CN102827608B - Nanometer red long-afterglow luminescent material and preparation method thereof - Google Patents
Nanometer red long-afterglow luminescent material and preparation method thereof Download PDFInfo
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- CN102827608B CN102827608B CN 201210186108 CN201210186108A CN102827608B CN 102827608 B CN102827608 B CN 102827608B CN 201210186108 CN201210186108 CN 201210186108 CN 201210186108 A CN201210186108 A CN 201210186108A CN 102827608 B CN102827608 B CN 102827608B
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Abstract
The invention discloses a nanometer red long-afterglow luminescent material and a preparation method of the nanometer red long-afterglow luminescent material, belonging to the technical field of nanometer luminescent materials. The chemical formula of the material is Y202S: xSm<3+> and x=0.01-0.08; the preparation method comprises the following steps: weighing water soluble yttrium salt, water soluble samarium salt, thiocarbamide, a surfactant and ethylene glycol according to a molar ratio of 2:(0.03-0.08):(6-8):(0.05-0.1):(40-60); mixing the weighed materials for dissolution to obtain a solution; preserving the heat of the solution at a temperature from 100 DEG C to 200 DEG C in an enclosed state for 6-24 hours to obtain a brown product; cooling the brown product, filtering, washing and drying the cooled brown product to obtain a precursor; and annealing the precursor at a temperature from 600 DEG C to 1100 DEG C in a reducing atmosphere for 2-3 hours to obtain the needed product. The nanometer red long-afterglow luminescent material disclosed by the invention is good in dispersity, uniform in size and hollow in sphere structure and can be widely used for bioluminescent markers, drug release and transmission materials, light filling materials and the like.
Description
Technical field
The present invention relates to the nano luminescent material technical field, be specifically related to a kind of nano red long after glow luminous material and preparation method thereof.
Background technology
Rare-earth ion activated long-lasting phosphor, it is embedded photoluminescent material of new generation, because it has the characteristics such as energy-conservation, corrosion-resistant and "dead", in fields such as building decoration, communications and transportation, military installations, fire-fighting emergent, daily necessities, demonstrated application prospect widely.The red yttrium oxysulfide long-afterglow material that wherein can send in the dark eye-catching red twilight sunset particularly has actual using value, is the emphasis that the researchist pays close attention to and develops always.For example, to have disclosed a kind of chemical constitution be Y to prior art
2o
2s:Sm, Mg, the rare-earth red long persistence phosphor of Ti.Adopt traditional sulfur melting method, with Y
2o
3with S as base starting material, Na
2cO
3as fusing assistant, Sm
3+for exciting agent, Mg
2+and Ti
4+as common exciting agent, gac is as reductive agent, and product high temperature is come out of the stove, hot salt acid soak 1.5 ~ 2.0 h, hot wash.The required temperature of this method is high, expends mass energy, and the material prepared easily sinters piece into, can not well control pattern and the size of product.In addition, in its process prepared, use hydrochloric acid soln, environment is produced and pollutes.
Nano material, owing to having excellent chemistry, magnetics, mechanics and optical property, has now become the key areas of investigation of materials.Existing commercialization red long afterglow luminous material is micron order, has limited the application of material.Hollow ball structure can effectively reduce the consumption of rare earth metal, reduces product cost, saves in a large number precious rare earth resources.In addition, because the yttrium oxysulfide hollow ball has low density, at surface treatment process hollow bulbus cordis raw material, more easily be dispersed, be conducive to improve the regularity of particle, form high packing density at coating layer, can be widely used in the slowly-releasing of fluorescence probe, novel bioluminescence marker thing, support of the catalyst, medicine and carry material and lightweight filler.Another denomination of invention that Patent Office of the People's Republic of China is authorized is " an a kind of one-step template-free method for preparing in a large number monodisperse ZnS hollow nanospheres " (patent No.: 200910061550.3), this patent discloses a kind of method that a simple one-step template-free prepares the monodisperse ZnS hollow ball, utilizes zinc acetate and thiocarbamide to be reacted under hydrothermal condition.In addition, it is hard template that Ai Pengfei etc. be take monodispersed carbon ball, adopts even coprecipitation method to synthesize Y
2o
2s:Eu
3+tiny balloon (Chinese Journal of Inorganic Chemistry, 2009,10:1753 ~ 1757).But also without template, can not prepare at present the report of yttrium oxide sulfide nanometer hollow ball both at home and abroad, therefore, the development yttrium oxysulfide red long afterglow luminous material nano-hollow sphere structured without template synthesis not only has important theory significance to the optical property research that promotes nano material, and to save energy and further develop China's rare earth resources and be of great practical significance.
