CN106635000B - A kind of europium doping chlorine oxygen bismuth red fluorescence powder and preparation method thereof - Google Patents
A kind of europium doping chlorine oxygen bismuth red fluorescence powder and preparation method thereof Download PDFInfo
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- CN106635000B CN106635000B CN201611262616.1A CN201611262616A CN106635000B CN 106635000 B CN106635000 B CN 106635000B CN 201611262616 A CN201611262616 A CN 201611262616A CN 106635000 B CN106635000 B CN 106635000B
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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
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
- C09K11/7732—Halogenides
- C09K11/7733—Halogenides with alkali or alkaline earth metals
Abstract
The invention discloses a kind of europium doping chlorine oxygen bismuth red fluorescence powders and preparation method thereof, comprising the following steps: with Eu2O3And Bi2O3As raw material, according to chemical formula BiOCl:xEu3+Stoichiometric ratio carry out raw material weigh, wherein x=0.005~0.010；Load weighted raw material is put into beaker, is slowly dropped into concentrated hydrochloric acid dropwise, is stirred during being added dropwise, until raw material is completely dissolved to form solution A；Ammonia spirit is slowly added dropwise in solution A, adjusting pH value is 8~9, continues stirring with magnetic stirring apparatus until generating white depositions；Hydrolyze method is selected to prepare BiOCl:Eu3+Red fluorescence powder, method is simple and easy, mild condition, economic and environment-friendly, is suitable for large-scale production.And the MODEL OF THE PHOSPHOR PARTICLE SIZE prepared is 3~5 μm uniform, particle size is small, regular appearance, good dispersion, and the light-emitting phosphor function admirable obtained.
Description
Technical field
The present invention relates to a kind of fluorescent powders and preparation method thereof, and in particular to a kind of europium doping chlorine oxygen bismuth red fluorescence powder and
Preparation method.
Background technique
It is had received widespread attention in illumination field by the rare earth ion doped luminescent material of representative of fluorescent material,
Absorbability is strong, high conversion efficiency, and the narrow emission of rare earth cooperation ion is conducive to total colouring, chemical and physical features
Stablize, receives great application in modern society.For example, exit passageway Warning Mark, biological monitoring, the side such as medical treatment detection
Face.And oxyhalide has low phonon energy, excellent chemical stability and mechanical performance, and has had both halide and oxygen
The characteristics of compound is a kind of luminous host material with fine development and application prospect.And BiOCl is one kind of oxyhalide,
It is simultaneously also a kind of novel wide bandgap semiconductor materials.It has unique electronic structure and crystal structure, can be ultraviolet
Effectively degradable organic pollutant under light and simulated solar irradiation, there are also good catalytic performance, optical property and stable objects
Change property etc., has been widely used in fields such as ferroelectric material, pigment and catalyst.
BiOCl crystal structure belongs to PbFCl type tetragonal crystalline structure, and space group is P4/nmm (No.129), symmetry
For D4h.[Cl-Bi-O-Bi-Cl] atomic layer is combined by non-strong power, and binding force is smaller, short texture, causes this layer structure
It is easy to dissociate along [001] direction.So these [Cl-Bi-O-Bi-Cl] layers are inclined to form layer structure.Since its is unique
Two-dimensional slice structure will form strong polarization electric field in crystals.Eu3+Ion is weight in the research of white light LEDs luminescent material
Active ions are wanted, level structure is simple, good luminous performance, quantum efficiency are high.Therefore when rare earth ion replaces Bi3+It is occupied in crystalline substance
When lattice point in lattice, ambient enviroment has low-symmetry and strong polarizability.This unique crystal field energy influences rare earth ion
Transition speed, and shining for rare earth ion may be enhanced.
BiOCl:Eu3+Traditional preparation methods be solid phase method, make the substance to react in phase interface by high-temperature calcination
On chemically reacted and shifted, this method has the advantages that technical maturity, at low cost, yield are big, is conducive to industrial volume production,
But what is refused to say yes or no is that its manufacturing cycle is too long and energy consumption is high, prepared particle, which exists, to be easy to reunite, and bad dispersibility is uneven
The problems such as even, does not meet the sustainable development that society advocates now.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of preparation method of europium doping chlorine oxygen bismuth red fluorescence powder, choosings
Select Hydrolyze method preparation BiOCl:Eu3+Red fluorescence powder, method is simple and easy, mild condition, economic and environment-friendly, is suitable for extensive raw
It produces.And the MODEL OF THE PHOSPHOR PARTICLE SIZE prepared is 3~5 μm uniform, particle size is small, regular appearance, good dispersion, and obtains glimmering
Light powder good luminescence property.
