CN1935938A - Method for preparing up-conversion fluorescent matrix material NaYF4 nano crystal - Google Patents
Method for preparing up-conversion fluorescent matrix material NaYF4 nano crystal Download PDFInfo
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Abstract
The invention discloses supra transition luminescence substrate material NaYF4 nanometer crystal preparing method. It includes the following steps: (1) dissolving rare earth yttrium oxide in perchloric acid or hydrochloric acid with 0.1-0.5mol/l density and 0-6 pH to produce perchloric acid yttrium or yttrium chloride solution; (2) preparing hydroxyl carboxyl series complexing agent with 0.2-1.0mol/l density, mixing it with the (1) solution, adjusting the pH at 0-6; the mol ratio of the perchlorate or hydrochloride and hydroxyl carboxyl series complexing agent is 1:1-5; (3) preparing sodium fluoride aqueous solution with 0.02-1mol/l density and 10 pH, adding the (2) solution at 0-45 degree centigrade, aging for 1-5h; the mol ratio of the sodium fluoride and the total rare earth ion is 1:1.2-30; (4) separating precipitate, washing, drying to gain nanometer NaYF4 particle. The produced NaYF4 particle has the advantages of controllable size with 10-25 nanometer, simple technology and device, good product quality and repeatability.
Description
Technical field
The present invention relates to a kind of preparation method of nanometer up-conversion fluorescence substrate material, more definite theory relates to nanometer up-conversion fluorescence substrate material NaYF
4Nanocrystalline technology of preparing belongs to nano-luminescent material preparation technology field.
Background technology
Upconverting fluorescent material is that a class excites the luminescent material that can send short-wavelength light down at long wavelength light.Cooperate infrarede emitting diode or semi-conductor infrared laser, this type of material can be made into the photodiode or laser apparatus (the 0pt Lett 1997 of different colours; 22:808-810.).In recent years, adopt upconverting fluorescent material to be subjected to people's extensive concern as the biomolecules fluorescence labeling material, this class material is as the fluorescent material probe, disturbs for a short time, and the detection sensitivity height is a kind of up-and-coming biomolecular labeling probe.
With NaYF
4For the upconverting fluorescent material of matrix is the most effective upconverting fluorescent material of finding up to now, caused people's extensive concern (Nano lett 2004; 11:2191-2196).As the biomolecules fluorescence labeling material, need little, the even particle distribution of the particle diameter of material own, and the luminous efficiency height.Consider in the practical application, luminescent material size after the doping is mainly determined by the primary particle size of substrate material, if it is littler therefore can to prepare particle diameter, and the substrate material that is evenly distributed, its research that is further used for the biomolecular labeling probe had certain meaning.CN1157462C discloses a kind of preparation method who adopts ammonia carboxylic class complexing agent, but the particle diameter of the nano particle that this technology is prepared is bigger, mainly is distributed in the 37-166 nanometer.If to modifications such as nanoparticle wrap up, its particle diameter will further become greatly, then can limit its Application Areas, so these also require substrate material to have littler particle diameter.
Summary of the invention
Technical problem to be solved by this invention provides a kind of up-conversion fluorescence substrate material NaYF
4Preparation of nano crystal to remedy the deficiencies in the prior art or defective, meets the demands of production and living.
In order to solve the problems of the technologies described above, the technical solution adopted in the present invention is: a kind of up-conversion fluorescence substrate material NaYF
4Preparation of nano crystal comprises the steps:
(1) be starting raw material with the rare-earth oxidation yttrium, being dissolved in concentration is that 0.1-0.5mol/l, pH value are in the perchloric acid or hydrochloric acid of 0-6, and formation concentration is that perchloric acid yttrium or the yttrium chloride solution of 0.1-0.5mol/l is standby;
(2) compound concentration is the hydroxyl carboxyl series enveloping agent solution of 0.2-1.0mol/l, mixes with the prepared solution of step (1), and the pH value of regulating solution after mixing is at 0-6, and the mol ratio of perchlorate or hydrochloride and hydroxyl carboxyl series complexing agent is 1: 1-5;
(3) compound concentration is that 0.02-1mol/l, pH value are 10 sodium fluoride aqueous solution, and violent stirring is injected the solution of step (2) gained at 0-45 ℃, under the room temperature ageing 1-5 hour; The mol ratio of total rare earth (TRE) ion and Sodium Fluoride is 1 in the solution: 1.2-30;
(4) also with deionized water and dehydrated alcohol supersound washing, 30-80 ℃ of drying promptly gets nano level NaYF to sediment separate out
4Particle.
