CN105778888B - A kind of sensitive response type nano structure luminescent material and preparation method thereof - Google Patents
A kind of sensitive response type nano structure luminescent material and preparation method thereof Download PDFInfo
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
- C09K11/7794—Vanadates; Chromates; Molybdates; Tungstates
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
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Abstract
The invention discloses a kind of sensitive response type nano structure luminescent material and preparation method thereof, include the following steps: for appropriate luminescent material or its predecessor to be placed in the solution containing the solute that can react with it shelling, carries out hydro-thermal or solvent thermal reaction；Hydrothermal synthesis product is heated, calcination obtains having isolated core-shell nanostructure luminescent material.The core-shell nano material of core surface portion cladding can be prepared in method of the invention easily, and shell is not connected to be distributed on core surface.By controlling the additive amount of reactant, the core-shell nano material of different interval distribution can be obtained.Opening is presented in the luminescent material being prepared using the method for the present invention in terms of structure and fluorescence, and discrete light-emitting is strong and has wide wavelength response characteristic, shows the characteristic of 1+1 > 2.Meanwhile the luminescent material that the method for the present invention is prepared has good stability, it is more convenient to use.
Description
Technical field
The present invention relates to a kind of nano-luminescent material and preparation method thereof, in particular to a kind of sensitive response type nano structure
Luminescent material and preparation method thereof.
Background technique
Fluorescent material with photoluminescent property it is glimmering will to usually require that it is excited as ion, the fluorescence probe of molecule
Light intensity, and its fluorescence intensity with micro ion, the inducing one to present significant of molecule and rule sexually revises.These fluorescence probes are usual
For quantum dot (Quantum dots, QDs), size is usually less than 10nm, such as CdR(R=S, Te or the S-Te of semi-conductor type)
QDs, Si QDs and these quantum dots are combined with plasma effect apparent nano metal Ag, Au.On the one hand, QDs due to
The too small surface energy of partial size is high, is easy to reunite；On the other hand, the preparation of hyperfluorescence type QDs requires in harsh nonaqueous solvents
Careful preparation, preparation cost are high；Finally, the thermal stability of numerous QDs is because own face effect is big and surface functional group is repaired
Decorations are influenced and malleable photoluminescent property by foeign element, use the problem for bringing detection data reproducibility low often.
The composite oxides fluorescent material of quantum dot rank, such as Y2O3: Eu3+, YVO4: Eu3+It is generally difficult to visit as fluorescence
Needle.Main cause be on the one hand, when size arrives quantum dot rank, because surface unsaturation dangling bonds is more, the multiple light of defect can be greatly
Amplitude weakens；On the other hand, usually there is great amount of hydroxy group group (- OH) on surface, to periphery ion, molecule susceptibility or combines energy
Power becomes extremely to weaken, its fluorescence changes small or regular shortcoming when foreign ion, molecule being caused to induce one；Finally, because of quantum ruler
Very little bring is easy to reunite to cause difficult dispersion, stability not high.
So far, wide wavelength response luminescent material usually requires that light emitting ionic is in discrete state each other, otherwise, because of spectrum weight
Folded bring transition competes based on a perhaps shifting or side.For this purpose, mostly using isolated core-shell structure, such as complex nucleus
The Y of shell nanostructure2O3: Eu3+@SiO2@YVO4: Eu3+, to the ultraviolet response of 220 ~ 350nm range.However, the knot of this material
Structure, which is designed, brings huge difficulty to preparation, and process control needs are high, and products obtained therefrom is easy to produce various discrete mixtures；Together
When because response sensitivity is low, fluorescence with surrounding molecular and ion concentration height change it is unobvious or present it is regular poor, it is this
Material generally cannot function as fluorescence probe use.
Developing one kind not only has wide wavelength response but also has stabilized illumination nano luminescent material, has extremely actual meaning
Justice.