Summary of the invention
The object of the invention is to the shortcoming and defect existed for prior art, a kind of good dispersity, size homogeneous, nano-hollow sphere structured red long afterglow luminous material are provided.
Another object of the present invention is to provide the preparation method of above-mentioned nano red long after glow luminous material.
The present invention is achieved through the following technical solutions above-mentioned purpose:
A kind of nano red long after glow luminous material, chemical formula is Y
2o
2s:x Sm
3+, x=0.01 ~ 0.08; Wherein, Y is yttrium, and O is oxygen, and S is sulphur, Sm
3+for samarium ion.This material is with Y
2o
2s is matrix, Sm
3+ion is active ions.
Above-mentioned nano red long after glow luminous material is the hollow ball of diameter in 140 ~ 220nm scope, good dispersity, size homogeneous.
The preparation method of above-mentioned nano red long after glow luminous material, step is as follows:
(1) consumption that is 2:0.03 ~ 0.08:6 ~ 8:0.05 ~ 0.1:40 ~ 60 by water-soluble yttrium salt, water-soluble samarium salt, thiocarbamide, tensio-active agent and ethylene glycol according to mol ratio takes rear stirring and dissolving, after the formation clear solution, under the state of sealing, in 100 ~ 200 ℃ of insulations, within 6 ~ 24 hours, obtains the brown product;
(2) cooled brown product is carried out to centrifugation, carry out filtration washing with deionized water and ethanol respectively, in 60 ~ 90 ℃ of dryings, within 6 ~ 12 hours, obtain precursor;
(3) precursor is annealed in the reducing atmosphere under 600 ~ 1100 ℃ 2 ~ 3 hours, make nano red long after glow luminous material.
Nano red long after glow luminous material hollow ball structure of the present invention forms mechanism and sees Fig. 1, and as described in Figure, the thiocarbamide pyrolysis produces NH
4+, OH
?, H
2s/CO
2, OH
?make the solution system pH value raise, with H
2s/CO
2bubble is template, and through forming the presoma of hollow structure after self-assembly and ostwald ripening process, then calcining obtains Y
2o
2s:Sm
3+nano-hollow ball.
In aforesaid method, step (1) is specially water-soluble yttrium salt and water-soluble samarium salt is mixed with respectively the aqueous solution, after measuring by its mol ratio in the situation that during magnetic agitation joins ethylene glycol, and with thiocarbamide and tensio-active agent mixed dissolution, form clear solution, under the state of sealing, in 100 ~ 200 ℃ of insulations, within 6 ~ 24 hours, obtain the brown product.
In the preparation method of above-mentioned nano red long after glow luminous material, described water-soluble yttrium salt is preferably Yttrium trinitrate, Yttrium trichloride or acetic acid yttrium; Water-soluble samarium salt is preferably samaric nitrate, samarium trichloride or acetic acid samarium; Tensio-active agent is preferably polyvinylpyrrolidone (PVP K30, M=40000).Described reducing atmosphere is the airtight corundum crucible that is covered with carbon dust and sulphur powder, and the plumbago crucible that is about to be equipped with presoma is built in the airtight corundum crucible that is covered with reduction C powder and sulphur powder and forms, and the part by weight of carbon dust and sulphur powder is preferably 5:3.
