CN102502752A - Method for regulating and controlling scale of functional alkaline-earth fluoride nanocrystals by doping of lanthanide ions - Google Patents
Method for regulating and controlling scale of functional alkaline-earth fluoride nanocrystals by doping of lanthanide ions Download PDFInfo
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- CN102502752A CN102502752A CN2011103482642A CN201110348264A CN102502752A CN 102502752 A CN102502752 A CN 102502752A CN 2011103482642 A CN2011103482642 A CN 2011103482642A CN 201110348264 A CN201110348264 A CN 201110348264A CN 102502752 A CN102502752 A CN 102502752A
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Abstract
A method for regulating and controlling the scale of functional alkaline-earth fluoride nanocrystals by the doping of lanthanide ions is disclosed, which belongs to the technical field of preparation for inorganic material. The method for regulating and controlling the scale of functional alkaline-earth fluoride nanocrystals by the doping of lanthanide ions disclosed by the invention comprises the following steps of: using soluble alkaline-earth ion salt and lanthanide ion salt as raw materials, and performing solvent thermal reaction for 8-24 hours at 150-200 DEG C in the mixed solvent of ethanol and oleic acid, so as to obtain alkaline-earth fluoride nanospheres with monodispersity, uniform scale and shape, and ultra-small size. After proper lanthanide ions are doped, the synthesised nanocrystals may have the double functions of up-conversion luminescence and room-temperature paramagnetism simultaneously, and are expected to be widely applied in the field of bio-labelling.
Description
Technical field
The invention belongs to the inorganic materials preparing technical field, relate to a kind of method through the nanocrystalline yardstick of lanthanide ion doping adjusting function alkaline earth fluoride.
Technical background
In recent years, the function nano material receives showing great attention to of scientific circles owing to being with a wide range of applications in fields such as laser, light demonstration, solar cell and biological detections.Function nano crystalline substance how to prepare single dispersion, yardstick and controllable shapes is to realize one of nano material key in application step.In traditional nanocrystalline compound method, generally be to wait the controlledly synthesis that realizes product through meticulous adjustment precursor amounts, reaction solvent, tensio-active agent, reaction times and temperature of reaction.This way is complicacy but also loaded down with trivial details not only, and effect is often not good.
As everyone knows, ion doping is one of effective means of giving performances such as nano material light, electricity, magnetic.Nearest research shows that doping also can produce remarkable influence for the process of growth of nano material.As in the spray pyrolysis reaction system, through Ti
4+Ion doping can be realized cerium oxide (CeO
2) nanocrystalline shape changes ［ Science, 312,1504 (2006) ］ by polyhedron to spheroid; In the solvent thermal reaction system, through Gd
3+Ion doping can impel yttrium fluoride natrium (NaYF
4) nanocrystallinely change ［ Nature, 463,1061 (2010) ］ to hexagonal structure by cubic structure.The present invention proposes a kind of method of function fluoride nano crystal yardstick being regulated and control through different valency ion doping realization.In the solvent thermal reaction system, through mixing the trivalent lanthanide ion, can regulate and control the nanocrystalline yardstick of alkaline earth fluoride, and then obtain to have visible up-conversion luminescence and the paramagnetic single extra small difunctional nanometer ball that disperses of room temperature.
Summary of the invention
The present invention proposes a kind of method through the nanocrystalline yardstick of lanthanide ion doping adjusting function alkaline earth fluoride, and purpose is to prepare the extra small difunctional alkaline earth fluoride nanometer ball of single dispersion that has visible up-conversion luminescence and room temperature paramagnetism, is expected to be applied to biomarker.
Technical scheme of the present invention is following:
(1) solubility divalence alkaline earth (M=Ca, Sr, Ba) ion salt and trivalent group of the lanthanides (Ln=La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y) ion salt are joined in the 10 ml deionized waters by certain molar ratio example (1.5≤M/Ln≤4), be made into the settled solution of 0.3～0.6 mol/L; Described soluble ionic salt is: nitrate salt, oxymuriate or acetate.
