CN103087705A - High-strength rare earth-doped up-conversion luminescence nanometer material and preparation method thereof - Google Patents
High-strength rare earth-doped up-conversion luminescence nanometer material and preparation method thereof Download PDFInfo
- Publication number
- CN103087705A CN103087705A CN2013100165940A CN201310016594A CN103087705A CN 103087705 A CN103087705 A CN 103087705A CN 2013100165940 A CN2013100165940 A CN 2013100165940A CN 201310016594 A CN201310016594 A CN 201310016594A CN 103087705 A CN103087705 A CN 103087705A
- Authority
- CN
- China
- Prior art keywords
- acid
- water
- ligand
- rare earth
- conversion luminescence
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- GDFAOVXKHJXLEI-UHFFFAOYSA-N CC(C(O)=O)NC Chemical compound CC(C(O)=O)NC GDFAOVXKHJXLEI-UHFFFAOYSA-N 0.000 description 1
- GYCKQBWUSACYIF-UHFFFAOYSA-N CCOC(c(cccc1)c1O)=O Chemical compound CCOC(c(cccc1)c1O)=O GYCKQBWUSACYIF-UHFFFAOYSA-N 0.000 description 1
Images
Landscapes
- Luminescent Compositions (AREA)
Abstract
The invention provides a method of improving luminous efficiency of a rare earth-doped up-conversion luminescence nanometer material through changing the usage of a ligand. According to the method, the synthesis adopts a hydrothermal-solvothermal method, an organic ligand is an organic compound such as monocarboxylic acid, dicarboxylic acid or polycarboxylic acid, and amine, the molar ratio of rare earth ions to the ligand is 2:1-1:100, the molar ratio of NaOH to the ligand is 0:1-1:1, water/alcohol, water/n-propanol alcohol, water/isopropyl alcohol, water/n-butyl alcohol, water/acetone or water/ethylene glycol is used as a solvent, the temperature ranges from 180-240 DEG C, the reaction time is 2-24h, and the F<->/Re value ranges from 4-12. With the method, the problems of selecting various ligands for synthesizing the up-conversion luminescence nanometer material, improving the luminous efficiency of the rare earth-doped up-conversion luminescence nanometer material, synthesizing the water-soluble up-conversion luminescence nanometer material, and the like can be mainly solved.
Description
Technical field
The present invention relates to a kind of high strength rare earth doping up-conversion luminescence nano material and preparation method thereof, belong to field of nano material preparation.
Background technology
Rear-earth-doped up-conversion luminescence nano material is due to its unique characteristics of luminescence, as: abundant optical property, narrow emission peak, illuminant colour purity is high, fluorescence lifetime is long, near infrared excites etc., makes it all have great potential application at aspects such as laser writer, optical data storage, biomarker, solar cells.The preparation method of up-conversion luminescent material mainly is divided into two kinds: high temperature oil phase method and hydro-thermal-solvent-thermal method, high temperature oil phase method is by using high boiling solvent at high temperature to react the synthesis of nano luminescent material, because its hot conditions makes the ligand species that can select less; And hydro-thermal-solvent thermal rule adopts the method for High Temperature High Pressure to obtain high-quality nano particle, this synthetic method makes temperature of reaction relatively gentle because of condition of high voltage, the range of choice of part is widened to a great extent, and the more lower boiling compound of some short carbon chains also can be applied to synthetic upper conversion nano luminescent material.
The luminous efficiency of up-conversion luminescent material is to hinder the principal element of its industrial application always, and the luminous efficiency that how to improve the up-conversion luminescence nano material receives very large concern always.Core-shell structured nanomaterials, plasma resonance method, the method such as metal-doped can improve the luminous efficiency of up-conversion nano material to a certain extent, but the shortcoming such as these all exist preparation to copy, and are expensive.
Along with the application development of up-conversion luminescence nano material at biology and field of medicaments, have water miscible upper conversion nano luminescent material and be badly in need of utilizing.Although replace or the method for polymer overmold can obtain having water miscible up-conversion luminescence nano material by part, these methods not only complicated operation, efficient is lower and cost is higher.
Summary of the invention
The objective of the invention is for solve less part optionally go up the conversion nano luminescent material preparation and by selecting different parts to synthesize high luminous intensity, color and the luminous material of water miscible upper conversion nano material.
Technical scheme of the present invention is kind and the quantity of the carbon chain lengths that changes part, coordination functional group, by reducing the nonradiative transition of the active ions that part causes by stretching vibration, improves the luminous efficiency of up-conversion luminescence nano material.
A kind of high strength rare earth doping up-conversion luminescence nano material, described material is that ligand L is passed through the coordination chemistry key and is combined the nano material that forms with the rare earth ion of rear-earth-doped up-conversion luminescence nano material, and described rear-earth-doped up-conversion luminescence nano material has following structure:
MNF
y:Yb
3+,Re
Wherein, M is selected from Na
+, Li
+, K
+, Mg
2+, Ca
2+And Ba
2+In a kind of; N is Y
3+, Gd
3+Or Lu
3+Y is 4 or 5; Re is Er
3+, Ho
3+Or Tm
3+
Described ligand L is organic compound take C1～C18 carbochain as skeleton, and described organic compound contains 1～6 substituting group, and described substituting group is selected from least a in carboxyl, hydroxyl and amino.
MNF of the present invention
y: Yb
3+, the Re compound refers to MNF
yType compound N position doping Yb
3+With the compound of Re ion, y is 4 when M position ion is monovalent ion, and during divalent ion, y is 5.M, N, the selection of Re ion, Yb in this compounds
3+With the prior art that is defined as art technology of the doping of Re ion, those skilled in the art can determine by the requirement to luminescent material luminous intensity etc.
The preferred described MNF of the present invention
y: Yb
3+, the Re compound is NaYF
4: Yb, Er, NaYF
4: Yb, Tm, NaYF
4: Yb, Ho, LiYF
4: Yb, Er, KYF
4: Yb, Er, MgYF
5: Yb, Er, CaYF
5: Yb, Er, BaYF
5: Yb, Er, NaGdF
4: Yb, Er or NaLuF
4: Yb, Er, more preferably NaYF
4: Yb, Er, NaYF
4: Yb, Tm or NaGdF
4: Yb, Er.
