真空烘箱内干燥 3小时后得 到稀土惨杂荧光纳米荧光粒子。 表 1是稀土掺杂荧光纳米粒子制备条件。 图 12是 稀土掺杂荧光纳米粒子样品 Y1的吸收光谱。
CePO4: Tb荧光纳米粒子制备条件
Figure imgf000015_0001
实施例 2: CePO4: Tb荧光纳米粒子的制备
混合 44g三辛基氧膦和 73ml十八烯，将混合物在容器内加热搅拌至 80°C直 至形成均相透明溶液。 将 22.5mmol CeCl3-7H2O和 7.5mmol TbCl3-6H2O与上述溶 液混合， 在 50°C下将其真空蒸馏除去水分， 形成阳离子前驱体溶液；
混合 36mmol磷酸、 36ml三辛胺、 45ml 3, 3，-二甲基二苯醚和 60ml十八'烯， 将混合物在另一容器内， 在常温下搅拌直至形成均相的阴离子前驱体溶液；
将阳离子前驱体溶液和阴离子前驱体溶液预热至 60°C后，分别在一定体积流 速 （见表 2 ) 下用注射泵送入 T型微混合器混合形成混合溶液。 所述混合溶液 依次流经前置微换热器、 微反应器、 后置微换热器和压力控制器， 经反应得到 稀土掺杂荧光纳米粒子溶液。 前置微换热器和微反应器的预设定温度为 320 °C。后置微换热器的预设定温度为室温。混合溶液在微反应器内的预设定停留 时间见表 2， 系统压力为 5bar。
将稀土掺杂荧光纳米粒子溶液从反应系统引出并收集， 加入含有稀土掺杂荧光 纳米粒子溶液 4倍体积的甲醇和异丙醇混合溶液 （甲醇与异丙醇体积比为 1 : 10) 混合形成悬浮液。 将悬浮液离心沉降， 除去离心沉降后的上层溶液得到稀土掺 杂荧光纳米粒子沉淀物， 重复上述洗涤过程 3次， 得到纯化的稀土掺杂荧光纳米 粒子沉淀物。 将稀土掺杂荧光纳米粒子沉淀物在 60°C下在真空烘箱内干燥 3小 时后得到稀土掺杂荧光纳米粒子。表 2是稀土掺杂荧光纳米粒子制备条件。 图 5 是稀土掺杂荧光纳米粒子样品 Y5 的透射电镜照片。 图 12是稀土掺杂荧光纳 米粒子样品 Y4和 Y5的吸收光谱。
CePO4: Tb荧光纳米粒子制备条件
Figure imgf000016_0001
实施例 3 : CePO4: Tb荧光纳米粒子的制备
混合 44g三辛基氧膦和 73ml3, 3'-二甲基二苯醚， 将混合物在容器内加热搅拌 至 80°C直至形成均相透明溶液。将 22.5mmol CeCl3-7H2O和 7.5mmol TbCl3-6H2O 与上述溶液混合， 在 50°C下将其真空蒸馏除去水分， 形成阳离子前驱体溶液； 混合 36mmol磷酸、 36ml三辛胺和 72ml 3, 3，-二甲基二苯醚， 将混合物在另一 容器内， 在常温下搅拌直至形成均相的阴离子前驱体溶液；
将阳离子前驱体溶液和阴离子前驱体溶液预热至 60°C后， 分别在一定体积流 速（见表 3 )下用注射泵送 T型微混合器混合形成混合溶液。 所述混合溶液依 次流经前置微换热器、 微反应器、 后置微换热器和压力控制器， 经反应得到稀 土掺杂荧光纳米粒子溶液。 前置微换热器和微反应器的预设定温度为 320°C。 后置微换热器的预设定温度为室温。混合溶液在微反应器内的预设定停留时间 见表 3， 系统压力为 4bar。