As optimized technical scheme: described hydroxyl carboxyl series complexing agent is a kind of in Seignette salt, Trisodium Citrate or the sodium malate.
The invention has the beneficial effects as follows: as the yttrium oxide solvent, adopt the hydroxyl carboxyl series complexing agent, the NaYF for preparing with perchloric acid or hydrochloric acid
4Particle size can be controlled in the 10-25 nanometer, and technology and equipment are simple, constant product quality, and good reproducibility.
Description of drawings
Fig. 1 main technique schema of the present invention
The nano NaY F that Fig. 2 method provided by the invention is prepared
4XRD analysis figure
Fig. 3 embodiment of the invention 1 prepared NaYF
4The upconverting fluorescent material transmission electron microscope picture of matrix, particle diameter are 10 nanometers
Fig. 4 embodiment of the invention 2 prepared NaYF
4The upconverting fluorescent material transmission electron microscope picture of matrix, particle diameter are 11 nanometers
Fig. 5 embodiment of the invention 3 prepared NaYF
4The upconverting fluorescent material transmission electron microscope picture of matrix, particle diameter are 12 nanometers
Fig. 6 embodiment of the invention 4 prepared NaYF
4The upconverting fluorescent material transmission electron microscope picture of matrix, particle diameter are 13 nanometers
Fig. 7 embodiment of the invention 5 prepared NaYF
4The upconverting fluorescent material transmission electron microscope picture of matrix, particle diameter are 14 nanometers
Fig. 8 embodiment of the invention 6 prepared NaYF
4The upconverting fluorescent material transmission electron microscope picture of matrix, particle diameter are 19 nanometers
Fig. 9 embodiment of the invention 7 prepared NaYF
4The upconverting fluorescent material transmission electron microscope picture of matrix, particle diameter are 25 nanometers
Embodiment
Below in conjunction with concrete enforcement side example the present invention is further elaborated.With reference to accompanying drawing 1-9.
Embodiment 1:
A) take by weighing the yttrium oxide of 0.01mol, the concentration that adds capacity is that 0.1mol/l, pH value are 6 perchloric acid, heating for dissolving, generate the perchloric acid yttrium of 0.02mol, add deionized water and be settled to 100ml, be made into the perchloric acid yttrium solution of 0.2mol/l, regulating its pH value is 2;
B) citric acid three sodium solution of preparation 0.6mol/l;
C) with step a) and b) the solution uniform mixing, wherein, the mol ratio of perchloric acid yttrium and citric acid three sodium solution is 1: 3;
D) take by weighing the 2.1g Fluorinse in addition, add deionized water, dissolving, regulator solution pH value is 10, stirs fast, adds step c) gained solution under the room temperature, ageing 1 hour; The mol ratio of total rare earth (TRE) ion and Sodium Fluoride is 1: 1.2 in the solution; Deionized water wash 3 times are used in centrifugation, and absolute ethanol washing 1 time places 60 ℃ of vacuum drying ovens dry.
Embodiment 2:
A) take by weighing the yttrium oxide of 0.01mol, the concentration that adds capacity is that 0.5mol/l, pH value are 0 hydrochloric acid, and heating for dissolving generates the Yttrium trichloride of 0.02mol, and the adding deionized water is settled to 100ml, is made into the yttrium chloride solution of 0.2mol/l respectively, and regulating its pH value is 0.
B) citric acid three sodium solution of preparation 0.2mol/l.
C) with a) and b) the solution uniform mixing, wherein, the mol ratio of citric acid three sodium solution and Yttrium trichloride is 1: 1.
D) take by weighing the 2.1g Fluorinse in addition, add the deionized water of 60ml, dissolving, regulator solution pH value is 10, stirs fast, 45 ℃ add in the step c) gained solution room temperature ageing 5 hours down; The mol ratio of total rare earth (TRE) ion and Sodium Fluoride is 1: 30 in the solution; Deionized water wash 3 times are used in centrifugation, and absolute ethanol washing 1 time places 30 ℃ of vacuum drying ovens dry.
Embodiment 3:
A) take by weighing the yttrium oxide of 0.01mol, the concentration that adds capacity is that 0.3mol/l, pH value are 4 perchloric acid, heating for dissolving, generate the perchloric acid yttrium of 0.02mol, add deionized water and be settled to 100ml, be made into the perchloric acid yttrium solution of 0.2mol/l, regulating its pH value is 6.
B) citric acid three sodium solution of preparation 1mol/l.
C) step a) and b) solution mixes, and wherein the mol ratio of citric acid three sodium solution and perchloric acid yttrium is 1: 5.
