CN103849395A - Lanthanum aluminate luminescent material and preparation method thereof - Google Patents
Lanthanum aluminate luminescent material and preparation method thereof Download PDFInfo
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- CN103849395A CN103849395A CN201210499960.8A CN201210499960A CN103849395A CN 103849395 A CN103849395 A CN 103849395A CN 201210499960 A CN201210499960 A CN 201210499960A CN 103849395 A CN103849395 A CN 103849395A
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Abstract
The invention belongs to the field of luminescent materials and discloses a lanthanum aluminate luminescent material and a preparation method thereof. The lanthanum aluminate luminescent material has a general molecular formula of La1-x-yReyLnxAlO3@Mz; and in the general molecular formula, Ln represents at least one of Tm, Tb, Sm and Eu, Re represents Y, Gd or Lu, M represents at least one of Ag, Au, Pt, Pd and Cu nanoparticles, @ represents coating, the M metal nanoparticle is used as a core, and La1-x-yReyLnxAlO3 is used as a shell. Through use of the M metal nanoparticles, the luminescence efficiency of the lanthanum aluminate luminescent material is greatly improved under the same excitation condition and emitted light wavelength is not changed. The lanthanum aluminate luminescent material has good luminescence performances and color purity and brightness of the excited emitted light are high. The lanthanum aluminate luminescent material can be used in a field emission device.
Description
Technical field
The present invention relates to field of light emitting materials, relate in particular to a kind of lanthanum aluminate light-emitting material and preparation method thereof.
Background technology
Feds is because its running voltage is low in recent years, power consumption is little, do not need deflector coil, without X-radiation, the advantage such as radioprotective and magneticinterference and receiving much concern, field-transmitting cathode and luminescent material be in conjunction with the field emission light source that can obtain high brightness, high colour developing, can apply and the field such as demonstration, various instruction, general lighting.One of key factor of preparing premium properties feds is the preparation of high-performance fluorescent powder.The fluorescent material that feds adopts is at present mainly some sulfide series for conventional cathode ray tube and projection TV teletron, oxide compound series and oxysulfide series phosphor powder.These fluorescent material, the poor and brightness irregularities of photochromic purity that luminescent material sends, and also luminous efficiency is lower.
Summary of the invention
Based on the problems referred to above, problem to be solved by this invention is to provide a kind of light high color purity, brightness even, and the higher lanthanum aluminate light-emitting material of luminous efficiency.
Technical scheme of the present invention is as follows:
A kind of lanthanum aluminate light-emitting material, its general molecular formula is: La
1-x-yre
yln
xalO
3@M
z; Wherein, Ln is at least one in Tm, Tb, Sm and Eu, and Re is Y, Gd or Lu, and M is at least one in Ag, Au, Pt, Pd and Cu metal nanoparticle, and@represents to be coated, and metal nanoparticle M is kernel, La
1-x-yre
yln
xalO
3for shell, the span of x is 0 < x≤0.2, the span of y is 1-x 0 ~ 0.2 times, z is metal nanoparticle M and La
1-x-yre
yln
xalO
3mole ratio, the span of z is 0 < z≤1 × 10
-2.
Described lanthanum aluminate light-emitting material, preferably, it is 0.001≤x≤0.1 that the value of x is enclosed; The span of y is 1 × 10
-5≤ x≤5 × 10
-3.
Described lanthanum aluminate light-emitting material, preferably, M is that mol ratio is Ag and the Au of 1:1.