将稀土掺杂荧光纳米粒子溶液从反应系统引出并收集， 加入含有稀土掺杂荧光 纳米粒子溶液 4倍体积的甲醇和异丙醇混合溶液 （甲醇与异丙醇体积比为 1 : 10) 混合形成悬浮液。 将悬浮液离心沉降， 除去离心沉降后的上层溶液得到稀土掺 杂荧光纳米粒子沉淀物。重复上述洗涤过程 3次， 得到纯化的稀土掺杂荧光纳米 粒子沉淀物， 将稀土掺杂荧光纳米粒子沉淀物在 60°C下在真空烘箱内干燥 3小 时后得到稀土掺杂荧光纳米粒子。表 3是稀土掺杂荧光纳米粒子制备条件。 图 7 是稀土掺杂荧光纳米粒子样品 Y8的透射电镜照片。 图 12是稀土掺杂荧光纳 米粒子样品 Y7和 Y9的吸收光谱。 CePO4: Tb荧光纳米粒子制备条件
Figure imgf000017_0001
实施例 4: LaPO4: Eu荧光纳米粒子的制备
混合 60g三辛基氧膦和 100ml十八烯，将混合物在容器内加热搅拌至 80Ό直 至形成均相透明溶液。 将 40mmol LaCl3-7H2O和 2mmol EuCl3与上述溶液混合， 在 50°C下将其真空蒸馏除去水分， 形成阳离子前驱体溶液；
混合 48mmol磷酸、 50ml三辛胺、 60ml 3, 3，-二甲基二苯醚和 100ml十八烯， 将混合物在另一容器内， 在常温下搅拌直至形成均相的阴离子前驱体溶液；
将阳离子前驱体溶液和阴离子前驱体溶液预热至 60°C后，分别在一定体积流 速（见表 4 ) 下用注射泵送入 T型微混合器混合形成混合溶液。 所述混合溶液 依次流经前置微换热器、微反应器和后置微换热器， 经反应得到稀土惨杂荧光 纳米粒子溶液。 前置微换热器和微反应器的预设定温度见表 4。 后置微换热器 的预设定温度为室温。 混合溶液在微反应器内的预设定停留时间见表 4。
将稀土掺杂荧光纳米粒子溶液从反应系统引出并收集， 加入含有稀土掺杂荧光 纳米粒子溶液 4倍体积的甲醇和异丙醇混合溶液 （甲醇与异丙醇体积比为 1 : 10) 混合形成悬浮液。 将悬浮液离心沉降， 除去离心沉降后的上层溶液得到稀土掺 杂荧光纳米粒子沉淀物， 重复上述洗涤过程 3次， 得到纯化的稀土掺杂荧光纳米 粒子沉淀物。 将稀土掺杂荧光纳米粒子沉淀物在 60°C下在真空烘箱内干燥 3小 时后得到稀土掺杂荧光纳米粒子。表 4是稀土掺杂荧光纳米粒子制备条件。 图 7 是稀土掺杂荧光纳米粒子样品 Y12的透射电镜照片。 图 13是稀土掺杂荧光纳 米粒子样品 Y10、 Y1 1的吸收光谱。 表 4: LaPO4: Eu荧光纳米粒子制备条件
Figure imgf000018_0001
实施例 5: LaPO4: Eu荧光纳米粒子的制备
混合 20mmol LaCl3-7H2O、 lmmol EuCl3、 30g三辛基氧膦和 50ml 三辛基膦， 将混合物在烧瓶内加热搅拌至 80°C直至粉末完全溶解。 50°C下真空蒸馏除去上述 溶液中的水， 形成阳离子前驱体溶液；
混合 24 mmol磷酸、 25 ml三辛胺、 15 ml 3, 3，-二甲基二苯醚和 45 ml三辛基 膦， 将混合物在另一容器内， 在常温下搅拌直至形成均相的阴离子前驱体溶液； 将阳离子前驱体溶液和阴离子前驱体溶液预热至 60°C后， 分别在一定体积流 速（见表 5 )下用注射泵送 T型微混合器混合形成混合溶液。 所述混合溶液流 经微反应器和后置微换热器， 在 320°C下反应得到稀土掺杂荧光纳米粒子溶 液， 工艺流程图见图 2。 后置微换热器的预设定温度为室温， 混合溶液在微反 应器内的预设定停留时间见表 5。
