CN103923658A - Metal particle-doped hollow structure orthophosphate luminescence material and preparation method thereof - Google Patents
Metal particle-doped hollow structure orthophosphate luminescence material and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the field of luminescence materials, and discloses a metal particle-doped hollow structure orthophosphate luminescence material and a preparation method thereof, wherein the structure general formula of the luminescence material is Ba3-xGd(PO4)3:Dyx@My, M is doped metal nanoparticles and is at least one selected from Ag, Au, Pt, Pd and Cu, @ represents cladding, M is the inner core, and Ba3-xGd(PO4)3:Dyx is the outer shell. According to the metal particle-doped hollow structure orthophosphate luminescence material, the dispersed carbon spheres are adopted as the template, such that the obtained hollow structure having the spherical orthophosphate has the controlled morphology; and due to introduction of the M metal nanoparticles, the luminescence efficiency of the orthophosphate luminescence material can be substantially increased under the same excitation condition, and the wavelength of the emission light is not changed.
Description
Technical field
The present invention relates to field of light emitting materials, relate in particular to hollow structure orthophosphoric acid salt luminescent material of a kind of doping metals particle and preparation method thereof.
Background technology
Present commercial luminescent material is prepared with high temperature solid-state method mostly, pyroreaction big energy-consuming and size distribution inequality, and powder pattern is different, need by the method for ball milling to obtain the fluorescent material of 2-8 micron grain size, and make powder granule size inconsistent, pattern is imperfect, causes coating inequality.People pass through to use sol-gel method, hydrothermal synthesis method, and the methods such as complexing gel method are prepared fluorescent material, and these methods can make up the deficiency of high temperature solid phase synthesis, but the luminous intensity of the fluorescent material of these method gained is not as high temperature solid phase synthesis.The target that to obtain size, pattern luminescent material controlled and good luminous performance be researchist's effort always.
Summary of the invention
Problem to be solved by this invention is to provide a kind of pattern even, the hollow structure orthophosphoric acid salt luminescent material of the good doping metals particle of luminescent properties
Technical scheme of the present invention is as follows:
A hollow structure orthophosphoric acid salt luminescent material for doping metals particle, its general structure is: Ba
3-xgd (PO
4)
3: Dy
x@M
y, wherein, M is metal nano particle-doped, and M is selected from least one in Ag, Au, Pt, Pd, Cu, and@represents to be coated, and M is kernel, Ba
3-xgd (PO
4)
3: Dy
xfor shell, the span of x is 0 < x≤0.2, and y is M and Ba
3-xgd (PO
4)
3: Dy
xmole ratio, the span of y is 0 < y≤1 × 10
-2.
The hollow structure orthophosphoric acid salt luminescent material of described doping metals particle, preferably, the span of x is 0.02≤x≤0.1; The span of y is 1 × 10
-5≤ y≤5 × 10
-3.
The present invention also provides the hollow structure orthophosphoric acid salt luminescent material of above-mentioned doping metals particle, comprises the steps:
By after the auxiliary agent and reductive agent hybrid reaction of the salts solution of M, a dissemination, make M nanometer particle colloid; Wherein, the content of the addition of described auxiliary agent in the M nanometer particle colloid finally obtaining is 1 × 10
-4g/mL～5 × 10
-2g/mL, the mol ratio of described reductive agent and M is 0.5:1～10:1;
In the ethanol solution of sucrose or glucose, add described M nanometer particle colloid, obtain mixing solutions, and by the described mixing solutions obtaining confined reaction at 120 ~ 200 DEG C, make the solution that contains C@M, contain C@M described in centrifugation
ysolution, the centrifugal solid phase obtaining is washed, is obtained C@M after dry
ycarbon ball template; Wherein ,@represents that C is coated M, and in M nanoparticle and sucrose or glucose, the ratio of the molar weight of C element is 5 × 10
-4~ 5 × 10
-2;
According to general structure Ba
3-xgd (PO
4)
3: Dy
x@M
yin stoichiometric ratio, the salts solution that measures respectively Ba, Gd and Dy mixes, and to regulate mixed salts solution pH be 1 ~ 3, then adds described C@M
ycarbon ball template, stirs 0.5-6h; Then add again (NH
4)
2hPO
4sinking agent, is precipitated, then follows stirring reaction 2-8h, and then suction filtration dry, obtains Ba
3-xgd (PO
4)
3: Dy
x@C@M
ypresoma; Wherein, C@M
ycarbon ball template and Ba
3-xgd (PO
4)
3: Dy
xmol ratio be 0.025:1 ~ 10:1; Ba
3-xgd (PO
4)
3: Dy
x@C@M
yrepresent Ba
3-xgd (PO
4)
3: Dy
xcoated C@M
y, C is carbon;
Described presoma is ground, and the powder that grinding is obtained was in 600 ~ 1000 DEG C of pre-burnings 1 ~ 6 hour, after cooling, ground, and then in 1100～1300 DEG C of calcining 1 ~ 8h, obtaining general structure is Ba
3-xgd (PO
4)
3: Dy
x@M
yhollow structure orthophosphoric acid salt luminescent material;
Wherein, M is metal nano particle-doped, and M is selected from least one in Ag, Au, Pt, Pd, Cu, and@represents to be coated, and M is kernel, Ba
3-xgd (PO
4)
3: Dy
xfor shell, the span of x is 0 < x≤0.2, and y is M and luminescent material Ba
3-xgd (PO
4)
3: Dy
xmole ratio, the span of y is 0 < y≤1 × 10
-2.
