CN105752957B - Using the method for preparing nano-scale rare earth phosphate phosphor from sacrifice template method - Google Patents
Using the method for preparing nano-scale rare earth phosphate phosphor from sacrifice template method Download PDFInfo
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Abstract
It is a kind of to use the method for preparing nano-scale rare earth phosphate phosphor from sacrifice template method：1) low temperature synthesis LRH nanometer sheet templates：By Y (NO3)3·6H2O or Gd (NO3)3·6H2O, Eu (NO3)3·6H2O and/or Tb (NO3)3·6H2O, is made into the aqueous solution；It is placed in ice-water bath, cools；Ammonia is slowly added dropwise, the suspension that pH is 6.5~9 is obtained；Ageing；Powdered LRH is dried to obtain in centrifugation；2) LRH sacrifices template certainly：LRH is disperseed with phosphate to react in deionized water, drying is centrifuged and obtains powdered ion exchange product；Calcining obtains nano-scale rare earth phosphate phosphor；The LRH nanometer sheet templates that the present invention is prepared using " step of low temperature one precipitation " technology, chemical composition is uniform, and nanoscale twins thickness is 2~5nm, and basis is provided for kinetics, can control particle size and pattern；Fluorescent powder grain fine uniform prepared by the present invention；Preparation method of the present invention, it is simple and easy to apply with low cost, a large amount of productions can be achieved.
Description
Technical field
It is more particularly to a kind of to prepare nano-scale rare earth phosphoric acid using from sacrifice template method the invention belongs to materials science field
The method of salt fluorescent material.
Background technology
Rare earth orthophosphates possesses many premium properties, including minimum water solubility, superior heat endurance and height
Refraction index etc..In addition, the tetrahedral structure of phosphate radical is a kind of good carrier to charge stable.These performances cause dilute
Native orthophosphates fluorescent material is in optical material, laser material, magneto-optic memory technique, magnetoresistance material, dielectric material, sorbing material, catalysis
Had a wide range of applications in terms of agent and chemical sensitisation.
In rare earth orthophosphates material, yttrium phosphate has good lattice compatibility to object cation, and Gadolinium monophosphate
There is good energy transmission effect as matrix to object cation.Therefore, rare earth ion doped yttrium phosphate and Gadolinium monophosphate
Nano-phosphor is widely used in preparing PDP fluorescent material, plasma flat-panel display, LED, high-pressure sodium lamp etc..Closely
Nian Lai, due to its importance in engineering, increasing synthetic technology is used to prepare using both phosphate as matrix,
The fluorescent material for different rare earth ions of adulterating.These synthetic technologys include：The hot method of hydrothermal/solvent, solid reaction process and combustion method etc..
Wherein, the hot method of hydrothermal/solvent generally requires certain organic or inorganic additive, to prepare nano level fluorescent material, and needs
Follow-up calcination processing removes the factor that hydroxyl, carboxyl and crystallization water etc. are unfavorable to fluorescence；And solid reaction process is usual
Tediously long process is needed, raw material mixing uniformity is not often good, and obtained particle size is larger and uneven；Although combustion method
It is swift in response, but a large amount of such as NO can be discharged in course of reaction2、SO2、P2O5Deng the material harmful to environment, human body, and it is difficult
To obtain nano level particle.These factors bring many difficulties to preparing nano level RE phosphate fluorescent material.
Rare earth layered hydroxide (abbreviation LRH) has had both the unique layer structure and rare earth element of inorganic layered compounds
The characteristics such as distinctive light, electricity, magnetic, it is expected to obtain important application in fields such as catalysis, luminous and photoelectric components.Such LRH is certainly
System has been obtained since being reported within 2006 in all many-sides such as synthesis, crystallographic structural analysis and application as luminescent material
Further investigation.There is ultra-thin nanometer laminated structure with the LRH that " step of low temperature one precipitation " technology is obtained (thickness is about 2~5nm).
At present, the research for LRH mainly has the following aspects：(1) on the premise of main stor(e)y plate is not destroyed, by LRH interlayers it is cloudy from
It is sub to be swapped with a variety of inorganic or organic anion, to obtain compound structure for new residence and more excellent fluorescence property；(2) will
LRH, which is peeled off, turns into ultrathin nanometer piece to construct LRH and oxide alignment films, so as to obtain the fluorescence intensity of multiplication；(3) to LRH
Calcination processing is carried out, corresponding rare-earth oxide phosphor is obtained.However, it is glimmering to prepare RE phosphate using LRH as sacrifice template
This means of light powder do not have report at home and abroad.