The present invention also provides a kind of preparation method of lanthanum aluminate light-emitting material, comprises the steps:
S1, will be containing making M nanometer particle colloid after salts solution, auxiliary agent and the reductive agent hybrid reaction of M; Wherein, the mol ratio of the addition of reductive agent and M ion is 0.5:1～10:1; 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;
S2, sucrose or glucose are dissolved in dehydrated alcohol, the described M nanometer particle colloid that adds again step S1 to make, obtain mixing solutions, again described mixing solutions is proceeded in sealed reactor, and at 120-200 DEG C of reaction 5-36h, prepare the carbon bead solution of coated M nanoparticle, then use deionized water and absolute ethanol washing repeatedly, centrifugation, 60-100 DEG C is dry, obtains the carbon bead template of coated M nanoparticle;
S3, according to chemical general formula La
1-x-yre
yln
xalO
3@M
zin each element chemistry metering ratio, nitrate solution corresponding to La, Re, Ln and Al provide respectively, add subsequently the carbon bead template of the described coated M nanoparticle that step S2 makes, stir, obtain precursor solution; Then presoma is joined in ammonium bicarbonate precipitation agent slowly, regulating pH value be 8-10, filters after reacting 2-6h under magnetic agitation, and by product use deionized water and absolute ethanol washing repeatedly, suction filtration, at 60 ~ 100 DEG C of oven dry throw outs; And to described throw out successively thermal pretreatment 0.5 ~ 6h at 600 ~ 900 DEG C, and calcination processing 0.5 ~ 5h at 1200～1500 DEG C, cooling, grinding, making chemical general formula is La
1-x-yre
yln
xalO
3@M
zlanthanum aluminate light-emitting material;
In above-mentioned steps, Ln is at least one in Tm, Tb, Sm and Eu, and Re is Y, Gd or Lu, and M is at least one in Ag, Au, Pt, Pd and Cu metal nanoparticle, and@represents to be coated, and metal nanoparticle M is kernel, La
1-x-yre
yln
xalO
3for shell, the span of x is 0 < x≤0.2, the span of y is 1-x 0 ~ 0.2 times, z is metal nanoparticle M and La
1-x-yre
yln
xalO
3mole ratio, the span of z is 0 < z≤1 × 10
-2.
The preparation method of described lanthanum aluminate light-emitting material, in step S1, the concentration that contains the salts solution of M is 1 × 10
-4mol/L～1 × 10
-2mol/L.
The preparation method of described lanthanum aluminate light-emitting material, in step S1, auxiliary agent is polyethylene arsenic pyrrolidone, Trisodium Citrate, cetyl trimethylammonium bromide, sodium lauryl sulphate or sodium laurylsulfonate; Described reductive agent is hydrazine hydrate, xitix, Trisodium Citrate or sodium borohydride.
The preparation method of described lanthanum aluminate light-emitting material, in step S1, the time of described hybrid reaction is 10min～45min.
The preparation method of described lanthanum aluminate light-emitting material, in step S2, the mol ratio of the M nanoparticle adding and carbon bead template is 1 × 10
-6: 1 ~ 0.4:1.
The preparation method of described lanthanum aluminate light-emitting material, in step S3, the concentration of the nitrate solution that La, Re, Ln and Al are corresponding is 0.01mol/L～5mol/L; La, Re, Ln and Al nitrate solution can be also that the each self-corresponding oxide compound of La, Re, Ln and Al is dissolved in nitric acid acquisition.
The preparation method of described lanthanum aluminate light-emitting material, the span of x is 0.001≤x≤0.1; The span of y is 1 × 10
-5≤ x≤5 × 10
-3.
In lanthanum aluminate light-emitting material provided by the invention, owing to having introduced M metal nanoparticle, the luminous efficiency of lanthanum aluminate light-emitting material under same shooting conditions is greatly improved, and radiative wavelength does not change; This lanthanum aluminate light-emitting material 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 lanthanum aluminate 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.
The preparation method of lanthanum aluminate light-emitting 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.
Brief description of the drawings
Fig. 1 is preparation technology's schema of lanthanum aluminate light-emitting material of the present invention;
Fig. 2 is that lanthanum aluminate light-emitting material prepared by embodiment 4 is the luminescent spectrum comparison diagram under the cathode-ray exciting under 3kV with contrast luminescent material at acceleration voltage; Wherein, curve 1 is lanthanum aluminate light-emitting material prepared by embodiment 4: the La of clad metal nano particle Ag
0.99tm
0.01alO
3@Ag
2.5 × 10-
4luminescent spectrum, curve 2 be contrast luminescent material: the not La of clad metal nano particle
0.99tm
0.01alO
3luminescent spectrum.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearer, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
Lanthanum aluminate light-emitting material provided by the invention, its general molecular formula is: La
1-x-yre
yln
xalO
3@M
z; Wherein, Ln is at least one in Tm, Tb, Sm and Eu, and Re is Y, Gd or Lu, and M is at least one in Ag, Au, Pt, Pd and Cu metal nanoparticle, and@represents to be coated, and metal nanoparticle M is kernel, La
1-x-yre
yln
xalO
3for shell, the span of x is 0 < x≤0.2, the span of y is 1-x 0 ~ 0.2 times, z is metal nanoparticle M and La
1-x-yre
yln
xalO
3mole ratio, the span of z is 0 < z≤1 × 10
-2.
In lanthanum aluminate light-emitting material, preferably, the span of x is 0.001≤x≤0.1; The span of y is 1 × 10
-5≤ x≤5 × 10
-3.
