CN103555332A - Preparation process for enhancing luminescent property of nanometer material through cationic substitution method - Google Patents
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Abstract
The invention discloses a preparation process for enhancing luminescent property of a nanometer material through a cationic substitution method, belonging to the technical field of functional modification of inorganic nanometer materials. According to the preparation process, an undoped precursor similar to the lattice of a nanometer crystal is added into a reaction system by utilizing a hot injection method, and a cationic substitution reaction is carried out on the surface of the nanometer crystal to form an inert thin layer, so that a functional enhancement effect is achieved. The nanometer crystal prepared by the process keeps the original appearance and crystal structure of a nanometer crystal hexagonal phase and has high dispersity, the particle size is not obviously changed, and most importantly, the up-conversion luminous intensity is improved by 29 times and the material has high longitudinal relaxation performance. According to the method, a series of inorganic nanocrystallines of which optical and magnetic performances are enhanced are expected to be obtained.
Description
Technical field
The invention belongs to inorganic nano material functionalized modification technical field, particularly a kind of positively charged ion method of substitution strengthens the preparation technology of nano material luminescent properties.
Technical background
Nano material refers to have one dimension at least in nanoscale scope (1-100nm) or the material that consists of as elementary cell them.Because the size of nanoparticle is enough little, the viewpoint of the sub-mechanics replacement of expense traditional mechanics is described its behavior, performance mainly contains the five large effects such as small size Xiao Ying ﹑ Biao Mian Xiao Ying ﹑ Liang size Xiao Ying ﹑ macro quanta tunnel effect and dielectric confinement, and macroscopical result that above effect causes is that the aspects such as the Guang Xing Zhi ﹑ superconduction of nanoparticle and plastic deformation, magnetic, thermal resistance, chemically reactive, catalytic and fusing point all make a big difference compared with ordinary particle.For example, gold bullion itself is not luminous, but when the size reduction of gold grain forms gold nanoclusters to 2 nanometer left and right, has good luminescent properties.The many unusual Wu Li ﹑ chemical property showing just because of nano material, the applied researcies such as nanotechnology fundamental research in recent years and developing material have all obtained development fast, and have obtained certain application in industries such as traditional material, anti-counterfeiting technology, medical device, electronics, space flight and aviation.Wherein, about the research of luminescent material, occupy an leading position.
Although Illuminant nanometer material has huge potential application in fields such as bio-sensing, cancer investigation, diagnosis, these materials be realized to more large-scale commerceization application and be need to improve, what wherein the most urgently have much room for improvement is the effectiveness of performance such as light, magnetic.For luminescent material, method be at material surface growth one deck and the similar shell of crystal inside lattice parameter, nucleocapsid structure is realized performance and is strengthened main by following two aspects: 1, prevent the interior light emitting ionic non-radiative decay formation of core surface imperfection; 2, by shell ion, excitation light source is passed to inside, strengthened effective utilization of exciting light.But existing synthetic kernel shell structure method is all first out to rejoin in new former proportion scale system as nucleus the system obtaining is centrifugal, realizes regrowth at material surface, or even independent growth crystallization.So process one side and pass through repeatedly Centrifugal dispersion, easily cause nanoparticle agglomerates, on the other hand, because being adds batching simultaneously, in nucleating surface growth, so obviously increase of particle size, this is unfavorable for the application in biological field.Therefore, develop under a set of prerequisite that maintains the original size of particle, effectively the method for enhancement function nano ZnO has actual using value.
Summary of the invention
The object of this invention is to provide the preparation technology that a kind of positively charged ion method of substitution strengthens nano material luminescent properties.The present invention utilizes hot injection to add the non-impurity-doped presoma approximate with nanocrystalline lattice in reaction system, in the substitution reaction of nanocrystal surface generation positively charged ion, forms inertia thin layer, practical function type reinforced effects.Adopt this method to be expected to obtain the inorganic nano-crystal that the performances such as a series of light, magnetic strengthen.