Nano red long after glow luminous material of the present invention is due to the low density of hollow ball structure, at surface treatment process hollow bulbus cordis raw material, more easily be dispersed, be conducive to improve the regularity of particle, form high packing density at coating layer, can be widely used in the slowly-releasing of fluorescence probe, novel bioluminescence marker thing, support of the catalyst, medicine and carry material and lightweight filler.
Compared with prior art, the present invention has following beneficial effect:
(1) preparation-obtained nano red long after glow luminous material is carried out to material phase analysis with the X-x ray diffractometer x, from the X-x ray diffration pattern x obtained, product is at 700 ℃ of Y that can obtain pure phase
2o
2s:Sm
3+, the high temperature solid-state method with respect to traditional, greatly reduce calcining temperature, saved the energy.
(2) prepared product is carried out to morphology analysis with scanning electron microscope and transmission electron microscope, from the electromicroscopic photograph obtained: this red nano long after glow luminous material is good dispersity, size homogeneous, the diameter hollow ball at 140 ~ 220nm.
(3) singly mix samarium and can realize the long-persistence luminous of yttrium oxysulfide, can prepare rare earth ion doped oxysulfide hollow ball without template, prepare the method for hollow ball with respect to traditional template of utilizing, saved the template raw material, and greatly reduced preparation section.
(4) hollow ball structure can effectively reduce the consumption of rare earth metal, has reduced product cost, saves in a large number precious rare earth resources.
(5) hollow ball structure has low density, at surface treatment process hollow bulbus cordis raw material, more easily is dispersed, and is conducive to improve the regularity of particle, at coating layer, forms high packing density, will have wide practical use.
The accompanying drawing explanation
Fig. 1. nano-hollow sphere structured formation mechanism figure.
Fig. 2. the luminescent material X-ray diffraction pattern of 600 ~ 1100 ℃ of calcinings under presoma X-ray diffraction pattern and reducing atmosphere.
Fig. 3. calcine the product scanning electron microscope (SEM) photograph obtained under presoma (A) and 700 ℃ (B), 900 ℃ (C), 1100 ℃ of (D) reducing atmospheres.
Fig. 4. low power transmission electron microscope picture (b), high power transmission electron microscope picture (c), HRTEM that presoma (a) transmission electron microscope picture and 700 ℃ of calcinings obtain product scheme (d).
Fig. 5. under reducing atmosphere, the exciting light spectrogram of the luminescent material of 700 ℃ of calcinings.
Fig. 6. under reducing atmosphere, the utilizing emitted light spectrogram of the luminescent material of 700 ℃ of calcinings.
Fig. 7. under reducing atmosphere, the uv light irradiation that the luminescent material of 700 ℃ of calcinings is 360nm with wavelength is after 3 minutes, the decay of afterglow curve obtained.
Embodiment
embodiment 1
(1) according to Yttrium trinitrate: the molar ratio of samaric nitrate: thiocarbamide: PVP: ethylene glycol=2:0.01:6:0.05:40, measure yttrium nitrate solution (0.5mol/L) 40mL, samarium nitrate solution (0.05mol/L) 2mL, ethylene glycol 250mL, take thiocarbamide 4.57g, PVP 20g, be placed in container for stirring and dissolve, and after the formation clear solution, under the state of sealing, in 120 ℃ of insulations, within 8 hours, obtains the brown product.
(2) cooled brown product is carried out to centrifugation, with after deionized water filtration washing 3 times, use again the ethanol filtration washing 2 times, in 60 ℃ of dryings, within 12 hours, obtain the precursor as shown in the curve a in Fig. 2, Fig. 3 A, Fig. 4 a.
(3) precursor is annealed 2 hours in the reducing atmosphere under 700 ℃.Wherein, reducing atmosphere is built in by the plumbago crucible that presoma will be housed the airtight corundum crucible that is covered with 5g reduction C powder and 3g sulphur powder and is formed, and makes the red nano long after glow luminous material as shown in the curve f in Fig. 2, Fig. 3 B, Fig. 4, Fig. 5, Fig. 6, Fig. 7.
The product chemical formula finally obtained is Y
2o
2s:x Sm
3+, x=0.01; The hollow ball diameter is about 200nm.