The preferred described MNF of the present invention
y: Yb
3+, Yb in the Re compound
3+With the mol ratio of Re be 10:1, further preferred Yb
3+With mole doping of Re ion be 20% and 2%.
C1 of the present invention～C18 carbochain comprises saturated alkyl, unsaturated alkyl (alkylene), aryl etc.Term used herein " alkyl " comprises straight chained alkyl and branched-chain alkyl.As mention single alkyl as " propyl group ", and only refer in particular to straight chained alkyl, as mention single branched-chain alkyl as " sec.-propyl ", only refer in particular to branched-chain alkyl.
The preferred described ligand L of high strength rare earth doping up-conversion luminescence nano material of the present invention is the organic compound with general formula I:
In formula, R
1Be C
1～C
17Saturated or unsaturated alkyl; Hydroxyl or the amino C that replaces
1～C
17Saturated alkyl; Hydroxyl or the amino C that replaces
1～C
17Unsaturated alkyl, aryl.
More preferably propionic acid, 4-pentenoic acid, maleic acid, alpha-hydroxybutyric acid, L-Ala, oleic acid, phenylformic acid or Whitfield's ointment, further be preferably propionic acid, 4-pentenoic acid, alpha-hydroxybutyric acid, L-Ala, phenylformic acid or Whitfield's ointment.
Propionic acid 4-pentenoic acid alpha-hydroxybutyric acid
The L-Ala benzoic acid salicylic acid
The preferred described ligand L of high strength rare earth doping up-conversion luminescence nano material of the present invention is the organic compound with general formula I I:
In formula: R
2Be C
1～C
16Saturated or unsaturated alkyl; The C of hydroxyl, amino or carboxyl substituted
1～C
16Saturated alkyl or unsaturated alkyl; The C of carboxyl substituted
1～C
16Unsaturated alkyl, phenyl, aryl.
More preferably succinic acid, oxysuccinic acid, tartrate, phthalic acid, citric acid or ethylenediamine tetraacetic acid (EDTA).
Succinic acid oxysuccinic acid tartrate
The phthalic acid ethylenediamine tetraacetic acid (EDTA)
The preferred described organic ligand L of high strength rare earth doping up-conversion luminescence nano material of the present invention is butylamine, quadrol or triethylene tetramine.
The butylamine quadrol
Triethylene tetramine
Principle of the present invention:
Adopt the synthetic rare earth doped upper conversion nano luminescent material of hydro-thermal-solvent-thermal method, because high-pressure sealed environment makes its temperature of reaction relatively low, the elevation of boiling point of reaction mass, thus make available part reduced by the restriction of ambient conditions, and namely available amount of ligand increases.Fig. 5 is the principle of luminosity of rear-earth-doped up-conversion luminescent material, and activator Er3+ has a plurality of energy levels, the corresponding different wave length of different energy levels, and extraneous energy vibration can cause Er
3+Transition at different energy levels.Be combined by the ligand complex bond between organic ligand and upper conversion nano luminescent material, contain the part of different carbon chain lengths and group because of the stretching vibration energy of himself, as: the 2800-3000cm of CH
-1The 3300-3400cm of stretching vibration energy, OH
-1The 3300-3500cm of stretching vibration energy, NH
-1The stretching vibration energy, with Er
3+ 4S
3/2-
4F
9/2With
4F
9/2-
4I
11/2Energy difference between energy level is complementary, the nonradiative transition of activator Er3+ in the conversion nano luminescent material in impact, thus cause the luminous intensity of conversion nano luminescent material and the change of glow color.The part of long carbochain makes part at 2800-3000cm because containing the number of CH key increases
-1Place's stretching vibration can strengthen, and has strengthened Er
3+ 4S
3/2-
4F
9/2Nonradiative transition between energy level, thus the luminous efficiency of upper conversion nano luminescent material further reduced.And-OH ,-NH
2Or-increase of COOH group, strengthened part at 3300-3500cm
-1The stretching vibration energy, strengthened
4F
9/2-
4I
11/2Nonradiative transition between energy level, and then reduced the luminous efficiency of upper conversion nano luminescent material.The different carbon chain lengths part or contain different numbers-OH ,-NH
2The water-soluble difference of part of ,-COOH group, and organic ligand with the form complexing of coordinate bond on the surface of upper conversion nano luminescent material, thereby make part and upper conversion nano luminescent material have in various degree water-soluble in conjunction with product.
Another object of the present invention is to provide above-mentioned high strength rare earth doping up-conversion luminescence preparations of nanomaterials method.
A kind of high strength rare earth doping up-conversion luminescence preparations of nanomaterials method, described method is hydro-thermal-organic solvent thermal synthesis method, according to target MNF
y: Yb
3+The Re compound is dissolved in rare earth ion source compound and ligand L compound in reaction solvent, and wherein the mol ratio of rare earth element ion and ligand compound is 2:1～1:100, adds NaOH, the mol ratio of NaOH and ligand L compound is 0:1～1:1, obtain solution A; Alkaline metal fluoride cpd is dissolved in reaction solvent, forms solution B; Add solution B in solution A, the mol ratio of fluorion and rare earth ion is 4～12, moves in reactor in 180～240 ℃ reaction 2～24h after mixing;
Wherein, reaction solvent is water-ethanol, water-methanol, water-Virahol, water-n-propyl alcohol, water-propyl carbinol or water-ethylene glycol solvent, wherein the volume ratio of water and organic solvent is 2:1～1:5, and more preferably water-ethanol is the reaction solvent that 1:1 forms by the volume ratio of water and ethanol.
Wherein, M is selected from Na
+, Li
+, K
+, Mg
2+, Ca
2+And Ba
2+In a kind of; N is Y
3+, Gd
3+Or Lu
3+Y is 4 or 5; Re is Er
3+, Ho
3+Or Tm
3+
Described ligand L is organic compound take C1～C18 carbochain as skeleton, and described organic compound contains 1～6 substituting group, and described substituting group is selected from least a in carboxyl, hydroxyl and amino.
