CN108384544A - A kind of tetragonal YPO4:Ln3+Spherical fluorescent grain and preparation method - Google Patents
A kind of tetragonal YPO4:Ln3+Spherical fluorescent grain and preparation method Download PDFInfo
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- CN108384544A CN108384544A CN201810018414.5A CN201810018414A CN108384544A CN 108384544 A CN108384544 A CN 108384544A CN 201810018414 A CN201810018414 A CN 201810018414A CN 108384544 A CN108384544 A CN 108384544A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 229910000164 yttrium(III) phosphate Inorganic materials 0.000 title claims abstract description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 61
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 55
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 44
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 41
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000004202 carbamide Substances 0.000 claims abstract description 33
- 239000012798 spherical particle Substances 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 11
- -1 rare earth nitrate Chemical class 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 72
- 150000002500 ions Chemical class 0.000 claims description 41
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 40
- 150000002910 rare earth metals Chemical class 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 13
- 229910052693 Europium Inorganic materials 0.000 claims description 11
- 229910052771 Terbium Inorganic materials 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 6
- 229910052689 Holmium Inorganic materials 0.000 claims description 6
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 6
- 229910052775 Thulium Inorganic materials 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 5
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 5
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 229910052691 Erbium Inorganic materials 0.000 claims description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims description 2
- 238000010790 dilution Methods 0.000 claims description 2
- 239000012895 dilution Substances 0.000 claims description 2
- MWFSXYMZCVAQCC-UHFFFAOYSA-N gadolinium(III) nitrate Inorganic materials [Gd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O MWFSXYMZCVAQCC-UHFFFAOYSA-N 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 238000006213 oxygenation reaction Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 1
- 238000009938 salting Methods 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 6
- 229910052593 corundum Inorganic materials 0.000 abstract description 4
- 239000010431 corundum Substances 0.000 abstract description 4
- 239000008187 granular material Substances 0.000 abstract description 4
- 230000035484 reaction time Effects 0.000 abstract description 3
- 238000004321 preservation Methods 0.000 abstract 1
- 229910019142 PO4 Inorganic materials 0.000 description 87
- 239000002245 particle Substances 0.000 description 32
- 239000010452 phosphate Substances 0.000 description 16
- 238000010586 diagram Methods 0.000 description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 12
- 230000002349 favourable effect Effects 0.000 description 8
- 239000003643 water by type Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 6
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- GAGGCOKRLXYWIV-UHFFFAOYSA-N europium(III) nitrate Inorganic materials [Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GAGGCOKRLXYWIV-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 229910017504 Nd(NO3)3 Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005672 electromagnetic field Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
- UXBZSSBXGPYSIL-UHFFFAOYSA-K yttrium(iii) phosphate Chemical compound [Y+3].[O-]P([O-])([O-])=O UXBZSSBXGPYSIL-UHFFFAOYSA-K 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- 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
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7777—Phosphates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- 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
- C09K11/7795—Phosphates
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Luminescent Compositions (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention belongs to materials science fields, are related to a kind of tetragonal YPO4:Ln3+ spherical shapes fluorescent grain and preparation method.Step 1：Cetyl trimethylammonium bromide is dissolved in deionized water, is added urea, after stirring and dissolving, yttrium nitrate solution and rare earth nitrate solution mixture is added, H is added3PO4And ethylene glycol solution, add deionized water to dilute solution, HNO is added in right amount3PH value is adjusted to 0.5~1.Step 2：25~35min is stirred at room temperature in the solution of above-mentioned clear.Step 3：80 100 degree of heating temperature, heat preservation 0 40min reactions terminate, and by solution cooled to room temperature, reaction product is centrifuged, cleans, and product, which is placed in corundum crucible, obtains monodisperse spherical particle YPO4:Ln3+.Technical scheme of the present invention is simple and practicable, and by controlling reaction temperature and reaction time, can obtain spheric granules of different sizes, it is controllable to realize size.
Description
Technical field
The invention belongs to materials science fields, and in particular to a kind of tetragonal YPO4:Ln3+ spherical shapes fluorescent grain and preparation
Method.
Background technology
RE phosphate material is because its absorbability is strong, high conversion efficiency, and physics and chemical property are stablized, it is ultraviolet-can
See-infrared region emissivities it is strong many advantages, such as, obtained the extensive concern of researcher in recent years, using RE phosphate as
Base Quality Research becomes hot spot.Currently, the preparation method of research RE phosphate system is in the majority with hydro-thermal method and sacrifice template,
And with the fluorescent powder of phosphate matrix obtained by the prior art be the anisometric grains such as sheet, fusiform, particle is to incident light
It scatters bigger.Practical application shows that spheric granules is the ideal pattern of fluorescent material.Size uniform and monodispersity good shot shape
Fluorescent grain is not only conducive to improve the resolution ratio of fluorescence component, but also is easily formed fine and close fluorescence coating to reduce to excitation
Optimal luminescent efficiency is presented in the scattering of light.But it is currently rarely seen with performance study about directly synthesizing for phosphate spheric granules
Report.
