CN104059656A - Metal nanoparticle-doped stannate luminescent material and preparation method thereof - Google Patents

Metal nanoparticle-doped stannate luminescent material and preparation method thereof Download PDF

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CN104059656A
CN104059656A CN201310089546.4A CN201310089546A CN104059656A CN 104059656 A CN104059656 A CN 104059656A CN 201310089546 A CN201310089546 A CN 201310089546A CN 104059656 A CN104059656 A CN 104059656A
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solution
doped
luminescent material
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metal nano
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周明杰
王荣
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Abstract

The invention discloses a metal nanoparticle-doped stannate luminescent material and a preparation method thereof, belonging to the field of luminescent materials. The general chemical formula of the luminescent material is Ln2-xEuxSn2O7@My, wherein M is at least one selected from metal nanoparticles consisting of Ag, Au, Pt, Pd and Cu, Ln is one selected from the group consisting of Gd, Y and La, x is more than 0 and no more than 1.5, and y is the mol ratio of M to Ln2-xEuxSn2O7 and is more than 0 and no more than 1 * 10<-2>. In the metal nanoparticle-doped stannate luminescent material, the M metal particle is introduced, so the stannate luminescent material has greatly improved luminous efficiency under same excitation conditions, the wavelength of emitted light is not changed, color purity and luminance of light emitted under excitation are high, and the stannate luminescent material can be applied to field emission devices.

Description

Metal nano particle-doped stannate luminescent material and preparation method
Technical field
The present invention relates to field of light emitting materials, relate in particular to a kind of metal nano particle-doped stannate luminescent material and preparation method.
Background technology
Field Emission Display (FED) is the flat-panel monitor that a kind of new development is got up, its principle of work and traditional cathode tube are similar, is imaging by the fluorescent material on beam bombardment display screen.Compare with other flat-panel monitor (FPD), FED all has potential advantage at aspects such as brightness, visual angle, time of response, operating temperature range, energy consumptions.One of key factor of preparing premium properties FED is the preparation of fluorescent material.Stannate has good chemical stability and thermostability, and inner textural defect is highly beneficial concerning it becomes the fluor of better quality, in luminescent material Application Areas, exists potential using value.
Summary of the invention
Problem to be solved by this invention is to provide the metal nano particle-doped stannate luminescent material that a kind of luminous efficiency is higher, can be used for field transmitting.
Technical scheme of the present invention is as follows:
A metal nano particle-doped stannate luminescent material, its chemical general formula is: Ln 2-xeu xsn 2o 7@M y, wherein, Ln 2-xeu xsn 2o 7for shell, M is kernel, and@represents to be coated; M is metal nano particle-doped, be selected from least one in Ag, Au, Pt, Pd, Cu metal nanoparticle, x is the mole number that Eu atom replaces Ln atom, and Ln is a kind of in Gd, Y, La, the span of x is 0<x≤1.5, and y is M and Ln 2-xeu xsn 2o 7mole ratio, value is 0 < y≤1 * 10 -2.
Described metal nano particle-doped stannate luminescent material, preferably, the span of x is 0.02≤x≤1.0, the span of y is 1 * 10 -5≤ y≤5 * 10 -3.