To achieve the goals above, the technical solution adopted by the present invention is that, a kind of europium doping chlorine oxygen bismuth red fluorescence powder
Preparation method, comprising the following steps:
1) with Eu2O3And Bi2O3As raw material, according to chemical formula BiOCl:xEu3+Stoichiometric ratio carry out raw material weigh,
Wherein, x=0.005~0.010；
2) load weighted raw material is put into beaker, is slowly dropped into concentrated hydrochloric acid dropwise, be stirred during being added dropwise, until
Raw material is completely dissolved to form solution A；
3) ammonia spirit is slowly added dropwise in solution A, adjusting pH value is 8~9, continues stirring with magnetic stirring apparatus until producing
Raw white depositions；
4) white depositions are centrifugated, are repeatedly washed with deionized water in removal white depositions residual solution
Cl—, use AgNO3Solution tests judgement to cleaning solution, to ensure Cl—It completely removes；
5) sediment after step 4) processing is dried.
The mass concentration of concentrated hydrochloric acid solution is 37% in step 2), and the dripping quantity of concentrated hydrochloric acid is 10mL~15mL.
It is carried out in step 2) using magnetic stirring apparatus.
Ammonia spirit mass concentration in step 3) is 25%, and dropwise addition mode is to be added dropwise.
Drying is finely ground with mortar after drying to dry under 60 DEG C~80 DEG C air atmospheres in an oven in step 5).
A kind of europium doping chlorine oxygen bismuth red fluorescence powder, chemical formula BiOCl:xEu3+, wherein x=0.005~0.010.
Compared with prior art, the present invention at least has technical effect beneficial below:
1) present invention prepares BiOCl:xEu using Hydrolyze method3+(x=0.005~0.010) red fluorescence powder, method are simple
It is easy, mild condition, economic and environment-friendly, it is suitable for large-scale production.For preparation compared to traditional high temperature solid-state method, shorten
In the period of its preparation, reduce energy consumption, meets the sustainable development of modern society's requirement, comply with the trend in epoch.
2) BiOCl:xEu that the present invention prepares3+3~5 μm of (x=0.005~0.010) phosphor powder epigranular,
Particle size is small, regular appearance, and fluorescent powder about 625nm emission peak prepared by the present invention is much higher than 700nm compared with solid phase method
The emission peak at place realizes that efficient energy transfer, quantum efficiency are up to 70% and high color purity.
Detailed description of the invention
Fig. 1 is BiOCl:0.005Eu made from the embodiment of the present invention 23+The XRD diagram of fluorescent powder；
Fig. 2 is BiOCl:0.005Eu made from the embodiment of the present invention 23+The SEM of fluorescent powder schemes；
Fig. 3 is BiOCl:0.005Eu made from the embodiment of the present invention 23+The launching light spectrogram of fluorescent powder；
Fig. 4 is BiOCl:0.005Eu made from the embodiment of the present invention 23+The exciting light spectrogram of fluorescent powder；
Specific embodiment
Hereinafter, we further do one detailed description to the present invention in conjunction with specific embodiments.
Embodiment 1
1) with Eu2O3And Bi2O3As raw material, according to chemical formula BiOCl:xEu3+Stoichiometric ratio carry out raw material weigh,
Wherein, x=0.005；
2) load weighted raw material is put into beaker, is slowly dropped into mass concentration dropwise and is 37% concentrated hydrochloric acid, and uses
Magnetic stirrer, until raw material is completely dissolved to form solution A；
3) it is 25% ammonia spirit 15mL that mass concentration is slowly added dropwise in solution A, and adjusting pH value is 8~9, and uses magnetic force
Blender continues stirring until generating white depositions in solution；
4) white depositions are centrifugated, are repeatedly washed with deionized water in removal white depositions residual solution
Cl—, use AgNO3Solution tests judgement to cleaning solution, to ensure Cl—It completely removes；
5) step 4) products therefrom is placed in baking oven under 60 DEG C~80 DEG C air atmospheres and is dried, ground after drying with mortar
Thin BiOCl:0.005Eu of the present invention to obtain the final product3+Red fluorescence powder.