Using urea as the precipitation from homogeneous solution technology (UBHP) of base being the one kind for preparing monodisperse phosphate spherical shape fluorescent grain has
Effect approach, it is utilized urea and in the slow decomposable process of (>=83 DEG C), a large amount of anion is generated, to obtain after heating
The good spherical powder particle of size uniform, pattern.Microwave process for synthesizing is a kind of new material developed rapidly in recent years
Technology of preparing, it is the microwave for emitting microwave reactor, and reactant system is passed to by absorbing medium, anti-to make
It answers system to be rapidly heated to required temperature, reaction is completed in the short period.Microwave heating be different from conventional heating methods, it be by
Body caused by dielectric loss in electromagnetic field heats, and heat is generated from material internal, can make inside component and whole same
Shi Fare will produce the growth course of crystal certain influence.In addition this method also have it is easy to operate, rapidly and efficiently, save
Shi Jieneng, low in the pollution of the environment, side reaction is few, product is relatively simple, conducive to the automation control and improvement work for realizing heating process
The advantages that making environment and operating condition.
Invention content
The present invention provides a kind of tetragonal YPO4:Ln3+Spherical fluorescent grain and preparation method, using microwave method research rare earth
Phosphate system, and successfully prepare be rarely reported using yttrium phosphate as matrix, adulterate different rare earth ions spherical phosphor
Particle can control the size of gained spherical phosphor particle by changing reaction temperature and reaction time.
Technical scheme of the present invention：
A kind of tetragonal YPO4:Ln3+Spherical fluorescent grain, it is female salt, urine which, which is with rare earth nitrades,
Element is precipitating reagent, ethylene glycol is mixed solvent, cetyl trimethylammonium bromide is size model that surfactant is prepared
Enclose the tetragonal YPO for 0.7 μm -1.5 μm4:Ln3+Monodisperse spherical particle；Wherein Ln is Ce, Pr, Eu, Tb, Dy, Ho, Tm, Tb
One kind in+Eu, Gd+Dy.
Above-mentioned tetragonal YPO4:Ln3+The preparation method of spherical fluorescent grain, steps are as follows：
Step 1：Cetyl trimethylammonium bromide is dissolved in deionized water, is added urea, after stirring and dissolving, rare earth is added
Nitrate solution mixture, the rare earth nitrades include yttrium nitrate and Ln nitrate；Add H3PO4And ethylene glycol solution,
Solution is diluted with deionized water；
Each constituent concentration of solution after dilution is：0.0075~0.03mol/L of rare earth ion concentration, glycol concentration 3.5
~9mol/L, H3PO4The molar concentration rate of 15~20mol/L of concentration, cetyl trimethylammonium bromide and rare earth ion be 1~
4:1；The molar concentration rate of urea and rare earth ion is 5~200:1；
HNO is added3PH value is adjusted to 0.5~1.0；
Step 2：25~35min is stirred at room temperature in the solution of above-mentioned clear, then solution is moved in container, is set
It is heated in microwave reactor, heating temperature is 80~100 DEG C, keeps the temperature 0~40min；
Step 3：Reaction terminates, and by solution cooled to room temperature, reaction product is centrifuged, cleans, drying, in oxygen
It is calcined respectively in gas and hydrogen, obtains monodisperse spherical particle YPO4:Ln3+。
Further, Ln nitrate is Ce, Pr, Nd, Eu, Tb, Dy, Ho, Er, Tm, Tb+Eu, Gd+Dy nitric acid in step 1
One kind in salt.
When the rare earth nitrades are Y (NO3)3、Tb(NO3)3With Eu (NO3)3When, wherein Y-ion, Tb ions and Eu
Ion is 98-x according to molar ratio:2:X, wherein 0.01≤x≤0.13.
When the rare earth nitrades are Y (NO3)3、Gd(NO3)3With Dy (NO3)3When, wherein Y-ion, Gd ions and Dy
Ion is 99-x according to molar ratio:x:0.01, wherein 0.01≤x≤0.13.
When the rare earth nitrades are Y (NO3)3、Tb(NO3)3When, wherein Y-ion and Tb solions according to mole
Than for 100-x:X, wherein 1≤x≤5.
In step 3, first calcination temperature is 600~1100 DEG C in oxygen, and calcination time is 1.5~2.5h；Later in hydrogen
Calcination temperature is 600~1100 DEG C in gas, and calcination time is 1.5~2.5h.