Summary of the invention
It is an object of the invention to
The technical solution used in the present invention is:
A kind of preparation method with isolated core-shell nanostructure luminescent material, includes the following steps:
1) appropriate luminescent material or its predecessor are placed in the solution containing the solute that can react with it shelling, are carried out
Hydro-thermal or solvent thermal reaction；
2) hydrothermal synthesis product is heated, calcination obtains having isolated core-shell nanostructure luminescent material.
Luminescent material is Y2O3: Eu3+Or its predecessor, the solute that can react with it shelling is vanadate.
Y2O3: Eu3+Or the molar ratio of its predecessor and vanadate is 1:(0.001~0.01), wherein Y2O3: Eu3+Forerunner
The mole of object is with Y2O3: Eu3+Meter, the mole of vanadate is with the molar amount of vanadium.
The temperature of hydro-thermal reaction is 120~200 DEG C.
Preferably, the heating temperature of hydrothermal synthesis product is 400~600 DEG C, and the temperature of calcination is 750~900 DEG C.
Y2O3: Eu3+Predecessor be selected from yttrium hydroxy nitrate europium.
Preferably, luminescent material or its predecessor are club-shaped material, and the length is 100nm~1000nm.
The beneficial effects of the present invention are:
The core-shell nano material of core surface portion cladding can be prepared in method of the invention easily, and shell is on core surface
It is not connected to be distributed.By controlling the additive amount of reactant, the core-shell nano material of different interval distribution can be obtained.Use this hair
Opening is presented in the luminescent material that bright method is prepared in terms of structure and fluorescence, and discrete light-emitting is strong and has wide wavelength
Response characteristic shows the characteristic of 1+1 > 2.Meanwhile the luminescent material that the method for the present invention is prepared has good stability, makes
With more convenient.
For the luminescent material being prepared using the method for the present invention as fluorescence probe, the range of choice of excitation wavelength is wider,
It can be conducive to evade part interfering ion or molecule according to the actually detected exciting light for needing to select different wave length.
Detailed description of the invention
Fig. 1 is hud typed composite nanostructure material Y2O3: Eu3+@nYVO4: Eu3+SEM figure, a ~ d respectively correspond n=0,
0.2,0.4,0.6；
Fig. 2 is hud typed composite nanostructure material Y2O3: Eu3+@nYVO4: Eu3+EDS figure, a ~ d respectively correspond n=0,
0.2,0.4,0.6；
Fig. 3 is hud typed composite nanostructure material Y2O3: Eu3+@nYVO4: Eu3+HRTEM figure, a ~ d respectively correspond n=
0,0.2,0.4,0.6；
Fig. 4 is hud typed composite nanostructure material Y2O3: Eu3+@nYVO4: Eu3+Powder xrd pattern, a ~ d respectively correspond n
=0,0.2,0.4,0.6；
Fig. 5 is hud typed composite nanostructure material Y2O3: Eu3+@nYVO4: Eu3+Exciting light spectrogram, a ~ d are right respectively
Answer n=0,0.2,0.4,0.6；
The hud typed composite nanostructure material Y of Fig. 62O3: Eu3+@xYVO4: Eu3+Exciting light spectrogram (a be pure Y2O3:
Eu3+Exciting light spectrogram, convenient for comparing), b ~ e corresponds to x value 0.001 (b), 0.01 (c), 0.1 (d), 0.2 (e)；
The hud typed composite nanostructure material Y of Fig. 72O3: Eu3+@0.01YVO4: Eu3+TEM(a), HRTEM(b) figure；
The hud typed composite nanostructure material Y of Fig. 82O3: Eu3+@0.01YVO4: Eu3+Wide wavelength response fluorescence；
The hud typed composite nanostructure material Y of Fig. 92O3: Eu3+@0.01YVO4: Eu3+Fluorescence with pH value variation
(a: λex = 254nm and b: λex= 300 nm；C is pure Y2O3: Eu3+, λex= 254nm；D is variation/initial sample
Fluorescence intensity ratio with pH variation diagram, i.e. I/I0Vs. pH schemes)；
The hud typed composite nanostructure material Y of Figure 102O3: Eu3+@0.01YVO4: Eu3+Fluorescence probe characteristic: copper from
Sub- response diagram, λex= 254nm；
The hud typed composite nanostructure material Y of Figure 112O3: Eu3+@0.01YVO4: Eu3+- Cu2+(10-8 Mol/L) fluorescence
" off-and-on " characteristic of probe: glycine response diagram, λex= 254 nm；
The hud typed composite nanostructure material Y of Figure 122O3: Eu3+@0.01YVO4: Eu3+- Cu2+(10-8 Mol/L) fluorescence
" off-and-on " characteristic of probe: leucine response diagram, λex = 395 nm。
Specific embodiment
A kind of preparation method with isolated core-shell nanostructure luminescent material, includes the following steps:
1) appropriate luminescent material or its predecessor are placed in the solution containing the solute that can react with it shelling, are carried out
Hydro-thermal or solvent thermal reaction；
2) hydrothermal synthesis product is heated, calcination obtains having isolated core-shell nanostructure luminescent material.