The preparation method who the invention still further relates to a kind of metal nano particle-doped stannate luminescent material, 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 solution;
In the ethanol solution of sucrose or glucose, add described M nanometer particle colloid solution, obtain mixing solutions, and by the described mixing solutions obtaining confined reaction at 120～200 ℃, make the solution that contains C@M, the solution that contains C@M described in centrifugation, obtains C@M carbon ball template after the solid phase obtaining is washed, is dried; Wherein, C represents carbon, and@represents that C is coated M, and the mol ratio of M nanoparticle and C@M carbon ball template is 1 * 10 -6: 1～0.4:1;
According to Ln 2-xeu xsn 2o 7@M yin each element chemistry metering ratio, measure each self-corresponding salts solution of Ln, Sn and Eu, put into beaker, then add described C M carbon ball template, at 50 ℃-80 ℃, heating in water bath stirs 0.5-2h; Then slowly add ammonium oxalate precipitation agent, and continue at 50 ℃ of-80 ℃ of water bath heat preservation 1h-6h, subsequent filtration, washing, dry sediment, obtain Ln 2-xeu xsn 2(C 2o 4) 7@C@M ypresoma; Wherein, Ln 2-xeu xsn 2(C 2o 4) 7@C@M yin, Ln 2-xeu xsn 2(C 2o 4) 7for shell, C is center, and M is kernel; C@M carbon ball template and Ln 2-xeu xsn 2o 7mol ratio be 0.025:1～10:1;
Described presoma is ground, grind powder and be put in air atmosphere in 1200 ℃～1500 ℃ calcining 2～24h, furnace cooling is cooled to room temperature, and resulting sample is ground to powder, and obtaining chemical general formula is Ln 2-xeu xsn 2o 7@M ymetal nano particle-doped stannate luminescent material;
In above-mentioned steps, Ln 2-xeu xsn 2o 7@M yin, Ln 2-xeu xsn 2o 7for shell, M is kernel, and@represents to be coated; M is metal nano particle-doped, be selected from least one in Ag, Au, Pt, Pd, Cu metal nanoparticle, x is the mole number that Eu atom replaces Ln atom, and Ln is a kind of in Gd, Y, La, the span of x is 0<x≤1.5, and y is M and Ln 2-xeu xsn 2o 7mole ratio, the span of y is 0 < y≤1 * 10 -2.
The preparation method of described metal nano particle-doped stannate luminescent material, preferably, auxiliary agent is at least one in polyethylene arsenic pyrrolidone, Trisodium Citrate, cetyl trimethylammonium bromide, sodium lauryl sulphate or sodium laurylsulfonate, and the content of the addition of auxiliary agent in the M metal nanometer particle colloid solution finally obtaining is 1 * 10 -4g/mL～5 * 10 -2g/mL.
The preparation method of described metal nano particle-doped stannate luminescent material, preferably, described reductive agent is at least one in hydrazine hydrate, xitix, Trisodium Citrate or sodium borohydride, the mol ratio of described reductive agent and M is 0.5:1～10:1; 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 described metal nano particle-doped stannate luminescent material, preferably, the time of the salts solution of M, auxiliary agent and reductive agent hybrid reaction is 10～45min.
The preparation method of described metal nano particle-doped stannate luminescent material, preferably, the confined reaction of sucrose or glucose and M nanometer particle colloid carries out in being with teflon-lined reactor.
The preparation method of described metal nano particle-doped stannate luminescent material, preferably, the washing process of the solid phase obtaining during the solution that contains C M described in centrifugation: use successively deionized water and repetitive scrubbing is repeatedly successively.
The preparation method of described metal nano particle-doped stannate luminescent material, preferably, described ammonium oxalate ((NH 4) 2c 2o 4) mole dosage of precipitation agent to be to guarantee the precipitation complete and excessive 25% of Ln, Sn and Eu ion, its effect is: while reacting during according to chemical equation, the precipitation that can guarantee Ln, Sn and Eu ion is complete, excessive effect all precipitates completely in order to ensure all metal ions exactly, unreacted ammonium oxalate is solution, when filtering, can wash away.
The preparation method of described metal nano particle-doped stannate luminescent material, wherein, each self-corresponding salts solution of Ln and Eu is respectively Ln (NO 3) 3solution and Eu (NO 3) 3solution, the salts solution of Sn is SnCl 4solution; Ln (NO 3) 3the concentration of solution is 0.2～2mol/L, Eu (NO 3) 3the concentration of solution is 0.01～2mol/L, SnCl 4solution is 0.4～2mol/L.
The nitrate solution of Ln and Eu, oxide compound and the carbonate of Ln and Eu of take is raw material, is dissolved in nitric acid, or to take acetate, the nitrate of Ln and Eu be raw material.
The preparation method of described metal nano particle-doped stannate luminescent material, preferably, presoma grinds the calcining of powder to carry out in retort furnace.
The preparation method of described metal nano particle-doped stannate luminescent material, preferably, the span of x is 0.02≤x≤1.0, the span of y is 1 * 10 -5≤ y≤5 * 10 -3.
The preparation method of metal nano particle-doped stannate luminescent material provided by the invention, first adopts hydrothermal method to prepare carbon bead, and then to take carbon bead C be template, adopts the ammonium oxalate precipitator method to prepare Ln 2-xeu xsn 2(C 2o 4) 7@C@M yprecursor powder, and then through calcining, in calcination process, carbon will be converted into CO 2overflow, finally obtain metal nano particle-doped Ln 2-xeu xsn 2o 7luminescent material.