The content of the invention
In view of the above-mentioned problems, it is an object of the invention to provide it is a kind of prepare rare earth phosphate nano-phosphor from sacrificial mold
Plate method, it is therefore an objective to be by " step of low temperature one precipitation " technology prepare LRH (chemical formula is Ln2(OH)5NO3·nH2O) template
Nano-lamellar structure, effectively control particle size and uniformity, so as to obtain the RE phosphate fluorescent material of Nano grade.
Technical solution of the present invention：The rare earth layered hydroxide (LRH) obtained by " step of low temperature one precipitation " technology has super
Thin nanometer laminated structure (thickness is about 2~5nm), its significantly exposed laminate provides kinetics base for ion exchange
Plinth, therefore, as template is sacrificed, to prepare nanoscale and evengranular RE phosphate fluorescent material.
Using from the method that template method prepares nano-scale rare earth phosphate phosphor is sacrificed, comprise the following steps：
Step 1, low temperature synthesis LRH nanometer sheet templates：
(1) A and B is mixed, is configured to rare earth ion concentration for 0.05~0.3mol/L mixed aqueous solutions；Wherein, in B
The molal quantity sum of rare earth ion：Molal quantity sum=0.001~0.15, A of A and B Rare Earth Ions is Y (NO3)3·6H2O
Or Gd (NO3)3·6H2O, B are Eu (NO3)3·6H2O and/or Tb (NO3)3·6H2O；
(2) by mixed aqueous solution, it is placed in ice-water bath, its temperature is reduced to 2~5 DEG C while stirring；
(3) into mixed aqueous solution, Ammonia is slowly added dropwise, the suspension that pH is 6.5~9 is obtained, wherein, hydrogen
The concentration of amine-oxides is 0.1~2mol/L；
(4) by suspension, it is aged 0.5~5h；
(5) centrifuge, cleaning and drying obtain powdered LRH；
Step 2, LRH sacrifices template certainly：
(1) it is LRH and phosphate is scattered in deionized water, 0.5~72h is stirred at room temperature；Wherein, in molar ratio, phosphoric acid
Root: rare earth element ion=(1~10) in LRH: 1；
(2) centrifuge, cleaning and drying obtain powdered phosphate ion and exchange product；
(3) phosphate ion is exchanged into product, calcines 2~8h in 600~1200 DEG C, obtain nano-scale rare earth phosphate glimmering
Light powder.
Wherein：
Described LRH is rare earth layered hydroxide；
In the step 1 (3), rate of addition is 0.2~5 drop/sec；
In the step 1 (5) and step 2 (2), furnace drying method is：6~48h is dried at 50~70 DEG C；
In the step 2 (1), phosphate is (NH4)2HPO4Or NH4H2PO4；
It is described to use from the granularity of nano-scale rare earth phosphate phosphor prepared by template method is sacrificed as 20~200nm.
The use of the present invention is from the method that template method prepares nano-scale rare earth phosphate phosphor is sacrificed, with prior art phase
Than beneficial effect is：
(1) use of the invention is from the method that template method prepares nano-scale rare earth phosphate phosphor is sacrificed, using " low temperature
LRH nanometer sheet templates prepared by one step precipitation " technology, because it is obtained in the solution, and raw material is atom level level, thus its
Chemical composition is uniform；
(2) preparation method of the invention, the distinctive nano-lamellar structure of LRH templates (thickness is about 2~5nm) is reaction
Dynamics provides the foundation, and can effectively control particle size and pattern.
(3) REPO prepared by the inventive method4：Ln fluorescent powder grain fine uniforms, be still after calcining at relatively high temperatures
Nano-scale particle, its light functionalization material has important researching value.
(4) preparation method of the present invention, simple and easy to apply, with low cost, operates easily controllable, achievable a large amount of productions.