In lanthanum aluminate light-emitting material, M is the one in Ag, Au, Pt, Pd and Cu metal nanoparticle, also can be wherein two or more, can be that mol ratio is the Ag of 1: 1 and Au, also can is that mol ratio is Ag and the Au of 2:3, can also be that mol ratio is Pd and the Pt of 3:7, can also be that mol ratio is Ag, Au and the Pt etc. of 1:4:5; Preferably, M is that mol ratio is Ag and the Au of 1:1.
At lanthanum aluminate light-emitting material La
1-x-yre
yln
xalO
3@M
zin, Re can be Y, Gd or Lu; Re also can not exist, and y is 0, and now, the general molecular formula of lanthanum aluminate light-emitting material is La
1-xln
xalO
3@M
z.
In lanthanum aluminate light-emitting material provided by the invention, owing to having introduced M metal nanoparticle, the luminous efficiency of lanthanum aluminate light-emitting material under same shooting conditions is greatly improved, and radiative wavelength does not change; This lanthanum aluminate light-emitting material 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 lanthanum aluminate 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.
The preparation method of lanthanum aluminate light-emitting material of the present invention, as shown in Figure 1, comprises the steps:
S1, will be containing making M nanometer particle colloid after salts solution, auxiliary agent and the reductive agent hybrid reaction of M; Wherein, the mol ratio of the addition of reductive agent and M ion is 0.5:1～10:1; 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;
S2, take sucrose or glucose is dissolved in dehydrated alcohol, the M nanometer particle colloid that adds again step S1 to make, solution is proceeded in 50mL band teflon-lined reactor, add a cover and screw, at 120-200 DEG C of reaction 5-36h, prepare the carbon bead solution of coated M nanoparticle, then use deionized water and absolute ethanol washing repeatedly, centrifugation, the 60-100 DEG C of dry carbon bead template (C M) that obtains clad metal nano particle;
S3, according to chemical general formula La
1-x-yre
yln
xalO
3@M
zin each element chemistry metering ratio, nitrate solution corresponding to La, Re, Ln and Al provide respectively, then add the carbon bead template of the coated M nanoparticle that step S2 makes, stir, obtain precursor solution; Precursor solution is joined in sodium bicarbonate precipitation agent slowly, regulating pH value is 8-10, under magnetic agitation, react 2-6h, product is used to deionized water and absolute ethanol washing repeatedly, and suction filtration, dries throw outs at 60 ~ 100 DEG C, to above-mentioned throw out successively thermal pretreatment 0.5 ~ 6h at 600 ~ 900 DEG C, and calcination processing 0.5 ~ 5h at 1200 ~ 1500 DEG C, cooling, grinding, making chemical general formula is La
1-x-yre
yln
xalO
3@M
zlanthanum aluminate light-emitting material; Wherein, thermal pretreatment is carried out under air atmosphere, and calcination processing can be carried out under air atmosphere or reduction atmosphere;
In above-mentioned steps, Ln is at least one in Tm, Tb, Sm and Eu, and Re is Y, Gd or Lu, and M is at least one in Ag, Au, Pt, Pd and Cu metal nanoparticle, and@represents to be coated, and metal nanoparticle M is kernel, La
1-x-yre
yln
xalO
3for shell, the span of x is 0 < x≤0.2, the span of y is 1-x 0 ~ 0.2 times, z is metal nanoparticle M and La
1-x-yre
yln
xalO
3mole ratio, the span of z is 0 < z≤1 × 10
-2.
The preparation method of above-mentioned lanthanum aluminate light-emitting material, in step S1, the concentration that contains the salts solution of M is 1 × 10
-4mol/L～1 × 10
-2mol/L.
The preparation method of above-mentioned lanthanum aluminate light-emitting material, in step S1, 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 metal nanometer particle colloid finally obtaining is 1 × 10
-4g/mL～5 × 10
-2g/mL.
The preparation method of above-mentioned lanthanum aluminate light-emitting material, in step S1, reductive agent is at least one in hydrazine hydrate, xitix, Trisodium Citrate or sodium borohydride; In the present embodiment, one of reductive agent adopts solution state, and preparing or be diluted to concentration by reductive agent is 1 × 10
-4the aqueous solution of mol/L～1mol/L, the addition of reductive agent and the mol ratio of metal ion are 3.6:1～18:1.
The preparation method of above-mentioned lanthanum aluminate light-emitting material, in step S1, obtains under the prerequisite of M nanometer particle colloid in guarantee, and for energy efficient, this step hybrid reaction time is preferably 10min～45min.