Positively charged ion method of substitution strengthens a preparation technology for nano material luminescent properties, and its concrete preparation process is:
A. prepare rare earth precursor A 1: in reactor, add successively 2.0-4.0ml oleic acid, 3.0-5.0ml dehydrated alcohol, the NaOH solution 4.0-9.0ml of 1.2-1.8mol/L, hexanaphthene 12-18ml, at least contains the rare earth soluble salt mixing solutions 8.0-12ml of two kinds of different rare earth elements, and the total concn of rare earth element is 0.4-0.8mol/L, fully stir, at 70-100 ℃, react 2-10h, reaction finishes the oil-phase solution on rear collection upper strata, then uses hexanaphthene constant volume at 18-22ml;
B. prepare rare earth precursor A 2: in reactor, add successively 2.0-4.0ml oleic acid, 3.0-5.0ml dehydrated alcohol, the NaOH solution 4.0-9.0ml of 1.2-1.8mol/L, hexanaphthene 12-18ml, a rare earth soluble salt solution 8.0-12ml containing a kind of rare earth element of 0.4-0.8mol/L, fully stir, at 70-100 ℃, react 2-10h, reaction finishes the oil-phase solution on rear collection upper strata, then oil-phase solution is heated to 70-90 ℃, constant temperature 10-30min, to forming light yellow gel, puts into refrigerator cold-storage and becomes solid state after naturally cooling;
C. prepare fluorine-containing precursor solution: add successively the dehydrated alcohol of 15-20ml oleyl amine, 50-100mmol fluorochemicals, 2.0-4.0ml hexanaphthene and 5.0-10ml, concussion shakes up to solution and clarifies and obtain fluorine-containing precursor solution;
D. in flask, add 0.3-0.4g sodium stearate, 3.0-15.0ml oleic acid, 0-12ml octadecylene, stir, under heating, make its dissolving, rise to the rare earth precursor A1 that adds wherein 3.0-5.0ml step a preparation after 80-100 ℃, after stirring, the fluorine-containing precursor solution that adds fast step c preparation, wherein the mol ratio of fluorine element and rare earth element is 3.0-5.0, then under protection of inert gas condition, temperature programming, to isothermal reaction 10min-60min after 280-330 ℃, obtains the Monodisperse nanocrystals of size 3-100 nanometer;
E. the rare earth precursor A 2 of being prepared by 0.1-1mmol step b directly joins in the reaction system of steps d and continues reaction 10-60min under 280-330 ℃, protection of inert gas condition, and reaction finishes the rear normal temperature of being naturally down to; Hexanaphthene dissolves, dehydrated alcohol precipitation, and under 5000-10000 rev/min of rotating speed, centrifuge washing is 2-3 time, finally with 2-4ml trichloromethane, disperses, and the luminescent properties of the nano material obtaining is significantly better than the Monodisperse nanocrystals that steps d obtains.
Described fluorochemicals is hydrofluoric acid, Neutral ammonium fluoride.
After adding rare earth precursor A 2 in step e, no longer add other negatively charged ion, so can effectively avoid growing into separately crystal with rare earth precursor A 2, the material obtaining can be uniformly distributed and keep little size.
Beneficial effect of the present invention: the present invention is a kind of synthesis technique that Monodisperse nanocrystals up-conversion fluorescence is significantly strengthened.Different from the nucleocapsid structure that plane of crystal regrowth obtains, this technique obtains by the substitution reaction of plane of crystal positively charged ion, therefore adopt pattern and the crystalline structure of the original nanocrystalline six side's phases of nanocrystalline maintenance that this technique obtains, particle size does not significantly change, and have good dispersiveness, most importantly Up-conversion Intensity has strengthened up to 29 times and has had good longitudinal relaxation performance.
Accompanying drawing explanation
Fig. 1 is that the gadolinium of embodiment 1 preparation replaces on the XRD(of luminescence nanocrystalline), embodiment 1 preparation single disperses in the XRD(of tetrafluoro yttrium natrium nanocrystalline), single XRD standard card figure that disperses tetrafluoro yttrium natrium nanocrystalline (under).
Fig. 2 is the single TEM photo (left side) of tetrafluoro yttrium natrium nanocrystalline, TEM photo (right side) that gadolinium replaces luminescence nanocrystalline of disperseing of embodiment 1 preparation.
Fig. 3 is the zeta electromotive force size distribution picture that the gadolinium of embodiment 1 preparation replaces luminescence nanocrystalline.
Fig. 4 is the longitudinal relaxation time (T that the gadolinium of embodiment 1 preparation replaces luminescence nanocrystalline
1) and utilize icp analysis gadolinium and ruthenium ion concentration.