The source compound of rare earth ion described in aforesaid method is preferably rare earth ion nitrate, and described rare earth ion is Y
3+, Gd
3+, Lu
3+, Er
3+, Ho
3+Or Tm
3+Alkaline metal fluoride cpd is NaF, KF.
Rare earth nitrate salt in the preferred described solution A of high strength rare earth doping up-conversion luminescence preparations of nanomaterials method of the present invention: deionized water: ethanol is than being 1:20:20(mmol:mL:mL); Metal fluoride in solution B: deionized water: the ethanol ratio is 4～12:10:10(mmol:mL:mL).
Aforesaid method further comprises the step of aftertreatment: after reactor is cooling, removes supernatant liquid, collects solid, and centrifugal with the mixing liquid washed twice of second alcohol and water, drying.
Preferred technical scheme of high strength rare earth doping up-conversion luminescence preparations of nanomaterials method of the present invention is:
Get 0.4M rare earth ion nitrate aqueous solution in beaker, rare earth ion nitrate aqueous solution by volume: deionized water: organic solvent is 2.5:2.5～30:11～40, add deionized water and organic solvent ethanol, add again ligand compound and NaOH, wherein, the mol ratio of rare earth element ion and ligand compound is 2:1～1:100, and the mol ratio of NaOH and ligand compound is 0:1～1:1, stir, form solution A;
By alkaline metal fluoride cpd: deionized water: the organic solvent ratio is 168～504:10:10(mg:mL:mL) NaF to be dissolved in deionized water and alcohol mixeding liquid, stirs, and forms solution B;
Under agitation, dropwise drip B solution in A, the mol ratio of fluorion and rare earth ion is 4～12, and after dripping, ultra-sonic dispersion is transferred in water heating kettle and heats, 180～240 ℃ of Heating temperatures, reaction 2～24h.
After reactor is cooling, remove supernatant liquid, collect solid, centrifugal with the mixing liquid washed twice of second alcohol and water, drying.
In high strength rare earth doping up-conversion luminescence preparations of nanomaterials method of the present invention, preferred described ligand L is the organic compound with general formula I:
In formula, R
1Be C
1～C
17Saturated or unsaturated alkyl; Hydroxyl or the amino C that replaces
1～C
17Saturated alkyl; Hydroxyl or the amino C that replaces
1～C
17Unsaturated alkyl, aryl.
More preferably propionic acid, 4-pentenoic acid, maleic acid, alpha-hydroxybutyric acid, L-Ala, oleic acid, phenylformic acid or Whitfield's ointment, further be preferably propionic acid, 4-pentenoic acid, alpha-hydroxybutyric acid, L-Ala, phenylformic acid or Whitfield's ointment.
Propionic acid 4-pentenoic acid alpha-hydroxybutyric acid
The L-Ala benzoic acid salicylic acid
In high strength rare earth doping up-conversion luminescence preparations of nanomaterials method of the present invention, preferred described ligand L is the organic compound with general formula I I:
In formula: R
2Be C
1～C
16Saturated or unsaturated alkyl; The C of hydroxyl, amino or carboxyl substituted
1～C
16Saturated alkyl or unsaturated alkyl; The C of carboxyl substituted
1～C
16Unsaturated alkyl, phenyl, aryl.
More preferably succinic acid, oxysuccinic acid, tartrate, phthalic acid, citric acid or ethylenediamine tetraacetic acid (EDTA).
Succinic acid oxysuccinic acid tartrate
The phthalic acid ethylenediamine tetraacetic acid (EDTA)
In high strength rare earth doping up-conversion luminescence preparations of nanomaterials method of the present invention, preferred described organic ligand L is butylamine, quadrol or triethylene tetramine.
The butylamine quadrol
Triethylene tetramine
Beneficial effect of the present invention is: the invention solves that the part selectivity is few, the shortcomings such as low luminous efficiency of rear-earth-doped upper conversion nano luminescent material, and can directly synthesize and have different water miscible upper conversion nano luminescent materials.In synthetic rare earth doped upper conversion nano luminescent material, the amount of ligand of having reported is very limited, as: oleic acid, Trisodium Citrate, disodium ethylene diamine tetraacetate, oleyl amine, tri octyl phosphine etc., the present invention can provide the multiclass part available.On improving in the method for conversion nano luminescent material luminous efficiency, the general methods such as nucleocapsid structure, plasma resonance, metal ion mixing that adopt, but these methods not only prepare complicated and expensive, by selecting the direct upper conversion nano luminescent material of synthesizing efficient rate of different ligands.In addition, by selecting dissimilar part, as the hydrophilic radical with different numbers or type, make with the part upper conversion nano luminescent material by the coordinate bond complexing have in various degree water-soluble.
Description of drawings
Fig. 1 is in embodiment 2～7, the NaYF that synthesizes take propionic acid, butyric acid, caproic acid, capric acid, TETRADECONIC ACID and oleic acid as part
4: Yb, the XRD figure of Er nanocrystal.Fig. 1 shows, take the carboxylic acid of different carbon chain lengths as part synthetic material XRD spectra and standard hexagonal crystal phase NaYF
4: Yb, the Er card is consistent, and namely synthetic material is all the NaYF of six side's phases
4: Yb, Er crystal.The change of part carbon chain lengths can not affect structure and the crystalline phase of product.
Fig. 2 is in embodiment 2～7, the NaYF that synthesizes take propionic acid, butyric acid, caproic acid, capric acid, TETRADECONIC ACID and oleic acid as part
4: Yb, the up-conversion fluorescence spectrogram of Er nanocrystal.Fig. 2 shows, along with the growth of part carbon chain lengths, NaYF
4: Yb, the luminous intensity of Er nanocrystal weakens gradually, and propionic acid is the synthetic NaYF of part
4: Yb, Er nanocrystal luminous intensity is weaker than the synthetic NaYF of butyric acid
4: Yb, Er nanocrystal are mainly because the reason that the part particle diameter reduces.The part carbochain is longer, synthetic NaYF
4: Yb, Er nanocrystal luminous intensity is more weak.