Embodiment 2
1) with Eu2O3And Bi2O3As raw material, according to chemical formula BiOCl:xEu3+Stoichiometric ratio carry out raw material weigh,
Wherein, x=0.005；
2) load weighted raw material is put into beaker, is slowly dropped into mass concentration dropwise and is 37% concentrated hydrochloric acid, and uses
Magnetic stirrer, until raw material is completely dissolved to form solution A；
3) it is 25% ammonia spirit 15mL that mass concentration is slowly added dropwise in solution A, and adjusting pH value is 8, and is stirred with magnetic force
It mixes device and continues stirring until generating white depositions in solution；
4) white depositions are centrifugated, are repeatedly washed with deionized water in removal white depositions residual solution
Cl—, use AgNO3Solution tests judgement to cleaning solution, to ensure Cl—It completely removes；
5) step 4) products therefrom is placed in baking oven under 70 DEG C of air atmospheres and is dried, it is finely ground with mortar after drying to obtain the final product
BiOCl:0.005Eu of the present invention3+Red fluorescence powder.
Fig. 1 is BiOCl:0.005Eu made from embodiment 23+The XRD diagram of fluorescent powder.As can be seen from the figure sample respectively spreads out
It penetrates peak and BiOCl standard card (JCPDS NO.06-0249) is almost the same, show that gained sample is single BiOCl phase, and
There is not miscellaneous phase.
Fig. 2 is BiOCl:0.005Eu made from embodiment 23+The SEM of fluorescent powder schemes.As can be seen from the figure the sample is brilliant
Mutually block-shaped for typical cube, powder size is uniform, having a size of 3~5 μm, particle size is small, regular appearance.
Fig. 3 is BiOCl:0.005Eu made from embodiment 23+The launching light spectrogram of fluorescent powder.As can be seen from the figure made
Standby fluorescent powder under the monitoring of 317nm wavelength it can be seen that 4 apparent characteristic peaks, be respectively 594nm (5D0→7F1),
622nm(5D0→7F2),653nm(5D0→7F3) and 700nm (5D0→7F4), in 622nm emission peak much higher than at 700nm
Emission peak, emissive porwer is high, and strong red emission may be implemented.From5D0→7F2The transmitting of electric dipole transition is obviously strong
In5D0→7F1The transmitting of magnetic dipole transition illustrates the Eu in BiOCl matrix3+Ion occupies the case of center of asymmetry, this with
The crystal structure of BiOCl is consistent.
Fig. 4 is BiOCl:0.005Eu made from embodiment 23+The exciting light spectrogram of fluorescent powder.As can be seen from the figure have three
A sharp emission peak, the emission peak of 319nm are caused by VB-CB transition, and the emission peak of 394nm and 466nm are due to Eu3+
's7F0-5L6With7F0-5D2Caused by transition, the Eu under the monitoring of 622nm wavelength3+Ion can produce under short wave ultraviolet light excitation
Very strong fluorescent emission.
Embodiment 3
1) with Eu2O3And Bi2O3As raw material, according to chemical formula BiOCl:xEu3+Stoichiometric ratio carry out raw material weigh,
Wherein, x=0.010；
2) load weighted raw material is put into beaker, is slowly dropped into mass concentration dropwise and is 37% concentrated hydrochloric acid, and uses
Magnetic stirrer, until raw material is completely dissolved to form solution A；
3) it is 25% ammonia spirit 15mL that mass concentration is slowly added dropwise in solution A, and adjusting pH value is 8, and is stirred with magnetic force
It mixes device and continues stirring until generating white depositions in solution；
4) white depositions are centrifugated, are repeatedly washed with deionized water in removal white depositions residual solution
Cl—, use AgNO3Solution tests judgement to cleaning solution, to ensure Cl—It completely removes；
5) step 4) products therefrom is placed in baking oven under 80 DEG C of air atmospheres and is dried, it is finely ground with mortar after drying to obtain the final product
BiOCl:0.01Eu of the present invention3+Red fluorescence powder.
Embodiment 4
1) with Eu2O3And Bi2O3As raw material, according to chemical formula BiOCl:xEu3+Stoichiometric ratio carry out raw material weigh,
Wherein, x=0.008；
2) load weighted raw material is put into beaker, is slowly dropped into mass concentration dropwise and is 37% concentrated hydrochloric acid, and uses
Magnetic stirrer, until raw material is completely dissolved to form solution A；
3) it is 25% ammonia spirit 15mL that mass concentration is slowly added dropwise in solution A, and adjusting pH value is 9, and is stirred with magnetic force
It mixes device and continues stirring until generating white depositions in solution；
4) white depositions are centrifugated, are repeatedly washed with deionized water in removal white depositions residual solution
Cl—, use AgNO3Solution tests judgement to cleaning solution, to ensure Cl—It completely removes；
5) step 4) products therefrom is placed in baking oven under 60 DEG C of air atmospheres and is dried, it is finely ground with mortar after drying to obtain the final product
BiOCl:0.008Eu of the present invention3+Red fluorescence powder.