将稀土掺杂荧光纳米粒子溶液从反应系统引出并收集， 加入含有稀土掺杂荧光 纳米粒子溶液 4倍体积的甲醇和异丙醇混合溶液 （甲醇与异丙醇体积比为 1 : 10) 混合形成悬浮液。 将悬浮液离心沉降， 除去离心沉降后的上层溶液得到稀土掺 杂荧光纳米粒子沉淀物， 重复上述洗涤过程 3次， 得到纯化的稀土掺杂荧光纳米 粒子沉淀物。 将稀土掺杂荧光纳米粒子沉淀物在 60°C下在真空烘箱内干燥 3小 时后得到稀土掺杂荧光纳米粒子。 表 5是稀土掺杂荧光纳米粒子制备条件。 表 5: LaPO4: Eu荧光纳米粒子制备条件
Figure imgf000019_0001
实施例 6: LaPO4: Eu荧光纳米粒子的制备
混合 40 mmol LaCl3'7H2O、 2 mmol EuCl3、 60 g三辛基氧膦和 100 ml 3, 3，-二甲 基二苯基醚， 将混合物在烧瓶内加热搅泮至 80°C直至粉末完全溶解。 50°C下真空 蒸熘除去上述溶液中的水， 形成阳离子前驱体溶液。
混合 48 mmol磷酸、 50 ml三辛胺和 120 ml 3, 3，-二甲基二苯醚，将混合物在另 一容器内， 在常温下搅拌直至形成均相的阴离子前驱体溶液；
将阳离子前驱体溶液和阴离子前驱体溶液预热至 60Ό后， 分别在一定体积流 速（见表 6 )下用注射泵送 T型微混合器混合形成混合溶液。 所述混合溶液流 经微反应器和后置微换热器， 在 300°C下反应得到稀土掺杂荧光纳米粒子溶 液。后置微换热器的预设定温度为室温。混合溶液在微反应器内的预设定停留 时间见表 6。
将稀土掺杂荧光纳米粒子溶液从反应系统引出并收集， 加入含有稀土掺杂荧光 纳米粒子溶液 4倍体积的甲醇和异丙醇混合溶液 （甲醇与异丙醇体积比为 1 : 10) 混合形成悬浮液。 将悬浮液离心沉降， 除去离心沉降后的上层溶液得到稀土掺 杂荧光纳米粒子沉淀物， 重复上述洗涤过程 3次， 得到纯化的稀土掺杂荧光纳米 粒子沉淀物。 将稀土掺杂荧光纳米粒子沉淀物在 60°C下在真空烘箱内干燥 3小 时后得到稀土掺杂荧光纳米粒子。 表 6是稀土掺杂荧光纳米粒子制备条件。 得 到的 LaPO4: Eu荧光纳米粒子重新分散在氯仿溶液中进行表征。 图 8、 9、 10分 别是稀土掺杂荧光纳米粒子样.品 Y18、 Υ19、 Υ20的透射电镜照片。 表 6: LaPO4: Eu荧光纳米粒子制备条件
Figure imgf000020_0001
实施例 7: LaPO4: Eu荧光纳米粒子的制备
混合 82 ml十八烯、45 g三辛基氧膦、 30mmol LaCl3'7H2O和 1.5mmol EuCl3 40 mmol LaCl3.7H2O、 2 mmol EuCl3、 60 g三辛基氧膦和 100 ml 3, 3，-二甲基二苯基醚， 将混合物在烧瓶内加热搅拌至 80°C直至粉末完全溶解。 50°C下真空蒸馏除去上 述溶液中的水， 形成阳离子前驱体溶液；
混合 36mmol磷酸, 36ml三辛胺 , 45 ml 3, 3，-二甲基二苯基醚和 90 ml十八烯， 将混合物在另一容器内， 在常温下搅拌直至形成均相的阴离子前驱体溶液；