Fig. 5 is single up-conversion luminescence spectrum disperseing after tetrafluoro yttrium natrium nanocrystalline add-on substitution reaction different from gadolinium half an hour in embodiment 1, and excitation wavelength is 980 nanometers.
Fig. 6 is single STEM photo (left side) disperseing after tetrafluoro yttrium natrium nanocrystalline is replaced by gadolinium of embodiment 1 preparation, and in element Y(), Gd(is right) can spectrogram.
Fig. 7 is that single tetrafluoro yttrium natrium nanocrystalline that disperses of embodiment 2 preparations is replaced the up-conversion luminescence spectrum of front and back by gadolinium, and excitation wavelength is 980 nanometers.
Fig. 8 is the TEM photo on (left side) rear (right side) before single dispersion tetrafluoro yttrium sodium nanometer rod of embodiment 3 preparations is replaced by gadolinium.
Fig. 9 is the TEM that embodiment 3 preparation single disperses tetrafluoro yttrium sodium nanometer rod and gadolinium substitution reaction different time (0,30,60,90min).
Embodiment
Embodiment 1:
A. prepare rare earth precursor A 1: in reactor, add successively 3.0ml oleic acid, 4.0ml dehydrated alcohol, the NaOH solution 6ml of 1.5mol/L, hexanaphthene 15ml, the rare earth nitrate mixed solution 10ml that the concentration ratio of ion is Y/Yb/Er=80:15:5, the total concn of its Rare Earth Ion is 0.5mol/L, fully stir, at 100 ℃, react 2h, reaction finishes the oil-phase solution on rear collection upper strata, then uses hexanaphthene constant volume at 20ml;
B. prepare gadolinium precursor A 2: in reactor, add successively 3.0ml oleic acid, 4.0ml dehydrated alcohol, the NaOH solution 6.0ml of 1.5mol/L, hexanaphthene 15ml, the six water Gadolinium trinitrate solution 10ml of 0.5mol/L, fully stir, at 100 ℃, react 2h, reaction finishes the oil-phase solution on rear collection upper strata, then oil-phase solution is heated to 90 ℃, constant temperature 15min is to light yellow gel, be intended to the lower boiling small molecules in vaporized precursor, as hexanaphthene, ethanol, a small amount of water etc., after naturally cooling, put into refrigerator cold-storage and become solid state, used time takes out again, normal temperature easily dissolves into gelinite under placing,
C. prepare fluorine-containing precursor solution: add successively the dehydrated alcohol of 17ml oleyl amine, 100mmol hydrofluoric acid, 3.0ml hexanaphthene and 7ml, concussion shakes up to solution and clarifies and obtain fluorine-containing precursor solution;
D. in flask, add 0.35g sodium stearate, 7ml oleic acid, 8ml octadecylene, stir, under heating, make it dissolve, rise to the rare earth precursor A1 that adds wherein 4ml step a preparation after 80 ℃, after stirring, the fluorine-containing precursor solution that adds fast 1.4ml step c preparation, under then nitrogen protection condition, after temperature programming to 310 ℃, isothermal reaction 30min obtains single tetrafluoro yttrium natrium nanocrystalline that disperses of size 10 nanometers left and right;
E. by 1.0,0.75,0.5 or the gadolinium precursor A 2 prepared of 0.25mmol step b, under 310 ℃, nitrogen protection condition, directly join respectively in the reaction system of steps d and carry out parallel test, continue reaction 30min, reaction finishes the rear normal temperature of being naturally down to; Hexanaphthene dissolves, dehydrated alcohol precipitation, and under 5000 revs/min of rotating speeds, centrifuge washing is 3 times, finally with 4ml trichloromethane, disperses, and the luminescent properties that the gadolinium obtaining replaces luminescence nanocrystalline is significantly better than the Monodisperse nanocrystals that steps d obtains.
After being put into 65 ℃ of oven dry of baking oven, the nano material obtaining after step e high speed centrifugation carries out the signs such as X-ray diffraction, Solid fluorescene spectrum, near infrared Fourier transform.Its XRD, TEM, size distribution figure, ICP-MS, photoluminescent property, scanning projection microscope-energy spectrum analysis are respectively as shown in Fig. 1,2,3,4,5,6.