The preparation method of above-mentioned lanthanum aluminate light-emitting material, in step S2, the mol ratio of the M nanoparticle adding and carbon bead template is 1 × 10
-6: 1 ~ 0.4:1.
The preparation method of above-mentioned lanthanum aluminate light-emitting material, in step S3, the nitrate solution that La, Re, Ln and Al are corresponding is to adopt following steps to make:
Oxide compound corresponding to La, Re, Ln and Al is dissolved in to salpeter solution, obtains each self-corresponding nitrate solution; And the concentration of the nitrate solution that La, Re, Ln and Al are corresponding is 0.01mol/L～5mol/L.
The preparation method of above-mentioned lanthanum aluminate light-emitting material, preferably, the span of x is 0.001≤x≤0.1; The span of y is 1 × 10
-5≤ x≤5 × 10
-3.
The preparation method of above-mentioned lanthanum aluminate light-emitting material, M is the one in Ag, Au, Pt, Pd and Cu metal nanoparticle, also can be wherein two or more, can be that mol ratio is the Ag of 1:1 and Au, also can is that mol ratio is Ag and the Au of 2:3, can also be that mol ratio is Pd and the Pt etc. of 3:7, can also be that mol ratio is Ag, Au and the Pt etc. of 1:4:5; Preferably, M is that mol ratio is Ag and the Au of 1:1.
Below in conjunction with accompanying drawing, preferred embodiment of the present invention is described in further detail.
Embodiment 1:La
0.999tm
0.001alO
3@Pd
1 × 10-
5:
The preparation of Pd nano particle colloidal sol: take 0.22mg Palladous chloride (PdCl
22H
2o) be dissolved in the deionized water of 10mL; After Palladous chloride dissolves completely, take 11.0mg Trisodium Citrate and 4.0mg sodium lauryl sulphate, and be dissolved in palladium chloride aqueous solution under the environment of magnetic agitation; Take 0.38mg sodium borohydride molten in 100mL deionized water, obtaining concentration is 1 × 10
-4the sodium borohydride reduction liquid of mol/L; Under the environment of magnetic agitation, in palladium chloride aqueous solution, add fast 10mL 1 × 10
-4the sodium borohydride aqueous solution of mol/L, continues reaction 20min afterwards, and obtaining 20mL Pd content is 5 × 10
-5the Pd nano particle colloidal sol of mol/L.
The glucose that takes 6.005g is dissolved in dehydrated alcohol, add again above-mentioned Pd metal nanometer particle colloid 4mL, solution is proceeded in 50mL band teflon-lined reactor, add a cover and screw, at 120 DEG C of reaction 36h, prepare the carbon bead solution of coated Pd nanoparticle, with deionized water and absolute ethanol washing repeatedly, centrifugation, 60 DEG C of dry carbon bead templates that obtain coated Pd nanoparticle, in order to stand-by;
According to La
0.999tm
0.001alO
3@Pd
1 × 10-
5in each element chemistry metering ratio, take 8.1378g La
2o
3, 2.5490g Al
2o
3tm with 0.0096g
2o
3be dissolved in nitric acid, be mixed with the solution of 250mL 0.2mol/L, then pipette above-mentioned solution 20mL in beaker with transfer pipet, after stirring, add the carbon bead template of the clad metal nano particle of 0.48g, stir, obtain precursor solution.Precursor solution is slowly added drop-wise in 25mL 0.5mol/L precipitation agent ammonium bicarbonate soln, and then adopts ammoniacal liquor to regulate pH value to 9, under magnetic agitation, react 2h, product is used to deionized water and absolute ethanol washing repeatedly, suction filtration, 60 DEG C of oven dry, collects and obtains precursor powder.To above-mentioned throw out prior to thermal pretreatment 6h at 600 DEG C, calcination processing 5h at lower 1200 DEG C of air atmosphere again after cooling grinding, cooling, grind, make described La
0.999tm
0.001alO
3@Pd
1 × 10-
5lanthanum aluminate light-emitting material
Embodiment 2:La
0.9y
0.05sm
0.05alO
3@Au
1 × 10-
2
The preparation of Au nano particle colloidal sol: take 41.2mg hydrochloro-auric acid (AuCl
3hCl4H
2o) be dissolved in the deionized water of 10mL; After hydrochloro-auric acid dissolves completely, take 14mg Trisodium Citrate and 6mg cetyl trimethylammonium bromide, and be dissolved in aqueous solution of chloraurate under the environment of magnetic agitation; Take 3.8mg sodium borohydride and 17.6mg xitix is dissolved into respectively in 10mL deionized water, obtaining 10mL concentration is 1 × 10
-2the sodium borohydride aqueous solution of mol/L and 10mL concentration are 1 × 10
-2the aqueous ascorbic acid of mol/L; Under the environment of magnetic agitation, first in aqueous solution of chloraurate, add 5mL sodium borohydride aqueous solution, after stirring reaction 5min, in aqueous solution of chloraurate, add 5mL1 × 10 again
-2the aqueous ascorbic acid of mol/L, continues reaction 30min afterwards, and obtaining 20mLAu content is 5 × 10
-3the Au nano particle colloidal sol of mol/L.