In above-mentioned metal nano particle-doped stannate luminescent material, owing to having introduced M metal nanoparticle, the luminous efficiency of stannate luminescent material under same shooting conditions is greatly improved, and radiative wavelength does not change, purity of color and the brightness of after being stimulated, launching bright dipping are all higher, can be applied to feds; In addition, the carbon bead adopt disperseing is template, and the stannate luminescent material obtaining is spherical metal nano particle-doped, and not only pattern is controlled, and can effectively reduce the consumption of rare earth metal, has reduced product cost, saves in a large number precious rare earth resources.
The preparation method of metal nano particle-doped stannate luminescent material of the present invention, processing step 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.
Accompanying drawing explanation
Fig. 1 is that luminescent material and the comparative example luminescent material that the embodiment of the present invention 2 makes is the luminescent spectrum comparison diagram under the cathode-ray exciting under 3KV at acceleration voltage; Wherein, curve 1 is the Y that is mixed with metal nanoparticle Ag of the present embodiment 2 preparations 1.9eu 0.1sn 2o 7@Ag 2.5 * 10the luminescent spectrum of-4 luminescent materials, curve 2 is Y that comparative example is not mixed with metal nanoparticle Ag 1.9eu 0.1sn 2o 7the 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 Y 1.98eu 0.02sn 2o 7@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, the above-mentioned colloidal sol of 4mL 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 ℃ of reaction 36h, prepare the solution that contains C@Pd, this solution of centrifugation obtains solid formation, with deionized water and dehydrated alcohol, wash respectively 2 times, and dry at 60 ℃, obtain C@Pd carbon ball template.
According to Y 1.98eu 0.02sn 2o 7stoichiometric ratio measure 7.92mL1mol/L Y (NO 3) 3solution, 8mL0.01mol/L Eu (NO 3) 3solution and 8mL1mol/L SnCl 4solution, in beaker, then adds C@Pd carbon ball template 4.8mg, and heating in water bath at 80 ℃ stirs 0.5h.Then slowly add 15mL1mol/L precipitation agent ammonium oxalate (NH 4) 2c 2o 4solution, at 80 ℃ of water bath heat preservation 6h.Filter, washing, dry, obtain Y 1.98eu 0.02sn 2(C 2o 4) 7@C@Pd 1 * 10-5 presomas.
Presoma is ground, be put in retort furnace in air in 1200 ℃ of calcining 10h, furnace cooling is cooled to room temperature, and resulting sample is ground to powder, obtains being mixed with the Y of metal nanoparticle 1.98eu 0.02sn 2o 7@Pd 1 * 10-5 luminescent materials.
Embodiment 2
The precipitator method are prepared Y 1.9eu 0.1sn 2o 7@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, the above-mentioned colloidal sol of 5mL 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 ℃ of reaction 24h, prepare the solution that contains C@Ag, this solution of centrifugation obtains solid formation, with deionized water and dehydrated alcohol, wash respectively 2 times, and dry at 60 ℃, obtain C@Ag carbon ball template.
According to Y 1.9eu 0.1sn 2o 7stoichiometric ratio measure 7.6mL1mol/L Y (NO 3) 3solution, 4mL0.1mol/L Eu (NO 3) 3solution and 8mL1mol/L SnCl 4solution, in beaker, then adds C@Ag carbon ball template 240mg, and heating in water bath at 60 ℃ stirs 1h.Then slowly add 15mL1mol/L precipitation agent ammonium oxalate (NH 4) 2c 2o 4solution, at 60 ℃ of water bath heat preservation 3h.Filter, washing, dry, obtain Y 1.9eu 0.1sn 2(C 2o 4) 7@C@Ag 2.5 * 10-4 presomas.
Presoma is ground, be put in retort furnace in air in 1400 ℃ of calcining 5h, furnace cooling is cooled to room temperature, and resulting sample is ground to powder, obtains being mixed with the Y of metal nanoparticle 1.9eu 0.1sn 2o 7@Ag 2.5 * 10-4 luminescent materials.