(2) step (1) obtained aqueous solution is dropwise joined in the mixed solution of 20 ml ethanol, 20 ml oleic acid and 5 g sodium oleates; Be moved in the 40 ml water heating kettles after fully stirring; Be added dropwise to hydrofluoric acid aqueous solution 4 ml of 1.0 mol/L subsequently; Under 150～200 ℃ of temperature, carry out solvent thermal reaction at last, soaking time is 8～24 hours.
(3) step (2) gained is nanocrystalline with ethanol and the washing of hexanaphthene mixed solution, after 40～80 ℃ of oven dry, obtain final product.
Powder X-ray diffractogram spectrum analysis and transmission electron microscope observation show that for unadulterated system, the synthetic product is that the alkaline earth fluoride that size is uneven, shape is various is nanocrystalline; Behind doping trivalent lanthanide ion, the product of acquisition is extra small (being about 5 nm) alkaline earth fluoride nanometer ball of single dispersion, yardstick and shape homogeneous.Gd
3+/ Yb
3+/ Er
3+The sample of ternary doping has green up-conversion luminescence and room temperature paramagnetism simultaneously.
The present invention has that technology of preparing is simple, cost is low, productive rate is high, produces advantages such as being easy to amplification.Products therefrom good dispersivity, shape homogeneous, narrow diameter distribution, yardstick are extra small, have green up-conversion luminescence and the room temperature paramagnetism is difunctional, are expected to be widely used in the biomarker field.
Description of drawings
Fig. 1 is do not mix in the instance 1 (a) and 20 mol% La
3+The nanocrystalline X ray diffracting spectrum of strontium fluoride of ion doping (b);
Fig. 2 is do not mix in the instance 1 (a) and 20 mol% La
3+The transmission electron microscope bright field image that the strontium fluoride of ion doping (b) is nanocrystalline;
Fig. 3 is 20 mol% La in the instance 1
3+The ability spectrogram that the strontium fluoride of ion doping is nanocrystalline;
Fig. 4 is 20 mol% Gd in the instance 1
3+The transmission electron microscope bright field image that the strontium fluoride of ion doping is nanocrystalline;
Fig. 5 is 20 mol% Yb in the instance 1
3+The transmission electron microscope bright field image that the strontium fluoride of ion doping is nanocrystalline;
Fig. 6 is do not mix in the instance 2 (a) and 20 mol% La
3+The transmission electron microscope bright field image that the Calcium Fluoride (Fluorspan) of ion doping (b) is nanocrystalline;
Fig. 7 is do not mix in the instance 3 (a) and 20 mol% La
3+The transmission electron microscope bright field image that the barium fluoride of ion doping (b) is nanocrystalline;
Fig. 8 is 10 mol% Gd in the instance 4
3+/ 10 mol% Yb
3+/ 2 mol% Er
3+Inversion spectrum on nanocrystalline visible under 975 nanometer lasers excite of ion co-doped strontium fluoride, illustration is the photo of luminous sample;
Fig. 9 is 10 mol% Gd in the instance 4
3+/ 10 mol% Yb
3+/ 2 mol% Er
3+The room temperature magnetzation curve that ion co-doped strontium fluoride is nanocrystalline.
Embodiment
Instance 1: the strontium nitrate of 0.4 mmol and the Lanthanum trinitrate of 0.1 mmol are joined in the deionized water of 10 ml, be made into the settled solution of 0.5 mol/L; Obtained aqueous solution is dropwise joined in the mixed solution of 20 ml ethanol, 20 ml oleic acid and 5 g sodium oleates composition; Be moved in the 40 ml water heating kettles after fully stirring; Drip hydrofluoric acid aqueous solution 4 ml of 1.0 mol/L subsequently; Under 180 ℃ of temperature, carry out solvent thermal reaction at last, the reaction times is 16 hours; Gained is nanocrystalline with ethanol and hexanaphthene mixed solution washing three times, after 70 ℃ of oven dry, obtain final product.