Luminescent material (predecessor) does not dissolve in solvent, constitutes the core of core-shell material；And solute itself can not form precipitating, because
This, the two is to pass through the mixing of both control by diffusion ecto-entad and luminescent material (predecessor) step-reaction when contacting
Than or control the reaction time, preferably control both mixing ratio, can control extremely conveniently reaction formed luminous shell thickness
Degree, to obtain the nano structural material that shell is spaced apart.Such as find that shell is blocked up, cause shell in it is continuously distributed when, it is possible to reduce
The amount of solute or the time for shortening hydro-thermal reaction, to obtain the Core-shell structure material of different requirements.
Further, luminescent material Y2O3: Eu3+Or its predecessor, the solute that can react with it shelling is vanadate.
Y2O3: Eu3+Or the molar ratio of its predecessor and vanadate is 1:(0.001~0.01), wherein Y2O3: Eu3+Forerunner
The mole of object is with Y2O3: Eu3+Meter, the mole of vanadate is with the molar amount of vanadium.
The temperature of hydro-thermal reaction is 120~200 DEG C.
Preferably, the heating temperature of hydrothermal synthesis product is 400~600 DEG C, and the temperature of calcination is 750~900 DEG C.
Y2O3: Eu3+Predecessor be selected from yttrium hydroxy nitrate europium.
Preferably, luminescent material or its predecessor are club-shaped material, and the length is 100nm~1000nm.
The predecessor of nano structural material of the present invention, Y are obtained with the preparation method in known document2O3: Eu3+Or hydroxyl nitre
Sour yttrium europium, hydro-thermal or solvent thermal reaction, subsequent calcination processing are common process in preparation process.Wherein hydro-thermal or solvent heat are anti-
It answers temperature generally at 120 ~ 220 DEG C, is used to prepare yttrium hydroxy nitrate europium, subsequent calcination technique mostly uses segmentation or temperature programming
Calcination prepares Y2O3: Eu3+, final state temperature range is 500 ~ 1400 DEG C, product Y2O3: Eu3+For the final state used when nano-scale
Calcination temperature is relatively low.It can refer to following documents progress in terms of process detail.
