CN103923658B - Hollow structure orthophosphoric acid salt luminescent material of doping metals particle and preparation method thereof - Google Patents
Hollow structure orthophosphoric acid salt luminescent material of doping metals particle and preparation method thereof Download PDFInfo
- Publication number
- CN103923658B CN103923658B CN201310011267.6A CN201310011267A CN103923658B CN 103923658 B CN103923658 B CN 103923658B CN 201310011267 A CN201310011267 A CN 201310011267A CN 103923658 B CN103923658 B CN 103923658B
- Authority
- CN
- China
- Prior art keywords
- luminescent material
- solution
- acid salt
- hollow structure
- orthophosphoric acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Luminescent Compositions (AREA)
Abstract
The invention belongs to field of light emitting materials, hollow structure orthophosphoric acid salt luminescent material that it discloses a kind of doping metals particle and preparation method thereof; The general structure of this luminescent material 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 coated, and M is kernel, Ba
3-xgd (PO
4)
3: Dy
xfor shell.In the hollow structure orthophosphoric acid salt luminescent material of doping metals particle provided by the invention, the carbon bead adopting dispersion is template, and the orthophosphoric acid salt obtained is spherical hollow structure, not only morphology controllable; And owing to introducing 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.
Description
Technical field
The present invention relates to field of light emitting materials, hollow structure orthophosphoric acid salt luminescent material particularly relating to 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 is uneven, and powder pattern is different, need by the method for ball milling to obtain the fluorescent material of 2-8 micron grain size, and making powder granule size inconsistent, pattern is imperfect, causes coating uneven.People are by using sol-gel method, hydrothermal synthesis method, and the methods such as complex coacervation method prepare 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.Obtain size, target that morphology controllable and the luminescent material of good luminous performance are researchist's effort always.
Summary of the invention
It is even that problem to be solved by this invention is to provide a kind of pattern, 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 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:
After the salts solution of M, the auxiliary agent playing dissemination and reductive agent hybrid reaction, obtained M nanometer particle colloid; Wherein, the content of addition in the M nanometer particle colloid finally obtained of described auxiliary agent 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 the described mixing solutions confined reaction at 120 ~ 200 DEG C that will obtain, the obtained solution containing C@M, containing C@M described in centrifugation
ysolution, the centrifugal solid phase obtained is washed, obtains C@M after drying
ycarbon ball template; Wherein ,@represents that coated M, the M nanoparticle of C is 5 × 10 with the ratio of the molar weight of C element in sucrose or glucose
-4~ 5 × 10
-2;
According to general structure Ba
3-xgd (PO
4)
3: Dy
x@M
yin stoichiometric ratio, measure the salts solution mixing of Ba, Gd and Dy respectively, and regulate mixed salts solution pH to be 1 ~ 3, then add described C@M
ycarbon ball template, stirs 0.5-6h; Then (NH is added again
4)
2hPO
4sinking agent, is precipitated, more then stirring reaction 2-8h, 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 powder grinding obtained was in 600 ~ 1000 DEG C of pre-burnings 1 ~ 6 hour, grinding after cooling, 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 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 polyvinyl 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 needs 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 the salts solution of M, auxiliary agent and reductive agent hybrid reaction 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 relative 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 adjustment of pH value uses, determines according to the salts solution of Ba, Gd and Dy, if salts solution is nitrate solution, then adopts nitric acid to regulate; If salts solution is Acetate Solution, regulate at employing acetic acid.
In the preparation method of the hollow structure orthophosphoric acid salt luminescent material of described doping metals particle, preferably, the washing process containing the solid phase obtained during the solution of C M described in centrifugation: use deionized water successively 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 obtained after the grinding of described presoma and calcining two processes are all in 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, the carbon bead adopting dispersion is template, and the orthophosphoric acid salt obtained is spherical hollow structure, not only morphology controllable; And owing to introducing 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 launching bright dipping after being stimulated are all higher, can be applied in feds.In addition, it is template that the present invention prepares the carbon bead adopting dispersion, and the orthophosphoric acid salt obtained is hollow nucleocapsid structure, effectively can reduce the consumption of rare earth metal, reduce product cost, a large amount of rare earth resources saving preciousness.
In the hollow structure orthophosphoric acid salt luminescent material preparation method of doping metals particle provided by the invention, hydrothermal method is first adopted to prepare the carbon bead of clad metal nano particle, and then with carbon bead for template adopts the precipitator method to prepare Ba
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
2effusion, finally obtains the Ba being mixed with metal nanoparticle
3-xgd (PO
4)
3: Dy
xluminescent material.Light-emitting phosphor is strengthened 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 simply; Processing condition are not harsh, easily reach, and cost is low; Do not introduce other impurity, the luminescent material quality obtained is high, can be widely used in the preparation of luminescent material.