Brief description of the drawings
The TEM shape appearance figures of the product of Fig. 1 embodiment of the present invention 1；Wherein, (a) is that phosphate ion exchanges product morphology, (b)
For (Y0.98Eu0.02)PO4Granule-morphology；
(Y prepared by Fig. 2 embodiment of the present invention 20.95Eu0.05)PO4The TEM shape appearance figures of particle；
(Y prepared by Fig. 3 embodiment of the present invention 30.90Eu0.10)PO4The TEM shape appearance figures of particle；
The XRD spectrum of nano-scale rare earth phosphate phosphor prepared by Fig. 4 embodiment of the present invention 1~3；
(Y prepared by Fig. 5 embodiment of the present invention 40.96Tb0.04)PO4The TEM shape appearance figures of particle；
(Y prepared by Fig. 6 embodiment of the present invention 50.92Tb0.04Eu0.04)PO4The TEM shape appearance figures of particle；
(Y prepared by Fig. 7 embodiment of the present invention 60.86Tb0.04Eu0.10)PO4The XRD spectrum of particle；
(Gd prepared by Fig. 8 embodiment of the present invention 70.98Eu0.02)PO4The SEM shape appearance figures of particle；
(Gd prepared by Fig. 9 embodiment of the present invention 80.95Eu0.05)PO4The SEM shape appearance figures of particle；
(Gd prepared by Figure 10 embodiment of the present invention 90.90Eu0.10)PO4The SEM shape appearance figures of particle；
(Gd prepared by Figure 11 embodiment of the present invention 100.96Tb0.04)PO4The SEM shape appearance figures of particle；
(the Gd that Figure 12 embodiment of the present invention 11 is prepared with example 120.92Tb0.04Eu0.04)PO4With (Gd0.86Tb0.04Eu0.10)PO4
The XRD spectrum of particle；Wherein, figure (a) correspondence embodiment 11, figure (b) correspondence embodiment 12.
Embodiment
Chemical reagent employed in present example is the pure level product of analysis；
The embodiment of the present invention carries out XRD analysis using the PW3040/60 types X-ray diffractometer of Philips companies of Holland；Adopt
With JSM~7001F types FE~SEM observing samples pattern (SEM) of Japanese JEOL companies；Using Japanese JEOL companies JEM~
1010 type TEM observing samples patterns (TEM)；
The baking oven that the embodiment of the present invention is used be electron temperature-control convection oven, the temperature difference be less than 1 DEG C, high temperature furnace be tube furnace,
1550 DEG C of rated temperature；
Embodiment 1
Using from the method that template method prepares nano-scale rare earth phosphate phosphor is sacrificed, comprise the following steps：
Step 1, low temperature synthesis LRH nanometer sheet templates：
(1) by Y (NO3)3·6H2O and Eu (NO3)3·6H2O, according to mol ratio Eu3+∶(Y3++Eu3+)=0.02 is mixed, and is matched somebody with somebody
The aqueous solution that rare earth ion concentration is 0.05mol/L is made；
(2) by mixed aqueous solution, it is placed in ice-water bath, its temperature is reduced to 5 DEG C while stirring；
(3) into mixed aqueous solution, Ammonia is slowly added dropwise, the suspension that pH is 9 is obtained, wherein, speed is added dropwise
Spend for 5 drops/sec, the concentration of ammonium hydroxide is 0.1mol/L；
(4) suspension is aged 5h；
(5) centrifuge, cleaning dries 6h at 70 DEG C, obtains powdered LRH；
Step 2, LRH sacrifices template certainly：
(1) by 1mmol LRH and (NH4)2HPO4Phosphate radical in molar ratio: rare earth element ion=1 in LRH: 1 mixing,
And add deionized water to be configured to suspension, 72h is stirred at room temperature；
(2) centrifuge, cleaning dries 6h at 70 DEG C, obtain powdered phosphate ion and exchange product；
(3) phosphate ion is exchanged into product, in O2In atmosphere, 8h is calcined in 600 DEG C, (Y is obtained0.98Eu0.02)PO4It is glimmering
Light powder.
Gained phosphate ion exchange product be reunion state nanostructured, its TEM pattern such as Fig. 1 (a), fluorescent material put down
Equal granularity is about 20nm, inherits LRH nanocrystal habit, its TEM pattern such as Fig. 1 (b), XRD spectrum such as Fig. 4 (a).
