CN102154012B - Preparation method of small-sized NaYF4 nano substrate material with hexagonal phase by inducement - Google Patents
Preparation method of small-sized NaYF4 nano substrate material with hexagonal phase by inducement Download PDFInfo
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Abstract
The invention belongs to the technical field of a nano up-conversion luminescent material, in particular relates to a preparation method for a small-sized NaYF4 nano substrate material with a hexagonal phase by inducement with rare earth nano crystal nucleus. In the method, rare earth ions are doped in the NaYF4 nano substrate material so as to obtain a nano material with a low up-conversion luminescence threshold and high luminescence strength. In the method, the small-sized beta-NaYF4 nano substrate material is generated by inducement with a hydrothermal (solvent) process in the presence of rare earth fluoride nano crystal nucleus, wherein the size of the particle is from 20nm to 200nm, and distribution of the size is even. According to the invention, a preparation method of the small-sized NaYF4 nano substrate material with the hexagonal phase is expanded, and the problem that the NaYF4 nano substrate material, especially water-soluble NaYF4 nano substrate material is difficultly generated at low temperature, is solved. By using the nano up-conversion luminescent material, the demand on biological fluorescent identification probes and disease diagnosis and treatment materials is met, and a foundation is established for the practicable application of the up-conversion luminescent material.
Description
Technical field
The invention belongs to the nano-sized upconversion phosphor technical field, be specifically related to a kind of preparation small size hexagonal phase NaYF that induces take rare earth fluoride nanocrystalline as nuclear
4The method of nano based material, this NaYF
4The nano based material can obtain the nano material that the up-conversion luminescence threshold value is low, luminous intensity is high after rare earth ion doped.
Background technology
Up-conversion luminescent material refers to absorb the low frequency photon and the material of launching the high frequency photon.Up-conversion luminescent material has very important application prospect in laser, communication, the energy, medical treatment, military affairs, aerospace and people's daily life.The fields such as in recent years, along with development little, nanotechnology, upper conversion is little, nano material progressively is applied to the energy, false proof, biological, demonstration.2010, Qin etc. prepared a kind of new infrared photocatalyst material that is comprised of up-conversion luminescent material and titanium dioxide, widened conductor photocatalysis material the absorbing wavelength scope (CHEMICAL COMMUNICATIONS, 2010,283,547-550).2003, the people such as the Chen Ruoyu of University Of Suzhou proposed the preparation infrared double-wave length and change marking materials in Chinese patent (CN 1415693A), be used for the anti-counterfeiting marks such as bill, paper money coin, trade mark.In addition, the up-conversion luminescence nano material is because its excitation wavelength is in the optical window of biological tissue, and its application at biological field has become worldwide study hotspot, and annual have a large amount of scientific researches to report with relevant achievements conversion.
NaYF
4Nano material is the substrate material that is widely used at present up-conversion luminescence.NaYF
4Have two kinds of crystalline phases of hexagonal phase and Emission in Cubic, in numerous conversion substrate materials, hexagonal phase NaYF
4(β-NaYF
4) be the substrate material with higher up-conversion luminescence efficient of generally acknowledging.With hexagonal phase NaYF
4Compare Emission in Cubic NaYF
4(α-NaYF
4) all comparatively inferior on lasing threshold, luminous intensity.Yet, because NaYF
4The chemical property of self has determined Emission in Cubic NaYF
4Be the dynamic stabilization phase, therefore work as nanocrystalline size less than 50 nanometers, when the simultaneous reactions temperature is low, generate easily α-NaYF
4, directly affect up-conversion luminescence threshold value and the luminous intensity of dopant ion.People are devoted to study small size hexagonal phase NaYF always
4The preparation method of nanometer matrix, particularly preparation can be applicable to the fields such as biologic medical, photochemical catalysis and have water miscible small size β-NaYF
4Especially challenging work.In various preparation methods, the methods such as general normal temperature co-precipitation, water (solvent) heat, microemulsion are difficult to obtain small size hexagonal phase NaYF
4Nanocrystalline, size mostly are Emission in Cubic or mixed phase during less than 100nm.High-temperature synthesis can preparation size less than the β-NaYF of 100 nanometers
4But preparation process requires to carry out in temperature is higher than 280 ℃ high-temperature medium, and can only obtain oil-soluble nanoparticle, transforms means through surface ligands such as ligand exchange, the two keys of oxidation part again and could obtain to have water miscible β-NaYF
4Nanocrystalline.Utilize the ligand exchange method to realize small size hexagonal phase NaYF
4Nanocrystalline water miscible method more complicated, and be difficult to realize transforming fully.And the method for utilizing the two keys of oxidized surface part can affect the up-conversion luminescence performance of fluoride nano particles.How to prepare small size, lasing threshold is low, luminous intensity is high, the hexagonal phase NaYF of good water solubility particularly
4Nano-sized upconversion phosphor has become the field of nano material preparation problem demanding prompt solution.