Fig. 1 is that luminescent material and the comparative example luminescent material that the embodiment of the present invention 2 makes is the luminescent spectrum comparison diagram under the cathode-ray exciting under 3KV at acceleration voltage; Wherein, curve 1 is the Y that is mixed with metal nanoparticle Ag of the present embodiment 2 preparations 1.9eu 0.1sn 2o 7@Ag 2.5 * 10the luminescent spectrum of-4 luminescent materials, curve 2 is the Y that are not mixed with metal nanoparticle Ag 1.9eu 0.1sn 2o 7the luminescent spectrum of luminescent material.
As can be seen from Figure 1, the emission peak at 580nm place, the luminous intensity of luminescent material prepared by the present embodiment has strengthened 25%.
Embodiment 3
The precipitator method are prepared Y 1.5eu 0.5sn 2o 7@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, the above-mentioned colloidal sol of 10mL 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 ℃ of reaction 10h, prepare the solution that contains C@Pt, this solution of centrifugation obtains solid formation, with deionized water and dehydrated alcohol, wash respectively 2 times, and dry at 70 ℃, obtain C@Pt carbon ball template.
According to Y 1.5eu 0.5sn 2o 7stoichiometric ratio measure 3mL2mol/L Y (CH 3cOO) 3solution, 2mL1mol/L Eu (CH 3cOO) 3solution and 16mL0.5mol/L SnCl 4solution, in beaker, then adds C@Pt carbon ball template 480mg, and heating in water bath at 50 ℃ stirs 2h.Then slowly add 15mL1mol/L precipitation agent ammonium oxalate (NH 4) 2c 2o 4solution, at 50 ℃ of water bath heat preservation 6h.Filter, washing, dry, obtain Y 1.5eu 0.5sn 2(C 2o 4) 7@C@Pt 5 * 10-3 presomas.
Presoma is ground, be put in retort furnace in air in 1300 ℃ of calcining 15h, furnace cooling is cooled to room temperature, and resulting sample is ground to powder, obtains being mixed with the Y of metal nanoparticle 1.5eu 0.5sn 2o 7@Pt 5 * 10-3 luminescent materials.
Embodiment 4
The precipitator method are prepared Gd 1.0eu 1.0sn 2o 7@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: take 0.0057g g sucrose dissolved and prepare the alcoholic solution of sucrose in the dehydrated alcohol of 24mL, the above-mentioned colloidal sol of 16mL 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 ℃ of reaction 20h, prepare the solution that contains C@Au, this solution of centrifugation obtains solid formation, with deionized water and dehydrated alcohol, wash respectively 3 times, and dry at 80 ℃, obtain C@Au carbon ball template.
Take 24.7262g Gd 2(CO 3) 3be dissolved in the Gd (NO that nitric acid obtains 100mL1mol/L 3) 3solution; Take 48.3800g Eu 2(CO 3) 3be dissolved in the Eu (NO that nitric acid obtains 100mL2mol/L 3) 3solution.According to Gd 1.0eu 1.0sn 2o 7stoichiometric ratio measure 4mL1mol/L Gd (NO 3) 3solution, 2mL2mol/L Eu (NO 3) 3solution and 8mL1mol/L SnCl 4solution, in beaker, then adds C@Au carbon ball template 1.2mg, and heating in water bath at 70 ℃ stirs 1h.Then slowly add 15mL 1mol/L precipitation agent ammonium oxalate (NH 4) 2c 2o 4solution, at 70 ℃ of water bath heat preservation 2h.Filter, washing, dry, obtain Gd 1.0eu 1.0sn 2(C 2o 4) 7@C@Au 1 * 10-2 presomas.
Presoma is ground, be put in retort furnace in air in 1200 ℃ of calcining 24h, furnace cooling is cooled to room temperature, and resulting sample is ground to powder, obtains being mixed with the Gd of metal nanoparticle 1.0eu 1.0sn 2o 7@Au 1 * 10-2 luminescent materials.
Embodiment 5
The precipitator method are prepared La 0.5eu 1.5sn 2o 7@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: take 0.1426g sucrose dissolved and prepare the alcoholic solution of sucrose in the dehydrated alcohol of 39.5mL, the above-mentioned colloidal sol of 0.5mL 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 ℃ of reaction 5h, prepare the solution that contains C@Cu, this solution of centrifugation obtains solid formation, with deionized water and dehydrated alcohol, wash respectively 2 times, and solid formation is dry at 75 ℃, obtain C@Cu carbon ball template.