将阳离子前驱体溶液和阴离子前驱体溶液预热至 60°C后， 分别以 lml/min体 积流速下用注射泵送入 T 型微混合器混合形成混合溶液。 所述混合溶液流经 微反应器和后置微换热器， 在 300°C下反应得到稀土掺杂荧光纳米粒子溶液。 后置微换热器的预设定温度为室温。混合溶液在微反应器内的预设定停留时间为 15min0
将稀土掺杂荧光纳米粒子溶液从反应系统引出并收集， 加入含有稀土掺杂荧光 纳米粒子溶液 4倍体积的甲醇和异丙醇混合溶液 （甲醇与异丙醇体积比为 1 : 10) 混合形成悬浮液。 将悬浮液离心沉降， 除去离心沉降后的上层溶液得到稀土掺 杂荧光纳米粒子沉淀物， 重复上述洗涤过程 3次， 得到纯化的稀土掺杂荧光纳米 粒子沉淀物。 将稀土掺杂荧光纳米粒子沉淀物在 60°C下在真空烘箱内干燥 3小 时后得到稀土掺杂荧光纳米粒子。 实施例 8: CePO4: Tb荧光纳米粒子的制备
混合 5 ml 甲醇， 3.75 mmol CeCly7H2O和 1.25 mmol TbCl3-6H2O，将混合物在 烧瓶内加热搅拌至 80°C直至粉末完全溶解。 将 40 ml三辛基膦和 8.5 g三辛基氧 膦与上述溶液混合， 并加热至 80°C , 搅拌 30min直至形成均相溶液。 50°C下将其 真空蒸馏除去水和甲醇， 并加入 50ml二卞醚形成阳离子前驱体溶液； 混合 l lmmol磷酸， 11ml三辛胺， 89ml二卞醚和 9ml三辛基氧膦， 将混合物在 另一容器内， 在常温下搅拌直至形成均相的阴离子前驱体溶液；
将阳离子前驱体溶液和阴离子前驱体溶液预热至 80Ό后， 分别在一定体积流 速（见表 7 ) 下用注射泵送入 T型微混合器混合形成混合溶液。 所述混合溶液 流经微反应器和后置微换热器， 在 320°C下反应得到稀土掺杂荧光纳米粒子溶 液。后置微换热器的预设定温度为室温， 混合溶液在微反应器内的预设定停留 时间见表 7。
将稀土掺杂荧光纳米粒子溶液从反应系统引出并收集， 加入含有稀土掺杂荧光 纳米粒子溶液 4倍体积的甲醇和异丙醇混合溶液 （甲醇与异丙醇体积比为 1 : 10) 混合形成悬浮液。 将悬浮液离心沉降， 除去离心沉降后的上层溶液得到稀土掾 杂荧光纳米粒子沉淀物， 重复上述洗涤过程 3次， 得到纯化的稀土掺杂荧光纳米 粒子沉淀物。 将稀土掺杂荧光纳米粒子沉淀物在 60°C下在真空烘箱内干燥 4小 时后得到稀土掺杂荧光纳米粒子。 表 7是稀土掺杂荧光纳米粒子制备条件。
表 7: CePO4: Tb荧光纳米粒子制备条件
Figure imgf000021_0001
实施例 9: LaPO4: Eu荧光纳米粒子的制备
混合 20ml 甲醇、 20mmol LaCl3'7H2O和 lmmol EuCl3 ， 将混合物在容器内加 热搅拌至 60°C至粉末完全溶解。将 22 ml磷酸三丁酯和 60ml二卞醚加入上述容器 内，在 80°C下搅拌 30min直至形成均相溶液。在 50 °C下真空蒸馏上述溶液以除去水 和甲醇， 形成阳离子前驱体溶液；
混合 22mmol磷酸， 20ml三辛胺和 60ml 二卞醚， 将混合物在另一容器内， 在 常温下搅拌直至形成均相的阴离子前驱体溶液
将阳离子前驱体溶液和阴离子前驱体溶液预热至 80Γ后， 分别在一定体积流 速下 （见表 8 ) 用注射泵送入 T型微混合器混合形成混合溶液。 所述混合溶液 流经微反应器和后置微换热器， 在所述微换热器的预设定温度下 （见表 8 ) 反 应得到稀土掺杂荧光纳米粒子溶液。后置微换热器的预设定温度为室温， 混合 溶液在微反应器内的预设定停留时间见表 8。