Fig. 3 is in embodiment 13～16, the NaYF that synthesizes take caproic acid, hexanodioic acid, citric acid and ethylenediamine tetraacetic acid (EDTA) as part
4: Yb, Er nanocrystal up-conversion fluorescence spectrogram.The carbon chain lengths of caproic acid, hexanodioic acid, citric acid and ethylenediamine tetraacetic acid (EDTA) is more or less the same, but the carboxylic acid number is respectively 1,2,3 and 4.Fig. 3 shows, along with the increase of carboxylic acid number in part, synthetic NaYF
4: Yb, Er nanocrystal luminous intensity weakens gradually.
Fig. 4 is in embodiment 17～19, the NaYF that synthesizes take butylamine, diethylenetriamine and triethylene tetramine as part
4: Yb, Er nanocrystal up-conversion fluorescence spectrogram.Fig. 4 demonstration, along with the increase of amino number in part, synthetic NaYF
4: Yb, Er nanocrystal luminous intensity weakens gradually.
Fig. 5 is the principle of luminosity of rear-earth-doped up-conversion luminescent material.
Embodiment
Following non-limiting example can make the present invention of those of ordinary skill in the art's comprehend, but does not limit the present invention in any way.
Embodiment 1
Get the 78%Y (NO of 2.5mL0.4M
3)
3, 20%Yb (NO
3)
3, 2%Er (NO
3)
3The aqueous solution adds the deionized water of 16mL and the ethanol of 18.5mL in beaker, then adds the oleic acid of 7ml, stirs, and forms solution A.The NaF that takes 504mg is dissolved in the ethanol of the water of 10mL and 10mL, stirs, and forms solution B.A under agitation, dropwise drips B solution after stirring 30min in A, after dripping, ultrasonic half an hour, be transferred in the 75mL water heating kettle, screw capping is put into baking oven and is heated, Heating temperature 200 degree, reaction 10h, cooling, remove supernatant liquid, solid below collecting, with the mixing liquid washed twice of second alcohol and water, centrifugal, drying obtains the NaYF of oleic acid part complexing
4: Yb, Er.
Embodiment 2～7
Get the 78%Y (NO of 2.5mL0.4M
3)
3, 20%Yb (NO
3)
3, 2%Er (NO
3)
3The aqueous solution adds the deionized water of 14mL and the ethanol of 16.5mL in beaker, add propionic acid, butyric acid, caproic acid, capric acid, TETRADECONIC ACID or the oleic acid of 7ml and the NaOH of 0.7g, stirs, and forms solution A.The NaF that takes 504mg is dissolved in the ethanol of the water of 10mL and 10mL, stirs, and forms solution B.A under agitation, dropwise drips B solution after stirring 30min in A, after dripping, ultrasonic half an hour, be transferred in the 75mL water heating kettle, screw capping is put into baking oven and is heated, Heating temperature 200 degree, reaction 7h, cooling, remove supernatant liquid, solid below collecting, with the mixing liquid washed twice of second alcohol and water, centrifugal, drying obtains the NaYF of different carbon chain lengths Carboxylic acid ligand complexing
4: Yb, Er nanocrystal.
Get the 78%Y (NO of 2.5mL0.4M
3)
3, 20%Yb (NO
3)
3, 2%Er (NO
3)
3The aqueous solution adds the deionized water of 17.5mL and the ethanol of 20mL in beaker, add phenylformic acid or the Whitfield's ointment of 1mmol, forms solution A.The NaF that takes 504mg is dissolved in the ethanol of the water of 10mL and 10mL, stirs, and forms solution B.A under agitation, dropwise drips B solution after stirring 30min in A, after dripping, ultrasonic half an hour, be transferred in the 75mL water heating kettle, screw capping is put into baking oven and is heated, Heating temperature 200 degree, reaction 7h, cooling, remove supernatant liquid, solid below collecting, with the mixing liquid washed twice of second alcohol and water, centrifugal, drying obtains the NaYF of phenylformic acid or Whitfield's ointment complexing
4: Yb, Er nanocrystal.
Get the 78%Y (NO of 2.5mL0.4M
3)
3, 20%Yb (NO
3)
3, 2%Er (NO
3)
3The aqueous solution adds the deionized water of 17.5mL and the ethanol of 20mL in beaker, add succinic acid, oxysuccinic acid or the tartrate of 1mmol, forms solution A.The NaF that takes 504mg is dissolved in the ethanol of the water of 10mL and 10mL, stirs, and forms solution B.A under agitation, dropwise drips B solution after stirring 30min in A, after dripping, ultrasonic half an hour, be transferred in the 75mL water heating kettle, screw capping is put into baking oven and is heated, Heating temperature 200 degree, reaction 7h, cooling, remove supernatant liquid, solid below collecting, with the mixing liquid washed twice of second alcohol and water, centrifugal, drying obtains the NaYF of succinic acid, oxysuccinic acid or tartrate complexing
4: Yb, Er nanocrystal.
Embodiment 13～16
Get the 78%Y (NO of 2.5mL0.4M
3)
3, 20%Yb (NO
3)
3, 2%Er (NO
3)
3The aqueous solution adds the deionized water of 17.5mL and the ethanol of 20mL in beaker, add caproic acid, hexanodioic acid, Trisodium Citrate or the disodium ethylene diamine tetraacetate of 1mmol, forms solution A.The NaF that takes 504mg is dissolved in the ethanol of the water of 10mL and 10mL, stirs, and forms solution B.A under agitation, dropwise drips B solution after stirring 30min in A, after dripping, ultrasonic half an hour, be transferred in the 75mL water heating kettle, screw capping is put into baking oven and is heated, Heating temperature 200 degree, reaction 7h, cooling, remove supernatant liquid, solid below collecting, with the mixing liquid washed twice of second alcohol and water, centrifugal, drying obtains the NaYF of different carboxylic acids number part complexing
4: Yb, Er nanocrystal.