Summary of the invention
The object of the present invention is to provide a kind of small size, lasing threshold is low, luminous intensity is high hexagonal phase NaYF of preparing
4The novel method of nano material is specifically related to induce preparation hexagonal phase NaYF take rare earth fluoride nanocrystalline as examining
4The method of nano based material.The method can be utilized the hot method of water (solvent) to induce under the condition that rare earth fluoride nanocrystalline exists and generate β-NaYF
4Nano material, particle size are from 20nm～200nm, and even size distribution can obtain the nano material that the up-conversion luminescence threshold value is low, luminous intensity is high after rare earth ion doped.It should be noted that especially and utilize preparation method involved in the present invention, can prepare and have water miscible, size less than the hexagonal phase NaYF of 50nm
4Nano material (specifically seeing embodiment 1).
The objective of the invention is to be achieved through the following technical solutions:
1. the rare earth fluoride nanocrystalline nuclear of preparation 10nm～100nm comprises NaREF
4, REF
3(RE is the rare earth ion abbreviation, specifically comprise ruthenium ion or lanthanide ion), the method for preparing rare earth fluoride nanocrystalline nuclear can be the precipitator method, the hot method of water (solvent), sol-gel method, high-temperature synthesis or microemulsion method, and the rare earth fluoride nanocrystalline nuclear of preparation is the molten or oil soluble of water (alcohol);
2. the rare earth fluoride nanocrystalline nuclear for preparing is dispersed in the solvent, utilizes the hot method of water (solvent), further generation hexagonal phase NaYF under the inducing of rare earth fluoride nanocrystalline nuclear
4The nano based material, concrete reactions steps is as follows:
(1) rare earth fluoride nanocrystalline nuclear is dispersed in the solvent under strong stirring or ultrasonic condition, obtains disperseing the solution of rare earth fluoride nanocrystalline nuclear;
(2) with rare-earth oxidation yttrium (Y
2O
3) powder dissolution in acid, prepare yttrium salt, or directly select yttrium salt as reactant; Yttrium salt is dissolved in the solvent identical with step (1), obtains the yttrium salts solution, yttrium salt comprises Yttrium trichloride, Yttrium trinitrate, yttrium stearate, trifluoroacetic acid yttrium or oleic acid yttrium;
(3) will be dissolved in the solvent identical with step (1) with the sodium salt that yttrium salt has an identical negatively charged ion, obtain sodium salt solution, sodium salt is sodium-chlor, SODIUMNITRATE, sodium stearate, sodium trifluoroacetate or sodium oleate;
(4) will obtain fluoride aqueous solution as the fluoride dissolution in fluorine source in the solvent identical with step (1), fluorochemical is one or more in Potassium monofluoride, Sodium Fluoride, Neutral ammonium fluoride, hydrofluoric acid, the trifluoroacetic acid;
(5) with surfactant dissolves in the solvent identical with step (1), obtain surfactant soln, tensio-active agent is one or both in cetyl trimethylammonium bromide (CTAB), ethylenediamine tetraacetic acid (EDTA) (EDTA), disodium edta (disodium or four sodium), citric acid, Trisodium Citrate, polyvinylpyrrolidone (PVP), polyimide (PEI), oleic acid (OA), the oleic acid amine;
(6) yttrium salts solution, sodium salt solution, fluorine source solution and surfactant soln are mixed, preparation contains Na
+, Y
3+, F
-Reactant solution, wherein the mol ratio of three kinds of ions is Na
+: Y
3+: F
-=1～10: 1: 5～10, the concentration of tensio-active agent is 0.005g/ml～0.5g/ml;
(7) solution of the dispersion rare earth fluoride nanocrystalline of preparation in the step (1) being examined and the reactant solution of step (6) preparation mix in the situation of strong stirring, and churning time is 2～24 hours, rare earth fluoride nanocrystalline nuclear and rare earth ion Y
3+Mol ratio be 0.2: 1～1: 1; The mixing solutions that obtains is packed in the autoclave with the tetrafluoroethylene liner, utilize the hot method of water (solvent), generation hexagonal phase NaYF under the inducing of rare earth fluoride nanocrystalline nuclear
4Nano based material, temperature of reaction are 150 ℃～220 ℃, and the reaction times is 2 hours～60 hours;
In step (6), further add the sensitizing agent rare earth ion (such as Yb
3+) and a kind of/multiple luminescence center rare earth ion (such as Tm
3+, Er
3+, Eu
3+, Ho
3+, Dy
3+, Gd
3+, Tb
3+, Nd
3+, Sm
3+), then can prepare with hexagonal phase NaYF
4The nano material with up-conversion luminescence character for substrate material.Wherein sensitizing agent rare earth ion and a kind of/multiple luminescence center rare earth ion occupy-place replace Y
3+So preparation has the hexagonal phase NaYF of up-conversion luminescence
4The reactant molar concentration rate of mentioning in step during nano material (6) is Na
+: RE
3+: F
-=1～10: 1: 5～10, RE wherein
3+Be all rare earth ions that comprise ruthenium ion, sensitizer ion, a kind of/multiple luminescence center rare earth ion.