Powder X-ray diffractogram spectrum analysis (as shown in Figure 1) and transmission electron microscope observation (as shown in Figure 2) show that for unadulterated system, the synthetic product is that the strontium fluoride that size is uneven, shape is various is nanocrystalline; As the 20 mol% La that mix
3+Behind the ion, the product of acquisition is the nanometer ball with strontium fluoride of single dispersion, yardstick and shape homogeneous, extra small (being about 5 nm).Energy spectrum analysis shows adulterated La
3+During the ion entering is nanocrystalline (as shown in Figure 3).Mix other lanthanide ion (like Gd
3+Or Yb
3+), final product is similarly evenly monodispersed extra small nanometer ball (like Fig. 4, shown in Figure 5).
Instance 2: the nitrocalcite of 0.4 mmol and the Lanthanum trinitrate of 0.1 mmol are joined in the deionized water of 10 ml, be made into the settled solution of 0.5 mol/L; Obtained aqueous solution is dropwise joined in the mixed solution of 20 ml ethanol, 20 ml oleic acid and 5 g sodium oleates composition; Be moved in the 40 ml water heating kettles after fully stirring; Be added dropwise to hydrofluoric acid aqueous solution 4 ml of 1.0 mol/L subsequently; Under 180 ℃ of temperature, carry out solvent thermal reaction at last, the reaction times is 16 hours; Gained is nanocrystalline with ethanol and hexanaphthene mixed solution washing three times, after 70 ℃ of oven dry, obtain final product.
Transmission electron microscope observation shows that for unadulterated system, the synthetic product is that the uneven Calcium Fluoride (Fluorspan) of size is nanocrystalline; As the 20 mol% La that mix
3+Behind the ion, the product of acquisition is the Calcium Fluoride (Fluorspan) nanometer ball (as shown in Figure 6) of single dispersion, yardstick and shape homogeneous, extra small (being about 5nm).
Instance 3: the nitrate of baryta of 0.4 mmol and the Lanthanum trinitrate of 0.1 mmol are joined in the 10 ml deionized waters, be made into the settled solution of 0.5 mol/L; Obtained aqueous solution is dropwise joined in the mixed solution of 20 ml ethanol, 20 ml oleic acid and 5 g sodium oleates composition; Be moved in the 40 ml water heating kettles after fully stirring; Drip hydrofluoric acid aqueous solution 4 ml of 1.0 mol/L subsequently; Under 180 ℃ of temperature, carry out solvent thermal reaction at last, the reaction times is 16 hours; Gained is nanocrystalline with ethanol and hexanaphthene mixed solution washing three times, after 70 ℃ of oven dry, obtain final product.
Transmission electron microscope observation shows that for unadulterated system, the synthetic product is that the barium fluoride that size is uneven, shape is various is nanocrystalline; As the 20 mol% La that mix
3+Behind the ion, the product of acquisition is the barium fluoride nanospheres (as shown in Figure 7) of single dispersion, yardstick and shape homogeneous, extra small (being about 5nm).
Instance 4: the strontium nitrate of 0.39 mmol, the ytterbium nitrate of 0.05 mmol, the gadolinium nitrate of 0.05 mmol and the erbium nitrate of 0.01 mmol are joined in the 10 ml deionized waters, be made into the settled solution of 0.5 mol/L; Obtained aqueous solution is dropwise joined in the mixed liquor of 20 ml ethanol, 20 ml oleic acid and 5 g enuatrols composition; Be moved in the 40 ml water heating kettles after fully stirring; Drip hydrofluoric acid aqueous solution 4 ml of 1.0 mol/L subsequently; Under 180 ℃ of temperature, carry out solvent thermal reaction at last, the reaction time is 16 hours; Nanocrystalline ethanol and the cyclohexane mixed liquor used of gained washed three times, after 70 ℃ of oven dry, obtain end product.