Drying temperature described in step 3 is at 40~60 DEG C.
Beneficial effects of the present invention：
The present invention for the first time studies RE phosphate system using microwave method, by with rare earth nitrades be female salt,
Urea is precipitating reagent, ethylene glycol (EG) is mixed solvent, cetyl trimethylammonium bromide is surfactant, is successfully prepared
The tetragonal YPO that size range is 0.7 μm -1.5 μm4:Ln3+(Ln=Ce, Pr, Eu, Tb, Dy, Ho, Tm, Tb+Eu, Gd+Dy) is single
Dispersing ball particle.Technical scheme of the present invention is simple and practicable, and by controlling reaction temperature and reaction time, can obtain big
Small different spheric granules, it is controllable to realize size.
Description of the drawings
Fig. 1 (a) is YPO prepared by the embodiment of the present invention 14:Ln3+(Ln3+=Ce) particle SEM shape appearance figures.
Fig. 1 (b) is YPO prepared by the embodiment of the present invention 14:Ln3+(Ln3+=Pr) particle SEM shape appearance figures.
Fig. 1 (c) is YPO prepared by the embodiment of the present invention 14:Ln3+(Ln3+=Nd) particle SEM shape appearance figures.
Fig. 1 (d) is YPO prepared by the embodiment of the present invention 14:Ln3+(Ln3+=Eu) particle SEM shape appearance figures.
Fig. 1 (e) is YPO prepared by the embodiment of the present invention 14:Ln3+(Ln3+=Tb) particle SEM shape appearance figures.
Fig. 1 (f) is YPO prepared by the embodiment of the present invention 14:Ln3+(Ln3+=Dy) particle SEM shape appearance figures.
Fig. 1 (g) is YPO prepared by the embodiment of the present invention 14:Ln3+(Ln3+=Ho) particle SEM shape appearance figures.
Fig. 1 (h) is YPO prepared by the embodiment of the present invention 14:Ln3+(Ln3+=Er) particle SEM shape appearance figures.
Fig. 1 (i) is YPO prepared by the embodiment of the present invention 14:Ln3+(Ln3+=Tm) particle SEM shape appearance figures.
Fig. 2 is the XRD diagram of product prepared by the embodiment of the present invention 1.
Fig. 3 (a) is that the embodiment of the present invention 2 prepares (Y0.98-xTb0.02Eux)PO4(0.01≤x≤0.13), x=0.01
The SEM shape appearance figures of grain.
Fig. 3 (b) is that the embodiment of the present invention 2 prepares (Y0.98-xTb0.02Eux)PO4(0.01≤x≤0.13), x=0.02
The SEM shape appearance figures of grain.
Fig. 3 (c) is that the embodiment of the present invention 2 prepares (Y0.98-xTb0.02Eux)PO4(0.01≤x≤0.13), x=0.03
The SEM shape appearance figures of grain.
Fig. 3 (d) is that the embodiment of the present invention 2 prepares (Y0.98-xTb0.02Eux)PO4(0.01≤x≤0.13), x=0.04
The SEM shape appearance figures of grain.
Fig. 3 (e) is that the embodiment of the present invention 2 prepares (Y0.98-xTb0.02Eux)PO4(0.01≤x≤0.13), x=0.05
The SEM shape appearance figures of grain.
Fig. 3 (f) is that the embodiment of the present invention 2 prepares (Y0.98-xTb0.02Eux)PO4(0.01≤x≤0.13), x=0.08
The SEM shape appearance figures of grain.
Fig. 3 (g) is that the embodiment of the present invention 2 prepares (Y0.98-xTb0.02Eux)PO4(0.01≤x≤0.13), x=0.010
The SEM shape appearance figures of particle.
Fig. 3 (h) is that the embodiment of the present invention 2 prepares (Y0.98-xTb0.02Eux)PO4(0.01≤x≤0.13), x=0.013
The SEM shape appearance figures of particle.
Fig. 4 is the XRD diagram of product prepared by the embodiment of the present invention 2.
Fig. 5 (a) is that the embodiment of the present invention 3 prepares (Y0.99-xGdxDy0.01)PO4(0.03≤x≤0.2), x=0.03,
The SEM shape appearance figures of grain.
Fig. 5 (b) is that the embodiment of the present invention 3 prepares (Y0.99-xGdxDy0.01)PO4(0.03≤x≤0.2), x=0.05
The SEM shape appearance figures of grain.
Fig. 5 (c) is that the embodiment of the present invention 3 prepares (Y0.99-xGdxDy0.01)PO4(0.03≤x≤0.2), x=0.10
The SEM shape appearance figures of grain.