The preparation method of the hollow structure orthophosphoric acid salt luminescent material of described doping metals particle, preferably, described auxiliary agent is at least one in polyethylene arsenic pyrrolidone, Trisodium Citrate, cetyl trimethylammonium bromide, sodium lauryl sulphate or sodium laurylsulfonate.
The preparation method of the hollow structure orthophosphoric acid salt luminescent material of described doping metals particle, preferably, described reductive agent is at least one in hydrazine hydrate, xitix, Trisodium Citrate or sodium borohydride; In actual use, reductive agent need to be configured to the aqueous solution, and its concentration is 1 × 10
-4mol/L～1mol/L.
The preparation method of the hollow structure orthophosphoric acid salt luminescent material of described doping metals particle, preferably, the time of salts solution, auxiliary agent and the reductive agent hybrid reaction of M is 10 ~ 45min.
The preparation method of the hollow structure orthophosphoric acid salt luminescent material of described doping metals particle, preferably, the confined reaction of sucrose or glucose and M nanometer particle colloid carries out being with in teflon-lined reactor.
The preparation method of the hollow structure orthophosphoric acid salt luminescent material of described doping metals particle, preferably, the salts solution of Ba, Gd and Dy is respectively nitrate solution or the oxalate solution of Ba, Gd and Dy; The concentration of the salts solution of Ba is 0.5 ~ 5mol/L; The concentration of the salts solution of Gd is 0.2 ~ 2mol/L; The concentration of the salts solution of Dy is 0.01 ~ 0.5mol/L.
The preparation method of the hollow structure orthophosphoric acid salt luminescent material of described doping metals particle, preferably, the mole dosage that described sinking agent is is with respect to Ba
2+and Gd
3+mole dosage excessive 25%; The effect of sinking agent is sedimentation Ba
2+and Gd
3+, its principle is as follows:
3Ba
2++3HPO
4 2-＋9H
＋＋6NH
4 ＋=Ba
3(PO
4)
2↓+PO
4 3-＋6NH
3
Gd
3++HPO
4 2-＋3H
＋＋2NH
4 ＋=Gd(PO
4)↓＋2NH
3。
In the preparation method of the hollow structure orthophosphoric acid salt luminescent material of described doping metals particle, preferably, the acid solution that the adjusting of pH value is used, determines according to the salts solution of Ba, Gd and Dy, if salts solution is nitrate solution, adopts nitric acid to regulate; If salts solution is acetate solution, adopting acetic acid to regulate.
In the preparation method of the hollow structure orthophosphoric acid salt luminescent material of described doping metals particle, preferably, the washing process of the solid phase obtaining when the solution that contains C M described in centrifugation: use successively deionized water and repetitive scrubbing is repeatedly successively.
The preparation method of the hollow structure orthophosphoric acid salt luminescent material of described doping metals particle, preferably, the pre-burning of the powder that described presoma obtains after grinding and two processes of calcining are all under air atmosphere, carry out in high temperature box furnace or retort furnace.
In the hollow structure orthophosphoric acid salt luminescent material of doping metals particle provided by the invention, adopting the carbon bead disperseing is template, and the orthophosphoric acid salt obtaining is spherical hollow structure, and not only pattern is controlled; And owing to having introduced M metal nanoparticle, the luminous efficiency of orthophosphoric acid salt luminescent material under same shooting conditions is greatly improved, and radiative wavelength does not change.Orthophosphoric acid salt luminescent material of the present invention has good luminescent properties, and purity of color and the brightness of after being stimulated, launching bright dipping are all higher, can be applied in feds.In addition, the carbon bead that the present invention prepares employing dispersion is template, and the orthophosphoric acid salt obtaining is hollow nucleocapsid structure, can effectively reduce the consumption of rare earth metal, has reduced product cost, saves in a large number precious rare earth resources.