Embodiment 5
1) with Eu2O3And Bi2O3As raw material, according to chemical formula BiOCl:xEu3+Stoichiometric ratio carry out raw material weigh,
Wherein, x=0.010；
2) load weighted raw material is put into beaker, is slowly dropped into mass concentration dropwise and is 37% concentrated hydrochloric acid, and uses
Magnetic stirrer, until raw material is completely dissolved to form solution A；
3) it is 25% ammonia spirit 15mL that mass concentration is slowly added dropwise in solution A, and adjusting pH value is 9, and is stirred with magnetic force
It mixes device and continues stirring until generating white depositions in solution；
4) white depositions are centrifugated, are repeatedly washed with deionized water in removal white depositions residual solution
Cl—, use AgNO3Solution tests judgement to cleaning solution, to ensure Cl—It completely removes；
5) step 4) products therefrom is placed in baking oven under 75 DEG C of air atmospheres and is dried, it is finely ground with mortar after drying to obtain the final product
BiOCl:0.01Eu of the present invention3+Red fluorescence powder.
Claims (3)
1. a kind of preparation method of europium doping chlorine oxygen bismuth red fluorescence powder, which comprises the following steps:
1) with Eu2O3And Bi2O3As raw material, according to chemical formula BiOCl:xEu3+Stoichiometric ratio carry out raw material weigh,
In, x=0.005~0.010；
2) load weighted raw material is put into beaker, is slowly dropped into concentrated hydrochloric acid dropwise, be stirred during being added dropwise, until raw material
It is completely dissolved to form solution A；
3) ammonia spirit is slowly added dropwise in solution A, adjusting pH value is 8~9, continues stirring with magnetic stirring apparatus until generating white
Color sediment；
4) white depositions are centrifugated, the Cl in removal white depositions residual solution is repeatedly washed with deionized water—, and
Use AgNO3Solution tests judgement to cleaning solution, to ensure Cl—It completely removes；
5) sediment after step 4) processing is dried；
The mass concentration of concentrated hydrochloric acid solution is 37% in step 2)；
Ammonia spirit mass concentration in step 3) is 25%, and dropwise addition mode is to be added dropwise；
Drying is finely ground with mortar after drying to dry under 60 DEG C~80 DEG C air atmospheres in an oven in step 5).
2. a kind of preparation method of europium doping chlorine oxygen bismuth red fluorescence powder according to claim 1, which is characterized in that step
2) it is carried out in using magnetic stirring apparatus.
3. adulterating chlorine oxygen bismuth red fluorescence powder, feature using europium made from the described in any item preparation methods of claim 1 to 2
It is, chemical formula BiOCl:xEu3+, wherein x=0.005~0.010, the crystal phase of the fluorescent powder be it is cube block-shaped,
Powder size is uniform, having a size of 3~5 μm.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103421511A (en) * | 2013-08-30 | 2013-12-04 | 昆明理工大学 | Bismuth oxyhalide light-emitting material with doped rare earth ions and preparation method thereof |
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- 2016-12-30 CN CN201611262616.1A patent/CN106635000B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103421511A (en) * | 2013-08-30 | 2013-12-04 | 昆明理工大学 | Bismuth oxyhalide light-emitting material with doped rare earth ions and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| Far-Red-Emitting BiOCl:Eu3+ Phosphor with Excellent Broadband NUV-Excitation for White-Light-Emitting Diodes;Yongjin Li等;《J. Am. Ceram. Soc.》;20150420;第98卷(第7期);2170–2176 |
| Photoluminescence, photocatalysis and Judd–Ofelt analysis of Eu3+-activated layered BiOCl phosphors;Rohit Saraf等;《RSC Adv.》;20141202;第5卷;4109–4120 |
| Red long lasting phosphorescence of Eu3+ doped BiOCl semiconducting polycrystals;ZHOU Yuting等;《JOURNAL OF RARE EARTHS》;20161215;第34卷(第12期);1188-1192 |
| Synthesis of three-dimensional flower-like BiOCl:RE3+(RE3+= Eu3+,Sm3+) globular microarchitectures and their luminescence properties;Yang-Yang Guo等;《Applied Surface Science》;20161201;第388卷;345–351 |
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