Fig. 5 (d) is that the embodiment of the present invention 3 prepares (Y0.99-xGdxDy0.01)PO4(0.03≤x≤0.2), x=0.15
The SEM shape appearance figures of grain.
Fig. 5 (e) is that the embodiment of the present invention 3 prepares (Y0.99-xGdxDy0.01)PO4(0.03≤x≤0.2), x=0.20
The SEM shape appearance figures of grain.
Fig. 6 is the XRD diagram of product prepared by the embodiment of the present invention 3.
Fig. 7 (a) is differential responses time (Y prepared by the embodiment of the present invention 40.98Tb0.02)PO4, the SEM of T=1min particles
Shape appearance figure.
Fig. 7 (b) is differential responses time (Y prepared by the embodiment of the present invention 40.98Tb0.02)PO4, the SEM of T=3min particles
Shape appearance figure.
Fig. 7 (c) is differential responses time (Y prepared by the embodiment of the present invention 40.98Tb0.02)PO4, the SEM of T=5min particles
Shape appearance figure.
Fig. 7 (d) is differential responses time (Y prepared by the embodiment of the present invention 40.98Tb0.02)PO4, T=10min particles
SEM shape appearance figures.
Fig. 7 (e) is differential responses time (Y prepared by the embodiment of the present invention 40.98Tb0.02)PO4, T=20min particles
SEM shape appearance figures.
Fig. 7 (f) is differential responses time (Y prepared by the embodiment of the present invention 40.98Tb0.02)PO4, T=40min particles
SEM shape appearance figures.
Fig. 8 is the XRD spectrum of product prepared by the embodiment of the present invention 4.
Fig. 9 (a) is differential responses temperature (Y prepared by the embodiment of the present invention 50.98Tb0.02)PO4, temperature is 80 DEG C of particles
SEM shape appearance figures.
Fig. 9 (b) is differential responses temperature (Y prepared by the embodiment of the present invention 50.98Tb0.02)PO4, temperature is 90 DEG C of particles
SEM shape appearance figures.
Fig. 9 (c) is differential responses temperature (Y prepared by the embodiment of the present invention 50.98Tb0.02)PO4, temperature is 100 DEG C of particles
SEM shape appearance figures.
Figure 10 (a) is CTAB prepared by the embodiment of the present invention 6：Rare earth element ion=1：When 1, (Y0.98Tb0.02)PO4
The SEM shape appearance figures of grain.
Figure 10 (b) is CTAB prepared by the embodiment of the present invention 6：Rare earth element ion=2：When 1, (Y0.98Tb0.02)PO4
The SEM shape appearance figures of grain.
Figure 10 (c) is CTAB prepared by the embodiment of the present invention 6：Rare earth element ion=4：When 1, (Y0.98Tb0.02)PO4
The SEM shape appearance figures of grain.
When Figure 11 (a) is rare earth element ion total mole number 0.00375mol prepared by the embodiment of the present invention 7
(Y0.95Eu0.05) the SEM shape appearance figures of PO4 particles.
When Figure 11 (b) is rare earth element ion total mole number 0.0075mol prepared by the embodiment of the present invention 7
(Y0.95Eu0.05) the SEM shape appearance figures of PO4 particles.
(Y when Figure 11 (c) is the rare earth element ion total mole number 0.015mol of the preparation of the embodiment of the present invention 70.95Eu0.05)
PO4The SEM shape appearance figures of particle.
Figure 12 is the XRD diagram of product prepared by 5-7 of the embodiment of the present invention.
(Y when Figure 13 (a) is the ethylene glycol solution content 125mL of the preparation of the embodiment of the present invention 80.95Eu0.05)PO4Particle
SEM shape appearance figures.
(Y when Figure 13 (b) is the ethylene glycol solution content 150mL of the preparation of the embodiment of the present invention 80.95Eu0.05)PO4Particle
SEM shape appearance figures.
(Y when Figure 13 (c) is the ethylene glycol solution content 200mL of the preparation of the embodiment of the present invention 80.95Eu0.05)PO4Particle
SEM shape appearance figures.
(Y when Figure 13 (d) is the ethylene glycol solution content 250mL of the preparation of the embodiment of the present invention 80.95Eu0.05)PO4Particle
SEM shape appearance figures.
Figure 14 is the XRD diagram of product prepared by the embodiment of the present invention 8.
Specific implementation mode
Specific embodiments of the present invention are described in detail below in conjunction with technical solution and attached drawing.