Embodiment 17～19
Get the 78%Y (NO of 2.5mL0.4M
3)
3, 20%Yb (NO
3)
3, 2%Er (NO
3)
3The aqueous solution adds the deionized water of 17.5mL and the ethanol of 20mL in beaker, add butylamine, diethylenetriamine or the triethylene tetramine of 0.2mL, forms solution A.The NaF that takes 504mg is dissolved in the ethanol of the water of 10mL and 10mL, stirs, and forms solution B.A under agitation, dropwise drips B solution after stirring 30min in A, after dripping, ultrasonic half an hour, be transferred in the 75mL water heating kettle, screw capping is put into baking oven and is heated, Heating temperature 200 degree, reaction 7h, cooling, remove supernatant liquid, solid below collecting, with the mixing liquid washed twice of second alcohol and water, centrifugal, drying obtains the NaYF of different amine complexings
4: Yb, Er nanocrystal.
Get the 78%Y (NO of 2.5mL0.4M
3)
3, 20%Yb (NO
3)
3, 2%Tm (NO
3)
3The aqueous solution adds the deionized water of 14mL and the ethanol of 16.5mL in beaker, then adds the oleic acid of 7ml and the NaOH of 0.7g, stirs, and forms solution A.The NaF that takes 504mg is dissolved in the ethanol of the water of 10mL and 10mL, stirs, and forms solution B.A under agitation, dropwise drips B solution after stirring 30min in A, after dripping, ultrasonic half an hour, be transferred in the 75mL water heating kettle, screw capping is put into baking oven and is heated, Heating temperature 200 degree, reaction 7h, cooling, remove supernatant liquid, solid below collecting, with the mixing liquid washed twice of second alcohol and water, centrifugal, drying obtains the NaYF of oleic acid part complexing
4: Yb, Tm.
Embodiment 21
Get the 78%Gd (NO of 2.5mL0.4M
3)
3, 20%Yb (NO
3)
3, 2%Tm (NO
3)
3The aqueous solution adds the deionized water of 14mL and the ethanol of 16.5mL in beaker, then adds the oleic acid of 7ml and the NaOH of 0.7g, stirs, and forms solution A.The NaF that takes 504mg is dissolved in the ethanol of the water of 10mL and 10mL, stirs, and forms solution B.A under agitation, dropwise drips B solution after stirring 30min in A, after dripping, ultrasonic half an hour, be transferred in the 75mL water heating kettle, screw capping is put into baking oven and is heated, Heating temperature 200 degree, reaction 7h, cooling, remove supernatant liquid, solid below collecting, with the mixing liquid washed twice of second alcohol and water, centrifugal, drying obtains the NaGdF of oleic acid part complexing
4: Yb, Tm.
Embodiment 22～27
Get the 78%Y (NO of 2.5mL0.4M
3)
3, 20%Yb (NO
3)
3, 2%Er (NO
3)
3The aqueous solution adds the deionized water of 14mL and methyl alcohol, n-propyl alcohol, Virahol, propyl carbinol, ethylene glycol or the acetone of 16.5mL in beaker, then adds the oleic acid of 73-30ml and the NaOH of 0.7g, stirs, and forms solution A.The NaF that takes 504mg is dissolved in methyl alcohol, n-propyl alcohol, Virahol, propyl carbinol or the acetone of the water of 10mL and 10mL, stirs, and forms solution B.A under agitation, dropwise drips B solution after stirring 30min in A, after dripping, ultrasonic half an hour, be transferred in the 75mL water heating kettle, screw capping is put into baking oven and is heated, Heating temperature 200 degree, reaction 7h, cooling, remove supernatant liquid, solid below collecting, with the mixing liquid washed twice of second alcohol and water, centrifugal, drying obtains the NaYF of oleic acid part complexing
4: Yb, Er.
Embodiment 28
Get the 78%Y (NO of 2.5mL0.4M
3)
3, 20%Yb (NO
3)
3, 2%Er (NO
3)
3The aqueous solution adds the deionized water of 1.5mL and the ethylene glycol of 45mL in beaker, then adds the oleic acid of 7ml, stirs, and forms solution A.The NaF that takes 504mg is dissolved in the water of 5mL, stirs, and forms solution B.A under agitation, dropwise drips B solution after stirring 30min in A, after dripping, ultrasonic half an hour, be transferred in the 75mL water heating kettle, screw capping is put into baking oven and is heated, Heating temperature 200 degree, reaction 12h, cooling, remove supernatant liquid, solid below collecting, with the mixing liquid washed twice of second alcohol and water, centrifugal, drying obtains the NaYF of oleic acid part complexing
4: Yb, Er.
Claims (8)
1. high strength rare earth doping up-conversion luminescence nano material, it is characterized in that: described material is that ligand L is passed through the rare earth ion of coordination chemistry key in rear-earth-doped up-conversion luminescence nano material and is combined the nano material that forms, and described rear-earth-doped up-conversion luminescence nano material has following structure:
MNF
y:Yb
3+,Re
Wherein, M is selected from Na
+, Li
+, K
+, Mg
2+, Ca
2+And Ba
2+In a kind of; N is Y
3+, Gd
3+Or Lu
3+Y is 4 or 5; Re is Er
3+, Ho
3+Or Tm
3+
Described ligand L is organic compound take C1～C18 carbochain as skeleton, and described organic compound contains 1～6 substituting group, and described substituting group is selected from least a in carboxyl, hydroxyl and amino.
2. material according to claim 1, it is characterized in that: described ligand L is the organic compound with general formula I:
In formula, R
1Be C
1～C
17Saturated or unsaturated alkyl; Hydroxyl or the amino C that replaces
1～C
17Saturated alkyl; Hydroxyl or the amino C that replaces
1～C
17Unsaturated alkyl, aryl.
3. material according to claim 1, it is characterized in that: described ligand L is the organic compound with general formula I I:
In formula, R
2Be C
1～C
16Saturated or unsaturated alkyl; The C of hydroxyl, amino or carboxyl substituted
1～C
16Saturated alkyl; The C of hydroxyl, amino or carboxyl substituted
1～C
16Unsaturated alkyl, aryl.