It is to utilize hot injection that positively charged ion occurs on tetrafluoro yttrium sodium luminescent material surface to replace formation tetrafluoro gadolinium sodium thin layer that the above-mentioned gadolinium making replaces luminescence nanocrystalline, the nano particle size obtaining is about 11nm, keeping pattern, size and the single crystal particle of original crystal to distribute, green light under 980 nm near-infrared optical excitation, and after adding 1.0mmol gadolinium precursor, upper transition effects strengthens nearly 29 times; Due to the existence of surperficial tetrafluoro gadolinium sodium, gained nano particle is with good longitudinal relaxation rate.
Embodiment 2:
A. prepare rare earth precursor A 1: in reactor, add successively 3.0ml oleic acid, 4.0ml dehydrated alcohol, the NaOH solution 6ml of 1.5mol/L, hexanaphthene 15ml, the rare earth nitrate mixed solution 10ml that the concentration ratio of ion is Y/Yb/Tm=80:15:5, the total concn of its Rare Earth Ion is 0.5mol/L, fully stir, at 80 ℃, react 4h, reaction finishes the oil-phase solution on rear collection upper strata, then uses hexanaphthene constant volume at 20ml;
B. prepare gadolinium precursor A 2: in reactor, add successively 3.0ml oleic acid, 4.0ml dehydrated alcohol, the NaOH solution 6.0ml of 1.5mol/L, hexanaphthene 15ml, the six water Gadolinium trinitrate solution 10ml of 0.5mol/L, fully stir, at 80 ℃, react 4h, reaction finishes the oil-phase solution on rear collection upper strata, then oil-phase solution is heated to 90 ℃, constant temperature 15min, to light yellow gel, puts into refrigerator cold-storage and becomes solid state after naturally cooling;
C. prepare fluorine-containing precursor solution: add successively the dehydrated alcohol of 17ml oleyl amine, 100mmol hydrofluoric acid, 3.0ml hexanaphthene and 7ml, concussion shakes up to solution and clarifies and obtain fluorine-containing precursor solution;
D. in flask, add 0.35g sodium stearate, 7ml oleic acid, 8ml octadecylene, stir, under heating, make it dissolve, rise to the rare earth precursor A1 that adds wherein 4ml step a preparation after 80 ℃, after stirring, the fluorine-containing precursor solution that adds fast 1.4ml step c preparation, under then nitrogen protection condition, after temperature programming to 310 ℃, isothermal reaction 30min obtains single tetrafluoro yttrium natrium nanocrystalline that disperses of size 10 nanometers left and right;
E. the gadolinium precursor A 2 of being prepared by 0.5mmol step b directly joins in the reaction system of steps d and continues reaction 30min under 310 ℃, nitrogen protection condition, and reaction finishes the rear normal temperature of being naturally down to; Hexanaphthene dissolves, dehydrated alcohol precipitation, and under 5000 revs/min of rotating speeds, centrifuge washing is 3 times, finally with 4ml trichloromethane, disperses, and the luminescent properties that the gadolinium obtaining replaces luminescence nanocrystalline is significantly better than the Monodisperse nanocrystals that steps d obtains.
After being put into 70 ℃ of oven dry of baking oven, the nano material obtaining after step e high speed centrifugation characterizes.
It is to utilize hot injection that positively charged ion occurs on tetrafluoro yttrium sodium luminescent material surface to replace formation tetrafluoro gadolinium sodium thin layer that the above-mentioned gadolinium making replaces luminescence nanocrystalline, the nano particle size obtaining is about 8nm, keeping pattern, size and the single crystal particle of original crystal to distribute, blue light-emitting under 980 nm near-infrared optical excitation, and upper transition effects strengthens nearly 11 times; Due to the existence of surperficial tetrafluoro gadolinium sodium, gained nano particle is with good longitudinal relaxation rate.