Further, various rare earth ions comprise Er
3+(molar content is 0.1%～10%), Tm
3+(molar content 0.1%～10%), Yb
3+(molar content is 5%～20%), Eu
3+(molar content is 0.1%～10%), Ho
3+(molar content is 0.1%～10%), Dy
3+(molar content is 0.1%～10%), Tb
3+(molar content is 0.1%～10%), Gd
3+(molar content is 0.1%～20%), Nd
3+(molar content is 0.1%～10%), Sm
3+In (molar content is 0.1%～10%) one or more.The rare earth ion that mixes partly replaces hexagonal phase NaYF
4Y in the substrate material
3+Ion.
Used solvent is water, ethanol, ethylene glycol, dimethyl sulfoxide (DMSO), glycerol, acetone, hexane, hexanaphthene, oleic acid, oleic acid amine, octadecylene, trioctylphosphine amine or tri octyl phosphine among the present invention, should keep disperseing the solvent and the consistence of dissolving yttrium salt, sodium salt, fluorine source and tenside/solvent of rare earth fluoride nanocrystalline in reaction process.
Beneficial effect of the present invention:
1. the nano level up-conversion fluorescence substrate material of present method preparation is the hexagonal phase NaYF with higher up-conversion luminescence efficient
4, epigranular, favorable dispersity;
2. pass through the ratio of size, reactant concn and the tensio-active agent of adjusting fluorochemical nucleus, induce the hexagonal phase NaYF of generation
4Particle diameter can be regulated and control in 20nm～200nm scope, and minimum size can reach 20nm;
3. select the hydrophilic surfactant active to prepare to have the small size hexagonal phase NaYF of water (alcohol) dissolubility
4Nano material;
4. method repeatability is high, and repeatedly the prepared nanoparticle size velocity of variation of repeated experiments is no more than 5%;
5. doping up-conversion luminescence rare earth ion in reaction process obtains to induce the hexagonal phase NaYF of preparation take rare earth fluoride nanocrystalline as nuclear
4The Emission in Cubic NaYF of nano based material and identical particle size
4The nano based material is compared, and Up-conversion Intensity obviously improves.
Description of drawings
Fig. 1: the rare earth NaLuF that utilizes the solvent-thermal method preparation
4The stereoscan photograph of nanocrystal, median size are 18nm;
Fig. 2: with the NaLuF among Fig. 1
4The nanocrystalline NaYF that generates hexagonal phase that induces for nuclear
4: Yb, transmission electron microscope (TEM) photo of the rare earth ion doped nanometer up-conversion of Er, median size is 24nm;
Fig. 3: the NaLuF of Emission in Cubic
4Nanocrystal (descending) is induced the NaYF that generates hexagonal phase with it
4: Yb, the rare earth ion doped nanometer up-conversion of Er (on) the XRD curve;
Fig. 1, Fig. 2, Fig. 3 are corresponding to embodiment 1.Fig. 1 is the rare earth NaLuF that (2) step reaction obtains among the embodiment 1
4The stereoscan photograph of nanocrystal, median size are 18nm.Its XRD diffraction peak shown in the black curve of Fig. 3 middle and lower part, each diffraction peak can with NaLuF
4The standard diffraction card (JCPDS27-725) of Emission in Cubic is complementary, the rare earth NaLuF in the explanatory view 1
4Nanocrystal is pure Emission in Cubic.NaLuF with this Emission in Cubic
4The nanocrystalline NaYF that induces the generation hexagonal phase for nuclear according to (3) step reaction among the embodiment 1
4: Yb, the Er nano material, its transmission electron microscope photo as shown in Figure 2, median size is 24nm, with respect to the NaLuF of Emission in Cubic
4The nanocrystal particle diameter increases to some extent.Superposed curve is with NaLuF among Fig. 3
4The nanocrystalline NaYF that generates hexagonal phase that induces for nuclear
4: Yb, the XRD curve of Er nano material wherein is positioned at 17.3 °, 30.08 °, 31.02 °, 43.66 ° the corresponding hexagonal phase NaYF of diffraction peak difference
4(100), (110), (101), (201) face.The NaYF of these diffraction peaks and hexagonal phase
4The diffraction peak of (JCPDS 16-0334) matches in the standard diffraction card, illustrates at NaLuF
4Generated the NaYF of hexagonal phase under the inducing of nanocrystal
4Nano material.And the diffraction peak that is positioned at 28.2 °, 32.62 °, 46.64 ° in the XRD curve is respectively Emission in Cubic NaLuF
4The diffraction peak of nanocrystal (111), (200), (220) face.