Accompanying drawing explanation
Fig. 1 is embodiment 2 luminescent material prepared and the luminescent spectrum comparison diagram contrasted under the cathode-ray exciting of luminescent material under acceleration voltage is 1.5KV; Wherein, curve 1 is luminescent material prepared by embodiment 3: the Ba being 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 prepare 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 to be dissolved in 100mL deionized water, obtaining concentration is 1 × 10
-4the sodium borohydride solution of mol/L; Under the condition of magnetic agitation, add the above-mentioned sodium borohydride solution of 10mL in above-mentioned palladium chloride solution fast, reaction 20min, obtaining 20mL Pd nanoparticle concentration is 5 × 10
-5the colloidal sol of mol/L.
The preparation of C@Pd: take 6.005g glucose and be dissolved in the alcoholic solution obtaining glucose in the dehydrated alcohol of 36mL, above-mentioned for 4mL colloidal sol is added in the alcoholic solution of glucose, obtain mixing solutions, mixing solutions being proceeded to 50mL is with in teflon-lined reactor, add a cover after screwing, in 120 DEG C of reaction 36h, prepare containing C@Pd
1 × 10the solution of-5, this solution of centrifugation obtains solid formation, washs 2 times respectively with deionized water and dehydrated alcohol, and dry at 60 DEG C, namely obtains 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, adjusts pH to be 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 deionized water the solution making 0.5mol/L, under agitation it slowly joined in mixing solutions, add-on is 30mL, is precipitated, then stirring reaction 2h.Then suction filtration is also dry, obtains Ba
2.8gd (PO
4)
3: Dy
0.2@C@Pd
1 × 10-5 presomas;
Presoma is ground, is put in atmosphere in 600 DEG C of pre-burnings 6 hours in retort furnace, grinding after cooling, and then in 1100 DEG C of calcining 8h, obtain the Ba being mixed with Pd nano particle
2.8gd (PO
4)
3: Dy
0.2@Pd
1 × 10-5 luminescent materials.
Embodiment 2
The precipitator method prepare 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 to 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, disposablely in above-mentioned silver nitrate solution add the above-mentioned sodium borohydride solution of 1.6mL, continue reaction 10min, obtaining 20mL Ag nanoparticle concentration is 1 × 10
-3the colloidal sol of mol/L.
The preparation of C@Ag: take 3.003g glucose and be dissolved in the alcoholic solution preparing glucose in the dehydrated alcohol of 35mL, above-mentioned for 5mL colloidal sol is added in the alcoholic solution of glucose, obtain mixing solutions, mixing solutions being proceeded to 50mL is with in teflon-lined reactor, add a cover after screwing, in 180 DEG C of reaction 24h, prepare containing C@Ag
2.5 × 10the solution of-4, this solution of centrifugation obtains solid formation, washs 2 times respectively with deionized water and dehydrated alcohol, and dry at 60 DEG C, namely obtains 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, adjusts pH to be 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 deionized water the solution making 0.5mol/L, under agitation it slowly joined in mixing solutions, add-on is 30mL, is precipitated, then stirring reaction 4h.Then suction filtration is also dry, obtains Ba
2.94gd (PO
4)
3: Dy
0.06@C@Ag
2.5 × 10-4 presomas;
Presoma is ground, is put in atmosphere in 800 DEG C of pre-burnings 2 hours in retort furnace, grinding after cooling, and then in 1200 DEG C of calcining 4h, obtain the Ba being mixed with Ag nano particle
2.94gd (PO
4)
3: Dy
0.06@Ag
2.5 × 10-4 luminescent materials.
Fig. 1 is embodiment 2 luminescent material prepared and the luminescent spectrum comparison diagram contrasted under the cathode-ray exciting of luminescent material under acceleration voltage is 1.5KV; Wherein, curve 1 is luminescent material prepared by embodiment 3: the Ba being 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 enhances 27%.
Embodiment 3
The precipitator method prepare 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 to 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 0.0150g glucose and be dissolved in the alcoholic solution preparing glucose in the dehydrated alcohol of 30mL, above-mentioned for 10mL colloidal sol is added in the alcoholic solution of glucose, obtain mixing solutions, mixing solutions being proceeded to 50mL is with in teflon-lined reactor again, add a cover after screwing, in 150 DEG C of reaction 10h, prepare containing C@Pt
5 × 10the solution of-3, this solution of centrifugation obtains solid formation, washs 2 times respectively with deionized water and dehydrated alcohol, and dry at 70 DEG C, namely obtains C Pt
5 × 10-3 carbon ball templates.