D) take by weighing the 2.1g Fluorinse in addition, add the deionized water of 60ml, dissolving, regulator solution pH value is 10.Stir fast, 0 ℃ adds in the step c) gained solution room temperature ageing 3 hours down; The mol ratio of total rare earth (TRE) ion and Sodium Fluoride is 1: 10 in the solution; Deionized water wash 3 times are used in centrifugation, and absolute ethanol washing 1 time places 80 ℃ of vacuum drying ovens dry.
Embodiment 4:
A) take by weighing the yttrium oxide of 0.01mol, adding concentration is that 0.5mol/l, pH value are 5 hydrochloric acid, and heating for dissolving generates the perchloric acid yttrium of 0.02mol, adds deionized water and is settled to 100ml, is made into the perchloric acid yttrium solution of 0.2mol/l, and regulating its pH value is 2.
B) citric acid three sodium solution of preparation 1.0mol/l.
C) with step a) and b) solution mixes, and wherein the mole ratio of the mole number of chloric acid yttrium and citric acid three sodium solution is 1: 5.
D) take by weighing the 2.1g Fluorinse in addition, add the deionized water of 60ml, dissolving, regulator solution pH value is 10.
E) solution with step c) stirs fast, adds d under the room temperature) in the solution, ageing 3 hours.
F) deionized water wash 3 times are used in centrifugation, and absolute ethanol washing 1 time places 50 ℃ of vacuum drying ovens dry.
Embodiment 5:
A) take by weighing the yttrium oxide of 0.01mol, the concentration that adds capacity is that 0.5mol/l, pH value are 5 perchloric acid, heating for dissolving, generate the perchloric acid yttrium of 0.02mol, add deionized water and be settled to 100ml, be made into the perchloric acid yttrium solution of 0.2mol/l, regulating its pH value is 2.
B) potassium sodium tartrate solution of preparation 1.0mol/l.
C) with step a) and b) solution mixes, and wherein the mole ratio of the mole number of perchloric acid yttrium and potassium sodium tartrate solution is 1: 5, after two place's solution mix.
D) take by weighing the 2.1g Fluorinse in addition, add the deionized water of 60ml, dissolving, regulator solution pH value is 10.
E) solution with step c) stirs fast, adds d under the room temperature) in the solution, ageing 3 hours.
F) deionized water wash 3 times are used in centrifugation, and absolute ethanol washing 1 time places 60 ℃ of vacuum drying ovens dry.
Embodiment 6:
A) take by weighing the yttrium oxide of 0.01mol, the concentration that adds capacity is that 0.5mol/l, pH value are 5 perchloric acid, heating for dissolving, generate the perchloric acid yttrium of 0.02mol, add deionized water and be settled to 100ml, be made into the perchloric acid yttrium solution of 0.2mol/l, regulating its pH value is 2.
B) potassium sodium tartrate solution of preparation 0.6mol/l.
C) with step a) and b) the solution uniform mixing, wherein the mole ratio of the mole number of perchloric acid yttrium and citric acid three sodium solution is 1: 3.
D) take by weighing the 2.1g Fluorinse in addition, add the deionized water of 60ml, dissolving, regulator solution pH value is 10.
E) solution with step c) stirs fast, adds d under the room temperature) in the solution, ageing 5 hours.
F) deionized water wash 3 times are used in centrifugation, and absolute ethanol washing 1 time places 40 ℃ of vacuum drying ovens dry.
Embodiment 7:
A) take by weighing the yttrium oxide of 0.01mol, the concentration that adds capacity is that 0.5mol/l, pH value are 5 perchloric acid, heating for dissolving, generate the perchloric acid yttrium of 0.02mol, add deionized water and be settled to 100ml, be made into the perchloric acid yttrium solution of 0.2mol/l, regulating its pH value is 2.
B) the sodium malate solution of preparation 0.8mol/l.
C) with step a) and b) the solution uniform mixing, wherein the mole ratio of the mole number of perchloric acid yttrium and sodium malate solution is 1: 4.
D) take by weighing the 2.1g Fluorinse in addition, add the deionized water of 60ml, dissolving, regulator solution pH value is 10.
E) solution with step c) stirs fast, adds d under the room temperature) in the solution, ageing 2 hours.
F) deionized water wash 3 times are used in centrifugation, and absolute ethanol washing 1 time places 70 ℃ of vacuum drying ovens dry.