In the hollow structure orthophosphoric acid salt luminescent material preparation method of doping metals particle provided by the invention, first adopt hydrothermal method to prepare the carbon bead of clad metal nano particle, and then adopt the precipitator method to prepare Ba taking carbon bead as template
3-xgd (PO
4)
3: Dy
x@C@M
yprecursor powder, and then through calcining, in calcination process, carbon bead will be converted into CO
2overflow, finally obtain being mixed with the Ba of metal nanoparticle
3-xgd (PO
4)
3: Dy
xluminescent material.Strengthen light-emitting phosphor by being mixed with metal nanoparticle.Make Ba
3-xgd (PO
4)
3: Dy
xthe luminous efficiency of luminescent material under same shooting conditions is greatly improved, and radiative wavelength does not change.Meanwhile, step of preparation process is few, relatively simple; Processing condition are not harsh, easily reach, and cost is low; Do not introduce other impurity, the luminescent material quality obtaining is high, can be widely used in the preparation of luminescent material.
Brief description of the drawings
Fig. 1 is that luminescent material and contrast luminescent material prepared by embodiment 2 is the luminescent spectrum comparison diagram under the cathode-ray exciting under 1.5KV at acceleration voltage; Wherein, curve 1 is luminescent material prepared by embodiment 3: the Ba that is mixed with Ag nano particle
2.94gd (PO
4)
3: Dy
0.06@Ag
2.5 × 10the luminescent spectrum of-4 luminescent materials, curve 2 is contrast luminescent material: Ba
2.94gd (PO
4)
3: Dy
0.06the luminescent spectrum of luminescent material.
Embodiment
Below in conjunction with accompanying drawing, preferred embodiment of the present invention is described in further detail.
Embodiment 1
The precipitator method are prepared Ba
2.8gd (PO
4)
3: Dy
0.2@Pd
1 × 10-5
Preparation containing Pd nanoparticle sol: take 0.22mg Palladous chloride (PdCl
22H
2o) be dissolved in the deionized water of 10mL; Under the condition of magnetic agitation, 11.0mg Trisodium Citrate and 4.0mg sodium lauryl sulphate are dissolved in above-mentioned palladium chloride solution; Take 0.38mg sodium borohydride and be dissolved in 100mL deionized water, obtaining concentration is 1 × 10
-4the sodium borohydride solution of mol/L; Under the condition of magnetic agitation, in above-mentioned palladium chloride solution, add fast the above-mentioned sodium borohydride solution of 10mL, reaction 20min, obtaining 20mL Pd nanoparticle concentration is 5 × 10
-5the colloidal sol of mol/L.
The preparation of C@Pd: take the alcoholic solution that obtains glucose in the dehydrated alcohol that 6.005g glucose is dissolved in 36mL, above-mentioned 4mL colloidal sol is added in the alcoholic solution of glucose, obtain mixing solutions, mixing solutions is proceeded in 50mL band teflon-lined reactor, after adding a cover and screwing, in 120 DEG C of reaction 36h, prepare and contain C@Pd
1 × 10-5 solution, this solution of centrifugation obtains solid formation, washs respectively 2 times with deionized water and dehydrated alcohol, and dry at 60 DEG C, obtain C Pd
1 × 10-5 carbon ball templates.
According to Ba
2.8gd (PO
4)
3: Dy
0.2stoichiometry ratio measure 22.4mL0.5mol/LBa (CH
3cOO)
2, 4mL1mol/L Gd (CH
3cOO)
3with 1.6mL0.5mol/L Dy (CH
3cOO)
3solution, adjusting pH is 1, then adds carbon ball C@Pd
1 × 10-5 480mg, stir 0.5h, obtain mixing solutions.Separately get (NH
4)
2hPO
4be dissolved in the solution of making 0.5mol/L in deionized water, under agitation it slowly joined in mixing solutions, add-on is 30mL, is precipitated, then stirring reaction 2h.Then suction filtration dry, obtains Ba
2.8gd (PO
4)
3: Dy
0.2@C@Pd
1 × 10-5 presomas;
Presoma is ground, be put in retort furnace in air in 600 DEG C of pre-burnings 6 hours, after cooling, grind, and then in 1100 DEG C of calcining 8h, obtain being mixed with the Ba of Pd nano particle
2.8gd (PO
4)
3: Dy
0.2@Pd
1 × 10-5 luminescent materials.