4. material according to claim 1, it is characterized in that: described ligand L is butylamine, quadrol or triethylene tetramine.
5. material according to claim 2, it is characterized in that: described ligand L is propionic acid, 4-pentenoic acid, maleic acid, alpha-hydroxybutyric acid, L-Ala, oleic acid, phenylformic acid or Whitfield's ointment.
6. material according to claim 3, it is characterized in that: described ligand L is succinic acid, oxysuccinic acid, tartrate, phthalic acid, citric acid or ethylenediamine tetraacetic acid (EDTA).
7. according to claim 1～6 described materials of arbitrary claim, it is characterized in that: described doping up-conversion luminescence nano material is NaYF
4: Yb, Er, NaYF
4: Yb, Tm, LiYF
4: Yb, Er, KYF
4: Yb, Er, MgYF
5: Yb, Er, CaYF
5: Yb, Er, BaYF
5: Yb, Er, NaGdF
4: Yb, Er or NaLuF
4: Yb, Er.
8. high strength rare earth doping up-conversion luminescence preparations of nanomaterials method, it is characterized in that: described method is hydro-thermal-organic solvent thermal synthesis method, according to target MNF
y: Yb
3+The Re compound is dissolved in rare earth ion source compound and ligand compound in reaction solvent, and wherein the mol ratio of rare earth element ion and ligand L compound is 2:1～1:100, adds NaOH, the mol ratio of NaOH and ligand L compound is 0:1～1:1, obtain solution A; Alkaline metal fluoride cpd is dissolved in reaction solvent, forms solution B; Add solution B in solution A, the mol ratio of fluorion and rare earth ion is 4～12, moves in reactor in 180～240 ℃ reaction 2～24h after mixing;
Wherein, reaction solvent is water-ethanol, water-methanol, water-Virahol, water-n-propyl alcohol, water-propyl carbinol or water-ethylene glycol solvent, and wherein the volume ratio of water and organic solvent is 2:1～1:5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013100165940A CN103087705A (en) | 2013-01-16 | 2013-01-16 | High-strength rare earth-doped up-conversion luminescence nanometer material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013100165940A CN103087705A (en) | 2013-01-16 | 2013-01-16 | High-strength rare earth-doped up-conversion luminescence nanometer material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103087705A true CN103087705A (en) | 2013-05-08 |
Family
ID=48200852
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2013100165940A Pending CN103087705A (en) | 2013-01-16 | 2013-01-16 | High-strength rare earth-doped up-conversion luminescence nanometer material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103087705A (en) |
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103666474A (en) * | 2013-12-19 | 2014-03-26 | 中国科学院苏州纳米技术与纳米仿生研究所 | Red light/near-infrared light double-color up-conversion luminescence nanomaterial and preparation method thereof |
| CN103911154A (en) * | 2014-04-09 | 2014-07-09 | 中国科学院长春应用化学研究所 | Monodisperse up-conversion luminescent micro/nano crystal and preparation method thereof |
| CN104327855A (en) * | 2014-11-21 | 2015-02-04 | 武汉理工大学 | Method for preparing rare-earth doped potassium yttrium fluoride up-conversion luminescence nano material |
| CN104386730A (en) * | 2014-10-15 | 2015-03-04 | 宁波大学 | Ho<3+>/Yb<3+> double doped Alpha-NaYF4 laser crystal and preparation method thereof |
| CN104591253A (en) * | 2015-02-02 | 2015-05-06 | 首都师范大学 | Microemulsion synthesis method of porous water-soluble rare earth nano material |
| CN104861978A (en) * | 2015-06-05 | 2015-08-26 | 武汉理工大学 | Method for synthesizing rare-earth metal codoped yttrium potassium pentafluoride nano crystal from waste fluorescent powder |
| CN104910915A (en) * | 2015-04-22 | 2015-09-16 | 南京工业大学 | Preparation method and application of hydrophilic rare earth nano material |
| CN105419780A (en) * | 2014-09-15 | 2016-03-23 | 中国科学院理化技术研究所 | Synthesis method of rare earth ion doped nano crystal for organic liquid laser working medium |
| CN105694888A (en) * | 2016-02-29 | 2016-06-22 | 武汉理工大学 | Mg2+ doped NaREF4 upconversion fluorescence material and preparation method thereof |
| CN105753891A (en) * | 2016-03-23 | 2016-07-13 | 浙江大学 | Rare earth organic framework material for fluorescence detection of trace water and preparation method of rare earth organic framework material |
| CN106010538A (en) * | 2016-06-01 | 2016-10-12 | 中国计量大学 | Method for inhibiting concentration quenching effect in Yb/Er:NaGdF4 up-conversion luminescent nanocrystals |
| CN106995701A (en) * | 2017-05-04 | 2017-08-01 | 湖北大学 | A kind of preparation method of rear-earth-doped up-conversion nanoparticles |
| CN107286928A (en) * | 2017-05-26 | 2017-10-24 | 安徽师范大学 | The detection method and application of up-conversion luminescence nanomaterial of citrate modification and preparation method thereof, hydrogen peroxide or uric acid |
| CN108034424A (en) * | 2017-12-05 | 2018-05-15 | 湖州师范学院 | A kind of overdelicate optical temperature sensing material and preparation method thereof |
| CN109735335B (en) * | 2018-12-25 | 2020-12-11 | 北京化工大学 | Synthetic method and application of BYT tracer |
| CN112683985A (en) * | 2020-12-28 | 2021-04-20 | 中国科学院苏州生物医学工程技术研究所 | Metal label based on rare earth doped nano metal organic framework material |
| CN109705767B (en) * | 2018-12-29 | 2021-06-04 | 苏州度辰新材料有限公司 | Structural white packaging adhesive film for solar cell module |
| CN113292988A (en) * | 2021-05-27 | 2021-08-24 | 深圳先进技术研究院 | Rare earth core-shell nano material and preparation method thereof |