[1] G. Bohus et al,Structural and luminescence properties of Y2O3:Eu3+
core–shell nanoparticles, Colloids and Surfaces A: Physicochem. Eng. Aspects
405 (2012) 6– 13
[2] Qi Zhu et al, Well-defined crystallites autoclaved from the
nitrate/NH4OH reaction system as the precursor for (Y,Eu)2O3 red phosphor:
Crystallization mechanism, phase and morphology control, and luminescent
Property, Journal of Solid State Chemistry, 192 (2012), 229-237
[3] Xiaoli Wu et al, Structure characterization and photoluminescence
properties of (Y0.95-xGdxEu0.05)2O3 red phosphors converted from layered rare-
earth hydroxide (LRH) nanoflake precursors, Journal of Alloys and Compounds
559 (2013) 188–195
[4] Q. Zhu et al, Nanometer-thin layered hydroxide platelets of
(Y0.95Eu0.05)2(OH)5NO3·xH2O: exfoliation-free synthesis, self-assembly, and the
derivation of dense oriented oxide films of high transparency and greatly
enhanced luminescence, J. Mater. Chem., 2011, 21, 6903-6908
[5] Liu Liang etc., stratiform rare-earth hydroxide hybrid luminescent materials progress, Chinese science: chemistry, 2015
(3):251-261
[6] Guixia Liu et al, Solvothermal Synthesis of Gd2O3 : Eu3+
Luminescent Nanowires, Journal of Nanomaterials,Volume 2010,1-5
[7] Xue Bai et al, Luminescent Properties of Pure Cubic Phase Y2O3/Eu3 + Nanotubes/Nanowires Prepared by a Hydrothermal Method, J. Phys. Chem. B
2005, 109, 15236-15242
[8] Guicun Li et al, Hydrothermal Synthesis and Characterization of
YVO4 and YVO4:Eu3+ Nanobelts and Polyhedral Micron Crystals, J. Phys. Chem. C,
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[9] Wu Ke etc., YVO4:Eu3+@YPO4The hydrothermal synthesis and characterization of nano-core-shell structure fluorescent powder, inorganic material
Expect journal, the 7th phase of volume 27,706-710
[10] Juan Wang et al, Hydrothermal synthesis of well-dispersed YVO4:Eu3+
Microspheres and their photoluminescence properties, Journal of Alloys and
Compounds, Volume 481, Issues 1-2,29 July 2009, Pages 896-902
[11]Y. L. Yan et al, Hydrothermal Synthesis of GdVO4:Eu 3+ Phosphors
by Optimizing its Preparation Conditions, Advanced Materials Research, Vols.
287-290, pp. 1360-1364, 2011
Below with common luminescent materials Y2O3: Eu3+For, further illustrate technical solution of the present invention.
Inventor is the study found that Y under certain condition2O3: Eu3+Or its predecessor, such as yttrium hydroxy nitrate europium, with vanadate
When hybrid reaction, by both control ratio, adjustment preparation process, this open part core-shell type nano knot can be obtained
Structure, it is wide that fluorescence is excited wave-length coverage, has discrete light-emitting material Y2O3: Eu3+With YVO4: Eu3+Double properties feature, more
It is important that shell is in entire nanostructure Y2O3: Eu3+@ p-YVO4: Eu3+Middle accounting very down to the ratio between the amount of 0.01(substance,n (p-YVO4: Eu3+):n (Y2O3: Eu3+=0.01) when, since discontinuous shell is very thin, part shell thickness is less than 10nm,
Quantum layer design feature is presented (p indicates that part covers).Due to the core-shell material centre of luminescence transition lifetime difference obviously with do not connect
The sensitive response characteristic of continuous quantum shell, wide wavelength simulated response and the sensitive response for having cast this novel nanostructure are special
Property.
Nano structural material Y2O3: Eu3+@ p-YVO4: Eu3+Preparation method, include the following steps:
1) by brand-new luminescent material Y2O3: Eu3+Or its predecessor ultrasonic disperse to setting volume solvent in, in proportion plus
Enter vanadate solution, carries out hydro-thermal or solvent thermal reaction certain time after mixing evenly；
2) by the separation of hydro-thermal reaction product, cleaning, drying, heating later, calcination processing are obtained as Y2O3: Eu3+Core,
Shell YVO4: Eu3+The nano structural material being spaced apart, is denoted as Y2O3: Eu3+@ p-YVO4: Eu3+。
Solvent can be water or ethyl alcohol or other solvents, and preferably water is as solvent.
Object Y2O3: Eu3+And the ratio between vanadate is identical as nucleocapsid accounting, i.e.,n(Y2O3: Eu3+):n(YVO4: Eu3+)=1:0.1
~ 0.001, preferred value 0.01.
Vanadate can be soluble metavanadic acid ammonium salt, sodium salt, or positive vanadic acid ammonium salt, sodium salt.