Embodiment 2
The precipitator method are prepared the Ba of hollow structure
2.94gd (PO
4)
3: Dy
0.06@Ag
2.5 × 10-4
Preparation containing Ag nanoparticle sol: take 3.4mg Silver Nitrate (AgNO
3) be dissolved in the deionized water of 18.4mL; Under the condition of magnetic agitation, 42mg Trisodium Citrate is dissolved in above-mentioned silver nitrate solution; Take 5.7mg sodium borohydride and be dissolved in 10mL deionized water, obtaining concentration is 1.5 × 10
-2the sodium borohydride solution of mol/L; Under the condition of magnetic agitation, to the disposable above-mentioned sodium borohydride solution of 1.6mL that adds in above-mentioned silver nitrate solution, continue reaction 10min, obtaining 20mL Ag nanoparticle concentration is 1 × 10
-3the colloidal sol of mol/L.
The preparation of C@Ag: take the alcoholic solution for preparing glucose in the dehydrated alcohol that 3.003g glucose is dissolved in 35mL, above-mentioned 5mL colloidal sol is added in the alcoholic solution of glucose, obtain mixing solutions, mixing solutions is proceeded in 50mL band teflon-lined reactor, after adding a cover and screwing, in 180 DEG C of reaction 24h, prepare and contain C@Ag
2.5 × 10-4 solution, this solution of centrifugation obtains solid formation, washs respectively 2 times with deionized water and dehydrated alcohol, and dry at 60 DEG C, obtain C Ag
2.5 × 10-4 carbon ball templates.
According to Ba
2.94gd (PO
4)
3: Dy
0.06stoichiometry ratio measure 11.76mL1mol/L Ba (NO
3)
2, 4mL1mol/L Gd (NO
3)
3with 4.8mL0.05mol/L Dy (NO
3)
3solution, adjusting pH is 2, then adds carbon ball C@Ag
2.5 × 10-4 240mg, stir 2h, obtain mixing solutions.Separately get (NH
4)
2hPO
4be dissolved in the solution of making 0.5mol/L in deionized water, under agitation it slowly joined in mixing solutions, add-on is 30mL, is precipitated, then stirring reaction 4h.Then suction filtration dry, obtains Ba
2.94gd (PO
4)
3: Dy
0.06@C@Ag
2.5 × 10-4 presomas;
Presoma is ground, be put in retort furnace in air in 800 DEG C of pre-burnings 2 hours, after cooling, grind, and then in 1200 DEG C of calcining 4h, obtain being mixed with the Ba of Ag nano particle
2.94gd (PO
4)
3: Dy
0.06@Ag
2.5 × 10-4 luminescent materials.
Fig. 1 is that luminescent material and contrast luminescent material prepared by embodiment 2 is the luminescent spectrum comparison diagram under the cathode-ray exciting under 1.5KV at acceleration voltage; Wherein, curve 1 is luminescent material prepared by embodiment 3: the Ba that is mixed with Ag nano particle
2.94gd (PO
4)
3: Dy
0.06@Ag
2.5 × 10the luminescent spectrum of-4 luminescent materials, curve 2 is contrast luminescent material: Ba
2.94gd (PO
4)
3: Dy
0.06the luminescent spectrum of luminescent material.
As can be seen from Figure 1,, at the emission peak at 581nm place, the luminous intensity of luminescent material prepared by the present embodiment has strengthened 27%.
Embodiment 3
The precipitator method are prepared the Ba of hollow structure
2.98gd (PO
4)
3: Dy
0.02@Pt
5 × 10-3
Preparation containing Pt nanoparticle sol: take 25.9mg Platinic chloride (H
2ptCl
66H
2o) be dissolved in the deionized water of 17mL; Under the condition of magnetic agitation, 400mg Trisodium Citrate and 600mg sodium laurylsulfonate are dissolved in above-mentioned platinum acid chloride solution; Take 1.9mg sodium borohydride and be dissolved in 10mL deionized water, obtaining concentration is 5 × 10
-3the sodium borohydride solution of mol/L; Prepare 10mL concentration is 5 × 10 simultaneously
-2the hydrazine hydrate solution of mol/L; Under the condition of magnetic agitation, first in above-mentioned platinum acid chloride solution, drip the above-mentioned sodium borohydride solution of 0.4mL, after reaction 5min, then add the above-mentioned hydrazine hydrate solution of 2.6mL in above-mentioned platinum acid chloride solution, continue reaction 40min, obtaining 20mL Pt nanoparticle concentration is 2.5 × 10
-3the colloidal sol of mol/L.