The sucrose that takes 0.0057g is dissolved in dehydrated alcohol, add again above-mentioned Au metal nanometer particle colloid 16mL, solution is proceeded in 50mL band teflon-lined reactor, add a cover and screw, at 160 DEG C of reaction 20h, prepare the carbon bead solution of coated Au nanoparticle, with deionized water and absolute ethanol washing repeatedly, centrifugation, 80 DEG C of dry carbon bead templates that obtain coated Au nanoparticle, in order to stand-by;
According to La
0.9y
0.05sm
0.05alO
3@Au
1 × 10-
2in each element chemistry metering ratio, pipette the La (NO of 9mL0.4mol/L with transfer pipet
3)
3solution, the Y (NO of 5mL 0.04mol/L
3)
3solution and 2mL 0.1mol/LSm (NO
3)
3solution, the Al (NO of 8mL 0.5mol/L
3)
3after solution stirs in beaker, add the carbon bead template of the clad metal nano particle of 1.2mg, stir, obtain precursor solution.Precursor solution is slowly added drop-wise in 25mL 1mol/L precipitation agent ammonia soln, and adopts ammoniacal liquor to regulate pH value to 10, under magnetic agitation, react 5h, product is used to deionized water and absolute ethanol washing repeatedly, suction filtration, 100 DEG C of oven dry, collects and obtains precursor powder.To above-mentioned throw out prior to thermal pretreatment 4h at 700 DEG C, calcination processing 0.5h at lower 1500 DEG C of air atmosphere again after cooling grinding, cooling, grind, make described La
0.9y
0.05sm
0.05alO
3@Au
1 × 10-
2lanthanum aluminate light-emitting material
Embodiment 3:La
0.7gd
0.1eu
0.2alO
3@Pt
5 × 10-
3:
The preparation of Pt nano particle colloidal sol: take 25.9mg Platinic chloride (H
2ptCl
66H
2o) be dissolved in the deionized water of 17mL; After Platinic chloride dissolves completely, take 400mg Trisodium Citrate and 600mg sodium laurylsulfonate, and be dissolved in chloroplatinic acid aqueous solution under the environment of magnetic agitation; Take 1.9mg sodium borohydride and be dissolved in 10mL deionized water, obtaining 10mL concentration is 5 × 10
-3the sodium borohydride aqueous solution of mol/L, prepare 10mL concentration is 5 × 10 simultaneously
-2the hydrazine hydrate solution of mol/L; Under the environment of magnetic agitation, first in chloroplatinic acid aqueous solution, drip 0.4mL sodium borohydride aqueous solution, stirring reaction 5min, and then drip 2.6mL 5 × 10 in chloroplatinic acid aqueous solution
-2the hydrazine hydrate solution of mol/L, continues reaction 40min afterwards, and obtaining 20mLPt content is 2.5 × 10
-3the Pt nano particle colloidal sol of mol/L.