Fig. 4: with NaLuF
4The nanocrystalline NaYF that generates hexagonal phase that induces for nuclear
4: Yb, the stereoscan photograph of Er, median size is 200nm;
Fig. 5: the NaLuF among Fig. 4
4Nanocrystal is induced and is generated hexagonal phase NaYF
4: Yb, the XRD curve of Er nano particle;
Fig. 4, Fig. 5 are corresponding to embodiment 3.Fig. 4 is that (3) step reaction obtains with NaLuF among the embodiment 3
4Nanocrystalline is that nuclear is induced the hexagonal phase NaYF of generation
4: Yb, Er nano particle stereoscan photograph, median size is 200nm.In the X ray diffracting spectrum of Fig. 5 sample, observed hexagonal phase NaYF
4Characteristic diffraction peak is positioned at 17.42 °, 30.14 °, 31.12 °, 43.76 ° and is respectively hexagonal phase NaYF
4(100), (110), (101), the diffraction peak of (201) face.Explanation is with NaLuF
4Nanocrystalline inducing for nuclear generated hexagonal phase NaYF
4: Yb, Er.Because the reaction times is longer, the NaYF of the hexagonal phase that obtains among the embodiment 3
4: Yb, Er sample particle diameter is larger, does not observe NaLuF
4The characteristic diffraction peak of nanocrystal.
Fig. 6: the NaGdF that utilizes the solvent-thermal method preparation
4The stereoscan photograph of nanocrystal, median size are 100nm;
Fig. 7: with NaGdF
4The nanocrystalline NaYF that generates hexagonal phase that induces for nuclear
4: Yb, the stereoscan photograph of Er, median size is 110nm;
Fig. 8: the NaGdF of hexagonal phase
4Nanocrystal is induced the NaYF that generates hexagonal phase with it
4: Yb, the XRD curve of Er nano particle.
Fig. 6, Fig. 7, Fig. 8 are corresponding to embodiment 4.Fig. 6 is the rare earth NaGdF that (2) step reaction obtains among the embodiment 4
4The stereoscan photograph of nanocrystal, median size are 100nm.Its XRD diffraction peak shown in the black curve of Fig. 8 middle and lower part, each diffraction peak can with NaGdF
4The standard diffraction card (JCPDS27-699) of Emission in Cubic is complementary, the rare earth NaGdF in the explanatory view 6
4Nanocrystal is pure hexagonal phase.Rare earth NaGdF with this hexagonal phase
4The nanocrystalline NaYF that induces the generation hexagonal phase for nuclear according to (3) step reaction among the embodiment 4
4: Yb, the Er nano material, its stereoscan photograph as shown in Figure 7, median size is 110nm, with respect to the NaGdF of hexagonal phase
4The nanocrystal particle diameter increases to some extent.Superposed curve is with NaGdF among Fig. 8
4The nanocrystalline NaYF that generates hexagonal phase that induces for nuclear
4: Yb, the XRD curve of Er nano material wherein is positioned at 17.46 °, 30.56 °, 31.08 °, 43.74 ° and is respectively hexagonal phase NaYF
4(100), (110), (101), the diffraction peak of (201) face.The NaYF of these diffraction peaks and hexagonal phase
4The diffraction peak of (JCPDS 16-0334) matches in the standard diffraction card, illustrates at NaGdF
4Generated the NaYF of hexagonal phase under the inducing of nanocrystal
4Nano material.The peak that is positioned at 17.46 °, 29.98 °, 30.56 °, 43.02 ° in X ray diffracting spectrum (Fig. 8, upper curve) is NaGdF
4The diffraction peak of nanocrystal (100), (110), (101), (201) face.Because NaYF
4With NaGdF
4The angle that differs of the diffraction peak of each face less, therefore locating the two at 17.46 ° and 30.56 ° has to a certain degree coincidence.