Chemical reagent employed in present example is the pure grade product of analysis；
Embodiment 1
Cetyl trimethylammonium bromide is dissolved in 100ml deionized waters, is added urea, after stirring and dissolving, Y is added
(NO3)3Solution respectively with Ce (NO3)3、Pr(NO3)3、Nd(NO3)3、Eu(NO3)3、Tb(NO3)3、Dy(NO3)3、Ho(NO3)3、Er
(NO3)3、Tm(NO3)3Solution is according to molar ratio Y/Ln=99:The mixture of 1 mixing, the addition of CTAB is in molar ratio
CTAB：Rare earth element ion=2：1, the addition of urea is urea in molar ratio：Rare earth element ion=33.333, rare earth member
Plain ion integral molar quantity is 0.0075mol.The H of 15mL is added3PO4With 125mL ethylene glycol solutions, deionized water is added to match solution
HNO is added in right amount after to 500mL3PH value is adjusted to 1.0.
The solution of above-mentioned clear is stirred into 30min at normal temperatures, then moves to solution in three-necked flask, is placed in micro-
It is heated to 100 DEG C in wave reactor and keeps the temperature 20min.
After reaction, three-necked flask is taken out, cooled to room temperature, reaction product is centrifuged, cleans, in 40 DEG C
Drying, product is placed in corundum crucible, 1.5h is calcined respectively in 600 DEG C of oxygen, 600 DEG C of hydrogen, obtains monodisperse spherical
Particle YPO4:Ln3+(Ce、Pr、Nd、Eu、Tb、Dy、Ho、Er、Tm)。
The spherical particle size of acquisition is about 1 μm, favorable dispersibility, such as Fig. 1 (a) (Y0.99Ce0.01)PO4, Fig. 1 (b)
(Y0.99Pr0.01)PO4, Fig. 1 (c) (Y0.99Nd0.01)PO4, Fig. 1 (d) (Y0.99Eu0.01)PO4, Fig. 1 (e) (Y0.99Tb0.01)PO4, Fig. 1
(f)(Y0.99Dy0.01)PO4, Fig. 1 (g) (Y0.99Ho0.01)PO4, Fig. 1 (h) (Y0.99Er0.01)PO4, Fig. 1 (i) (Y0.99Tm0.01)PO4。
Its XRD diagram is as shown in Fig. 2, what is as can be seen from the figure obtained is phosphate pure phase.
Embodiment 2
Cetyl trimethylammonium bromide (CTAB) is dissolved in 100ml deionized waters, is added urea, after stirring and dissolving, is added
Enter Y (NO3)3Solution and Tb (NO3)3、Eu(NO3)3Solution is according to molar ratio Y/Tb/Eu=98-x:2:x(0.01≤x≤0.13)
Mixed mixture, the addition of CTAB are CTAB in molar ratio：Rare earth element ion=2：1, the addition of urea is massage
You compare urea：Rare earth element ion=5, rare earth element ion integral molar quantity are 0.0075mol.The H of 15mL is added3PO4With
HNO is added after adding deionized water that solution is assigned to 500mL in 125mL ethylene glycol solutions in right amount3PH value is adjusted to 0.75.
The solution of above-mentioned clear is stirred into 25min at normal temperatures, then moves to solution in three-necked flask, is placed in micro-
It is heated to 90 DEG C in wave reactor and keeps the temperature 20min.
After reaction, three-necked flask is taken out, cooled to room temperature, reaction product is centrifuged, cleans, in 45 DEG C
Drying, product is placed in corundum crucible, 2h is calcined respectively in 1000 DEG C of oxygen, 1000 DEG C of hydrogen, obtains monodisperse spherical
Particle (Y0.98-xTb0.02Eux)PO4(0.01≤x≤0.13)。
The spherical particle size of acquisition is about 1 μm, favorable dispersibility, such as Fig. 3 (a) (Y0.97Tb0.02Eu0.01)PO4, Fig. 3
(b)(Y0.96Tb0.02Eu0.02)PO4, Fig. 3 (c) (Y0.95Tb0.02Eu0.03)PO4, Fig. 3 (d) (Y0.94Tb0.02Eu0.04)PO4, Fig. 3 (e)
(Y0.93Tb0.02Eu0.05)PO4, Fig. 3 (f) (Y0.90Tb0.02Eu0.08)PO4, Fig. 3 (g) (Y0.88Tb0.02Eu0.10)PO4, Fig. 3 (h)
(Y0.85Tb0.02Eu0.13)PO4。
Its XRD diagram is as shown in figure 4, what is as can be seen from the figure obtained is phosphate pure phase.