The glucose that takes 0.015g is dissolved in dehydrated alcohol, add again Pt nanometer particle colloid 10mL, solution is proceeded in 50mL band teflon-lined reactor, add a cover and screw, at 150 DEG C of reaction 10h, prepare the carbon bead solution of coated Pt nanoparticle, use deionized water and absolute ethanol washing repeatedly, 70 DEG C of dry carbon bead templates that obtain coated Pt nanoparticle of centrifugation, in order to stand-by;
According to La
0.7gd
0.1eu
0.2alO
3@Pt
5 × 10-
3in each element chemistry metering ratio, pipette the La (NO of 0.56mL5mol/L with transfer pipet
3)
3solution, the Gd (NO of 4mL 0.1mol/L
3)
3solution and 4mL 0.2mol/LEu (NO
3)
3solution, the Al (NO of 8mL 0.5mol/L
3)
3after solution stirs in beaker, add the carbon bead template of the clad metal nano particle of 480mg, stir, obtain precursor solution.Precursor solution is slowly added drop-wise in 25mL 0.5mol/L precipitation agent ammonium bicarbonate soln, adopts ammoniacal liquor to regulate pH value to 8, under magnetic agitation, react 4h, product is used to deionized water and absolute ethanol washing repeatedly, suction filtration, 90 DEG C of oven dry, collects and obtains precursor powder.To above-mentioned throw out prior to thermal pretreatment 0.5h at 900 DEG C, calcination processing 4h at lower 1300 DEG C of air atmosphere again after cooling grinding, cooling, grind, make described La
0.7gd
0.1eu
0.2alO
3@Pt
5 × 10-
3lanthanum aluminate light-emitting material
Embodiment 4:La
0.99tm
0.01alO
3@Ag
2.5 × 10-
4:
The preparation of Ag nano particle colloidal sol: take 3.4mg Silver Nitrate (AgNO
3) be dissolved in the deionized water of 18.4mL; After Silver Nitrate dissolves completely, take 42mg Trisodium Citrate and be dissolved in silver nitrate aqueous solution under the environment of magnetic agitation; Take 5.7mg sodium borohydride molten in 10mL deionized water, obtaining 10mL concentration is 1.5 × 10
-2the sodium borohydride aqueous solution of mol/L; Under the environment of magnetic agitation, toward disposable 1.6mL1.5 × 10 that add in silver nitrate aqueous solution
-2the sodium borohydride aqueous solution of mol/L, continues reaction 10min afterwards, and obtaining 20mL Ag content is 1 × 10
-3the Ag nano particle colloidal sol of mol/L.
Taking the raw materials such as 3.003g glucose is dissolved in dehydrated alcohol, add again Ag nanometer particle colloid 5mL, solution is proceeded in 50mL band teflon-lined reactor, add a cover and screw, at 180 DEG C of reaction 24h, prepare the carbon bead solution of coated Ag nanoparticle, with deionized water and absolute ethanol washing repeatedly, centrifugation, 60 DEG C of dry carbon bead templates that obtain coated Ag nanoparticle, in order to stand-by;
According to La
0.99tm
0.01alO
3@Ag
2.5 × 10-
4in each element chemistry metering ratio, pipette the La (NO of 9.9mL0.4mol/L with transfer pipet
3)
3solution and 4mL 0.01mol/L Tm (NO
3)
3solution, the Al (NO of 8mL 0.5mol/L
3)
3after solution stirs in beaker, add the carbon bead template of the clad metal nano particle of 240mg, stir, obtain precursor solution.Precursor solution is slowly added drop-wise in 25mL 0.5mol/L precipitation agent ammonium bicarbonate soln, adopts ammoniacal liquor to regulate pH value to 9, under magnetic agitation, react 6h, product is used to deionized water and absolute ethanol washing repeatedly, suction filtration, 80 DEG C of oven dry, collects and obtains precursor powder.Prior to thermal pretreatment 2h at 800 DEG C, again in the lower 1400 DEG C of calcination processing 1h of air atmosphere, cooling, grind after cooling grinding to above-mentioned throw out, make described La
0.99tm
0.01alO
3@Ag
2.5 × 10-
4lanthanum aluminate light-emitting material
Fig. 2 is that lanthanum aluminate light-emitting material prepared by embodiment 4 is the luminescent spectrum comparison diagram under the cathode-ray exciting under 3kV with contrast luminescent material at acceleration voltage; Wherein, curve 1 is lanthanum aluminate light-emitting material prepared by embodiment 4: the La of clad metal nano particle Ag
0.99tm
0.01alO
3@Ag
2.5 × 10-
4luminescent spectrum, curve 2 be contrast luminescent material: the not La of clad metal nano particle
0.99tm
0.01alO
3luminescent spectrum.
From Fig. 2 can, go out the emission peak at 456nm place, after clad metal nano particle, the luminous intensity of luminescent material has strengthened 26% before more coated.
Embodiment 5:La
0.9tb
0.1alO
3@Cu
1 × 10-
4:
The preparation of Cu nano particle colloidal sol: take in the ethanol that 1.6mg cupric nitrate is dissolved into 16mL, after dissolving completely, stir while add 2mg PVP, then slowly splash into 0.4mg sodium borohydride molten to obtain in 10mL ethanol 1 × 10
-3the sodium borohydride alcoholic solution 4mL of mol/L, continues stirring reaction 10min, obtains 20mL 4 × 10
-4the Cu nanometer particle colloid of mol/L.