Embodiment
The present invention is further elaborated below in conjunction with specific embodiment.These embodiment of the present invention only are used for the specific embodiment of the present invention of explaining, rather than limit the scope of the invention.After reading the content of the present invention's instruction, those skilled in the art can make various changes or modification to the present invention, and these equivalent form of values fall within the scope defined in the application's appended claims equally.
Utilize the NaLuF of solvent-thermal method preparation among the embodiment
4And NaGdF
4The nanocrystalline NaYF that induces generation small size, hexagonal phase, ytterbium (Yb) and erbium (Er) codoped as rare earth fluoride nanocrystalline nuclear
4The brilliant material of upper conversion nano.It is reactant that rare-earth salts and sodium salt are chosen muriate, and Potassium monofluoride is as the fluorine source, and polyvinylpyrrolidone (PVP) is tensio-active agent, and ethylene glycol carries out solvent thermal reaction as reaction solvent.
Embodiment 1:
(1) the various reaction reagent solution of preparation.Take by weighing Yttrium trichloride 12.1306 grams, add 80ml ethylene glycol, be stirred to dissolving, the ethylene glycol solution of the Yttrium trichloride that be mixed with this moment is for preserving as storage liquid, and the concentration of ruthenium ion is 0.5mol/L in the solution.The same, take by weighing Erbium trichloride 1.528 grams, Ytterbium trichloride 7.7472 grams, thulium chloride 3.0663 grams, lutecium chloride 31.16 grams, sodium-chlor 4.675 grams, all add 80ml ethylene glycol, be made into the various muriatic ethylene glycol solution that concentration is respectively 0.05mol/L, 0.25mol/L, 0.1mol/L, 1mol/L, 1mol/L.
(2) preparation utilizes ethylene glycol to prepare rare earth fluoride nanocrystalline nuclear for solvent utilizes solvent-thermal method.Take by weighing 0.5 gram tensio-active agent PVP, add 8ml ethylene glycol, be stirred to dissolving, the lutecium chloride solution 1ml, the sodium chloride solution 1ml that get in proportion preparation in the step (1) add in the PVP solution, and the normal temperature lower magnetic force stirred 1 hour.Adding 8ml contains the ethylene glycol solution of 0.47 gram Potassium monofluoride, stirs 30 minutes.Above mixing solutions is transferred in the reactor, and temperature is 180 degrees centigrade, and the reaction times is 24 hours.After reaction finishes, obtain to disperse NaLuF
4Nanocrystalline ethylene glycol solution.X-ray diffraction experiment shows, the NaLuF of preparation
4Nanocrystal is pure Emission in Cubic NaLuF
4(seeing Fig. 3, lower curve) utilizes scanning electron microscopic observation rare earth fluoride nanocrystalline nuclear median size to be 18nm (Fig. 1).
(3) utilize the rare earth fluoride nanocrystalline nuclear of preparation in the step (2) to induce the NaYF that generates small size, hexagonal phase, ytterbium (Yb) and erbium (Er) codoped
4The brilliant material of upper conversion nano.Take by weighing 0.25 gram PVP, be dissolved in 3ml ethylene glycol, add yttrium chloride solution (0.76ml), Ytterbium trichloride solution (0.4ml), Erbium trichloride solution (0.2ml), sodium chloride solution (1ml), the normal temperature lower magnetic force stirred 1 hour.The dispersion NaLuF that adds preparation in the 9ml step (2)
4Ethylene glycol solution, strong stirring 1 hour.0.47 gram Potassium monofluoride is dissolved in 4ml ethylene glycol, adds mentioned solution, stirred 30 minutes, be transferred in the reactor, 180 degrees centigrade of lower reactions 24 hours.Use acetone precipitation, water and washing with alcohol, centrifugal, obtain white powder through 80 degrees centigrade of oven dry again.
(4) in X ray diffracting spectrum, observed hexagonal phase NaYF
4Characteristic diffraction peak (Fig. 3, upper curve), 17.3 °, 30.08 °, 31.02 °, 43.66 ° are respectively hexagonal phase NaYF
4(100), (110), (101), the diffraction peak of (201) face.And, utilize transmission electron microscope observing to be 24nm (Fig. 2) to the median size of nano particle, with pure Emission in Cubic NaLuF
4Nanocrystal is compared size to be increased to some extent, illustrates with NaLuF
4Nanocrystalline inducing for nuclear generated small size, hexagonal phase NaYF
4: Yb, Er.The peak that is positioned at 28.2 °, 32.62 °, 46.64 ° is NaLuF
4The diffraction peak of nanocrystal.