Embodiment 3
Cetyl trimethylammonium bromide is dissolved in 100ml deionized waters, is added urea, after stirring and dissolving, Y is added
(NO3)3Solution and Gd (NO3)3、Dy(NO3)3Solution is according to molar ratio Y/Gd/Dy=99-x:x:0.01(0.01≤x≤0.13)
Mixed mixture, the addition of CTAB are CTAB in molar ratio：Rare earth element ion=2：1, the addition of urea is massage
You compare urea：Rare earth element ion=50, rare earth element ion integral molar quantity are 0.0075mol.The H of 15mL is added3PO4With
HNO is added after adding deionized water that solution is assigned to 500mL in 125mL ethylene glycol solutions in right amount3PH value is adjusted to 0.7.
The solution of above-mentioned clear is stirred into 35min at normal temperatures, then moves to solution in three-necked flask, is placed in micro-
It is heated to 80 DEG C in wave reactor and keeps the temperature 5min.
After reaction, three-necked flask is taken out, cooled to room temperature, reaction product is centrifuged, cleans, in 50 DEG C
Drying, product is placed in corundum crucible, in 1100 DEG C of air roasting 2.5h, obtains monodisperse spherical particle (Y0.99- xGdxDy0.01)PO4(0.03≤x≤0.2)。
The spherical particle size of acquisition is about 1 μm, favorable dispersibility, such as Fig. 5 (a) (Y0.96Gd0.03Dy0.01)PO4, Fig. 5
(b)(Y0.94Gd0.05Dy0.01)PO4, Fig. 5 (c) (Y0.89Gd0.10Dy0.01)PO4, Fig. 5 (d) (Y0.84Gd0.15Dy0.01)PO4Fig. 5 (e)
(Y0.79Gd0.20Dy0.01)PO4。
Its XRD diagram is as shown in fig. 6, what is as can be seen from the figure obtained is phosphate pure phase.
Embodiment 4
Cetyl trimethylammonium bromide (CTAB) is dissolved in 100ml deionized waters, is added urea, after stirring and dissolving, is added
Enter Y (NO3)3Solution and Tb (NO3)3Solution is according to molar ratio Y/Tb=98:The addition of the mixture of 2 mixing, CTAB is massage
You compare CTAB：Rare earth element ion=2：1, the addition of urea is urea in molar ratio：Rare earth element ion=80, rare earth member
Plain ion integral molar quantity is 0.0075mol.The H of 15mL is added3PO4With 125mL ethylene glycol solutions, deionized water is added to match solution
HNO is added in right amount after to 500mL3PH value is adjusted to 0.65.
The solution of above-mentioned clear is stirred into 30min at normal temperatures, then moves to solution in three-necked flask, is placed in micro-
It is heated to 85 DEG C in wave reactor, takes reaction solution when 1min, 3min, 5min, 10min, 20min, 40min respectively.
By reaction solution cooled to room temperature, reaction product is centrifuged, cleans, and in 55 DEG C of drying, is reacted
Monodisperse spherical particle (Y under different time0.98Tb0.02)PO4。
The spherical particle size of acquisition is 450nm-1.5 μm, favorable dispersibility, such as Fig. 7 (a) 1min, Fig. 7 (b) 3min, figure
7 (c) 5min, Fig. 7 (d) 10min, Fig. 7 (e) 20min, Fig. 7 (f) 40min.
Its XRD diagram is as shown in figure 8, as can be seen from the figure react different phase acquisition is phosphate pure phase.
Embodiment 5
Cetyl trimethylammonium bromide (CTAB) is dissolved in 100ml deionized waters, is added urea, after stirring and dissolving, is added
Enter Y (NO3)3Solution and Tb (NO3)3Solution is according to molar ratio Y/Tb=98:The mixture of 2 mixing, the addition of CTAB are respectively
CTAB in molar ratio：Rare earth element ion=2：1, the addition of urea is urea in molar ratio：Rare earth element ion=100,
Rare earth element ion integral molar quantity is 0.0075mol.The H of 15mL is added3PO4With 125mL ethylene glycol solutions, add deionized water will
HNO is added after being assigned to 500mL in solution in right amount3PH value is adjusted to 0.6.
The solution of above-mentioned clear is stirred into 30min at normal temperatures, then moves to solution in three-necked flask, is placed in micro-
It is separately heated to 80 DEG C, 90 DEG C, 100 DEG C in wave reactor and keeps the temperature 10min.
By reaction solution cooled to room temperature, reaction product is centrifuged, cleans, and in 60 DEG C of drying, obtains difference
Monodisperse spherical particle (Y under reaction temperature0.98Tb0.02)PO4。
The spherical particle size of acquisition is 1 μm or so, favorable dispersibility, such as 80 DEG C of Fig. 9 (a), 90 DEG C of Fig. 9 (b), Fig. 9 (c)
100℃。
As can be seen from the figure it is phosphate pure phase shown in its XRD diagram such as Figure 12 (a), Figure 12 (b), Figure 12 (c).