Embodiment 3:
A. prepare rare earth precursor A 1: in reactor, add successively 3.0ml oleic acid, 4.0ml dehydrated alcohol, the NaOH solution 6ml of 1.5mol/L, hexanaphthene 15ml, the rare earth nitrate mixed solution 10ml that the concentration ratio of ion is Y/Yb/Er/Tm=80:13:5:2, the total concn of its Rare Earth Ion is 0.5mol/L, fully stir, at 100 ℃, react 2h, reaction finishes the oil-phase solution on rear collection upper strata, then uses hexanaphthene constant volume at 20ml;
B. prepare gadolinium precursor A 2: in reactor, add successively 3.0ml oleic acid, 4.0ml dehydrated alcohol, the NaOH solution 6.0ml of 1.5mol/L, hexanaphthene 15ml, the six water Gadolinium trinitrate solution 10ml of 0.5mol/L, fully stir, at 100 ℃, react 2h, reaction finishes the oil-phase solution on rear collection upper strata, then oil-phase solution is heated to 90 ℃, constant temperature 15min, to light yellow gel, puts into refrigerator cold-storage and becomes solid state after naturally cooling;
C. prepare fluorine-containing precursor solution: add successively the dehydrated alcohol of 17ml oleyl amine, 100mmol hydrofluoric acid, 3.0ml hexanaphthene and 7ml, concussion shakes up to solution and clarifies and obtain fluorine-containing precursor solution;
D. in flask, add 0.35g sodium stearate, 15ml oleic acid, do not add octadecylene, stir, under heating, make it dissolve, rise to the rare earth precursor A1 that adds wherein 4ml step a preparation after 80 ℃, after stirring, the fluorine-containing precursor solution that adds fast 1.4ml step c preparation, under then protection of inert gas condition, after temperature programming to 310 ℃, isothermal reaction 30min obtains single tetrafluoro yttrium natrium nanocrystalline that disperses that size is about 42 * 26 nanometers left and right;
E. the gadolinium precursor A 2 of being prepared by 0.5mmol step b directly joins in the reaction system of steps d and continues reaction certain hour 30min under 310 ℃, nitrogen protection condition, and reaction finishes the rear normal temperature of being naturally down to; Hexanaphthene dissolves, dehydrated alcohol precipitation, and under 5000 revs/min of rotating speeds, centrifuge washing is 3 times, finally with 4ml trichloromethane, disperses, and the luminescent properties that the gadolinium obtaining replaces luminescence nanocrystalline is significantly better than the Monodisperse nanocrystals that steps d obtains.
After being put into 70 ℃ of oven dry of baking oven, the nano material obtaining after step e high speed centrifugation characterizes.
The granular size that the gadolinium making replaces Illuminant nanometer rod is about 42 * 26 nanometers, and keeps single crystal particle to distribute.Its TEM respectively as shown in Figure 8,9, issues strong white light in 980 nm near-infrared optical excitation, and the bar-shaped tetrafluoro yttrium sodium pattern after gadolinium replaces occurs significantly to change, and the nano particle that up-conversion fluorescence reinforced effects and gadolinium replace is similar.
Embodiment 4:
A. prepare rare earth precursor A 1: in reactor, add successively 3.0ml oleic acid, 4.0ml dehydrated alcohol, the NaOH solution 6ml of 1.5mol/L, hexanaphthene 15ml, the rare earth nitrate mixed solution 10ml that the concentration ratio of ion is La/Ce/Tb=80:15:5, the total concn of its Rare Earth Ion is 0.5mol/L, fully stir, at 100 ℃, react 2h, reaction finishes the oil-phase solution on rear collection upper strata, then uses hexanaphthene constant volume at 20ml;
B. prepare gadolinium precursor A 2: in reactor, add successively 3.0ml oleic acid, 4.0ml dehydrated alcohol, the NaOH solution 6.0ml of 1.5mol/L, hexanaphthene 15ml, the six water Gadolinium trinitrate solution 10ml of 0.5mol/L, fully stir, at 100 ℃, react 2h, reaction finishes the oil-phase solution on rear collection upper strata, then oil-phase solution is heated to 90 ℃, constant temperature 15min is to light yellow gel, be intended to the lower boiling small molecules in vaporized precursor, as hexanaphthene, ethanol, a small amount of water etc., after naturally cooling, put into refrigerator cold-storage and become solid state, used time takes out again, normal temperature easily dissolves into gelinite under placing,
C. prepare fluorine-containing precursor solution: add successively the dehydrated alcohol of 17ml oleyl amine, 100mmol Neutral ammonium fluoride, 3.0ml hexanaphthene and 7ml, concussion shakes up to solution and clarifies and obtain fluorine-containing precursor solution;
D. in flask, add 0.35g sodium stearate, 7ml oleic acid, 8ml octadecylene, stir, under heating, make it dissolve, rise to the rare earth precursor A1 that adds wherein 4ml step a preparation after 80 ℃, after stirring, the fluorine-containing precursor solution that adds fast 1.4ml step c preparation, under then protection of inert gas condition after temperature programming to 310 ℃ isothermal reaction 30min to obtain single lanthanum trifluoride that disperses of size 10 nanometers left and right nanocrystalline;
E. the gadolinium precursor A 2 of being prepared by 0.5mmol step b directly joins in the reaction system of steps d and continues reaction 30min under 310 ℃, nitrogen protection condition, and reaction finishes the rear normal temperature of being naturally down to; Hexanaphthene dissolves, dehydrated alcohol precipitation, and under 5000 revs/min of rotating speeds, centrifuge washing is 3 times, finally with 4ml trichloromethane, disperses, and the luminescent properties that the gadolinium obtaining replaces luminescence nanocrystalline is significantly better than the Monodisperse nanocrystals that steps d obtains.