(1) according to Yttrium trichloride: the molar ratio of samarium trichloride: thiocarbamide: PVP: ethylene glycol=2:0.03:7:0.08:50, measure yttrium chloride solution (0.5mol/L) 40mL, samarium trichloride solution (0.05mol/L) 6mL, ethylene glycol 300mL, take thiocarbamide 5.33g, PVP 32g, be placed in container for stirring and dissolve, and after the formation clear solution, under the state of sealing, in 140 ℃ of insulations, within 10 hours, obtains the brown product.
(2) cooled brown product is carried out to centrifugation, with after deionized water filtration washing 3 times, use again the ethanol filtration washing 2 times, in 60 ℃ of dryings, within 12 hours, obtain precursor.
(3) precursor is annealed 3 hours in the reducing atmosphere under 800 ℃.Wherein, reducing atmosphere is built in by the plumbago crucible that presoma will be housed the airtight corundum crucible that is covered with 5g reduction C powder and 3g sulphur powder and is formed, and makes the red nano long after glow luminous material as shown in the curve e in Fig. 2.
The product chemical formula finally obtained is Y
2o
2s:x Sm
3+, x=0.03; The hollow ball diameter is about 160nm.
embodiment 3
(1) according to the acetic acid yttrium: the molar ratio of acetic acid samarium: thiocarbamide: PVP: ethylene glycol=2:0.05:8:0.1:60, measure acetic acid yttrium solution (0.5mol/L) 40mL, acetic acid samarium solution (0.05mol/L) 10mL, ethylene glycol 350mL, take thiocarbamide 6.09g, PVP 40g, be placed in container for stirring and dissolve, and after the formation clear solution, under the state of sealing, in 160 ℃ of insulations, within 12 hours, obtains the brown product.
(2) cooled brown product is carried out to centrifugation, with after deionized water filtration washing 3 times, use again the ethanol filtration washing 2 times, in 70 ℃ of dryings, within 10 hours, obtain precursor.
(3) precursor is annealed 2 hours in the reducing atmosphere under 900 ℃.Wherein, reducing atmosphere is built in by the plumbago crucible that presoma will be housed the airtight corundum crucible that is covered with 5g reduction C powder and 3g sulphur powder and is formed, and makes as the curve d in Fig. 2, the red nano long after glow luminous material as shown in Fig. 3 C.
The product chemical formula finally obtained is Y
2o
2s:x Sm
3+, x=0.05; The hollow ball diameter is about 140nm.
(1) according to Yttrium trinitrate: the molar ratio of samaric nitrate: thiocarbamide: PVP: ethylene glycol=2:0.08:6:0.05:40, measure yttrium nitrate solution (0.5mol/L) 40mL, samarium nitrate solution (0.05mol/L) 16mL, ethylene glycol 250mL, take thiocarbamide 4.57g, PVP 20g, be placed in container for stirring and dissolve, and after the formation clear solution, under the state of sealing, in 180 ℃ of insulations, within 16 hours, obtains the brown product.
(2) cooled brown product is carried out to centrifugation, with after deionized water filtration washing 3 times, use again the ethanol filtration washing 2 times, in 80 ℃ of dryings, within 8 hours, obtain precursor.
(3) precursor is annealed 3 hours in the reducing atmosphere under 1000 ℃.Wherein, reducing atmosphere is built in by the plumbago crucible that presoma will be housed the airtight corundum crucible that is covered with 5g reduction C powder and 3g sulphur powder and is formed, and makes the red nano long after glow luminous material as shown in the curve c in Fig. 2.
The product chemical formula finally obtained is Y
2o
2s:x Sm
3+, x=0.08; The hollow ball diameter is about 170nm.
embodiment 5
(1) according to the acetic acid yttrium: the molar ratio of acetic acid samarium: thiocarbamide: PVP: ethylene glycol=2:0.06:7:0.05:40, measure acetic acid yttrium solution (0.5mol/L) 40mL, acetic acid samarium solution (0.05mol/L) 12mL, ethylene glycol 250mL, take thiocarbamide 5.33g, PVP 20g, be placed in container for stirring and dissolve, and after the formation clear solution, under the state of sealing, in 200 ℃ of insulations, within 24 hours, obtains the brown product.