Embodiment 6
Cetyl trimethylammonium bromide (CTAB) is dissolved in 100ml deionized waters, the addition of CTAB is massage respectively
You compare CTAB：Rare earth element ion=1：1、2：1、4：1, urea is added, after stirring and dissolving, Y (NO are added3)3Solution and Tb
(NO3)3Solution is according to molar ratio Y/Tb=98:The mixtures of 2 mixing, the addition of urea are urea in molar ratio：Rare earth element
Ion=120, rare earth element ion integral molar quantity are 0.0075mol.The H of 15mL is added3PO4With 125mL ethylene glycol solutions, add
HNO is added after solution is assigned to 500mL in deionized water in right amount3PH value is adjusted to 0.5.
The solution of above-mentioned clear is stirred into 30min at normal temperatures, then moves to solution in three-necked flask, is placed in micro-
It is heated to 90 DEG C in wave reactor and keeps the temperature 20min.
By reaction solution cooled to room temperature, reaction product is centrifuged, cleans, and in 50 DEG C of drying, is reacted
Monodisperse spherical particle (Y under different time0.98Tb0.02)PO4。
The spherical particle size of acquisition is 1 μm or so, favorable dispersibility, such as Figure 10 (a) CTAB：Rare earth element ion=1：
1, Figure 10 (b) CTAB：Rare earth element ion=2：1, Figure 10 (c) CTAB：Rare earth element ion=4：1.
As can be seen from the figure it is phosphate pure phase shown in its XRD diagram such as Figure 12 (d), Figure 12 (e), Figure 12 (f).
Embodiment 7
Cetyl trimethylammonium bromide (CTAB) is dissolved in 100ml deionized waters, the addition of CTAB is massage respectively
You compare CTAB：Rare earth element ion=1：1、2：1、4：1, urea is added, after stirring and dissolving, Y (NO are added3)3Solution and Tb
(NO3)3Solution is according to molar ratio Y/Eu=95:The mixtures of 5 mixing, the addition of urea are urea in molar ratio：Rare earth element
Ion=150, rare earth element ion integral molar quantity are respectively 0.00375mol, 0.0075mol, 0.015mol.It is added 15mL's
H3PO4With 125mL ethylene glycol solutions, HNO is added in right amount after adding deionized water that solution is assigned to 500mL3PH value is adjusted to 0.85.
The solution of above-mentioned clear is stirred into 30min at normal temperatures, then moves to solution in three-necked flask, is placed in micro-
It is heated to 95 DEG C in wave reactor and keeps the temperature 30min.
By reaction solution cooled to room temperature, reaction product is centrifuged, cleans, and in 50 DEG C of drying, is reacted
Monodisperse spherical particle (Y under different time0.98Tb0.02)PO4。
The spherical particle size of acquisition is 1 μm or so, favorable dispersibility, as shown in figure 11, wherein Figure 12 (a)
0.00375mol, Figure 12 (b) 0.0075mol, Figure 12 (c) 0.015mol.
As can be seen from the figure it is phosphate pure phase shown in its XRD diagram such as Figure 12 (g), Figure 12 (h), Figure 12 (i).
Embodiment 8
Cetyl trimethylammonium bromide (CTAB) is dissolved in 100ml deionized waters, the addition of CTAB is massage respectively
You compare CTAB：Rare earth element ion=2：1, urea is added, after stirring and dissolving, Y (NO are added3)3Solution and Tb (NO3)3Solution is pressed
According to molar ratio Y/Eu=95:The mixtures of 5 mixing, the addition of urea are urea in molar ratio：Rare earth element ion=200,
Rare earth element ion integral molar quantity is respectively 0.0075mol.The H of 15mL is added3PO4, be separately added into 125mL, 150mL, 200mL,
HNO is added after adding deionized water that solution is assigned to 500mL in 250mL ethylene glycol solutions in right amount3PH value is adjusted to 0.9.
The solution of above-mentioned clear is stirred into 30min at normal temperatures, then moves to solution in three-necked flask, is placed in micro-
It is heated to 100 DEG C in wave reactor and keeps the temperature 40min.
By reaction solution cooled to room temperature, reaction product is centrifuged, cleans, and in 50 DEG C of drying, is reacted
Monodisperse spherical particle (Y under different time0.98Tb0.02)PO4。
The spherical particle size of acquisition is 500nm-1 μm, favorable dispersibility, such as Figure 13 (a), Figure 13 (b), Figure 13 (c), figure
13(d)。
Its XRD diagram is as shown in figure 14, is as can be seen from the figure phosphate pure phase.