The sucrose that takes 0.1426g is dissolved in dehydrated alcohol, add again Cu nanometer particle colloid 5mL, solution is proceeded in 50mL band teflon-lined reactor, add a cover and screw, at 200 DEG C of reaction 5h, prepare the carbon bead solution of coated Cu nanoparticle, with deionized water and absolute ethanol washing repeatedly, centrifugation, 75 DEG C of dry carbon bead templates that obtain coated Cu nanoparticle, in order to stand-by;
According to La
0.9tb
0.1alO
3@Cu
1 × 10-
4in each element chemistry metering ratio, pipette the La (NO of 18.5mL0.4mol/L with transfer pipet
3)
3solution and 5mL 0.3mol/L Eu (NO
3)
3solution, the Al (NO of 2mL 2mol/L
3)
3after solution stirs in beaker, add the carbon bead template of the clad metal nano particle of 120mg, stir, obtain precursor solution.Precursor solution is slowly added drop-wise in 25mL 0.5mol/L precipitation agent ammonium bicarbonate soln, adopts ammoniacal liquor to regulate pH value to 9, under magnetic agitation, react 6h, product is used to deionized water and absolute ethanol washing repeatedly, suction filtration, 70 DEG C of oven dry, collects and obtains precursor powder.To above-mentioned throw out prior to thermal pretreatment 3h at 700 DEG C, after cooling grinding again in 95v%N
2+ 5v%H
2the lower 1300 DEG C of calcination processing 4h of reducing atmosphere, cooling, grind, make described La
0.
9tb
0.
1alO
3@Cu
1×
10-
4lanthanum aluminate light-emitting material.
Embodiment 6:La
0.65lu
0.2tb
0.15alO
3@(Ag
0.5/ Au
0.5)
1.25 × 10-
3:
Ag
0.5/ Au
0.5the preparation of nano particle colloidal sol: take 6.2mg hydrochloro-auric acid (AuCl
3hCl4H
2and 2.5mgAgNO O)
3be dissolved in the deionized water of 28mL; After dissolving completely, take 22mg Trisodium Citrate and 20mgPVP, and under the environment of magnetic agitation, be dissolved in above-mentioned mixing solutions; Take freshly prepd 380mg sodium borohydride molten in 10mL deionized water, obtain the sodium borohydride aqueous solution that 10mL concentration is 1mol/L; Under the environment of magnetic agitation, toward the disposable sodium borohydride aqueous solution that adds 0.3mL1mol/L in above-mentioned mixing solutions, continue afterwards reaction 20min, obtaining the total metal concentration of 30mL is 1 × 10
-3the Ag/Au nano particle colloidal sol of mol/L.
The sucrose that takes 0.7131g is dissolved in dehydrated alcohol, add again Ag/Au nanoparticle glue 10mL, solution is proceeded in 50mL band teflon-lined reactor, add a cover and screw, at 140 DEG C of reaction 15h, prepare the carbon bead solution of coated Ag/Au nanoparticle, with deionized water and absolute ethanol washing repeatedly, centrifugation, 80 DEG C of dry carbon bead templates that obtain coated Ag/Au nanoparticle, in order to stand-by;
According to La
0.65lu
0.2tb
0.15alO
3@(Ag
0.5/ Au
0.5)
1.25 × 10-
3in each element chemistry metering ratio, pipette the Y (NO of 19.5mL 0.4mol/L with transfer pipet
3)
3solution and 3.2mL 0.1mol/L Eu (NO
3)
3solution, the Al (NO of 4mL1mol/L
3)
3after solution stirs in beaker, add the carbon bead template of the clad metal nano particle of 150mg, stir, obtain precursor solution.Precursor solution is slowly added drop-wise in 25mL0.5mol/L precipitation agent ammonium bicarbonate soln, adopts ammoniacal liquor to regulate pH value to 9, under magnetic agitation, react 3h, product is used to deionized water and absolute ethanol washing repeatedly, suction filtration, 75 DEG C of oven dry, collects and obtains precursor powder.To above-mentioned throw out prior to thermal pretreatment 1.5h at 800 DEG C, after cooling grinding again in pure H
2the lower 1300 DEG C of calcination processing 4h of reducing atmosphere, cooling, grinding, makes described La
0.65lu
0.2tb
0.15alO3@(Ag
0.5/ Au
0.5)
1.25 × 10-
3lanthanum aluminate light-emitting material.