After being put into 70 ℃ of oven dry of baking oven, the nano material obtaining after step e high speed centrifugation characterizes.
It is to utilize hot injection, on lanthanum trifluoride luminescent material surface, positively charged ion occurs to replace formation three gadolinium fluoride thin layers that the above-mentioned gadolinium making replaces luminescence nanocrystalline, the nano particle size obtaining is about 8nm, keeping pattern, size and the single crystal particle of original crystal to distribute, under ultraviolet excitation, send green glow visible ray, and luminous efficiency obviously strengthens.
Embodiment 5:
A. prepare rare earth precursor A 1: in reactor, add successively 3.0ml oleic acid, 4.0ml dehydrated alcohol, the NaOH solution 6ml of 1.5mol/L, hexanaphthene 15ml, the rare earth nitrate mixed solution 10ml that the concentration ratio of ion is Lu/Yb/Ho=80:15:5, the total concn of its Rare Earth Ion is 0.5mol/L, fully stir, at 100 ℃, react 2h, reaction finishes the oil-phase solution on rear collection upper strata, then uses hexanaphthene constant volume at 20ml;
B. prepare yttrium precursor A 2: in reactor, add successively 3.0ml oleic acid, 4.0ml dehydrated alcohol, the NaOH solution 6.0ml of 1.5mol/L, hexanaphthene 15ml, the six water yttrium nitrate solution 10ml of 0.5mol/L, fully stir, at 100 ℃, react 2h, reaction finishes the oil-phase solution on rear collection upper strata, then oil-phase solution is heated to 90 ℃, constant temperature 15min is to light yellow gel, be intended to the lower boiling small molecules in vaporized precursor, as hexanaphthene, ethanol, a small amount of water etc., after naturally cooling, put into refrigerator cold-storage and become solid state, used time takes out again, normal temperature easily dissolves into gelinite under placing,
C. prepare fluorine-containing precursor solution: add successively the dehydrated alcohol of 17ml oleyl amine, 100mmol hydrofluoric acid, 3.0ml hexanaphthene and 7ml, concussion shakes up to solution and clarifies and obtain fluorine-containing precursor solution;
D. in flask, add 0.35g sodium stearate, 7ml oleic acid, 8ml octadecylene, stir, under heating, make it dissolve, rise to the rare earth precursor A1 that adds wherein 4ml step a preparation after 80 ℃, after stirring, the fluorine-containing precursor solution that adds fast 1.4ml step c preparation, under then protection of inert gas condition, after temperature programming to 310 ℃, isothermal reaction 30min obtains single tetrafluoro lutetium natrium nanocrystalline that disperses of size 10 nanometers left and right;
E. the yttrium precursor A 2 of being prepared by 0.5mmol step b directly joins in the reaction system of steps d and continues reaction 30min under 310 ℃, nitrogen protection condition, and reaction finishes the rear normal temperature of being naturally down to; Hexanaphthene dissolves, dehydrated alcohol precipitation, and under 5000 revs/min of rotating speeds, centrifuge washing is 3 times, finally with 4ml trichloromethane, disperses, and the luminescent properties that the yttrium obtaining replaces luminescence nanocrystalline is significantly better than the Monodisperse nanocrystals that steps d obtains.
After being put into 70 ℃ of oven dry of baking oven, the nano material obtaining after step e high speed centrifugation characterizes.
It is to utilize hot injection that positively charged ion occurs on tetrafluoro lutetium sodium luminescent material surface to replace formation tetrafluoro yttrium sodium thin layer that the above-mentioned yttrium making replaces luminescence nanocrystalline, the nano particle size obtaining is about 10nm, keeping pattern, size and the single crystal particle of original crystal to distribute, in 980 nm near-infrared optical excitation, issue yellow green light, and upper transition effects obviously strengthens.