Hydro-thermal or the temperature of solvent thermal reaction can be conventional hydro-thermal or solvent thermal reaction temperature, and such as 120 DEG C~200
DEG C, guarantee vanadate can gradually with Y2O3: Eu3+Or its predecessor reaction.
Brand-new luminescent material Y2O3: Eu3+Or brand-new its predecessor can be by well known method system such as yttrium hydroxy nitrate europium
The standby product for obtaining or directly buying commercialization.
Luminescent material Y2O3: Eu3+Surface portion covering modification YVO4: Eu3+Referred to as Y2O3: Eu3+@ p-YVO4: Eu3+。
For the sake of facilitating comparison, luminescent material Y used in following embodiment2O3: Eu3+Or brand-new its predecessor, such as hydroxyl
Base yttrium nitrate europium, is prepared as follows to obtain:
Take 1.061g Y2O3With 0.106g Eu2O3Powder is added after 20ml deionized water is added in the beaker of 100ml
A certain amount of nitric acid solution；Then it dissolves by heating, and excessive nitric acid is allowed to volatilize away；It is molten with NaOH solution and nitric acid after cooling
PH is adjusted 12 or so in liquid；Then it places the beaker in ultrasound environments, is packed into reaction kettle after ultrasonic 15min.Then it falls
Into 180 DEG C of heating are heated in hydrothermal reaction kettle for 24 hours, after being centrifuged after the completion of hydro-thermal reaction, wash with water 3 times, drying is to get brand-new
Yttrium hydroxy nitrate europium, then respectively in 500,800 DEG C of heating 2h.Products obtained therefrom is rod-like nano Y2O3: Eu3+, Fig. 1 a, Fig. 2 a points
Not Wei its SEM, element form EDS figure, it is seen that its be rod-like nano material.
Examples 1 to 3
Three parts of the brand-new yttrium hydroxy nitrate europium of phase homogenous quantities is taken respectively, and ultrasonic disperse is separately added into corresponding into aqueous solution
The sodium metavanadate of ratio makes the ratio between amount of product materials keep n(YVO4): n(Y2O3)=x:1 (x=0,0.2,0.4,0.6(x=
0.2,0.4,0.6 respectively corresponds embodiment 1,2,3)), after stirring 15min, it is for 24 hours, then cold to be put into 180 DEG C of processing in hydro-thermal pot
But sample is taken out, it is dry after being centrifuged, washing with water 3 times, respectively in 500,800 DEG C of heating 2h.Up to compound core-shell type nano knot
Structure material Y2O3: Eu3+@nYVO4 : Eu3+(n=0,0.2,0.4,0.6).Fig. 1 (c-d), Fig. 2 (c-d) are respectively its SEM, element group
Scheme at EDS.Fig. 3 is Y2O3: Eu3+@nYVO4: Eu3+HRTEM figure, Fig. 4 Y2O3: Eu3+@nYVO4: Eu3+Powder xrd pattern,
Fig. 5 is Y2O3: Eu3+@nYVO4: Eu3+Exciting light spectrogram, n=0,0.2,0.4,0.6；Fig. 3 shows, serial Y2O3: Eu3+@
nYVO4: Eu3+In sample, n=0.2 is the nano-core-shell structure of continuous shell, and shell thickness is with YVO when 0.4,0.64:
Eu3+Accounting increases and increases；Fig. 4 then illustrates in the structure of these samples simultaneously containing cubic oxide yttrium phase (corresponding XRD card
PDF#17-0341), cubic Yttrium Orthovanadate phase (corresponding XRD card PDF#41-1105), regularity is presented with n value in their content
Variation；Shell YVO is presented in Fig. 5 excitation spectrum4: Eu3+Shine.