The preparation of C@Pt: take the alcoholic solution for preparing glucose in the dehydrated alcohol that 0.0150g glucose is dissolved in 30mL, above-mentioned 10mL colloidal sol is added in the alcoholic solution of glucose, obtain mixing solutions, again mixing solutions is proceeded in 50mL band teflon-lined reactor, after adding a cover and screwing, in 150 DEG C of reaction 10h, prepare and contain C@Pt
5 × 10-3 solution, this solution of centrifugation obtains solid formation, washs respectively 2 times with deionized water and dehydrated alcohol, and dry at 70 DEG C, obtain C Pt
5 × 10-3 carbon ball templates.
The BaO that takes 30.6658g is dissolved in nitric acid and obtains the Ba (NO of 100mL2mol/L
3)
2solution, takes 9.0623g Gd
2o
3be dissolved in the Gd (NO that nitric acid obtains 100mL0.5mol/L
3)
3solution and take 3.7300gDy
2o
3be dissolved in the Dy (NO that nitric acid obtains 100mL0.2mol/L
3)
3solution.
According to Ba
2.98gd (PO
4)
3: Dy
0.02stoichiometry ratio measure 5.96mL2mol/L Ba (NO
3)
2, 8mL0.5mol/L Gd (NO
3)
3with 0.4mL0.2mol/L Dy (NO
3)
3solution, adjusting pH is 3, then adds carbon ball C@Pt
5 × 10-3 4.8mg, stir 6h, obtain mixing solutions.Separately get (NH
4)
2hPO
4be dissolved in the solution of making 1mol/L in deionized water, under agitation it slowly joined in mixing solutions, add-on is 15mL, is precipitated, then stirring reaction 8h.Then suction filtration dry, obtains Ba
2.98gd (PO
4)
3: Dy
0.02@Pt
5 × 10-3 presomas;
Presoma is ground, be put in high temperature box furnace calcining at constant temperature 1h at 1000 DEG C, after cooling, grind, and then in 1150 DEG C of calcining 3h, obtain being mixed with the Ba of Pt nano particle
2.98gd (PO
4)
3: Dy
0.02@Pt
5 × 10-3 luminescent materials.
Embodiment 4
The precipitator method are prepared the Ba of hollow structure
2.9gd (PO
4)
3: Dy
0.1@Au
1 × 10-2
Preparation containing Au nanoparticle sol: take 48.4mg hydrochloro-auric acid (AuCl
3hCl4H
2o) be dissolved in the deionized water of 10mL; Under the condition of magnetic agitation, 14mg Trisodium Citrate and 6mg cetyl trimethylammonium bromide are dissolved in above-mentioned chlorauric acid solution; Take 1.9mg sodium borohydride and be dissolved in 10mL deionized water, obtaining concentration is 5 × 10
-3the sodium borohydride solution of mol/L; Take 17.6mg dissolution of ascorbic acid in 10mL deionized water, obtaining concentration is 1 × 10
-2the ascorbic acid solution of mol/L; Under the condition of magnetic agitation, first in above-mentioned chlorauric acid solution, add the above-mentioned sodium borohydride solution of 5mL, after reaction 5min, then add the above-mentioned ascorbic acid solution of 5mL in above-mentioned chlorauric acid solution, continue reaction 20min, obtaining 20mLAu nanoparticle concentration is 5 × 10
-3the colloidal sol of mol/L.
The preparation of C@Au: the alcoholic solution that takes 0.0057g g sucrose dissolved and prepare sucrose in the dehydrated alcohol of 24mL, above-mentioned 16mL colloidal sol is added in the alcoholic solution of sucrose, obtain mixing solutions, mixing solutions is proceeded in 50mL band teflon-lined reactor, after adding a cover and screwing, in 160 DEG C of reaction 20h, prepare and contain C@Au
1 × 10-2 solution, this solution of centrifugation obtains solid formation, washs respectively 3 times with deionized water and dehydrated alcohol, and dry at 80 DEG C, obtain C Au
1 × 10-2 carbon ball templates.
Take the sorbitol solution that 5g glucose is dissolved in dehydrated alcohol and obtains 40mL, this solution is proceeded in 50mL band teflon-lined reactor, after adding a cover and screwing, in 180 DEG C of reaction 24h, prepare the solution of carbon bead, this solution of centrifugation obtains solid formation, washs respectively 2 times with deionized water and dehydrated alcohol, and dry at 60 DEG C, obtain carbon bead.
Take the BaCO of 98.6700g
3be dissolved in the Ba (NO that nitric acid obtains 100mL5mol/L
3)
2solution, takes 4.9452g Gd
2(CO
3)
3be dissolved in the Gd (NO that nitric acid obtains 100mL0.2mol/L
3)
3solution and take 2.5251gDy
2(CO
3)
3be dissolved in the Dy (NO that nitric acid obtains 100mL0.1mol/L
3)
3solution.