Claims (9)
1. a kind of tetragonal YPO4:Ln3+Spherical fluorescent grain, which is characterized in that the spherical shape fluorescent grain is with rare earth nitrades
For female salt, urea be precipitating reagent, ethylene glycol is mixed solvent, cetyl trimethylammonium bromide is that surfactant is prepared
Size range be 0.7 μm -1.5 μm of tetragonal YPO4:Ln3+Monodisperse spherical particle；Wherein Ln be Ce, Pr, Eu, Tb, Dy,
One kind in Ho, Tm, Tb+Eu, Gd+Dy.
2. tetragonal YPO described in claim 14:Ln3+The preparation method of spherical fluorescent grain, which is characterized in that steps are as follows：
Step 1：Cetyl trimethylammonium bromide is dissolved in deionized water, is added urea, after stirring and dissolving, rare earth nitric acid is added
Salting liquid mixture, the rare earth nitrades include yttrium nitrate and Ln nitrate；Add H3PO4And ethylene glycol solution, it spends
Ionized water dilutes solution；
Each constituent concentration of solution after dilution is：0.0075~0.03mol/L of rare earth ion concentration, glycol concentration 3.5~
9mol/L, H3PO4The molar concentration rate of 15~20mol/L of concentration, cetyl trimethylammonium bromide and rare earth ion is 1~4:
1；The molar concentration rate of urea and rare earth ion is 5~200:1；
HNO is added3PH value is adjusted to 0.5~1.0；
Step 2：25~35min is stirred at room temperature in the solution of above-mentioned clear, then solution is moved in container, is placed in micro-
It is heated in wave reactor, heating temperature is 80~100oC, keeps the temperature 0~40min；
Step 3：Reaction terminates, and by solution cooled to room temperature, reaction product is centrifuged, cleans, drying, in oxygen and
It is calcined respectively in hydrogen, obtains monodisperse spherical particle YPO4:Ln3+。
3. tetragonal YPO according to claim 24:Ln3+The preparation method of spherical fluorescent grain, which is characterized in that step
Ln nitrate is one kind in Ce, Pr, Nd, Eu, Tb, Dy, Ho, Er, Tm, Tb+Eu, Gd+Dy nitrate in 1.
4. tetragonal YPO according to claim 34:Ln3+The preparation method of spherical fluorescent grain, which is characterized in that step
In 1, when the rare earth nitrades are Y (NO3)3、Tb(NO3)3With Eu (NO3)3When, wherein Y-ion, Tb ions and Eu ions
It is 98-x according to molar ratio:2:X, wherein 0.01≤x≤0.13.
5. tetragonal YPO according to claim 34:Ln3+The preparation method of spherical fluorescent grain, which is characterized in that step
In 1, when the rare earth nitrades are Y (NO3)3、Gd(NO3)3With Dy (NO3)3When, wherein Y-ion, Gd ions and Dy ions
It is 99-x according to molar ratio:x:0.01, wherein 0.01≤x≤0.13.
6. tetragonal YPO according to claim 34:Ln3+The preparation method of spherical fluorescent grain, which is characterized in that step
In 1, when the rare earth nitrades are Y (NO3)3、Tb(NO3)3When, wherein Y-ion and Tb solions are according to molar ratio
100-x:X, wherein 1≤x≤5.
7. the tetragonal YPO according to claim 2~6 any one4:Ln3+The preparation side of spherical fluorescent grain
Method, which is characterized in that in step 3, first calcination temperature is 600~1100 DEG C in oxygen, and calcination time is 1.5~2.5h；It
Calcination temperature is 600~1100 DEG C in hydrogen afterwards, and calcination time is 1.5~2.5h.
8. the tetragonal YPO according to claim 2~6 any one4:Ln3+The preparation method of spherical fluorescent grain, it is special
Sign is that the drying temperature described in step 3 is at 40~60 DEG C.
9. tetragonal YPO as claimed in claim 74:Ln3+The preparation method of spherical fluorescent grain, which is characterized in that step 3
Described in drying temperature at 40~60 DEG C.
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| CN103979515A (en) * | 2014-05-15 | 2014-08-13 | 陕西科技大学 | YPO4 nano particle synthesized by assist of surfactant cetyltrimethyl ammonium bromide (CTAB) and preparation method of YPO4 nano particle |
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| SONIA RODRIGUEZ-LIVIANO ET AL.: "Microwave-Assisted Synthesis and Luminescence of Mesoporous RE-Doped YPO4 (RE=Eu, Ce, Tb, and Ce+Tb) Nanophosphors with Lenticular shape", 《CRYSTAL GROWTH & DESIGN》 * |
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| CN110156036B (en) * | 2019-05-30 | 2020-10-16 | 东北大学 | Monoclinic RE3BO6Process for preparing spherical particles |
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