将稀土掺杂荧光纳米粒子溶液从反应系统引出并收集， 加入含有稀土掺杂荧光 纳米粒子溶液 4倍体积的甲醇和异丙醇混合溶液 （甲醇与异丙醇体积比为 1 : 10) 混合形成悬浮液。 将悬浮液离心沉降， 除去离心沉降后的上层溶液得到稀土掺 杂荧光纳米粒子沉淀物， 重复上述洗涤过程 4次， 得到纯化的稀土掺杂荧光纳米 粒子沉淀物。 将稀土掾杂荧光纳米粒子沉淀物在 60°C下在真空烘箱内干燥 4小 时后得到稀土掺杂荧光纳米粒子。 表 8是稀土掺杂荧光纳米粒子制备条件。
表 8: LaPO4: Eu荧光纳米粒子制备条件
Figure imgf000022_0001
实施例 10: LaPO4: Eu荧光纳米粒子的制备
混合 10ml 甲醇、 20 mmol LaCl3-7H2O和 0.5mmol EuCl3 ， 将混合物在烧瓶内 加热搅拌至 60Ό直至粉末完全溶解。 将 40 ml三辛基膦和 10 g三辛基氧膦与上述 溶液混合， 并加热至 80°C， 搅拌 30min直至形成均相溶液。 50°C下将其真空蒸馏 除去水和甲醇， 形成阳离子前驱体溶液；
混合 l lmmol磷酸， 11ml三辛胺和 89ml二卞醚， 将混合物在另一容器内， 在 常温下搅拌直至形成均相的阴离子前驱体溶液；
将阳离子前驱体溶液和阴离子前驱体溶液预热至 80°C后， 分别在 0.5ml/min、 0.5ml/min体积流速下用注射泵送入 T型微混合器混合形成混合溶液。 所述混 合溶液流经前置微换热器、 微反应器、 后置微换热器和压力控制器， 经反应得 到稀土掺杂荧光纳米粒子溶液。前置微换热器、微反应器和后置微换热器的预 设定温度依次为 320°C、 300°C和 30°C。 混合溶液在微反应器内的预设定停留 时间为 30min。 系统压力为 3bar。 将甲醇和异丙醇混合溶液 （甲醇与异丙醇体积比为 1 : 10) 通过 HPLC 泵以 4ml/min 的体积流速与稀土掺杂荧光纳米粒子溶液在阀式微混合器中混合形成悬浮 液。将悬浮液离心沉降， 除去离心沉降后的上层溶液得到稀土掺杂荧光纳米粒 子沉淀物。重复上述洗涤过程 3次，得到纯化的稀土掺杂荧光纳米粒子沉淀物， 将稀土惨杂荧光纳米粒子沉淀物在 60°C下在真空烘箱内干燥 4小时后得到棒 状稀土掺杂荧光纳米荧光粒子。 图 14是本实施例得到的稀土掺杂荧光纳米粒 子的透射电镜照片。 实施例 11 : NaYF4: Yb: Er荧光纳米粒子的制备
混合 19.4 ol Y2O3 lO mmol Yb2O3 l mmol Er2O3 80 ml 去离子水和 120 ml三氟醋酸， 将混合物在烧瓶内加热至溶液回流温度， 搅拌直至形成均相溶液。 在 100°C下真空蒸馏除去上述溶液中过量的三氟醋酸和水， 得到干燥的混合粉末。 将 100 mmol三氟醋酸钠和 240 ml油胺加入上述烧瓶中， 并加热至 100 °C于真空下搅 拌 30min形成溶液， 除去溶液中的微量水和氧气， 然后在氮气气氛下搅拌直至形成 均相溶液。