The explanation of sample spectrum diagram obtained by Examples 1 to 3, core-shell type nano structural material Y2O3: Eu3+@nYVO4: Eu3+(n=
0.2,0.4,0.6) since shell is in continuous state, there is closure, because transition competes, core Y2O3: Eu3+It shines because of fluorescence lifetime
Length has effectively been transferred to service life short shell YVO4: Eu3+, and shell YVO is only presented4: Eu3+Shine, wide sound can not be obtained
The luminescent material answered.
Embodiment 4~7
Brand-new Y is taken respectively2O3: Eu3+Three parts of ultrasonic disperses are separately added into the ammonium metavanadate of corresponding proportion into aqueous solution,
The ratio between amount of substance in product is set to keep n(YVO4): n(Y2O3(x=0.001,0.01,0.1,0.2 respectively correspond implementation to)=x:1
Example 4~7), after stirring 15min, being put into 180 DEG C of processing in hydro-thermal pot, for 24 hours, then cooling taking-up sample, is centrifuged, washes with water 3
It is dry after secondary, respectively in 500,800 DEG C of heating 2h.Up to hud typed composite nanostructure material Y2O3: Eu3+@xYVO4: Eu3 +.Fig. 6 (b-e) give they exciting light spectrogram (a be pure Y2O3: Eu3+Exciting light spectrogram, convenient for comparing), Fig. 7 be sample
Y2O3: Eu3+@0.01YVO4: Eu3+HRTEM figure.Fig. 6 clearly shows that Y2O3: Eu3+@nYVO4: Eu3+N value drops in series of samples
The recombination luminescence that discrete core-shell material is presented when as low as 0.1 and 0.1 or less, in this range, gained nucleocapsid luminescent material is in structure
It is in open characteristics in terms of with fluorescence, fluorescence response wider range of material and relatively stable when n value is 0.01, that is,
It says, the corresponding sample in n=0.1,0.01 and 0.001 belongs to the core-shell type nano structural material Y of part covering2O3: Eu3+@p-
YVO4: Eu3+, suitable n value is 0.01, at this point, resulting materials fluorescence changes less with excitation wavelength；Fig. 7 then shows sample Y2O3:
Eu3+@0.01YVO4: Eu3+Shell be it is discontinuous, thickness of the shell changes in gradient, thickness be less than 6nm, reach quantum size rank.
Fig. 8 furthermore presents hud typed composite nanostructure material Y2O3: Eu3+@0.01YVO4: Eu3+Wide wavelength response fluorescence,
Fluorescence intensity change is little, is suitble to do fluorescence probe.It is noted that can deduce according to Fig. 6 (b, d), the sample at two excitation peak
Y2O3: Eu3+@0.001YVO4: Eu3+、Y2O3: Eu3+@0.1YVO4: Eu3+Also there is wide wavelength response fluorescent characteristic, but fluorescence is strong
Degree changes with excitation wavelength and changes big.
Sensitive response characteristic: fluorescence probe application
In order to verify hud typed composite nanostructure material Y2O3: Eu3+@p-YVO4: Eu3+Fluorescence probe characteristic, with
Y2O3: Eu3+@0.01YVO4: Eu3+For design and complete series include pH, C(Cu2+) response experiment.Toward pH=2 5mL, 4,
6, the compound nucleocapsid nano structural material Y of 3mg is added in 8,10 buffer solution or various concentration copper ion solution2O3: Eu3+@
0.01YVO4: Eu3+, shake and place and test dispersion fluorescence after 30min, be as a result compiled in Fig. 9 (a, b, c, d), in 10.Fig. 9
(a-d) illustrate Y2O3: Eu3+@0.01YVO4: Eu3+It is sensitiveer to pH variation that (fluorescence intensity is with OH- The degree that concentration changes is big),
It is presented good linear relationship (fitting R value 0.995) in pH=4 ~ 8 ranges, and simple nanometer Y2O3: Eu3+Or and YVO4: Eu3+?