According to Ba
2.9gd (PO
4)
3: Dy
0.1stoichiometry ratio measure 2.32mL5mol/L Ba (NO
3)
2, 20mL0.2mol/L Gd (NO
3)
3with 4mL0.1mol/L Dy (NO
3)
3solution, adjusting pH is 1, then adds carbon ball C@Au1.2mg, stirs 5h, obtains mixing solutions.Separately get (NH
4)
2hPO
4be dissolved in the solution of making 1mol/L in deionized water, under agitation it slowly joined in mixing solutions, add-on is 15mL, is precipitated, then stirring reaction 6h.Then suction filtration dry, obtains Ba
2.9gd (PO
4)
3: Dy
0.1@C@Au
1 × 10-2 presomas;
Presoma is ground, be put in high temperature box furnace calcining at constant temperature 1h at 800 DEG C, after cooling, grind, and then in 1200 DEG C of calcining 5h, obtain being mixed with the Ba of Au nano particle
2.9gd (PO
4)
3: Dy
0.1@Au
1 × 10-2 luminescent materials.
Embodiment 5
The precipitator method are prepared the Ba of hollow structure
2.97gd (PO
4)
3: Dy
0.03@Cu
1 × 10-4
Preparation containing Cu nanoparticle sol: take 1.6mg cupric nitrate (Cu (NO
3)
2) be dissolved in the deionized water of 16mL; Under the condition of magnetic agitation, 2mg polyethylene arsenic pyrrolidone (PVP) is dissolved in above-mentioned copper nitrate solution; Take 0.4mg sodium borohydride and be dissolved in 10mL ethanol, obtaining concentration is 1 × 10
-3the sodium borohydride alcoholic solution of mol/L; Under the condition of magnetic agitation, in above-mentioned copper nitrate solution, slowly splash into the above-mentioned sodium borohydride alcoholic solution of 4mL, continue reaction 10min, obtaining 20mL Cu nanoparticle concentration is 4 × 10
-4the colloidal sol of mol/L.
The preparation of C@Cu: the alcoholic solution that takes 0.1426g sucrose dissolved and prepare sucrose in the dehydrated alcohol of 39.5mL, above-mentioned 0.5mL colloidal sol is added in the alcoholic solution of sucrose, obtain mixing solutions, again mixing solutions is proceeded in 50mL band teflon-lined reactor, after adding a cover and screwing, in 200 DEG C of reaction 5h, prepare and contain C@Cu
1 × 10-4 solution, this solution of centrifugation obtains solid formation, washs respectively 2 times with deionized water and dehydrated alcohol, and solid formation is dry at 75 DEG C, obtain C Cu
1 × 10-4 carbon ball templates.
According to Ba
2.97gd (PO
4)
3: Dy
0.03stoichiometry ratio measure 11.88mL1mol/L Ba (NO
3)
2, 4mL1mol/L Gd (NO
3)
3with 6mL0.02mol/L Dy (NO
3)
3solution, adjusting pH is 2, then adds carbon ball C@Cu
1 × 10-4 120mg, stir 4h, obtain mixing solutions.Separately get (NH
4)
2hPO
4be dissolved in the solution of making 1mol/L in deionized water, under agitation it slowly joined in mixing solutions, add-on is 15mL, is precipitated, then stirring reaction 5h.Then suction filtration dry, obtains Ba
2.97gd (PO
4)
3: Dy
0.03@C@Cu
1 × 10-4 presomas;
Presoma is ground, be put in high temperature box furnace calcining at constant temperature 3h at 900 DEG C, after cooling, grind, and then in 1300 DEG C of calcining 1h, obtain being mixed with the Ba of Cu nano particle
2.97gd (PO
4)
3: Dy
0.03@Cu
1 × 10-4 luminescent materials.
Embodiment 6
The precipitator method are prepared the Ba of hollow structure
2.995gd (PO
4)
3: Dy
0.005@(Ag
0.5/ Au
0.5)
1.25 × 10-3
Preparation containing Ag and Au nanoparticle sol: take 6.2mg hydrochloro-auric acid (AuCl
3hCl4H
2and 2.5mg Silver Nitrate (AgNO O)
3) be dissolved in the deionized water of 28mL, obtain mixing solutions; Under the condition of magnetic agitation, 22mg Trisodium Citrate and 20mg polyethylene arsenic pyrrolidone (PVP) are dissolved in above-mentioned mixing solutions; Take 5.7mg sodium borohydride and be dissolved in 10mL deionization, obtaining concentration is 1.5 × 10
-2the sodium borohydride solution of mol/L; Under the condition of magnetic agitation, to the disposable above-mentioned sodium borohydride solution of 2mL that adds in above-mentioned mixing solutions, continue reaction 20min, obtain 30mL Ag and Au nanoparticle concentration sum is 1 × 10
-3the colloidal sol of mol/L.