溶液在一定体积流速 （见表 9) 下用高效液相色谱泵送入 T型微混合器形成混 合溶液。 所述混合溶液流经前置微换热器、 微反应器和后置微换热器， 经反应得到 稀土掺杂荧光纳米粒子溶液。 前置微换热器和微反应器的预设定温度见表 9。 后置 微换热器的预设定温度为室温。混合溶液在微反应器内的预设定停留时间为 15min 将稀土惨杂荧光纳米粒子溶液从反应系统引出并收集， 加入含有稀土掺杂荧光 纳米粒子溶液 4倍体积的甲醇和环己烷混合溶液（甲醇与环己垸体积比为 9: 1 )混 合形成悬浮液。 将悬浮液离心沉降， 除去离心沉降后的上层溶液得到稀土掺杂 荧光纳米粒子沉淀物。 然后上述沉淀用 3倍体积的甲醇和异丙醇混合溶液 （体 积比 9: 1 ) 洗涤 3次， 得到纯化的稀土掺杂荧光纳米粒子沉淀物， 将稀土掺杂 荧光纳米粒子沉淀物在 60°C下在真空烘箱内干燥 2小时后得到稀土掺杂荧光纳 米粒子。 表 9是稀土揍杂荧光纳米粒子制备条件。 图 11 是稀土掺杂荧光纳米 粒子样品 Y31的透射电镜照片。 表 9: NaYF4: Yb: Er荧光纳米粒子制备条件
Figure imgf000024_0001
实施例 12: LaPO4: Ce: Dy荧光纳米粒子的制备
混合 12 ml 甲醇、 8.9 mmol LaCl3 7H2O、 lmmol CeCl3-7H2O 、 10 ml三辛基膦 和 8.33 g三辛基氧膦和 O.lmmol DyCl3 ， 将混合物在烧瓶内加热搅拌至 60 °C直至 粉末完全溶解。 50°C下真空蒸馏除去上述溶液中的水和甲醇； 在上述溶液中加入 lOmmol磷酸和 82ml三辛基膦， 搅拌直至形成均相透明的溶液。
上述混合溶液在常温下以 lml/min 体积流速依次流经前置微换热器和微反 应器， 反应得到稀土惨杂荧光纳米粒子溶液。 前置微换热器得预设定温度为 340 °C , 微反应器的预设定温度为 300°C。 混合溶液在微反应器内的预设定停 留时间为 30min。
将稀土掺杂荧光纳米粒子溶液从反应系统引出并收集， 经自然冷却后， 加入含 有稀土掺杂荧光纳米粒子溶液 4倍体积的甲醇和异丙醇混合溶液 （甲醇与异丙醇体 积比为 1 : 10)混合形成悬浮液。 将悬浮液离心沉降， 除去离心沉降后的上层溶 液得到稀土掺杂荧光纳米粒子沉淀物。 重复上述洗涤过程 4 次， 得到纯化的稀 土掺杂荧光纳米粒子沉淀物。将稀土惨杂荧光纳米粒子沉淀物在 60°C下在真空烘 箱内干燥 4小时后得到稀土掺杂荧光纳米粒子。 实施例 13: LaBO3: Ce: Dy荧光纳米粒子的制备
混合 4ml 甲醇、 35.6 匪 ol LaCl3-7H2O、 4mmol CeCl3-7H2O 、 0.4mmol DyCl3 、
45 ml磷酸三辛酯和 125ml二苯醚，将混合物在烧瓶内加热搅拌至 50°C直至粉末完 全溶解。50°C下真空蒸馏除去上述溶液中的水和甲醇;在上述溶液中加入 40mmol磷 酸、 30ml二己醚和 42ml三己胺， 搅拌直至形成均相溶液。
上述混合溶液在常温下以 5ml/min体积流速依次流经前置微换热器、微反应 器和压力控制器， 反应得到稀土掺杂荧光纳米粒子溶液。前置微换热器的预设 定温度为 340°C， 微反应器的预设定温度为 300°C， 系统压力为 5bar。 混合溶 液在微反应器内的预设定停留时间为 6min。 将稀土掺杂荧光纳米粒子溶液从反应系统引出并收集， 自然冷却后， 加入含有 稀土掺杂荧光纳米粒子溶液 4倍体积的甲醇和异丙醇混合溶液 （甲醇与异丙醇体积 比为 1 : 10)混合形成悬浮液。 将悬浮液离心沉降， 除去离心沉降后的上层溶液 得到稀土掺杂荧光纳米粒子沉淀物。 重复上述洗涤过程 4 次， 得到纯化的稀土 掺杂荧光纳米粒子沉淀物。将稀土掺杂荧光纳米粒子沉淀物在 60°C下在真空烘箱 内干燥 4小时后得到稀土掺杂荧光纳米粒子。 实施例 14: CePO4: Tb荧光纳米粒子的制备