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 lanthanum aluminate light-emitting material, is characterized in that, its general molecular formula is: La
1-x-yre
yln
xalO
3@M
z; Wherein, Ln is at least one in Tm, Tb, Sm and Eu, and Re is Y, Gd or Lu, and M is at least one in Ag, Au, Pt, Pd and Cu metal nanoparticle, and@represents to be coated, and metal nanoparticle M is kernel, La
1-x-yre
yln
xalO
3for shell, the span of x is 0 < x≤0.2, the span of y is 1-x 0 ~ 0.2 times, z is metal nanoparticle M and La
1-x-yre
yln
xalO
3mole ratio, the span of z is 0 < z≤1 × 10
-2.
2. lanthanum aluminate light-emitting material according to claim 1, is characterized in that, the span of x is 0.001≤x≤0.1; The span of y is 1 × 10
-5≤ x≤5 × 10
-3.
3. lanthanum aluminate light-emitting material according to claim 1, is characterized in that, M is that mol ratio is Ag and the Au of 1:1.
4. a preparation method for lanthanum aluminate light-emitting material, is characterized in that, comprises the steps:
S1, will be containing making M nanometer particle colloid after salts solution, auxiliary agent and the reductive agent hybrid reaction of M; Wherein, the mol ratio of the addition of reductive agent and M ion is 0.5:1～10:1; 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;
S2, sucrose or glucose are dissolved in dehydrated alcohol, the described M nanometer particle colloid that adds again step S1 to make, obtain mixing solutions, again described mixing solutions is proceeded in sealed reactor, and at 120-200 DEG C of reaction 5-36h, prepare the carbon bead solution of coated M nanoparticle, then use deionized water and absolute ethanol washing repeatedly, centrifugation, 60-100 DEG C is dry, obtains the carbon bead template of coated M nanoparticle;
S3, according to chemical general formula La
1-x-yre
yln
xalO
3@M
zin each element chemistry metering ratio, nitrate solution corresponding to La, Re, Ln and Al provide respectively, add subsequently the carbon bead template of the described coated M nanoparticle that step S2 makes, stir, obtain precursor solution; Then presoma is joined in ammonium bicarbonate precipitation agent slowly, regulating pH value be 8-10, filters after reacting 2-6h under magnetic agitation, and by product use deionized water and absolute ethanol washing repeatedly, suction filtration, at 60 ~ 100 DEG C of oven dry throw outs; And to described throw out successively thermal pretreatment 0.5 ~ 6h at 600 ~ 900 DEG C, and calcination processing 0.5 ~ 5h at 1200 ~ 1500 DEG C, cooling, grinding, making chemical general formula is La
1-x-yre
yln
xalO
3@M
zlanthanum aluminate light-emitting material;
In above-mentioned steps, Ln is at least one in Tm, Tb, Sm and Eu, and Re is Y, Gd or Lu, and M is at least one in Ag, Au, Pt, Pd and Cu metal nanoparticle, and@represents to be coated, and metal nanoparticle M is kernel, La
1-x-yre
yln
xalO
3for shell, the span of x is 0 < x≤0.2, the span of y is 1-x 0 ~ 0.2 times, z is metal nanoparticle M and La
1-x-yre
yln
xalO
3mole ratio, the span of z is 0 < z≤1 × 10
-2.
5. the preparation method of lanthanum aluminate light-emitting material according to claim 4, is characterized in that, in step S1, the concentration that contains the salts solution of M is 1 × 10
-4mol/L～1 × 10
-2mol/L.
6. the preparation method of lanthanum aluminate light-emitting material according to claim 4, is characterized in that, in step S1, auxiliary agent is polyethylene arsenic pyrrolidone, Trisodium Citrate, cetyl trimethylammonium bromide, sodium lauryl sulphate or sodium laurylsulfonate; Described reductive agent is hydrazine hydrate, xitix, Trisodium Citrate or sodium borohydride.
7. the preparation method of lanthanum aluminate light-emitting material according to claim 4, is characterized in that, in step S1, the time of described hybrid reaction is 10min～45min.
8. the preparation method of lanthanum aluminate light-emitting material according to claim 4, is characterized in that, in step S2, the mol ratio of the M nanoparticle adding and carbon bead template is 1 × 10
-6: 1 ~ 0.4:1.
9. the preparation method of lanthanum aluminate light-emitting material according to claim 4, is characterized in that, in step S3, the concentration of the nitrate solution that La, Re, Ln and Al are corresponding is 0.01mol/L ~ 5mol/L.
10. the preparation method of lanthanum aluminate light-emitting material according to claim 4, is characterized in that, the span of x is 0.001≤x≤0.1; The span of y is 1 × 10
-5≤ x≤5 × 10
-3.
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