Embodiment 2
Using from the method that template method prepares nano-scale rare earth phosphate phosphor is sacrificed, comprise the following steps：
Step 1, low temperature synthesis LRH nanometer sheet templates：
(1) by Y (NO3)3·6H2O and Eu (NO3)3·6H2O, according to mol ratio Eu3+∶(Y3++Eu3+)=0.05 is mixed, and is matched somebody with somebody
The aqueous solution that rare earth ion concentration is 0.05mol/L is made；
(2) by mixed aqueous solution, it is placed in ice-water bath, its temperature is reduced to 5 DEG C while stirring；
(3) into mixed aqueous solution, Ammonia is slowly added dropwise, the suspension that pH is 8.5 is obtained, wherein, it is added dropwise
Speed is 5 drops/sec, and the concentration of ammonium hydroxide is 0.2mol/L；
(4) suspension is aged 5h；
(5) centrifuge, cleaning dries 6h at 70 DEG C, obtains powdered LRH；
Step 2, LRH sacrifices template certainly：
(1) by 1mmol LRH and (NH4)2HPO4Phosphate radical in molar ratio: rare earth element ion=1: 1 mixing, and add and go
Ionized water is configured to suspension, and 36h is stirred at room temperature；
(2) centrifuge, cleaning dries 6h at 70 DEG C, obtain powdered phosphate ion and exchange product；
(3) phosphate ion is exchanged into product, in O2In atmosphere, 4h is calcined in 700 DEG C, (Y is obtained0.95Eu0.05)PO4It is glimmering
Light powder.
The particle mean size of gained fluorescent material is about 20nm, its TEM pattern such as Fig. 2, XRD spectrum such as Fig. 4 (b).
Embodiment 3
Using from the method that template method prepares nano-scale rare earth phosphate phosphor is sacrificed, comprise the following steps：
Step 1, low temperature synthesis LRH nanometer sheet templates：
(1) by Y (NO3)3·6H2O and Eu (NO3)3·6H2O is according to mol ratio Eu3+∶(Y3++Eu3+)=0.1 is mixed, and is prepared
Into the aqueous solution that rare earth ion concentration is 0.1mol/L；
(2) by mixed aqueous solution, it is placed in ice-water bath, its temperature is reduced to 5 DEG C while stirring；
(3) into mixed aqueous solution, Ammonia is slowly added dropwise, the suspension that pH is 8.5 is obtained, wherein, it is added dropwise
Speed is 2 drops/sec, and the concentration of ammonium hydroxide is 0.2mol/L；
(4) by suspension, it is aged 3h；
(5) centrifuge, cleaning dries 12h at 70 DEG C, obtains powdered LRH；
Step 2, LRH sacrifices template certainly：
(1) by 1mmol LRH and (NH4)2HPO4Phosphate radical in molar ratio: rare earth element ion=1: 1 mixing, and add and go
Ionized water is configured to suspension, and 24h is stirred at room temperature；
(2) centrifuge, cleaning dries 12h at 70 DEG C, obtain powdered phosphate ion and exchange product；
(3) phosphate ion is exchanged into product, in O2In atmosphere, 2h is calcined in 900 DEG C, (Y is obtained0.90Eu0.10)PO4It is glimmering
Light powder.
The particle mean size of gained fluorescent material is about 20nm, its TEM pattern such as Fig. 3, XRD spectrum such as Fig. 4 (c).
Embodiment 4
Using from the method that template method prepares nano-scale rare earth phosphate phosphor is sacrificed, comprise the following steps：
Step 1, low temperature synthesis LRH nanometer sheet templates：
(1) by Y (NO3)3·6H2O and Tb (NO3)3·6H2O is according to mol ratio Tb3+∶(Y3++Tb3+)=0.04 is mixed, and is matched somebody with somebody
The aqueous solution that rare earth ion concentration is 0.1mol/L is made；
(2) by mixed aqueous solution, it is placed in ice-water bath, its temperature is reduced to 5 DEG C while stirring；
(3) into mixed aqueous solution, Ammonia is slowly added dropwise, the suspension that pH is 8 is obtained, wherein, speed is added dropwise
Spend for 2 drops/sec, the concentration of ammonium hydroxide is 0.5mol/L；
(4) suspension is aged 3h；
(5) centrifuge, cleaning dries 12h at 70 DEG C, obtains powdered LRH；
Step 2, LRH sacrifices template certainly：
(1) by 1mmol LRH and NH4H2PO4Phosphate radical in molar ratio: rare earth element ion=2: 1 mixing, and add go from
Sub- water is configured to suspension, and 12h is stirred at room temperature；
(2) centrifuge, cleaning dries 12h at 70 DEG C, obtain powdered phosphate ion and exchange product；
(3) phosphate ion is exchanged into product, in H2In atmosphere, 2h is calcined in 1000 DEG C, (Y is obtained0.96Tb0.04)PO4It is glimmering
Light powder.