混合 10ml甲醇、 22.5mmol CeCl3 7H2O和 7.5匪 ol TbCl3 6H2O、 30ml二甲苯 基醚和 11ml磷酸三辛酯， 将混合物在烧瓶内加热搅拌至 50°C直至粉末完全溶解。 室温下真空蒸馏除去上述溶液中的甲醇； 在上述溶液中加入 30mmol磷酸和 11ml 三己胺， 搅拌直至形成均相溶液。
将上述混合溶液预热至 60°C， 以 lml/min体积流速依次流经前置微换热器、微 反应器、 后置微换热器和压力控制器， 反应得到稀土掺杂荧光纳米粒子溶液。 前 置微换热器、微反应器和后置微换热器的预设定温度分别为 300°C、 280°C和 25°C， 系统压力为 5bar。 混合溶液在微反应器内的预设定停留时间为 30min。
将甲醇和异丙醇混合溶液 （甲醇与异丙醇体积比为 1 : 10)通过高效液相色谱 泵以 4rnl/min的体积流速与稀土掺杂荧光纳米粒子溶液在阔式微混合器中混合形成 悬浮液。将悬浮液离心沉降，除去离心沉降后的上层溶液得到稀土掺杂荧光纳米粒 子沉淀物。 重复上述洗涤过程 3 次， 得到纯化的稀土掺杂荧光纳米粒子沉淀物， 将稀土掺杂荧光纳米粒子沉淀物在 60°C下在真空烘箱内干燥 3小时后得到棒状稀 土掺杂荧光纳米荧光粒子。 图 14是本实施例得到的稀土掺杂荧光纳米粒子的透射 电镜照片。

Claims

权利要求书
1. 一种连续制备稀土掺杂荧光纳米粒子溶液的方法， 包括以下步骤： 混合阳离子源化合物、阴离子源化合物和至少一种用于控制所述稀土掺杂 荧光纳米粒子晶体生长的溶剂， 形成一个混合溶液， 和
使所述混合溶液在一个微反应器中在一个预设定温度停留一预设定时间， 得到所述稀土掺杂荧光纳米粒子溶液， 其中， 所述微反应器包括一个微混合装 置和一个微换热装置， 所述微混合装置用于持续混合所述混合溶液， 所述微换 热装置用于调节所述微反应器的温度至所述预设定温度。
2. 如权利要求 1 所述的制备方法， 进一步包括步骤： 控制所述微反应器 压力， 使所述稀土掺杂荧光纳米粒子溶液维持液相。
3. 如权利要求 1或 2所述的制备方法， 其中， 所述稀土掺杂荧光纳米粒 子选自下面的一种：
LnPO4: Ce: W、
LnPO4: Eu、
LnVO4: Ce: W、
LnVO4: Eu、
Ln(VO4)x(PO4)y： B (x+y=l , 其中， 0≤x≤l)、
AYF4: G、
AYC14: G、
AYBr4: G、
NaQF4: Yb: B、
NaQCl4: Yb: B、
NaQBr4: Yb: B、
LnBO3： Ce : W、
LnBO3： Eu、
(YGd)BO3: Eu、
DSO4: B、
DSO4: Mn、 和
Zn2(SiO4): Mn;
其中， Ln代表镧系元素、 Y或 Sc; D代表 Ba、 Sr或 Ca; E代表 Cu、 Ag、 Eu、 Bi、 Al或 Au ; G代表 Pr、 Tm、 Er、 Yb或 Ho; Q代表 Gd、 Y、 Li 或 K; W代表 Tb或 Dy; A选自下面的一种或多种 Li、 Na、 K、 Rb、 Mgo.5、 Bao.5、 Cao.5和 SrQ.5; B代表镧系元素。