| CN114181700A (en) * | 2021-12-14 | 2022-03-15 | 广西经正涂料有限公司 | Organic-inorganic hybrid fluorine titanium potassium red-light fluorescent powder and preparation method thereof |
| CN114835910A (en) * | 2022-03-31 | 2022-08-02 | 许昌学院 | Nd-based metal organic framework Nd-MOF material and preparation method thereof |
| CN115274901A (en) * | 2022-07-18 | 2022-11-01 | 江苏中来新材科技有限公司 | Up-conversion photovoltaic backboard and double-sided photovoltaic module |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009157879A1 (en) * | 2008-06-26 | 2009-12-30 | National University Of Singapore | A photovoltaic apparatus |
| CN102382654A (en) * | 2011-09-15 | 2012-03-21 | 上海大学 | Preparation method of up-conversion fluorescent material rare earth doped NaYF4 nanocrystal |
| CN102030356B (en) * | 2010-10-26 | 2012-06-06 | 北京化工大学 | Method for preparing polychromatic luminous nanocrystalline of monodisperse NaYF4 |
-
2013
- 2013-01-16 CN CN2013100165940A patent/CN103087705A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009157879A1 (en) * | 2008-06-26 | 2009-12-30 | National University Of Singapore | A photovoltaic apparatus |
| CN102030356B (en) * | 2010-10-26 | 2012-06-06 | 北京化工大学 | Method for preparing polychromatic luminous nanocrystalline of monodisperse NaYF4 |
| CN102382654A (en) * | 2011-09-15 | 2012-03-21 | 上海大学 | Preparation method of up-conversion fluorescent material rare earth doped NaYF4 nanocrystal |
Non-Patent Citations (5)
| Title |
|---|
| 《J. Mater. Chem.》 20110621 Wenbin Niu等 Utilizing the amidation reaction to address the ''cooperative effect'' of carboxylic acid/amine on the size, shape, and multicolor output of fluoride upconversion nanoparticles 10894-10902 1,2,5,7 第21卷, * |
| 《Journal of Nanomaterials》 20120131 SuliWu 等 Hydrothermal Synthesis of beta-NaYF4:Yb, Er Nanocrystals with Upconversion Fluorescence Using Tetraethylene Pentamine as Chelating Ligand ID 369605，参见第2页左栏2.2 1－3，5－8 , * |
| SULIWU 等: "Hydrothermal Synthesis of β-NaYF4:Yb, Er Nanocrystals with Upconversion Fluorescence Using Tetraethylene Pentamine as Chelating Ligand", 《JOURNAL OF NANOMATERIALS》, 31 January 2012 (2012-01-31) * |
| WENBIN NIU等: "Multicolor output and shape controlled synthesis of lanthanide-ion doped fluorides upconversion nanoparticles", 《DALTON TRANS.》, vol. 40, 28 February 2011 (2011-02-28), pages 3305 - 3314 * |
| WENBIN NIU等: "Utilizing the amidation reaction to address the ‘‘cooperative effect’’ of carboxylic acid/amine on the size, shape, and multicolor output of fluoride upconversion nanoparticles", 《J. MATER. CHEM.》, vol. 21, 21 June 2011 (2011-06-21), pages 10894 - 10902 * |
Cited By (31)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103666474A (en) * | 2013-12-19 | 2014-03-26 | 中国科学院苏州纳米技术与纳米仿生研究所 | Red light/near-infrared light double-color up-conversion luminescence nanomaterial and preparation method thereof |
| CN103911154A (en) * | 2014-04-09 | 2014-07-09 | 中国科学院长春应用化学研究所 | Monodisperse up-conversion luminescent micro/nano crystal and preparation method thereof |
| CN103911154B (en) * | 2014-04-09 | 2016-03-30 | 中国科学院长春应用化学研究所 | Micro nanocrystalline of a kind of single dispersing up-conversion luminescence and preparation method thereof |
| CN105419780A (en) * | 2014-09-15 | 2016-03-23 | 中国科学院理化技术研究所 | Synthesis method of rare earth ion doped nano crystal for organic liquid laser working medium |
| CN105419780B (en) * | 2014-09-15 | 2017-12-15 | 中国科学院理化技术研究所 | Synthesis method of rare earth ion doped nano crystal for organic liquid laser working medium |
| CN104386730A (en) * | 2014-10-15 | 2015-03-04 | 宁波大学 | Ho<3+>/Yb<3+> double doped Alpha-NaYF4 laser crystal and preparation method thereof |
| CN104327855A (en) * | 2014-11-21 | 2015-02-04 | 武汉理工大学 | Method for preparing rare-earth doped potassium yttrium fluoride up-conversion luminescence nano material |
| CN104327855B (en) * | 2014-11-21 | 2016-01-06 | 武汉理工大学 | A kind of preparation method of rear-earth-doped yttrium fluoride potassium up-conversion luminescence nanomaterial |
| CN104591253A (en) * | 2015-02-02 | 2015-05-06 | 首都师范大学 | Microemulsion synthesis method of porous water-soluble rare earth nano material |
| CN104910915A (en) * | 2015-04-22 | 2015-09-16 | 南京工业大学 | Preparation method and application of hydrophilic rare earth nano material |
| CN104861978B (en) * | 2015-06-05 | 2017-03-08 | 武汉理工大学 | The nanocrystalline method of the five fluorine yttrium potassium that are co-doped with using waste phosphor powder synthesizing rare-earth metal |
| CN104861978A (en) * | 2015-06-05 | 2015-08-26 | 武汉理工大学 | Method for synthesizing rare-earth metal codoped yttrium potassium pentafluoride nano crystal from waste fluorescent powder |
| CN105694888A (en) * | 2016-02-29 | 2016-06-22 | 武汉理工大学 | Mg2+ doped NaREF4 upconversion fluorescence material and preparation method thereof |
| CN105694888B (en) * | 2016-02-29 | 2019-02-26 | 武汉理工大学 | A kind of Mg2+Adulterate NaREF4Upconverting fluorescent material and preparation method thereof |
| CN105753891A (en) * | 2016-03-23 | 2016-07-13 | 浙江大学 | Rare earth organic framework material for fluorescence detection of trace water and preparation method of rare earth organic framework material |
| CN106010538A (en) * | 2016-06-01 | 2016-10-12 | 中国计量大学 | Method for inhibiting concentration quenching effect in Yb/Er:NaGdF4 up-conversion luminescent nanocrystals |