Take 16.2898g La 2o 3be dissolved in the La (NO that nitric acid obtains 100mL1mol/L 3) 3solution; Take 17.5950g Eu 2o 3be dissolved in the Eu (NO that nitric acid obtains 100mL1mol/L 3) 3solution.According to La 0.5eu 1.5sn 2o 7stoichiometric ratio measure 4mL0.5mol/L La (NO 3) 3solution, 6mL1mol/L Eu (NO 3) 3solution and 20mL0.4mol/L SnCl 4solution, in beaker, then adds C@Cu carbon ball template 120mg, and heating in water bath at 65 ℃ stirs 1h.Then slowly add 15mL1mol/L precipitation agent ammonium oxalate (NH 4) 2c 2o 4solution, at 75 ℃ of water bath heat preservation 2h.Filter, washing, dry, obtain La 0.5eu 1.5sn 2(C 2o 4) 7@C@Cu 1 * 10-4 presomas.
Presoma is ground, be put in retort furnace in air in 1200 ℃ of calcining 12h, furnace cooling is cooled to room temperature, and resulting sample is ground to powder, obtains being mixed with the La of metal nanoparticle 0.5eu 1.5sn 2o 7@Cu 1 * 10-4 luminescent materials.
Embodiment 6
The precipitator method are prepared La 1.5eu 0.5sn 2o 7@(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 2o) and 2.5mg Silver Nitrate (AgNO 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): take 0.7131g sucrose dissolved and prepare the alcoholic solution of sucrose in the dehydrated alcohol of 30mL, the above-mentioned colloidal sol of 10mL 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 ℃ of reaction 15h, prepare the solution that contains C@(Ag/Au), this solution of centrifugation obtains solid formation, with deionized water and dehydrated alcohol, wash respectively 2 times, and dry at 80 ℃, obtain C@(Ag/Au).Take 5.705g sucrose dissolved and in dehydrated alcohol, obtain the sucrose alcohol solution of 40mL, this solution is proceeded in 50mL band teflon-lined reactor, after adding a cover and screwing, in 140 ℃ of reaction 15h, prepare the solution of carbon bead, this solution of centrifugation obtains solid formation, with deionized water and dehydrated alcohol, washs respectively 2 times, and dry at 80 ℃, obtain carbon bead.Take 5.705g sucrose dissolved and in dehydrated alcohol, obtain the sucrose alcohol solution of 40mL, this solution is proceeded in 50mL band teflon-lined reactor, after adding a cover and screwing, in 140 ℃ of reaction 15h, prepare the solution of carbon bead, this solution of centrifugation obtains solid formation, with deionized water and dehydrated alcohol, washs respectively 2 times, and dry at 80 ℃, obtain C@(Ag/Au) carbon ball template.
According to La 1.5eu 0.5sn 2o 7stoichiometric ratio measure 30mL0.2mol/L La (NO 3) 3solution, 2mL1mol/L Eu (NO 3) 3solution and 4mL2mol/L SnCl 4solution, in beaker, then adds C@(Ag/Au) carbon ball template 150mg, and heating in water bath at 60 ℃ stirs 0.5h.Then slowly add 15mL1mol/L precipitation agent ammonium oxalate (NH 4) 2c 2o 4solution, at 70 ℃ of water bath heat preservation 3h.Filter, washing, dry, obtain La 1.5eu 0.5sn 2(C 2o 4) 7@C@(Ag 0.5/ Au 0.5) 1.25 * 10-3 presomas.
Presoma is ground, be put in retort furnace in air in 1500 ℃ of calcining 2h, furnace cooling is cooled to room temperature, and resulting sample is ground to powder, obtains being mixed with the La of metal nanoparticle 1.5eu 0.5sn 2o 7@(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 metal nano particle-doped stannate luminescent material, is characterized in that, its chemical general formula is: Ln 2-xeu xsn 2o 7@M y, wherein, Ln 2-xeu xsn 2o 7for shell, M is kernel, and@represents to be coated; M is metal nano particle-doped, be selected from least one in Ag, Au, Pt, Pd, Cu metal nanoparticle, x is the mole number that Eu atom replaces Ln atom, and Ln is a kind of in Gd, Y, La, the span of x is 0<x≤1.5, and y is M and Ln 2-xeu xsn 2o 7mole ratio, the span of y is 0 < y≤1 * 10 -2.