The preparation of C@(Ag/Au): the alcoholic solution that takes 0.7131g sucrose dissolved and prepare sucrose in the dehydrated alcohol of 30mL, above-mentioned 10mL colloidal sol is added in the alcoholic solution of above-mentioned sucrose, obtain mixing solutions, above-mentioned mixing solutions is proceeded in 50mL band teflon-lined reactor, after adding a cover and screwing, in 140 DEG C of reaction 15h, prepare and contain C@(Ag
0.5/ Au
0.5)
1.25 × 10-3 solution, this solution of centrifugation obtains solid formation, washs respectively 2 times with deionized water and dehydrated alcohol, and dry at 80 DEG C, obtain C (Ag
0.5/ Au
0.5)
1.25 × 10-3.
According to Ba
2.995gd (PO
4)
3: Dy
0.005stoichiometry ratio measure 11.98mL1mol/L Ba (NO
3)
2, 2mL2mol/L Gd (NO
3)
3with 2mL0.01mol/L Dy (NO
3)
3solution, adjusting pH is 1, then adds carbon ball C@(Ag
0.5/ Au
0.5)
1.25 × 10-3 150mg, stir 3h, obtain mixing solutions.Separately get (NH
4)
2hPO
4be dissolved in the solution of making 0.5mol/L in deionized water, under agitation it slowly joined in mixing solutions, add-on is 30mL, is precipitated, then stirring reaction 3h.Then suction filtration dry, obtains Ba
2.995gd (PO
4)
3: Dy
0.005@C@(Ag
0.5/ Au
0.5)
1.25 × 10-3 presomas;
Presoma is ground, be put in high temperature box furnace calcining at constant temperature 2h at 750 DEG C, after cooling, grind, and then in 1200 DEG C of calcining 4h, obtain being mixed with the Ba of alloy (Ag/Au) nano particle
2.995gd (PO
4)
3: Dy
0.005@(Ag
0.5/ Au
0.5)
1.25 × 10-3 luminescent materials.
Should be understood that, the above-mentioned statement for preferred embodiment of the present invention is comparatively detailed, can not therefore think the restriction to scope of patent protection of the present invention, and scope of patent protection of the present invention should be as the criterion with claims.
Claims (10)
1. a hollow structure orthophosphoric acid salt luminescent material for doping metals particle, is characterized in that, its general structure is: Ba
3-xgd (PO
4)
3: Dy
x@M
y, wherein, M is metal nano particle-doped, and M is selected from least one in Ag, Au, Pt, Pd, Cu, and@represents to be coated, and M is kernel, Ba
3-xgd (PO
4)
3: Dy
xfor shell, the span of x is 0 < x≤0.2, and y is M and Ba
3-xgd (PO
4)
3: Dy
xmole ratio, the span of y is 0 < y≤1 × 10
-2.
2. the hollow structure orthophosphoric acid salt luminescent material of doping metals particle according to claim 1, is characterized in that, the span of x is 0.02≤x≤0.1; The span of y is 1 × 10
-5≤ y≤5 × 10
-3.
3. a hollow structure orthophosphoric acid salt luminescent material for doping metals particle, is characterized in that, comprises the steps:
By after the salts solution of M, auxiliary agent and reductive agent hybrid reaction, make M nanometer particle colloid; Wherein, the content of the addition of described auxiliary agent in the M nanometer particle colloid finally obtaining is 1 × 10
-4g/mL～5 × 10
-2g/mL, the mol ratio of described reductive agent and M is 0.5:1～10:1;
In the ethanol solution of sucrose or glucose, add described M nanometer particle colloid, obtain mixing solutions, and by the described mixing solutions obtaining confined reaction at 120 ~ 200 DEG C, make the solution that contains C@M, contain C@M described in centrifugation
ysolution, the centrifugal solid phase obtaining is washed, is obtained C@M after dry
ycarbon ball template; Wherein ,@represents that C is coated M, and in M nanoparticle and sucrose or glucose, the ratio of the molar weight of C element is 5 × 10
-4~ 5 × 10
-2;
According to general structure Ba
3-xgd (PO
4)
3: Dy
x@M
yin stoichiometric ratio, the salts solution that measures respectively Ba, Gd and Dy mixes, and to regulate mixed salts solution pH be 1 ~ 3, then adds described C@M
ycarbon ball template, stirs 0.5-6h; Then add again (NH
4)
2hPO
4sinking agent, is precipitated, then follows stirring reaction 2-8h, and then suction filtration dry, obtains Ba
3-xgd (PO
4)
3: Dy
x@C@M
ypresoma; Wherein, C@M
ycarbon ball template and Ba
3-xgd (PO
4)
3: Dy
xmol ratio be 0.025:1 ~ 10: 1;
Described presoma is ground, and the powder that grinding is obtained was in 600 ~ 1000 DEG C of pre-burnings 1 ~ 6 hour, after cooling, ground, and then in 1100～1300 DEG C of calcining 1 ~ 8h, obtaining general structure is Ba
3-xgd (PO
4)
3: Dy
x@M
yhollow structure orthophosphoric acid salt luminescent material;
Wherein, M is metal nano particle-doped, and M is selected from least one in Ag, Au, Pt, Pd, Cu, and@represents to be coated, and M is kernel, Ba
3-xgd (PO
4)
3: Dy
xfor shell, the span of x is 0 < x≤0.2, and y is M and Ba
3-xgd (PO
4)
3: Dy
xmole ratio, the span of y is 0 < y≤1 × 10
-2.