Claims (2)
1. positively charged ion method of substitution strengthens a preparation technology for nano material luminescent properties, it is characterized in that, its concrete preparation process is:
A. prepare rare earth precursor A 1: in reactor, add successively 2.0-4.0ml oleic acid, 3.0-5.0ml dehydrated alcohol, the NaOH solution 4.0-9.0ml of 1.2-1.8mol/L, hexanaphthene 12-18ml, at least contains the rare earth soluble salt mixing solutions 8.0-12ml of two kinds of different rare earth elements, and the total concn of rare earth element is 0.4-0.8mol/L, fully stir, at 70-100 ℃, react 2-10h, reaction finishes the oil-phase solution on rear collection upper strata, then uses hexanaphthene constant volume at 18-22ml;
B. prepare rare earth precursor A 2: in reactor, add successively 2.0-4.0ml oleic acid, 3.0-5.0ml dehydrated alcohol, the NaOH solution 4.0-9.0ml of 1.2-1.8mol/L, hexanaphthene 12-18ml, a rare earth soluble salt solution 8.0-12ml containing a kind of rare earth element of 0.4-0.8mol/L, fully stir, at 70-100 ℃, react 2-10h, reaction finishes the oil-phase solution on rear collection upper strata, then oil-phase solution is heated to 70-90 ℃, constant temperature 10-30min, to forming light yellow gel, puts into refrigerator cold-storage and becomes solid state after naturally cooling;
C. prepare fluorine-containing precursor solution: add successively the dehydrated alcohol of 15-20ml oleyl amine, 50-100mmol fluorochemicals, 2.0-4.0ml hexanaphthene and 5.0-10ml, concussion shakes up to solution and clarifies and obtain fluorine-containing precursor solution;
D. in flask, add 0.3-0.4g sodium stearate, 3.0-15.0ml oleic acid, 0-12ml octadecylene, stir, under heating, make its dissolving, rise to the rare earth precursor A1 that adds wherein 3.0-5.0ml step a preparation after 80-100 ℃, after stirring, the fluorine-containing precursor solution that adds fast step c preparation, wherein the mol ratio of fluorine element and rare earth element is 3.0-5.0, then under protection of inert gas condition, temperature programming, to isothermal reaction 10min-60min after 280-330 ℃, obtains the Monodisperse nanocrystals of size 3-100 nanometer;
E. the rare earth precursor A 2 of being prepared by 0.1-1mmol step b directly joins in the reaction system of steps d and continues reaction 10-60min under 280-330 ℃, protection of inert gas condition, and reaction finishes the rear normal temperature of being naturally down to; Hexanaphthene dissolves, dehydrated alcohol precipitation, and under 5000-10000 rev/min of rotating speed, centrifuge washing is 2-3 time, finally with 2-4ml trichloromethane, disperses, and the luminescent properties of the nano material obtaining is significantly better than the Monodisperse nanocrystals that steps d obtains.
2. preparation technology according to claim 1, is characterized in that, described fluorochemicals is hydrofluoric acid, Neutral ammonium fluoride.
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| CN105602566A (en) * | 2016-02-29 | 2016-05-25 | 武汉理工大学 | Rare earth-doped NaGdF4 upconversion nanocrystalline and preparation method thereof |
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| CN102030356A (en) * | 2010-10-26 | 2011-04-27 | 北京化工大学 | Method for preparing polychromatic luminous nanocrystalline of monodisperse NaYF4 |
| CN102965112A (en) * | 2012-12-07 | 2013-03-13 | 东北林业大学 | Intense ultraviolet up-converting micron fluoride material and preparation method thereof |
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| CN105238398A (en) * | 2015-09-28 | 2016-01-13 | 浙江大学 | Rare-earth doped strontium titanate upconversion luminescent nanoparticles and preparation method thereof |
| CN105602566A (en) * | 2016-02-29 | 2016-05-25 | 武汉理工大学 | Rare earth-doped NaGdF4 upconversion nanocrystalline and preparation method thereof |
| CN105602566B (en) * | 2016-02-29 | 2017-12-29 | 武汉理工大学 | A kind of rear-earth-doped NaGdF4Upper conversion nano crystalline substance and preparation method thereof |
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