2. metal nano particle-doped stannate luminescent material according to claim 1, is characterized in that, the span of x is 0.02≤x≤1.0, and the span of y is 1 * 10 -5≤ y≤5 * 10 -3.
3. a preparation method for metal nano particle-doped stannate luminescent material, is characterized in that, comprises the steps:
By after the auxiliary agent and reductive agent hybrid reaction of the salts solution containing M, a dissemination, make M nanometer particle colloid solution;
In the ethanol solution of sucrose or glucose, add described M nanometer particle colloid solution, obtain mixing solutions, and by the described mixing solutions obtaining confined reaction at 120～200 ℃, make the solution that contains C@M, the solution that contains C@M described in centrifugation, obtains C@M carbon ball template after the solid phase obtaining is washed, is dried; Wherein ,@represents that C is coated M, and the mol ratio of M nanoparticle and C@M carbon ball template is 1 * 10 -6: 1～0.4:1;
According to Ln 2-xeu xsn 2o 7@M yin each element chemistry metering ratio, measure each self-corresponding salts solution of Ln, Sn and Eu, put into beaker, then add described C M carbon ball template, at 50 ℃-80 ℃, heating in water bath stirs 0.5-2h; Then slowly add ammonium oxalate precipitation agent, and continue at 50 ℃ of-80 ℃ of water bath heat preservation 1h-6h, subsequent filtration, washing, dry sediment, obtain Ln 2-xeu xsn 2(C 2o 4) 7@C@M ypresoma wherein, C@M carbon ball template and Ln 2-xeu xsn 2o 7mol ratio be 0.025:1～10:1;
Described presoma is ground, grind powder and be put in air atmosphere in 1200 ℃～1500 ℃ calcining 2～24h, furnace cooling is cooled to room temperature, and resulting sample is ground to powder, and obtaining chemical general formula is Ln 2-xeu xsn 2o 7@M ymetal nano particle-doped stannate luminescent material;
In above-mentioned steps, Ln 2-xeu xsn 2o 7for shell, M is kernel, and@represents to be coated; M is metal nano particle-doped, be selected from least one in Ag, Au, Pt, Pd, Cu metal nanoparticle, x is the mole number that Eu atom replaces Ln atom, and Ln is a kind of in Gd, Y, La, the span of x is 0<x≤1.5, and y is M and Ln 2-xeu xsn 2o 7mole ratio, the span of y is 0 < y≤1 * 10 -2.
4. the preparation method of metal nano particle-doped stannate luminescent material 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, and the content of the addition of described auxiliary agent in the M nanometer particle colloid solution finally obtaining is 1 * 10 -4g/mL～5 * 10 -2g/mL.
5. the preparation method of metal nano particle-doped stannate luminescent material according to claim 3, it is characterized in that, described reductive agent is at least one in hydrazine hydrate, xitix, Trisodium Citrate or sodium borohydride, and the mol ratio of described reductive agent and M is 0.5:1～10:1.
6. the preparation method of metal nano particle-doped stannate luminescent material according to claim 3, is characterized in that, the time that contains salts solution, auxiliary agent and the reductive agent hybrid reaction of M is 10～45min.
7. the preparation method of metal nano particle-doped stannate luminescent material according to claim 3, is characterized in that, the confined reaction of sucrose or glucose and M nanometer particle colloid carries out in being with teflon-lined reactor.
8. the preparation method of metal nano particle-doped stannate luminescent material according to claim 3, is characterized in that, the mole dosage of described ammonium oxalate precipitation agent is to guarantee the precipitation complete and excessive 25% of Ln, Sn and Eu ion.
9. the preparation method of metal nano particle-doped stannate luminescent material according to claim 3, is characterized in that, each self-corresponding salts solution of Ln and Eu is respectively Ln (NO 3) 3solution and Eu (NO 3) 3solution, the salts solution of Sn is SnCl 4solution.
10. the preparation method of metal nano particle-doped stannate luminescent material according to claim 3, is characterized in that, the span of x is 0.02≤x≤1.0, and the span of y is 1 * 10 -5≤ y≤5 * 10 -3.
CN201310089546.4A 2013-03-20 2013-03-20 Metal nanoparticle-doped stannate luminescent material and preparation method thereof Pending CN104059656A (en)

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Application publication date: 20140924