Embodiment 2:
(1) with embodiment 1 step (1).
(2) preparation utilizes ethylene glycol to prepare rare earth fluoride nanocrystalline nuclear for solvent utilizes solvent-thermal method.Take by weighing tensio-active agent PVP0.5 gram, add 8ml ethylene glycol, be stirred to dissolving, the lutecium chloride solution 1ml, the sodium chloride solution 1ml that get in proportion preparation in the step (1) add in the PVP solution, and the normal temperature lower magnetic force stirred 1 hour.Adding 8ml contains the ethylene glycol solution of 0.56 gram Potassium monofluoride, stirs 30 minutes.Above mixing solutions is transferred in the reactor, and temperature is 180 degrees centigrade, and the reaction times is 24 hours.After reaction finishes, obtain to disperse NaLuF
4Nanocrystalline ethylene glycol solution.NaLuF
4Nanocrystalline is pure Emission in Cubic, and median size is 25nm.
(3) induce the NaYF that generates small size, hexagonal phase, ytterbium (Yb) and erbium (Er) codoped with the rare earth fluoride nanocrystalline nuclear of preparation in the step (2)
4The brilliant material of upper conversion nano.Take by weighing 0.25 gram PVP, be dissolved in 3ml ethylene glycol, add yttrium chloride solution (0.76ml), Ytterbium trichloride solution (0.4ml), Erbium trichloride solution (0.2ml), sodium chloride solution (1ml), the normal temperature lower magnetic force stirred 1 hour.The NaLuF that adds preparation in the 9ml step (2)
4Ethylene glycol solution, strong stirring 1 hour.0.56 gram Potassium monofluoride is dissolved in 4ml ethylene glycol, adds mentioned solution, stirred 30 minutes, be transferred in the reactor, 200 degrees centigrade of lower reactions 36 hours.Use acetone precipitation, water and washing with alcohol, centrifugal, obtain white powder through 80 degrees centigrade of oven dry again.
(4) in the X ray diffracting spectrum of step (3) acquisition sample, observed hexagonal phase NaYF
4Characteristic diffraction peak is positioned at 17.22 °, 30.07 °, 30.77 °, 43.65 ° and is respectively hexagonal phase NaYF
4(100), (110), (101), the diffraction peak of (201) face.Explanation is with NaLuF
4Nanocrystalline inducing for nuclear generated hexagonal phase NaYF
4: Yb, Er.Scanning electron microscopic observation is that median size is 100nm to the median size of nano particle.
Embodiment 3:
(1) with embodiment 1 step (1).
(2) preparation utilizes ethylene glycol to prepare rare earth fluoride nanocrystalline nuclear for solvent utilizes solvent-thermal method.Take by weighing tensio-active agent PVP 0.5 gram, add 8ml ethylene glycol, be stirred to dissolving, the lutecium chloride solution 1ml, the sodium chloride solution 1ml that get in proportion preparation in the step (1) add in the PVP solution, and the normal temperature lower magnetic force stirred 1 hour.Adding 8ml contains the 4ml ethylene glycol solution of 0.56 gram Potassium monofluoride, stirs 30 minutes.Above mixing solutions is transferred in the reactor, and temperature is 180 degrees centigrade, and the reaction times is 24 hours.After reaction finishes, obtain to disperse NaLuF
4Nanocrystalline ethylene glycol solution.NaLuF
4Nanocrystalline is pure Emission in Cubic, and median size is 25nm.
(3) induce the NaYF that generates small size, hexagonal phase, ytterbium (Yb) and erbium (Er) codoped with the rare earth fluoride nanocrystalline nuclear of preparation in the step (2)
4The brilliant material of upper conversion nano.Take by weighing 0.25 gram PVP, be dissolved in 3ml ethylene glycol, add yttrium chloride solution (0.76ml), Ytterbium trichloride solution (0.4ml), Erbium trichloride solution (0.2ml), sodium chloride solution (1ml), the normal temperature lower magnetic force stirred 1 hour.The NaLuF that adds preparation in the 9ml step (2)
4Ethylene glycol solution, strong stirring 1 hour.0.56 gram Potassium monofluoride is dissolved in 4ml ethylene glycol, adds mentioned solution, stirred 30 minutes, be transferred in the reactor, 220 degrees centigrade of lower reactions 48 hours.Use acetone precipitation, water and washing with alcohol, centrifugal, obtain white powder through 80 degrees centigrade of oven dry again.Obtain with NaLuF
4The nanocrystalline NaYF that generates hexagonal phase that induces for nuclear
4: Yb, Er, median size is 200nm.