4. 如权利要求 1或 2所述的制备方法， 其中， 所述微反应器的预设定温 度是 200°C以上。
5. 如权利要求 1或 2所述的制备方法， 其中， 所述微反应器的预设定停 留时间是 30s〜 7200s。
6. 如权利要求 1或 2所述的制备方法， 其中， 所述微反应器前端安装至 少一个前置微换热器， 所述前置微换热器用于加热所述混合溶液。
7. 如权利要求 1或 2所述的制备方法， 其中， 所述微反应器后端安装至 少一个后置微换热器，所述后置微换热器用于冷却所述稀土掺杂荧光纳米粒子 溶液。
8. 如权利要求 1或 2所述的制备方法， 其中， 所述混合溶液包含水， 以 得到棒状的稀土掺杂荧光纳米粒子， 所述水来自阳离子源化合物或直接加入。
9. 一种连续制备稀土掺杂荧光纳米粒子的方法， 包括以下步骤： 将权利要求 1-8 中任意一种方法制备的稀土掺杂荧光纳米粒子溶液与一 极性溶剂混合形成一悬浮液； 和
分离所述悬浮液得到所述稀土掺杂荧光纳米粒子。
10. 一种连续制备稀土惨杂荧光纳米粒子溶液的系统， 所述系统包括： 一个混合器， 用于将阳离子源化合物、 阴离子源化合物和至少一种用于控 制所述稀土掺杂荧光纳米粒子晶体生长的溶剂混合形成一个混合溶液，
一个前置微换热器， 用于加热所述混合溶液，
至少一个微反应器，用于使所述混合溶液在一个预设定温度停留一预设定 时间， 得到所述稀土惨杂荧光纳米粒子溶液， 其中， 所述微反应器包括一个微 混合装置和一个微换热装置， 所述微混合装置用于持续混合所述混合溶液， 所 述微换热装置用于调节所述微反应器的温度至所述预设定温度，
一个后置微换热器， 用于冷却所述稀土掺杂荧光纳米粒子溶液， 和 一个压力控制器， 用于控制所述系统的压力， 使所述混合溶液和所述稀土 掺杂荧光纳米粒子溶液维持液相。
11. 一种连续制备稀土掺杂荧光纳米粒子的系统， 所述系统包括： 一个混合器， 用于将阳离子源化合物、 阴离子源化合物和至少一种用于 控制所述稀土掺杂荧光纳米粒子晶体生长的溶剂混合形成一个混合溶液， 一个前置微换热器， 用于加热所述混合溶液，
至少一个微反应器，用于使所述混合溶液在一个预设定温度停留一预设定 时间， 得到一稀土掺杂荧光纳米粒子溶液， 其中， 所述微反应器包括一个微混 合装置和一个微换热装置， 所述微混合装置用于持续混合所述混合溶液， 所述 微换热装置用于调节所述微反应器的温度至所述预设定温度，
一个后置微换热器， 用于冷却所述稀土掺杂荧光纳米粒子溶液， 一个压力控制器， 用于控制所述系统的压力， 使所述混合溶液和所述稀土 掺杂荧光纳米粒子溶液维持液相，
一个混合装置，用于将所述稀土掺杂荧光纳米粒子溶液与一极性溶剂混合 形成一悬浮液， 和
一个分离装置， 用于分离所述悬浮液， 得到所述稀土惨杂荧光纳米粒子。
PCT/CN2011/000936 2011-06-03 2011-06-03 一种稀土掺杂荧光纳米粒子及其溶液的制备方法和系统 Ceased WO2012162858A1 (zh)

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