The particle mean size of gained fluorescent material is about 30nm, its TEM pattern such as Fig. 5, it is seen that under higher calcining heat, product
It still is able to maintain nanotopography.
Embodiment 5
Using from the method that template method prepares nano-scale rare earth phosphate phosphor is sacrificed, comprise the following steps：
Step 1, low temperature synthesis LRH nanometer sheet templates：
(1) by Y (NO3)3·6H2O、Tb(NO3)3·6H2O and Eu (NO3)3·6H2O, according to mol ratio (Tb3++Eu3+)∶
(Y3++Tb3++Eu3+)=0.08 is mixed, and is configured to the aqueous solution that rare earth ion concentration is 0.1mol/L；
(2) by mixed aqueous solution, it is placed in ice-water bath, its temperature is reduced to 3 DEG C while stirring；
(3) into mixed aqueous solution, Ammonia is slowly added dropwise, the suspension that pH is 8 is obtained, wherein, speed is added dropwise
Spend for 1 drop/sec, the concentration of ammonium hydroxide is 0.5mol/L；
(4) suspension is aged 2h；
(5) centrifuge, cleaning dries 12h at 60 DEG C, obtains powdered LRH；
Step 2, LRH sacrifices template certainly：
(1) by 5mmol LRH and NH4H2PO4Phosphate radical in molar ratio: rare earth element ion=2: 1 mixing, and add go from
Sub- water is configured to suspension, and 12h is stirred at room temperature；
(2) centrifuge, cleaning dries 12h at 60 DEG C, obtain powdered phosphate ion and exchange product；
(3) phosphate ion is exchanged into product, in H2In atmosphere, 2h is calcined in 1000 DEG C, (Y is obtained0.92Tb0.04Eu0.04)
PO4Fluorescent material.
The particle mean size of gained fluorescent material is 30nm, its TEM pattern such as Fig. 6.
Embodiment 6
Using from the method that template method prepares nano-scale rare earth phosphate phosphor is sacrificed, comprise the following steps：
Step 1, low temperature synthesis LRH nanometer sheet templates：
(1) by Y (NO3)3·6H2O、Tb(NO3)3·6H2O and Eu (NO3)3·6H2O, according to mol ratio (Tb3++Eu3+)∶
(Y3++Tb3++Eu3+)=0.14 is mixed, and is configured to the aqueous solution that rare earth ion concentration is 0.1mol/L；
(2) by mixed aqueous solution, it is placed in ice-water bath, its temperature is reduced to 3 DEG C while stirring；
(3) into mixed aqueous solution, Ammonia is slowly added dropwise, the suspension that pH is 8 is obtained, wherein, speed is added dropwise
Spend for 1 drop/sec, the concentration of ammonium hydroxide is 1mol/L；
(4) suspension is aged 2h；
(5) centrifuge, cleaning dries 24h at 60 DEG C, obtains powdered LRH；
Step 2, LRH sacrifices template certainly：
(1) by 5mmol LRH and NH4H2PO4Phosphate radical in molar ratio: rare earth element ion=2: 1 mixing, and add go from
Sub- water is configured to suspension, and 6h is stirred at room temperature；
(2) centrifuge, cleaning dries 24h at 60 DEG C, obtain powdered phosphate ion and exchange product；
(3) phosphate ion is exchanged into product, in H2In atmosphere, 2h is calcined in 1000 DEG C, (Y is obtained0.86Tb0.04Eu0.10)
PO4Fluorescent material.
The XRD spectrum of gained fluorescent material such as Fig. 7, it is seen that product has excellent crystallinity, and in rare earth ion doped amount
The thing phase of yttrium phosphate matrix is able to maintain that in the case of higher, compatible good to rare earth ion of yttrium phosphate matrix lattice is indicated
Property.