(4) observed hexagonal phase NaYF in the sample X ray diffracting spectrum that step (3) obtains
4Characteristic diffraction peak is positioned at 17.42 °, 30.14 °, 31.12 °, 43.76 ° and is respectively hexagonal phase NaYF
4(100), (110), (101), the diffraction peak of (201) face.Explanation is with NaLuF
4Nanocrystalline inducing for nuclear generated hexagonal phase NaYF
4: Yb, Er.Scanning electron microscopic observation is that median size is 200nm to the median size of nano particle.。Because the reaction times is longer, the NaYF of the hexagonal phase that step (3) obtains
4: Yb, Er sample particle diameter is larger, does not observe NaLuF
4The characteristic diffraction peak of nanocrystal.
Embodiment 4:
(1) the various reaction reagent solution of preparation.Take by weighing Yttrium trichloride 12.1306 grams, add 80ml ethylene glycol, be stirred to dissolving, the Yttrium trichloride ethylene glycol solution that be mixed with this moment is for preserving as storage liquid, and the concentration of ruthenium ion is 0.5mol/L in the solution.The same, take by weighing Erbium trichloride 1.528 grams, Ytterbium trichloride 7.7472 grams, thulium chloride 3.0663 grams, Gadolinium trichloride 29.729 grams, sodium-chlor 4.675 grams, all add 80ml ethylene glycol, be made into the various muriate ethylene glycol solutions that concentration is respectively 0.05mol/L, 0.25mol/L, 0.1mol/L, 1mol/L, 1mol/L.
(2) preparation utilizes ethylene glycol to prepare rare earth fluoride nanocrystalline nuclear for solvent utilizes solvent-thermal method.Take by weighing tensio-active agent PVP0.5 gram, add 8ml ethylene glycol, be stirred to dissolving, the Gadolinium trichloride solution 1ml, the sodium chloride solution 1ml that get in proportion preparation in the step (1) add in the PVP solution, and the normal temperature lower magnetic force stirred 1 hour.Adding 8ml contains the ethylene glycol solution of 0.47 gram Potassium monofluoride, stirs 30 minutes.Above mixing solutions is transferred in the reactor, and temperature is 180 degrees centigrade, and the reaction times is 24 hours.After reaction finishes, obtain to disperse NaGdF
4Nanocrystalline ethylene glycol solution.X-ray diffraction experiment shows, the NaGdF of preparation
4Nanocrystal is pure hexagonal phase NaGdF
4(seeing Fig. 8, lower curve) utilizes scanning electron microscopic observation rare earth fluoride nanocrystalline nuclear median size to be 100nm (Fig. 6).
(3) induce the NaYF that generates small size, hexagonal phase, ytterbium (Yb) and erbium (Er) codoped with the rare earth fluoride nanocrystalline nuclear of preparation in the step (2)
4The brilliant material of upper conversion nano.Take by weighing 0.25 gram PVP, be dissolved in 3ml ethylene glycol, add yttrium chloride solution (0.76ml), Ytterbium trichloride solution (0.4ml), Erbium trichloride solution (0.2ml), sodium chloride solution (1ml), the normal temperature lower magnetic force stirred 1 hour.The NaGdF that adds preparation in the 9ml step (2)
4Ethylene glycol solution, strong stirring 1 hour.0.235 gram Potassium monofluoride is dissolved in 4ml ethylene glycol, adds mentioned solution, stirred 30 minutes, be transferred in the reactor, 180 degrees centigrade of lower reactions 24 hours.Use acetone precipitation, water and washing with alcohol, centrifugal, obtain white powder through 80 degrees centigrade of oven dry again.Obtain with NaGdF
4The nanocrystalline NaYF that generates hexagonal phase that induces for nuclear
4: Yb, Er, median size is 110nm.
(4) observed hexagonal phase NaYF in the sample (Fig. 8, upper curve) that step (3) obtains
4Characteristic diffraction peak is positioned at 17.46 °, 30.56 °, 31.08 °, 43.74 ° and is respectively hexagonal phase NaYF
4(100), (110), (101), the diffraction peak of (201) face.Explanation is with NaGdF
4Nanocrystalline inducing for nuclear generated hexagonal phase NaYF
4: Yb, Er.Scanning electron microscopic observation is that median size is 110nm (Fig. 7) to the median size of nano particle.The peak that is positioned at 17.46 °, 29.98 °, 30.56 °, 43.02 ° in X ray diffracting spectrum (Fig. 8, upper curve) is NaGdF
4The diffraction peak of nanocrystal (100), (110), (101), (201) face.Because NaYF
4With NaGdF
4The angle that differs of the diffraction peak of each face less, therefore locating the two at 17.46 ° and 30.56 ° has to a certain degree coincidence.