4. the preparation method of the hollow structure orthophosphoric acid salt luminescent material of doping metals particle according to claim 3, it is characterized in that, described auxiliary agent is at least one in polyethylene arsenic pyrrolidone, Trisodium Citrate, cetyl trimethylammonium bromide, sodium lauryl sulphate or sodium laurylsulfonate.
5. the preparation method of the hollow structure orthophosphoric acid salt luminescent material of doping metals particle according to claim 3, is characterized in that, described reductive agent is at least one in hydrazine hydrate, xitix, Trisodium Citrate or sodium borohydride.
6. the preparation method of the hollow structure orthophosphoric acid salt luminescent material of doping metals particle according to claim 3, is characterized in that, the time of salts solution, auxiliary agent and the reductive agent hybrid reaction of M is 10 ~ 45min.
7. the preparation method of the hollow structure orthophosphoric acid salt luminescent material of doping metals particle according to claim 3, is characterized in that, the confined reaction of sucrose or glucose and M nanometer particle colloid carries out being with in teflon-lined reactor.
8. the preparation method of the hollow structure orthophosphoric acid salt luminescent material of doping metals particle according to claim 3, is characterized in that, the salts solution of Ba, Gd and Dy is respectively nitrate solution or the oxalate solution of Ba, Gd and Dy; The concentration of the salts solution of Ba is 0.5 ~ 5mol/L; The concentration of the salts solution of Gd is 0.2 ~ 2mol/L; The concentration of the salts solution of Dy is 0.01 ~ 0.5mol/L.
9. the preparation method of the hollow structure orthophosphoric acid salt luminescent material of doping metals particle according to claim 3, is characterized in that, the mole dosage of described sinking agent is with respect to Ba
2+and Gd
3+mole dosage excessive 25%.
10. the preparation method of the hollow structure orthophosphoric acid salt luminescent material of doping metals particle according to claim 3, it is characterized in that, the pre-burning of the powder that described presoma obtains after grinding and two processes of calcining are all under air atmosphere, carry out in high temperature box furnace or retort furnace.
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Cited By (3)
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| CN104946254A (en) * | 2015-06-02 | 2015-09-30 | 杭州萤鹤光电材料有限公司 | Rare earth ion-activated multiphase fluorescent material |
| CN108020448A (en) * | 2016-11-03 | 2018-05-11 | 中国辐射防护研究院 | A kind of method that polonium purifies source processed in aerosol |
| CN113024244A (en) * | 2021-03-24 | 2021-06-25 | 山东大学 | Orthophosphate thermal barrier coating material with high thermal expansion coefficient and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104946254A (en) * | 2015-06-02 | 2015-09-30 | 杭州萤鹤光电材料有限公司 | Rare earth ion-activated multiphase fluorescent material |
| CN104946254B (en) * | 2015-06-02 | 2017-04-12 | 杭州萤鹤光电材料有限公司 | Rare earth ion-activated multiphase fluorescent material |
| CN108020448A (en) * | 2016-11-03 | 2018-05-11 | 中国辐射防护研究院 | A kind of method that polonium purifies source processed in aerosol |
| CN113024244A (en) * | 2021-03-24 | 2021-06-25 | 山东大学 | Orthophosphate thermal barrier coating material with high thermal expansion coefficient and preparation method thereof |
| CN113024244B (en) * | 2021-03-24 | 2022-05-06 | 山东大学 | Orthophosphate thermal barrier coating material with high thermal expansion coefficient and preparation method thereof |
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| CN103923658B (en) | 2015-08-05 |
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