The BaO taking 30.6658g is dissolved in the Ba (NO that nitric acid obtains 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, adjusts pH to be 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 deionized water the solution making 1mol/L, under agitation it slowly joined in mixing solutions, add-on is 15mL, is precipitated, then stirring reaction 8h.Then suction filtration is also dry, obtains Ba
2.98gd (PO
4)
3: Dy
0.02@Pt
5 × 10-3 presomas;
Presoma is ground, is put in high temperature box furnace calcining at constant temperature 1h at 1000 DEG C, grinding after cooling, and then in 1150 DEG C of calcining 3h, obtain the Ba being mixed with Pt nano particle
2.98gd (PO
4)
3: Dy
0.02@Pt
5 × 10-3 luminescent materials.
Embodiment 4
The precipitator method prepare 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 to 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: take the alcoholic solution that 0.0057g g sucrose dissolved prepares sucrose in the dehydrated alcohol of 24mL, above-mentioned for 16mL colloidal sol is added in the alcoholic solution of sucrose, obtain mixing solutions, mixing solutions being proceeded to 50mL is with in teflon-lined reactor, add a cover after screwing, in 160 DEG C of reaction 20h, prepare containing C@Au
1 × 10the solution of-2, this solution of centrifugation obtains solid formation, washs 3 times respectively with deionized water and dehydrated alcohol, and dry at 80 DEG C, namely obtains C Au
1 × 10-2 carbon ball templates.
Take 5g glucose and be dissolved in the sorbitol solution that dehydrated alcohol obtains 40mL, this solution being proceeded to 50mL is with in teflon-lined reactor, add a cover after screwing, in 180 DEG C of reaction 24h, prepare the solution of carbon bead, this solution of centrifugation obtains solid formation, washs 2 times respectively with deionized water and dehydrated alcohol, and dry at 60 DEG C, namely 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, adjusts pH to be 1, then adds carbon ball [email protected], stirs 5h, obtains mixing solutions.Separately get (NH
4)
2hPO
4be dissolved in deionized water the solution making 1mol/L, under agitation it slowly joined in mixing solutions, add-on is 15mL, is precipitated, then stirring reaction 6h.Then suction filtration is also dry, obtains Ba
2.9gd (PO
4)
3: Dy
0.1@C@Au
1 × 10-2 presomas;
Presoma is ground, is put in high temperature box furnace calcining at constant temperature 1h at 800 DEG C, grinding after cooling, and then in 1200 DEG C of calcining 5h, obtain the Ba being mixed with Au nano particle
2.9gd (PO
4)
3: Dy
0.1@Au
1 × 10-2 luminescent materials.
Embodiment 5
The precipitator method prepare 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 polyvinyl pyrrolidone (PVP) is dissolved in above-mentioned copper nitrate solution; Take 0.4mg sodium borohydride to 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 instill 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: take the alcoholic solution that 0.1426g sucrose dissolved prepares sucrose in the dehydrated alcohol of 39.5mL, above-mentioned for 0.5mL colloidal sol is added in the alcoholic solution of sucrose, obtain mixing solutions, mixing solutions being proceeded to 50mL is with in teflon-lined reactor again, add a cover after screwing, in 200 DEG C of reaction 5h, prepare containing C@Cu
1 × 10the solution of-4, this solution of centrifugation obtains solid formation, washs 2 times respectively with deionized water and dehydrated alcohol, and solid formation is dry at 75 DEG C, namely obtains 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, adjusts pH to be 2, then adds carbon ball C@Cu
1 × 10-4 120mg, stir 4h, obtain mixing solutions.Separately get (NH
4)
2hPO
4be dissolved in deionized water the solution making 1mol/L, under agitation it slowly joined in mixing solutions, add-on is 15mL, is precipitated, then stirring reaction 5h.Then suction filtration is also dry, obtains Ba
2.97gd (PO
4)
3: Dy
0.03@C@Cu
1 × 10-4 presomas;
Presoma is ground, is put in high temperature box furnace calcining at constant temperature 3h at 900 DEG C, grinding after cooling, and then in 1300 DEG C of calcining 1h, obtain the Ba being mixed with Cu nano particle
2.97gd (PO
4)
3: Dy
0.03@Cu
1 × 10-4 luminescent materials.