(2) cooled brown product is carried out to centrifugation, with after deionized water filtration washing 3 times, use again the ethanol filtration washing 2 times, in 90 ℃ of dryings, within 6 hours, obtain precursor.
(3) precursor is annealed 2 hours in the reducing atmosphere under 1100 ℃.Wherein, reducing atmosphere is built in by the plumbago crucible that presoma will be housed the airtight corundum crucible that is covered with 5g reduction C powder and 3g sulphur powder and is formed, and makes as the curve b in Fig. 2, the red nano long after glow luminous material as shown in Fig. 3 D.
The product chemical formula finally obtained is Y
2o
2s:x Sm
3+, x=0.06; For solid nanoparticle, particle diameter is about 300nm.
Claims (5)
1. the preparation method of a nano red long after glow luminous material is characterized in that step is as follows:
(1) consumption that is 2:0.03～0.08:6～8:0.05～0.1:40～60 by water-soluble yttrium salt, water-soluble samarium salt, thiocarbamide, polyvinylpyrrolidone and ethylene glycol according to mol ratio takes rear stirring and dissolving, after the formation clear solution, under the state of sealing, in 100～200 ℃ of insulations, within 6～24 hours, obtains the brown product;
(2) cooled brown product is carried out to centrifugation, carry out filtration washing with deionized water and ethanol respectively, in 60～90 ℃ of dryings, within 6～12 hours, obtain presoma;
(3) presoma is annealed in the reducing atmosphere under 600～1100 ℃ 2～3 hours, make nano red long after glow luminous material;
The chemical formula of described nano red long after glow luminous material is Y
2o
2s:x Sm
3+, x=0.01～0.08; Wherein, Y is yttrium, and O is oxygen, and S is sulphur, Sm
3+for samarium ion;
Described nano red long after glow luminous material is the hollow ball of diameter in 140～220nm scope.
2. the preparation method of nano red long after glow luminous material according to claim 1, is characterized in that, described water-soluble yttrium salt is Yttrium trinitrate, Yttrium trichloride or acetic acid yttrium.
3. the preparation method of nano red long after glow luminous material according to claim 1, is characterized in that, described water-soluble samarium salt is samaric nitrate, samarium trichloride or acetic acid samarium.
4. the preparation method of nano red long after glow luminous material according to claim 1, is characterized in that, described reducing atmosphere is the airtight corundum crucible that is covered with carbon dust and sulphur powder.
5. the preparation method of nano red long after glow luminous material according to claim 1, is characterized in that, the part by weight of described carbon dust and sulphur powder is 5:3.
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| CN103146388B (en) * | 2013-03-13 | 2015-02-11 | 太原理工大学 | Method for synthesizing one-dimensional red long afterglow material |
| CN104830323B (en) * | 2015-05-25 | 2016-08-31 | 广东工业大学 | A kind of Yb3+/ Er3+codope MnF2the preparation method of interior hollow ball |
| CN106967431A (en) * | 2017-03-22 | 2017-07-21 | 安徽师范大学 | Fluorescent material and preparation method thereof |
| CN111454294B (en) * | 2019-01-18 | 2021-05-25 | 天津大学 | Afterglow slurry based on D-A type organic doped crystal afterglow material, and preparation method and application thereof |
| CN113528139B (en) * | 2021-08-04 | 2022-11-08 | 北京科技大学 | Processing method for regulating and controlling morphology and particle size of sulfur oxide fluorescent powder through laser irradiation |
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| CN101376808A (en) * | 2008-08-22 | 2009-03-04 | 浙江理工大学 | Method for synthesizing red long afterglow luminescent powder La2O2S: Sm |
| CN102286285B (en) * | 2011-09-02 | 2013-10-09 | 东华大学 | Orange-red light long-lag powder La2O2S:Sm<3+> and preparation method thereof |
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