Embodiment 7
Using from the method that template method prepares nano-scale rare earth phosphate phosphor is sacrificed, comprise the following steps：
Step 1, low temperature synthesis LRH nanometer sheet templates：
(1) by Gd (NO3)3·6H2O and Eu (NO3)3·6H2O, according to mol ratio Eu3+∶(Gd3++Eu3+)=0.02 is mixed,
It is configured to the aqueous solution that rare earth ion concentration is 0.2mol/L；
(2) by mixed aqueous solution, it is placed in ice-water bath, its temperature is reduced to 3 DEG C while stirring；
(3) into mixed aqueous solution, Ammonia is slowly added dropwise, the suspension that pH is 8 is obtained, wherein, speed is added dropwise
Spend for 1 drop/sec, the concentration of ammonium hydroxide is 1mol/L；
(4) suspension is aged 2h；
(5) centrifuge, cleaning dries 24h at 60 DEG C, obtains powdered LRH；
Step 2, LRH sacrifices template certainly：
(1) by 5mmol LRH and (NH4)2HPO4Phosphate radical in molar ratio: rare earth element ion=4: 1 mixing, and add and go
Ionized water is configured to suspension, and 6h is stirred at room temperature；
(2) centrifuge, cleaning dries 24h at 60 DEG C, obtain powdered phosphate ion and exchange product；
(3) phosphate ion is exchanged into product, in O2In atmosphere, 4h is calcined in 900 DEG C, (Gd is obtained0.98Eu0.02)PO4It is glimmering
Light powder.
The particle mean size of gained fluorescent material is 40nm, its SEM pattern such as Fig. 8, it can be seen that forged under higher calcining heat
The long period is burnt, product can still keep nano-scale.
Embodiment 8
Using from the method that template method prepares nano-scale rare earth phosphate phosphor is sacrificed, comprise the following steps：
Step 1, low temperature synthesis LRH nanometer sheet templates：
(1) by Gd (NO3)3·6H2O and Eu (NO3)3·6H2O, according to mol ratio Eu3+∶(Gd3++Eu3+)=0.05 is mixed,
It is configured to the aqueous solution that rare earth ion concentration is 0.2mol/L；
(2) by mixed aqueous solution, it is placed in ice-water bath, its temperature is reduced to 3 DEG C while stirring；
(3) into mixed aqueous solution, Ammonia is slowly added dropwise, the suspension that pH is 8 is obtained, wherein, speed is added dropwise
Spend for 0.5 drop/sec, the concentration of ammonium hydroxide is 1mol/L；
(4) suspension is aged 1h；
(5) centrifuge, cleaning dries 24h at 60 DEG C, obtains powdered LRH；
Step 2, LRH sacrifices template certainly：
(1) by 5mmol LRH and (NH4)2HPO4Phosphate radical in molar ratio: rare earth element ion=4: 1 mixing, and add and go
Ionized water is configured to suspension, and 2h is stirred at room temperature；
(2) centrifuge, cleaning dries 24h at 60 DEG C, obtain powdered phosphate ion and exchange product；
(3) phosphate ion is exchanged into product, in O2In atmosphere, 2h is calcined in 1200 DEG C, (Gd is obtained0.95Eu0.05)PO4
Fluorescent material.
The average particle size particle size of gained fluorescent material is about 200nm, its SEM pattern such as Fig. 9.
Embodiment 9
Using from the method that template method prepares nano-scale rare earth phosphate phosphor is sacrificed, comprise the following steps：
Step 1, low temperature synthesis LRH nanometer sheet templates：
(1) by Gd (NO3)3·6H2O and Eu (NO3)3·6H2O, according to mol ratio Eu3+∶(Gd3++Eu3+)=0.10 is mixed,
It is configured to the aqueous solution that rare earth ion concentration is 0.2mol/L；
(2) by mixed aqueous solution, it is placed in ice-water bath, its temperature is reduced to 2 DEG C while stirring；
(3) into mixed aqueous solution, Ammonia is slowly added dropwise, the suspension that pH is 7.5 is obtained, wherein, it is added dropwise
Speed is 0.5 drop/sec, and the concentration of ammonium hydroxide is 1mol/L；
(4) suspension is aged 1h；
(5) centrifuge, cleaning dries 24h at 60 DEG C, obtains powdered LRH；
Step 2, LRH sacrifices template certainly：
(1) by 10mmol LRH and (NH4)2HPO4Phosphate radical in molar ratio: rare earth element ion=4: 1 mixing, and add and go
Ionized water is configured to suspension, and 2h is stirred at room temperature；
(2) centrifuge, cleaning dries 24h at 60 DEG C, obtain powdered phosphate ion and exchange product；
(3) phosphate ion is exchanged into product, in O2In atmosphere, 2h is calcined in 1200 DEG C, (Gd is obtained0.90Eu0.10)PO4
Fluorescent material.