It cannot function as the fluorescence probe of pH variation；Equally, Figure 10 result illustrates Y2O3: Eu3+@0.01YVO4: Eu3+To copper ion concentration
It is good to change sensitiveer and linear relationship, in C (Cu2+)=10-4 ~ 10-10Good linear relationship (fitting R value is presented in mol/L range
0.990), and in this range in addition to simple nanometer Y2O3: Eu3+In C (Cu2+)=10-4 ~ 10-8Good linear is presented in mol/L range
Relationship (fitting R value 0.998) outside, nanometer Y2O3: Eu3+And 0.01molYVO4: Eu3+Or simple YVO4: Eu3+Because insensitive or
Its fluorescence changes not shown regularity variation and cannot function as C (Cu2+) variation fluorescence probe.
On the other hand, the Y of (quenching, off) dimmed in Figure 10 is selected2O3: Eu3+@0.01YVO4: Eu3+- Cu2+(10-8
Mol/L) solution can be used for detecting energy and Cu as new fluorescence probe2+The trace molecule of complexing, such as various amino acid, at this point,
System fluorescence increases with amino acid concentration, and copper ion is desorbed and enhances and (brighten, on).Figure 11 gives hud typed composite Nano
Structural material Y2O3: Eu3+@0.01YVO4: Eu3+- Cu2+(10-8 Mol/L) " off-and-on " characteristic of fluorescence probe: sweet ammonia
Sour response diagram, λex= 254 nm；Figure 12 then gives hud typed composite nanostructure material Y2O3: Eu3+@0.01YVO4: Eu3 +- Cu2+(10-8 Mol/L) " off-and-on " characteristic of fluorescence probe: leucine response diagram, λex= 395 nm.The two is in trace
It measures concentration C (glycine or leucine)=0.1 × 10-8 ~ 2.0×10-8Good linear relationship (match value is presented in mol/L range
It is all larger than 0.99).
It can to sum up obtain, novel Y2O3: Eu3+@p-YVO4: Eu3+Wide wavelength response nano structural material due to structure with it is glimmering
It is presented in terms of light open, it is expected to develop into a kind of excellent fluorescence probe, trace detection lewis' acid is expected to potential answer
For various fields.
Similar, it can be prepared using other luminescent materials as core, surface has the nanostructure material for being spaced apart shell
Material.
Claims (7)
1. a kind of preparation method with isolated core-shell nanostructure luminescent material, includes the following steps:
1) by appropriate luminescent material Y2O3: Eu3+Or its predecessor is placed in containing the molten of the vanadate solute that can react with it shelling
In liquid, hydro-thermal or solvent thermal reaction are carried out；
2) hydrothermal synthesis product is heated, calcination obtains having isolated core-shell nanostructure luminescent material；
Wherein, Y2O3: Eu3+Or the molar ratio of its predecessor and vanadate is 1:(0.001~0.01), wherein Y2O3: Eu3+Forerunner
The mole of object is with Y2O3: Eu3+Meter, the mole of vanadate is with the molar amount of vanadium.
2. preparation method according to claim 1, it is characterised in that: the temperature of hydro-thermal reaction is 120~200 DEG C.
3. preparation method according to claim 1, it is characterised in that: the heating temperature of hydrothermal synthesis product is 400~600
DEG C, the temperature of calcination is 750~900 DEG C.
4. preparation method according to claim 2, it is characterised in that: Y2O3: Eu3+Predecessor be selected from yttrium hydroxy nitrate europium.
5. preparation method according to claim 1, it is characterised in that: luminescent material or its predecessor are club-shaped material,
Length is 100nm~1000nm.
6. one kind has isolated core-shell nanostructure luminescent material, the preparation of the method as described in Claims 1 to 5 any one
It obtains.
7. have isolated core-shell nanostructure luminescent material preparing the application in fluorescence probe, it is characterised in that: have every
It is prepared from formula core-shell nanostructure luminescent material by method described in Claims 1 to 5 any one.
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| Menglei Chang等.Fabrication of novel luminor Y2O3:Eu3+@SiO2@YVO4:Eu3+ with core/shell heteronanostructure.《Nanotechnology》.2008,第19卷(第7期),试验部分2.1-2.4和结论部分. * |
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