Claims (7)
1. induce preparation small size hexagonal phase NaYF for one kind
4The method of nano based material, its step is as follows:
(a) water-soluble, the molten or oil-soluble NaREF of alcohol of preparation 10nm～100nm
4Or REF
3Rare earth fluoride nanocrystalline nuclear, wherein RE is ruthenium ion or lanthanide ion;
(b) rare earth fluoride nanocrystalline nuclear is dispersed in the solvent under strong stirring or ultrasonic condition, obtains disperseing the solution of rare earth fluoride nanocrystalline nuclear;
(c) with rare-earth oxidation yttrium Y
2O
3Powder dissolution prepares yttrium salt in acid, or directly selects yttrium salt as reactant; Yttrium salt is dissolved in the solvent identical with step (b) again, obtains the yttrium salts solution;
(d) will be dissolved in the solvent identical with step (b) with the sodium salt that yttrium salt has an identical negatively charged ion, obtain sodium salt solution;
(e) will as the fluoride dissolution in fluorine source in the solvent identical with step (b), obtain fluoride aqueous solution;
(f) with surfactant dissolves in the solvent identical with step (b), obtain surfactant soln;
(g) yttrium salts solution, sodium salt solution, fluorine source solution and surfactant soln are mixed, preparation contains Na
+, Y
3+, F
-Reactant solution, wherein the mol ratio of three kinds of ions is Na
+: Y
3+: F
-=1～10:1:5～10, the concentration of tensio-active agent are 0.005g/ml～0.5g/ml;
(h) solution of the dispersion rare earth fluoride nanocrystalline of preparation in the step (b) being examined and the reactant solution of step (g) preparation mix in the situation of strong stirring, and churning time is 2～24 hours, rare earth fluoride nanocrystalline nuclear and rare earth ion Y
3+Mol ratio be 0.2:1～1:1; The mixing solutions that obtains is packed in the autoclave with the tetrafluoroethylene liner, utilize water or solvent-thermal method, generation hexagonal phase NaYF under the inducing of rare earth fluoride nanocrystalline nuclear
4Nano based material, particle size are from 20nm～200nm, and temperature of reaction is 150 ℃～220 ℃, and the reaction times is 2 hours～60 hours.
2. a kind of inducing as claimed in claim 1 prepares small size hexagonal phase NaYF
4The method of nano based material is characterized in that: be to adopt the precipitator method, water or solvent-thermal method, sol-gel method, high-temperature synthesis or microemulsion method to prepare NaREF in the step (a)
4Or REF
3Rare earth fluoride nanocrystalline nuclear.
3. a kind of inducing as claimed in claim 1 prepares small size hexagonal phase NaYF
4The method of nano based material is characterized in that: the solvent in the step (b) is water, ethanol, ethylene glycol, dimethyl sulfoxide (DMSO), glycerol, acetone, hexane, hexanaphthene, oleic acid, oleic acid amine, octadecylene, trioctylphosphine amine or tri octyl phosphine.
4. a kind of inducing as claimed in claim 1 prepares small size hexagonal phase NaYF
4The method of nano based material is characterized in that: the yttrium salt in the step (c) is Yttrium trichloride, Yttrium trinitrate, yttrium stearate, trifluoroacetic acid yttrium or oleic acid yttrium.
5. a kind of inducing as claimed in claim 1 prepares small size hexagonal phase NaYF
4The method of nano based material is characterized in that: sodium salt is sodium-chlor, SODIUMNITRATE, sodium stearate, sodium trifluoroacetate or sodium oleate in the step (d).
6. a kind of inducing as claimed in claim 1 prepares small size hexagonal phase NaYF
4The method of nano based material is characterized in that: the fluorochemical of step (e) is one or more in Potassium monofluoride, Sodium Fluoride, Neutral ammonium fluoride, hydrofluoric acid, the trifluoroacetic acid.
7. a kind of inducing as claimed in claim 1 prepares small size hexagonal phase NaYF
4The method of nano based material is characterized in that: the tensio-active agent of step (f) is one or both in the disodium edta, citric acid, Trisodium Citrate, polyvinylpyrrolidone PVP, polyimide, oleic acid OA, oleic acid amine of cetyl trimethylammonium bromide CTAB, edta edta, disodium or four sodium.
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| CN106892449B (en) * | 2017-04-25 | 2019-03-15 | 辽宁大学 | NaYF4Colloidal sol and its preparation method and application |
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