Transmission electron microscope observation shows that formed product is the nanometer ball with strontium fluoride of single dispersion, yardstick and shape homogeneous, extra small (being about 5nm).Adopt the FLS920 XRF to measure switching emission spectrum on the room temperature, excite down at 975 nanometer lasers, sample shows bright green emission (as shown in Figure 8); Adopt PPMS-7 magnetism testing appearance to measure the room temperature magnetzation curve, sample shows strong paramagnetism (as shown in Figure 9).
Claims (1)
1. the method through the nanocrystalline yardstick of lanthanide ion doping adjusting function alkaline earth fluoride is characterized in that this method comprises the steps:
(1) solubility divalence alkaline earth M=Ca, Sr, Ba ion salt and trivalent group of the lanthanides Ln=La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y ion salt are joined in the 10 ml deionized waters example 1.5≤M/Ln≤4 in molar ratio, be made into the settled solution of 0.3～0.6 mol/L; Described soluble ionic salt is: nitrate salt, oxymuriate or acetate;
(2) step (1) obtained aqueous solution is dropwise joined in the mixed solution of 20 ml ethanol, 20 ml oleic acid and 5 g sodium oleates composition; Be moved in the 40 ml water heating kettles after fully stirring; Drip hydrofluoric acid aqueous solution 4 ml of 1.0 mol/L subsequently; Under 150～200 ℃ of temperature, carry out solvent thermal reaction at last, the reaction times is 8～24 hours;
(3) step (2) gained is nanocrystalline with ethanol and the washing of hexanaphthene mixed solution, after 40～80 ℃ of oven dry, obtain final product.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103774211A (en) * | 2014-02-20 | 2014-05-07 | 宁波大学 | Terbium/ytterbium rare earth ion codoped lithium gadolinium lutetium fluoride upconversion luminescent crystal and preparation method thereof |
| RU2545304C2 (en) * | 2013-06-27 | 2015-03-27 | Федеральное государственное бюджетное учреждение науки "Институт общей физики им. А.М. Прохорова Российской академии наук" (ИОФ РАН) | Method of obtaining barium fluoride powder, activated with cerium fluoride for scintillation ceramics |
Citations (3)
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|---|---|---|---|---|
| CN1880406A (en) * | 2005-06-03 | 2006-12-20 | 纳幕尔杜邦公司 | Method for preparing rare-earth doped fluoride nanoparticles |
| CN101462696A (en) * | 2007-12-21 | 2009-06-24 | 纳幕尔杜邦公司 | Novel rare earth doping fluoride and preparation thereof |
| CN101746804A (en) * | 2009-12-15 | 2010-06-23 | 东北师范大学 | Method for synthesizing rare earth doped micron-size barium fluoride hollow spheres |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1880406A (en) * | 2005-06-03 | 2006-12-20 | 纳幕尔杜邦公司 | Method for preparing rare-earth doped fluoride nanoparticles |
| CN101462696A (en) * | 2007-12-21 | 2009-06-24 | 纳幕尔杜邦公司 | Novel rare earth doping fluoride and preparation thereof |
| CN101746804A (en) * | 2009-12-15 | 2010-06-23 | 东北师范大学 | Method for synthesizing rare earth doped micron-size barium fluoride hollow spheres |
Non-Patent Citations (1)
| Title |
|---|
| DAQIN CHEN, ET AL.: "Modifying the Size and Shape of Monodisperse Bifunctional Alkaline-Earth Fluoride Nanocrystals through Lanthanide Doping", 《J. AM. CHEM. SOC》, vol. 132, 1 July 2010 (2010-07-01), pages 9976 - 9978 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2545304C2 (en) * | 2013-06-27 | 2015-03-27 | Федеральное государственное бюджетное учреждение науки "Институт общей физики им. А.М. Прохорова Российской академии наук" (ИОФ РАН) | Method of obtaining barium fluoride powder, activated with cerium fluoride for scintillation ceramics |
| CN103774211A (en) * | 2014-02-20 | 2014-05-07 | 宁波大学 | Terbium/ytterbium rare earth ion codoped lithium gadolinium lutetium fluoride upconversion luminescent crystal and preparation method thereof |
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Application publication date: 20120620 |