The average particle size particle size of gained fluorescent material is about 200nm, its SEM pattern such as Figure 10.
Embodiment 10
Using from the method that template method prepares nano-scale rare earth phosphate phosphor is sacrificed, comprise the following steps：
Step 1, low temperature synthesis LRH nanometer sheet templates：
(1) by Gd (NO3)3·6H2O and Tb (NO3)3·6H2O, according to mol ratio Tb3+∶(Gd3++Tb3+)=0.04 is mixed,
It is configured to the aqueous solution that rare earth ion concentration is 0.2mol/L；
(2) by mixed aqueous solution, it is placed in ice-water bath, its temperature is reduced to 2 DEG C while stirring；
(3) into mixed aqueous solution, Ammonia is slowly added dropwise, the suspension that pH is 7.5 is obtained, wherein, it is added dropwise
Speed is 0.5 drop/sec, and the concentration of ammonium hydroxide is 2mol/L；
(4) suspension is aged 1h；
(5) centrifuge, cleaning dries 24h at 50 DEG C, obtains powdered LRH；
Step 2, LRH sacrifices template certainly：
(1) by 10mmol LRH and NH4H2PO4Phosphate radical in molar ratio: rare earth element ion=8: 1 mixing, and add go from
Sub- water is configured to suspension, and 1h is stirred at room temperature；
(2) centrifuge, cleaning dries 24h at 50 DEG C, obtain powdered phosphate ion and exchange product；
(3) phosphate ion is exchanged into product, in H2In atmosphere, 2h is calcined in 1200 DEG C, (Gd is obtained0.96Tb0.04)PO4
Fluorescent material.
The average particle size particle size of gained fluorescent material is about 200nm, its SEM pattern such as Figure 11.Embodiment 8-10 explanations are passed through
Higher temperature calcination, fluorescent material is still nanostructured.
Embodiment 11
Using from the method that template method prepares nano-scale rare earth phosphate phosphor is sacrificed, comprise the following steps：
Step 1, low temperature synthesis LRH nanometer sheet templates：
(1) by Gd (NO3)3·6H2O、Tb(NO3)3·6H2O and Eu (NO3)3·6H2O is according to mol ratio (Tb3++Eu3+)∶
(Gd3++Tb3++Eu3+)=0.08 is mixed, and is configured to the aqueous solution that rare earth ion concentration is 0.3mol/L；
(2) by mixed aqueous solution, it is placed in ice-water bath, its temperature is reduced to 2 DEG C while stirring；
(3) into mixed aqueous solution, Ammonia is slowly added dropwise, the suspension that pH is 7 is obtained, wherein, speed is added dropwise
Spend for 0.2 drop/sec, the concentration of ammonium hydroxide is 2mol/L；
(4) suspension is aged 0.5h；
(5) centrifuge, cleaning dries 48h at 50 DEG C, obtains powdered LRH；
Step 2, LRH sacrifices template certainly：
(1) by 10mmol LRH and NH4H2PO4Phosphate radical in molar ratio: rare earth element ion=8: 1 mixing, and add go from
Sub- water is configured to suspension, and 1h is stirred at room temperature；
(2) centrifuge, cleaning dries 48h at 50 DEG C, obtain powdered phosphate ion and exchange product；
(3) phosphate ion is exchanged into product, in H2In atmosphere, 2h is calcined in 1000 DEG C, (Gd is obtained0.92Tb0.04Eu0.04)
PO4Fluorescent material.
The XRD spectrum of gained fluorescent material such as Figure 12 (a).