Embodiment 6
The precipitator method prepare 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 polyvinyl pyrrolidone (PVP) are dissolved in above-mentioned mixing solutions; Take 5.7mg sodium borohydride to be dissolved in 10mL deionization, obtaining concentration is 1.5 × 10
-2the sodium borohydride solution of mol/L; Under the condition of magnetic agitation, disposablely in above-mentioned mixing solutions add the above-mentioned sodium borohydride solution of 2mL, 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): take the alcoholic solution that 0.7131g sucrose dissolved prepares sucrose in the dehydrated alcohol of 30mL, above-mentioned for 10mL colloidal sol is added in the alcoholic solution of above-mentioned sucrose, obtain mixing solutions, above-mentioned mixing solutions being proceeded to 50mL is with in teflon-lined reactor, add a cover after screwing, in 140 DEG C of reaction 15h, prepare containing C@(Ag
0.5/ Au
0.5)
1.25 × 10the solution of-3, this solution of centrifugation obtains solid formation, washs 2 times respectively with deionized water and dehydrated alcohol, and dry at 80 DEG C, namely obtains 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, adjusts pH to be 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 deionized water the solution making 0.5mol/L, under agitation it slowly joined in mixing solutions, add-on is 30mL, is precipitated, then stirring reaction 3h.Then suction filtration is also 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, is put in high temperature box furnace calcining at constant temperature 2h at 750 DEG C, grinding after cooling, and then in 1200 DEG C of calcining 4h, obtain the Ba being mixed with 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 present pre-ferred embodiments is comparatively detailed, and therefore can not think the restriction to scope of patent protection of the present invention, scope of patent protection of the present invention should be as the criterion with claims.
Claims (8)
1. a preparation method for the hollow structure orthophosphoric acid salt luminescent material of doping metals particle, it is special
Levy and be, comprise the steps:
After the salts solution of M, auxiliary agent and reductive agent hybrid reaction, obtained M nanometer particle colloid; Wherein, the content of addition in the M nanometer particle colloid finally obtained of described auxiliary agent 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 the described mixing solutions confined reaction at 120 ~ 200 DEG C that will obtain, the obtained solution containing C@M, containing C@M described in centrifugation
ysolution, the centrifugal solid phase obtained is washed, obtains C@M after drying
ycarbon ball template; Wherein ,@represents that coated M, the M nanoparticle of C is 5 × 10 with the ratio of the molar weight of C element in sucrose or glucose
-4~ 5 × 10
-2;
According to general structure Ba
3-xgd (PO
4)
3: Dy
x@M
yin stoichiometric ratio, measure the salts solution mixing of Ba, Gd and Dy respectively, and regulate mixed salts solution pH to be 1 ~ 3, then add described C@M
ycarbon ball template, stirs 0.5-6h; Then (NH is added again
4)
2hPO
4sinking agent, is precipitated, more then stirring reaction 2-8h, 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 powder grinding obtained was in 600 ~ 1000 DEG C of pre-burnings 1 ~ 6 hour, grinding after cooling, 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 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 preparation method of the hollow structure orthophosphoric acid salt luminescent material of doping metals particle according to claim 1, it is characterized in that, described auxiliary agent is at least one in polyvinylpyrrolidone, Trisodium Citrate, cetyl trimethylammonium bromide, sodium lauryl sulphate or sodium laurylsulfonate.
3. the preparation method of the hollow structure orthophosphoric acid salt luminescent material of doping metals particle according to claim 1, is characterized in that, described reductive agent is at least one in hydrazine hydrate, xitix, Trisodium Citrate or sodium borohydride.
4. the preparation method of the hollow structure orthophosphoric acid salt luminescent material of doping metals particle according to claim 1, is characterized in that, the time of the salts solution of M, auxiliary agent and reductive agent hybrid reaction is 10 ~ 45min.
5. the preparation method of the hollow structure orthophosphoric acid salt luminescent material of doping metals particle according to claim 1, is characterized in that, the confined reaction of sucrose or glucose and M nanometer particle colloid carries out being with in teflon-lined reactor.
6. the preparation method of the hollow structure orthophosphoric acid salt luminescent material of doping metals particle according to claim 1, 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.
7. the preparation method of the hollow structure orthophosphoric acid salt luminescent material of doping metals particle according to claim 1, it is characterized in that, the mole dosage of described sinking agent is relative to Ba
2+and Gd
3+mole dosage excessive 25%.