| CN106010538B (en) * | 2016-06-01 | 2018-02-13 | 中国计量大学 | One kind is used to suppress Yb/Er:NaGdF4The method of concentration quenching effect in up-conversion luminescence nanometer crystal |
| CN106995701A (en) * | 2017-05-04 | 2017-08-01 | 湖北大学 | A kind of preparation method of rear-earth-doped up-conversion nanoparticles |
| CN107286928A (en) * | 2017-05-26 | 2017-10-24 | 安徽师范大学 | The detection method and application of up-conversion luminescence nanomaterial of citrate modification and preparation method thereof, hydrogen peroxide or uric acid |
| CN107286928B (en) * | 2017-05-26 | 2019-11-05 | 安徽师范大学 | Up-conversion luminescence nanomaterial of citrate modification and preparation method thereof, the detection method and application of hydrogen peroxide or uric acid |
| CN108034424A (en) * | 2017-12-05 | 2018-05-15 | 湖州师范学院 | A kind of overdelicate optical temperature sensing material and preparation method thereof |
| CN109735335B (en) * | 2018-12-25 | 2020-12-11 | 北京化工大学 | Synthetic method and application of BYT tracer |
| CN109705767B (en) * | 2018-12-29 | 2021-06-04 | 苏州度辰新材料有限公司 | Structural white packaging adhesive film for solar cell module |
| CN112683985B (en) * | 2020-12-28 | 2023-03-14 | 中国科学院苏州生物医学工程技术研究所 | Metal label based on rare earth doped nano metal organic framework material |
| CN112683985A (en) * | 2020-12-28 | 2021-04-20 | 中国科学院苏州生物医学工程技术研究所 | Metal label based on rare earth doped nano metal organic framework material |
| CN113292988A (en) * | 2021-05-27 | 2021-08-24 | 深圳先进技术研究院 | Rare earth core-shell nano material and preparation method thereof |
| CN114181700A (en) * | 2021-12-14 | 2022-03-15 | 广西经正涂料有限公司 | Organic-inorganic hybrid fluorine titanium potassium red-light fluorescent powder and preparation method thereof |
| CN114181700B (en) * | 2021-12-14 | 2023-08-18 | 广西经正涂料有限公司 | Organic-inorganic hybrid potassium-titanium fluoride red fluorescent powder and preparation method thereof |
| CN114835910A (en) * | 2022-03-31 | 2022-08-02 | 许昌学院 | Nd-based metal organic framework Nd-MOF material and preparation method thereof |
| CN115274901A (en) * | 2022-07-18 | 2022-11-01 | 江苏中来新材科技有限公司 | Up-conversion photovoltaic backboard and double-sided photovoltaic module |
| CN115274901B (en) * | 2022-07-18 | 2023-08-11 | 江苏中来新材科技有限公司 | Up-conversion photovoltaic backboard and double-sided photovoltaic module |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103087705A (en) | High-strength rare earth-doped up-conversion luminescence nanometer material and preparation method thereof | |
| CN110157408B (en) | Method for synthesizing efficient and stable all-inorganic halogen perovskite quantum dot scintillator by equivalent ligand | |
| CN101591540B (en) | Method for preparing rare-earth vanadate LaVO4:Eu red fluorescent powder | |
| CN107226914B (en) | Terbium organic framework complex and preparation method thereof | |
| CN111138294A (en) | Novel two-dimensional double perovskite BA4AgSbBr8Method for producing single crystal | |
| CN102477294A (en) | Calcium titanate luminescent material and preparation method thereof | |
| CN103979596A (en) | Preparation method of organic anion pillared rare earth hydroxide nanosheet sol | |
| CN108728090A (en) | A method of additive Mn perovskite quantum dot is quickly prepared based on ultrasound | |
| CN1568288A (en) | Colloidal dispersion of particles of a rare earth vanadate or phosphovanadate | |
| CN102286284B (en) | Method for synthesizing unidimensional red long-afterglow phosphor material | |
| CN102212360A (en) | Field emission fluorescent material and preparation method thereof | |
| CN114276803A (en) | Carbon dot and rare earth ion doped SrF2Composite material and synthesis method thereof | |
| CN101538466A (en) | Molybdate luminescent powder doped with rare earth ion and reparation method thereof | |
| CN108165269A (en) | A kind of fluorination lutetium potassium that phase change delay and Up-conversion Intensity greatly improve is nanocrystalline and preparation method thereof | |
| CN100489059C (en) | Green-light nano fluorescent material preparing method | |
| CN101875844B (en) | Nanomaterial capable of emitting white fluorescent light and preparation method thereof | |
| CN101928563A (en) | Method for preparing yttrium oxide substrate nano-oxide fluorescent powder | |
| CN108003867B (en) | Terbium complex green fluorescent luminescent material and preparation method thereof | |
| CN101434599B (en) | Mixed metal complex emitting white light and preparation thereof | |
| CN106243055B (en) | Triazine radical tricarboxylic acids heavy rare earth coordination compounds and preparation method, characterizing method and application | |
| CN109180711A (en) | A kind of organic boronic-rare earth-HPAs complex and preparation method thereof and the application in photo luminescent devices | |
| Wang et al. | Structural determination of new eight-coordinate NH 4 [Eu III (Cydta)(H 2 O) 2]· 4.5 H 2 O and K 2 [Eu 2 III (pdta) 2 (H 2 O) 2]· 6H 2 O complexes | |
| CN103834384A (en) | New crystal form of benzoxazolyl quinoline cuprous complex luminescent material | |
| CN102617617A (en) | Imidazo[4,5-f]1,10-phenanthroline cerium complex and preparation method thereof | |
| CN103540314A (en) | Low-temperature synthesized fluorosilicate nanorod red fluorescent powder and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20130508 |