Claims (2)
1, a kind of up-conversion fluorescence substrate material NaYF
4Preparation of nano crystal is characterized in that, comprises the steps:
(1) be starting raw material with the rare-earth oxidation yttrium, being dissolved in concentration is that 0.1-0.5mol/l, pH value are in the perchloric acid or hydrochloric acid of 0-6, and formation concentration is that perchloric acid yttrium or the yttrium chloride solution of 0.1-0.5mol/l is standby;
(2) compound concentration is the hydroxyl carboxyl series enveloping agent solution of 0.2-1.0mol/l, with step
(1) prepared solution mixes, and the pH value of regulating solution after mixing is at 0-6, and the mol ratio of perchlorate or hydrochloride and hydroxyl carboxyl series complexing agent is 1: 1-5;
(3) compound concentration is that 0.02-1mol/l, pH value are 10 sodium fluoride aqueous solution, and violent stirring is injected the solution of step (2) gained at 0-45 ℃, under the room temperature ageing 1-5 hour; The mol ratio of total rare earth (TRE) ion and Sodium Fluoride is 1 in the solution: 1.2-30;
(4) also with deionized water and dehydrated alcohol supersound washing, 30-80 ℃ of drying promptly gets nano level NaYF to sediment separate out
4Particle.
2, preparation method according to claim 1 is characterized in that, described hydroxyl carboxyl series complexing agent is a kind of in Seignette salt, Trisodium Citrate or the sodium malate.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101235288B (en) * | 2008-03-05 | 2010-12-08 | 东华大学 | Room temperature oil-water diphase preparation method for NaYF4-based upper conversion luminescent material |
| CN102030356A (en) * | 2010-10-26 | 2011-04-27 | 北京化工大学 | Method for preparing polychromatic luminous nanocrystalline of monodisperse NaYF4 |
| CN101407938B (en) * | 2008-11-05 | 2011-07-20 | 东华大学 | Method for preparing crystal form-controllable yttrium fluoride natrium nanocrystalline under normal temperature |
| CN102897817A (en) * | 2012-10-17 | 2013-01-30 | 沈阳化工大学 | Preparation method for NaEuF4 microspheres |
| CN104449732A (en) * | 2015-01-06 | 2015-03-25 | 东华大学 | A seed crystal method is used to prepare nanometer KYF4: yb3+, er3+materials |
| CN104449731A (en) * | 2014-11-18 | 2015-03-25 | 东南大学 | Composite nanostructure based on rare earth up-conversion luminescent material as well as preparation method and application of composite nanostructure |
| CN104449662A (en) * | 2014-11-11 | 2015-03-25 | 合肥工业大学 | Surface modification method of oil-soluble upconversion luminescent nanometer material |
| CN110964527A (en) * | 2019-12-16 | 2020-04-07 | 陕西师范大学 | Method for controllably preparing strong-luminescence rare earth up-conversion material |
-
2006
- 2006-09-20 CN CNB2006101162460A patent/CN100554374C/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101235288B (en) * | 2008-03-05 | 2010-12-08 | 东华大学 | Room temperature oil-water diphase preparation method for NaYF4-based upper conversion luminescent material |
| CN101407938B (en) * | 2008-11-05 | 2011-07-20 | 东华大学 | Method for preparing crystal form-controllable yttrium fluoride natrium nanocrystalline under normal temperature |
| CN102030356A (en) * | 2010-10-26 | 2011-04-27 | 北京化工大学 | Method for preparing polychromatic luminous nanocrystalline of monodisperse NaYF4 |
| CN102030356B (en) * | 2010-10-26 | 2012-06-06 | 北京化工大学 | Method for preparing polychromatic luminous nanocrystalline of monodisperse NaYF4 |
| CN102897817A (en) * | 2012-10-17 | 2013-01-30 | 沈阳化工大学 | Preparation method for NaEuF4 microspheres |
| CN102897817B (en) * | 2012-10-17 | 2015-01-28 | 沈阳化工大学 | Preparation method for NaEuF4 microspheres |
| CN104449662A (en) * | 2014-11-11 | 2015-03-25 | 合肥工业大学 | Surface modification method of oil-soluble upconversion luminescent nanometer material |
| CN104449731A (en) * | 2014-11-18 | 2015-03-25 | 东南大学 | Composite nanostructure based on rare earth up-conversion luminescent material as well as preparation method and application of composite nanostructure |
| CN104449732A (en) * | 2015-01-06 | 2015-03-25 | 东华大学 | A seed crystal method is used to prepare nanometer KYF4: yb3+, er3+materials |
| CN104449732B (en) * | 2015-01-06 | 2016-08-24 | 东华大学 | An a kind of utilization kind crystallization prepares KYF4: Yb3+, Er3+the method of nano material |
| CN110964527A (en) * | 2019-12-16 | 2020-04-07 | 陕西师范大学 | Method for controllably preparing strong-luminescence rare earth up-conversion material |
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