Embodiment 12
Using from the method that template method prepares nano-scale rare earth phosphate phosphor is sacrificed, comprise the following steps：
Step 1, low temperature synthesis LRH nanometer sheet templates：
(1) by Gd (NO3)3·6H2O、Tb(NO3)3·6H2O and Eu (NO3)3·6H2O is according to mol ratio (Tb3++Eu3+)∶
(Gd3++Tb3++Eu3+)=0.14 is mixed, and is configured to the aqueous solution that rare earth ion concentration is 0.3mol/L；
(2) by mixed aqueous solution, it is placed in ice-water bath, its temperature is reduced to 2 DEG C while stirring；
(3) into mixed aqueous solution, Ammonia is slowly added dropwise, the suspension that pH is 6.5 is obtained, wherein, it is added dropwise
Speed is 0.2 drop/sec, and the concentration of ammonium hydroxide is 2mol/L；
(4) suspension is aged 0.5h；
(5) centrifuge, cleaning dries 48h at 50 DEG C, obtains powdered LRH；
Step 2, LRH sacrifices template certainly：
(1) by 10mmol LRH and NH4H2PO4Phosphate radical in molar ratio: rare earth element ion=10: 1 mixing, and add and go
Ionized water is configured to suspension, and 0.5h is stirred at room temperature；
(2) centrifuge, cleaning dries 48h at 50 DEG C, obtain powdered phosphate ion and exchange product；
(3) phosphate ion is exchanged into product, in H2In atmosphere, 2h is calcined in 1200 DEG C, (Gd is obtained0.86Tb0.04Eu0.10)
PO4Fluorescent material.
The XRD spectrum of gained fluorescent material such as Figure 12 (b).Embodiment 11-12 illustrates the good crystallinity of product, and dilute
In the case that native doping is higher, fluorescent material still is able to maintain the thing phase of Gadolinium monophosphate matrix in itself.
Claims (5)
1. a kind of using from sacrificing the template method method for preparing nano-scale rare earth phosphate phosphor, it is characterised in that including with
Lower step：
Step 1, low temperature synthesizing rare-earth layered hydroxide nanometer sheet template：
(1) A and B is mixed, is configured to rare earth ion concentration for 0.05~0.3mol/L mixed aqueous solutions；Wherein, the rare earth in B
The molal quantity sum of ion：Molal quantity sum=0.001~0.15, A of A and B Rare Earth Ions is Y (NO3)3·6H2O or Gd
(NO3)3·6H2O, B are Eu (NO3)3·6H2O and/or Tb (NO3)3·6H2O；
(2) by mixed aqueous solution, it is placed in ice-water bath, its temperature is reduced to 2~5 DEG C while stirring；
(3) into mixed aqueous solution, Ammonia is slowly added dropwise, the suspension that pH is 6.5~9 is obtained, wherein, hydroxide
The concentration of ammonium is 0.1~2mol/L；
(4) by suspension, it is aged 0.5~5h；
(5) centrifuge, cleaning and drying obtain powdered rare earth layered hydroxide；
Step 2, rare earth layered hydroxide sacrifices template certainly：
(1) it is rare earth layered hydroxide and phosphate is scattered in deionized water, 0.5~72h is stirred at room temperature；Wherein, massage
You compare, phosphate radical: rare earth element ion=(1~10) in rare earth layered hydroxide: 1；
(2) centrifuge, cleaning and drying obtain powdered phosphate ion and exchange product；
(3) phosphate ion is exchanged into product, calcines 2~8h in 600~1200 DEG C, obtain nano-scale rare earth phosphate fluorescence
Powder.
2. according to claim 1 use the method for preparing nano-scale rare earth phosphate phosphor from sacrifice template method, its
It is characterised by, in the step 1 (3), rate of addition is 0.2~5 drop/sec.
3. according to claim 1 use the method for preparing nano-scale rare earth phosphate phosphor from sacrifice template method, its
It is characterised by, in the step 1 (5) and step 2 (2), furnace drying method is：12~48h is dried at 50~70 DEG C.
4. according to claim 1 use the method for preparing nano-scale rare earth phosphate phosphor from sacrifice template method, its
It is characterised by, in the step 2 (1), phosphate is (NH4)2HPO4Or NH4H2PO4。
5. according to claim 1 use the method for preparing nano-scale rare earth phosphate phosphor from sacrifice template method, its
It is characterised by, it is described to use from the granularity of nano-scale rare earth phosphate phosphor prepared by template method is sacrificed as 20~200nm.
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