8. the preparation method of the hollow structure orthophosphoric acid salt luminescent material of doping metals particle according to claim 1, it is characterized in that, the pre-burning of the powder obtained after the grinding of described presoma and calcining two processes are all in air atmosphere, carry out in high temperature box furnace or retort furnace.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310011267.6A CN103923658B (en) | 2013-01-11 | 2013-01-11 | Hollow structure orthophosphoric acid salt luminescent material of doping metals particle and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310011267.6A CN103923658B (en) | 2013-01-11 | 2013-01-11 | Hollow structure orthophosphoric acid salt luminescent material of doping metals particle and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103923658A CN103923658A (en) | 2014-07-16 |
| CN103923658B true CN103923658B (en) | 2015-08-05 |
Family
ID=51142060
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310011267.6A Expired - Fee Related CN103923658B (en) | 2013-01-11 | 2013-01-11 | Hollow structure orthophosphoric acid salt luminescent material of doping metals particle and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103923658B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102337136A (en) * | 2010-07-21 | 2012-02-01 | 海洋王照明科技股份有限公司 | Metal-nanoparticle-doped oxide luminescent material with hollow structure and preparation method thereof |
| CN102477294A (en) * | 2010-11-25 | 2012-05-30 | 海洋王照明科技股份有限公司 | Calcium titanate luminescent material and preparation method thereof |
-
2013
- 2013-01-11 CN CN201310011267.6A patent/CN103923658B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102337136A (en) * | 2010-07-21 | 2012-02-01 | 海洋王照明科技股份有限公司 | Metal-nanoparticle-doped oxide luminescent material with hollow structure and preparation method thereof |
| CN102477294A (en) * | 2010-11-25 | 2012-05-30 | 海洋王照明科技股份有限公司 | Calcium titanate luminescent material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| Luminescent materials and spectroscopic properties of Dy3+ ion;Qiang Su et al;《JOURNAL OF LUMINESCENCE》;20060314;第122-123卷;第927-930页 * |
| Luminescent materials and spectroscopic properties of Dy3+ ion;Qiang Su et al;《JOURNAL OF LUMINESCENCE》;20060314;第122-123卷;第928页右栏第1-5行 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103923658A (en) | 2014-07-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103923658B (en) | Hollow structure orthophosphoric acid salt luminescent material of doping metals particle and preparation method thereof | |
| US9193901B2 (en) | Metal nanoparticle-coating silicate luminescent material and preparation method therefor | |
| EP2565252B1 (en) | Aluminate fluorescent materials and preparation methods thereof | |
| CN103923651B (en) | Hollow structure calcium titanate praseodymium luminescent material of doping metals particle and preparation method thereof | |
| CN104059651A (en) | Metal nanoparticle-doped yttrium columbate luminescent material and preparation method thereof | |
| CN104059636B (en) | Metal nano particle-doped ternary sulfide luminescent material and preparation method | |
| CN103923650B (en) | Hollow structure calcium stannate luminescent material of doping metals particle and preparation method thereof | |
| CN104119915B (en) | A kind of oxysulfide luminescent material and its preparation method | |
| CN103849389B (en) | Calcium yttrium stannate luminescent material and preparation method thereof | |
| CN104059638B (en) | Metal nano particle-doped alkaline earth strontium thiogallate luminescent material and preparation method | |
| US20150240156A1 (en) | Lutecium oxide luminescent material and preparation method thereof | |
| CN104119875B (en) | Strontium aluminate terbium luminescent material of a kind of hollow structure and preparation method thereof | |
| CN104059661A (en) | Metal nanoparticles-doped gadolinium acid calcium luminescent material and preparation method thereof | |
| CN103881717A (en) | Doped yttrium aluminum garnet luminescence material and preparation method thereof | |
| CN103849402B (en) | Lanthanum gallate calcium luminescent material and preparation method thereof | |
| CN104059654A (en) | Metal nanoparticle-doped hollow-structured yttrium calcium stannate luminescent material and preparation method thereof | |
| CN104059637B (en) | Metal nano particle-doped strontium thiogallate luminescent material and preparation method | |
| CN104059664A (en) | Metal nanoparticle-doped gallate luminescent material and preparation method thereof | |
| CN104119876B (en) | Strontium aluminate luminous material of a kind of hollow structure and preparation method thereof | |
| CN104119917A (en) | Sulfide core-shell structure luminescent material and preparation method thereof | |
| CN104059656A (en) | Metal nanoparticle-doped stannate luminescent material and preparation method thereof | |
| US9650562B2 (en) | Rare earth oxysulfide luminescent material and preparation method therefor | |
| CN104119918B (en) | A kind of sulfur lanthana luminescent material and preparation method thereof | |
| CN104119918A (en) | Lanthanum oxide sulfide luminescent material and preparation method thereof | |
| CN104119909A (en) | Hollow structure aluminate yttrium europium luminescent material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150805 Termination date: 20190111 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |