CN102408892A - Titanate luminescent material and preparation method thereof - Google Patents
Titanate luminescent material and preparation method thereof Download PDFInfo
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- CN102408892A CN102408892A CN2010102925066A CN201010292506A CN102408892A CN 102408892 A CN102408892 A CN 102408892A CN 2010102925066 A CN2010102925066 A CN 2010102925066A CN 201010292506 A CN201010292506 A CN 201010292506A CN 102408892 A CN102408892 A CN 102408892A
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Abstract
The invention belongs to the field of luminescent materials, and discloses a titanate luminescent material and a preparation method thereof. The general chemical formula of the titanate luminescent material is as follows: M1TiO3.xPr.yM2, wherein M1 is selected from at least one of Ca, Sr and Ba, M2 is selected from at least one of Ag, Au, Pt and Pd nanoparticles, x is equal to 5*10<-5>-1*10<-2>, and y is equal to 5*10<-7>-1*10<-4>. The titanate luminescent material disclosed by the invention is simple in manufacturing processes and low in equipment requirements; and compared with the luminescent property of the fluorescent powder prepared without doping metal particles, the luminescent property of the fluorescent powder prepared by doping metal particles is greatly improved.
Description
Technical field
The present invention relates to field of light emitting materials, relate in particular to a kind of titanate luminescent material.The invention still further relates to a kind of preparation method of titanate luminescent material.
Background technology
The novel red long after glow luminous material CaTiO from 1997
3: Pr
3+Be applied to since FED (FED) field Pr
3+Adulterated titanates of alkali-earth metals MTiO
3: Pr
3+(wherein, M is at least a among Ca, Sr, the Ba) caused domestic and international investigators interest and concern greatly as a kind of FED red light material of great exploitation potential for its.
Research shows, MTiO
3: Pr
3+Chromaticity coordinates x=0.680, y=0.311, be the calcium titanium ore structure system of pure ruddiness.The wavelength of its emission peak is corresponding to Pr about 614nm
3+ 1D
2→
3H
4Conversion.Pr
3+Doped titanate MTiO
3, one side Pr
3+Get into parent lattice and replace Ca
2+, Sr
2+, Ba
2+Case forms the emitting red light center; On the other hand, Pr
3+To Ca
2+, Sr
2+, Ba
2+The non-equivalence electric charge replace to form different valency ion doping crystalline network, for keeping electroneutral, formed the positively charged ion hole in the lattice.In addition, have part Pr in the material prepn process
3+Oxidized generation Pr
4+, the electron trap center appears.These all make MTiO
3: Pr becomes a kind of red long afterglow material with good luminous performance.But, the disadvantage that this system exists at present be exactly luminosity not enough, if will be applied to lighting field, its luminous intensity is still waiting further raising.
Summary of the invention
In order to address the above problem, the present invention provides a kind of titanate luminescent material, and its chemical general formula is: M
1TiO
3XPryM
2Wherein, M
1At least a among Ca, Sr or the Ba, M
2At least a in Ag, Au, Pt or the Pd nano particle, the x value is 5 * 10
-5～1 * 10
-2, the y value is 5 * 10
-7～1 * 10
-4
The preparation method of the also above-mentioned titanate luminescent material of the present invention, preparation flow is following:
One, M
2The preparation of nano particle colloidal sol
1) with M
2Source compound, be dissolved in water or the alcohol solvent like Silver Nitrate, hydrochloro-auric acid, Platinic chloride, Palladous chloride, prepare to such an extent that contain M
2Ion solution; Wherein, M
2At least a among Ag, Au, Pt or the Pd;
2) be solvent with water or ethanol, Hydrazine Hydrate 80, xitix, Peng Qinghuana are solute, prepare reductant solution;
3) under the state of magnetic agitation, one or more surface treatment agent is dissolved into above-mentioned 1) in the solution, and to make surface treatment agent can be 5 * 10 at the content in the metal nanoparticle colloidal sol that finally obtains
-4G/mL～4 * 10
-3G/mL; Wherein, surface treatment agent is at least a in Vilaterm arsenic pyrrolidone (PVP), Trisodium Citrate, cetyl trimethylammonium bromide, sodium lauryl sulphate, the sodium laurylsulfonate;
4) under the environment of magnetic agitation, be 0.5: 1～4.8: 1 ratio in the ratio of reductive agent and the amount of substance of metals ion, toward above-mentioned 1) the resulting M that contains
2Adding above-mentioned 2 in the ion solution) reductant solution that obtains, whole system continue promptly to obtain M behind stirring reaction 10min～45min
2Nano particle colloidal sol.
Two, the preparation of titanate luminescent material
1) be solvent with absolute ethyl alcohol or deionized water, preparation Pr (NO
3)
3And Ca (NO
3)
2, Sr (NO
3)
2, Ba (NO
3)
2Solution;
2) press Pr
3+And Ca
2+, Sr
2+Or Ba
2+Ratio be 5 * 10
-5: 1～1 * 10
-2: 1 ratio, with Pr (NO
3)
3Solution and Ca (NO
3)
2, Sr (NO
3)
2Or Ba (NO
3)
2Solution mixes;
3) M that above-mentioned (one) step is prepared
2Nano particle colloidal sol join above-mentioned 2) in the mixed solution of gained, M
2Add-on be M
2With Ca
2+, Sr
2+Or Ba
2+Molar ratio be 5 * 10
-7: 1～1 * 10
-4: 1;
4) with Glacial acetic acid min. 99.5 or nitric acid with above-mentioned 3) pH regulator of the mixing solutions of gained is 1～6;
5) with the absolute ethyl alcohol be solvent, preparation tetrabutyl titanate ethanolic soln is pressed chemical general formula M
1TiO
3: Pr
3+(wherein, M
1At least a in Ca, Sr, the Ba ion) Ti and M in
1Stoichiometric ratio, under the mode of stirring at normal temperature, than toward above-mentioned 4) mixed solution in the dropwise adding tetrabutyl titanate ethanolic soln;
6) continue stirring reaction; Form the semi-gelled attitude until system; Then gel is put into that be 24h～36h time of drying in 80 ℃～120 ℃ the baking oven; Afterwards dry thing is put in the High Temperature Furnaces Heating Apparatus that the insulation calcination time is 3～8h under 900 ℃～1500 ℃ temperature, takes out to grind to obtain the titanate luminescent material.
Compared with prior art, the present invention has the following advantages:
A kind of rare earth ion doped titanate luminescent material provided by the invention, technology are made simply, equipment requirements is low, wide adaptability; Adopt Prepared by Sol Gel Method, can metal be incorporated in the titanate fluorescent powder preferably, make that the luminescent properties of titanate fluorescent powder greatly improves than the titanate fluorescent powder that does not have the gold doping metal particles behind the gold doping metal particles.
Description of drawings
Fig. 1 is preparation technology's schema of titanate luminescent material of the present invention;
Fig. 2 does not have gold doping to belong to the luminous spectrogram of cathode-ray exciting of the calcium titanate praseodymium of preparation for the calcium titanate praseodymium of mixing the Ag metal of embodiment 2 preparations with method, and TV is 3.0 kilovolts.
Fig. 3 does not have gold doping to belong to the luminous spectrogram of cathode-ray exciting of the calcium titanate praseodymium of preparation for the calcium titanate praseodymium of mixing the Ag metal of embodiment 3 preparations with method, and TV is 5.0 kilovolts.
Fig. 4 does not have gold doping to belong to the luminous spectrogram of cathode-ray exciting of the calcium titanate praseodymium of preparation for the calcium titanate praseodymium of mixing the Au metal of embodiment 4 preparations with method, and TV is 7.0 kilovolts.
Embodiment
The present invention provides a kind of titanate luminescent material, and its chemical general formula is: M
1TiO
3XPryM
2Wherein, M
1At least a among Ca, Sr or the Ba, M
2At least a in Ag, Au, Pt or the Pd nano particle, the x value is 5 * 10
-5～1 * 10
-2, the y value is 5 * 10
-7～1 * 10
-4
The preparation method of above-mentioned a kind of titanate luminescent material, as shown in Figure 1, preparation flow is following:
Step S 1, according to chemical general formula M
1TiO
3X PryM
2In the stoichiometric ratio of each element, M is provided
2Nano particle colloidal sol, source compound and the M of Pr
1Source compound; Wherein, M
1At least a among Ca, Sr or the Ba, M
2At least a in Ag, Au, Pt or the Pd nano particle, the x value is 5 * 10
-5～1 * 10
-2, the y value is 5 * 10
-7～1 * 10
-4
Step S2, with source compound and the M of said Pr
1Source compound be dissolved in respectively in ethanol or the water, be configured to contain the Pr ion solution and contain M
1Ion solution;
Step S3, with the Pr ion solution of above-mentioned configuration according to 5 * 10
-5: 1～1 * 10
-2: 1 molar ratio, add to and contain M
1In the ion solution; Add said M subsequently successively
2Nano particle colloidal sol and acid solution, and to make the pH value of this mixing solutions be 1～6, wherein, M
2With M
1Molar ratio is 5 * 10
-7: 1～1 * 10
-4: 1;
Step S4, according to chemical general formula M
1TiO
3X PryM
2Middle Ti and M
1Stoichiometric ratio, toward above-mentioned mixed solution and dripping tetrabutyl titanate ethanolic soln, stir, make gel;
Step S5, with said gel after drying treatment and calcination processing, cooling, grind, obtain said titanate luminescent material.
Among the above-mentioned steps S1, said M
2Nano particle colloidal sol adopt following step to make:
Step S11, with M
2Source compound be dissolved in ethanol or the water, be configured to M
2Ion solution; Preferably, M
2Source compound be a kind of in Silver Nitrate, hydrochloro-auric acid, Platinic chloride or the Palladous chloride;
Under the state of step S12, magnetic agitation, toward above-mentioned M
2Add surface treatment agent in the ion solution, make and contain M
2Ionic mixing solutions, and the M that this surface treatment agent is finally being obtained
2Content in the nano particle colloidal sol is 5 * 10
-4G/mL～4 * 10
-3G/mL; Preferably, surface treatment agent is at least a in Vilaterm arsenic pyrrolidone, Trisodium Citrate, cetyl trimethylammonium bromide, sodium lauryl sulphate, the sodium laurylsulfonate;
Step S13, the past above-mentioned M that contains
2Add reductant solution in the ionic mixing solutions, stir, make said M
2Nano particle colloidal sol; Wherein, in the reductant solution, reductive agent and M
2The ionic mol ratio is 0.5: 1～4.8: 1; Preferably, reductant solution is the ethanol or the aqueous solution of Hydrazine Hydrate 80, xitix, Peng Qinghuana.
Among the above-mentioned steps S2, the source compound of Pr and M
1Source compound be respectively Pr (NO
3)
3And Ca (NO
3)
2, Sr (NO
3)
2, Ba (NO
3)
2
In step S5, obtain a drying and calcining effect in order to make gel, preferred, the drying treatment temperature is 80～120 ℃, the drying treatment time is 24～36h; The calcination processing temperature is 900～1500 ℃, and calcination time is 3～8h.
Below in conjunction with accompanying drawing, further explain is done in preferred embodiment of the present invention.
Embodiment 1:
One, the preparation of Pt nano particle colloidal sol
Take by weighing 5.18mg Platinic chloride (H
2PtCl
66H
2O) be dissolved in the deionized water of 15.2mL; After Platinic chloride dissolves fully, take by weighing 8.0mg Trisodium Citrate and 12.0mg sodium laurylsulfonate, and under the environment of magnetic agitation, be dissolved in the chloroplatinic acid aqueous solution; Take by weighing the 3.8mg Peng Qinghuana and be dissolved in the 10mL deionized water, obtaining 10mL concentration is 1 * 10
-2The sodium borohydride aqueous solution of mol/L; Under the environment of magnetic agitation, be 4.8: 1 ratio in the ratio of reductive agent and the amount of metal ion species, in chloroplatinic acid aqueous solution, drip the 4.8mL sodium borohydride aqueous solution, continue reaction 45min afterwards, promptly getting 20mLPt content is 5 * 10
-4The Pt nano particle colloidal sol of mol/L.
Two, mix the preparation of the calcium titanate praseodymium fluorescent material of Pt nano particle
1) with the absolute ethyl alcohol is solvent, the Ca (NO of preparation 1mol/L
3)
2Ethanolic soln and 1 * 10
-3Pr (the NO of mol/L
3)
3Ethanolic soln;
2) press Pr
3+And Ca
2+Ratio be 5 * 10
-5: 1 ratio is with the Ca (NO of 40mL
3)
2Pr (the NO of ethanolic soln and 2mL
3)
3Ethanolic soln mixes, and obtains Pr
3+And Ca
2+Mixing solutions;
3) press metal and Ca
2+Molar ratio be 1 * 10
-6: 1 ratio adds the Pt nano particle colloidal sol that 0.08mL above-mentioned () prepares in mixed solution;
4) with Glacial acetic acid min. 99.5 with above-mentioned 3) the pH value of the mixing solutions that obtains is adjusted to 6;
5) press chemical general formula CaTiO
3: Pr
3+The stoichiometric ratio of middle Ca and Ti is got the tetrabutyl titanate of 0.04mol, and tetrabutyl titanate is scattered in the absolute ethyl alcohol of 10mL, obtains the tetrabutyl titanate ethanolic soln;
6) under the situation of stirring at normal temperature; The tetrabutyl titanate ethanolic soln is added drop-wise to above-mentioned 4) in the mixing solutions that obtains; Reinforced finishing continues to stir until forming gel, then gel is put into dry 36h in 80 ℃ the baking oven; Afterwards dry thing is put in the High Temperature Furnaces Heating Apparatus insulation calcining 8h under 900 ℃ of temperature, is chilled to take out to grind after the room temperature and obtains product.
Embodiment 2:
One, the preparation of Ag nano particle colloidal sol
Take by weighing 17.0mg Silver Nitrate (AgNO
3) be dissolved in the deionized water of 19.5mL; After Silver Nitrate dissolves fully, take by weighing the 60mg Trisodium Citrate, and under the environment of magnetic agitation, be dissolved in the silver nitrate aqueous solution; Dilution preparation 10mL concentration is the hydrazine hydrate solution of 0.1mol/L; Under the environment of magnetic agitation, be 0.5: 1 ratio in the ratio of reductive agent and the amount of metal ion species, the hydrazine hydrate solution of disposable adding 0.5mL0.1mol/L continues reaction 25min afterwards in the silver nitrate aqueous solution, and promptly getting the 20mL silver content is 5 * 10
-3The Ag nano particle colloidal sol of mol/L.
Two, mix the preparation of the calcium titanate praseodymium fluorescent material of Ag nano particle
1) with the absolute ethyl alcohol is solvent, the Ca (NO of preparation 1.5mol/L
3)
2Ethanolic soln and 5 * 10
-3Pr (the NO of mol/L
3)
3Ethanolic soln;
2) press Pr
3+And Ca
2+Ratio be 5 * 10
-4: 1 ratio is with the Ca (NO of 30mL
3)
2Pr (the NO of ethanolic soln and 4.5mL
3)
3Ethanolic soln mixes, and obtains Pr
3+And Ca
2+Mixing solutions;
3) press metal and Ca
2+Molar ratio be 5 * 10
-5: 1 ratio adds the Ag nano particle colloidal sol that 0.45mL above-mentioned () prepares in mixed solution;
4) with Glacial acetic acid min. 99.5 with above-mentioned 3) the pH value of the mixing solutions that obtains is adjusted to 5;
5) press chemical general formula CaTiO
3: Pr
3+The stoichiometric ratio of middle Ca and Ti is got the tetrabutyl titanate of 0.045mol, and tetrabutyl titanate is scattered in the absolute ethyl alcohol of 15mL, obtains the tetrabutyl titanate ethanolic soln;
6) under the situation of stirring at normal temperature; The tetrabutyl titanate ethanolic soln is added drop-wise to above-mentioned 4) in the mixing solutions that obtains; Reinforced finishing continues to stir until forming gel, then gel is put into dry 36h in 90 ℃ the baking oven; Afterwards dry thing is put in the High Temperature Furnaces Heating Apparatus insulation calcining 7h under 1100 ℃ of temperature, is chilled to take out to grind after the room temperature and obtains product.
The calcium titanate praseodymium of mixing the Ag metal of present embodiment preparation and do not mix the luminous spectrum of the cathode-ray exciting of calcium titanate praseodymium of Ag metal preparation with method as shown in Figure 2; Can know by Fig. 2, mix the luminous enhancing about 51% that the luminous ratio of calcium titanate praseodymium is not mixed the calcium titanate praseodymium of Ag metal behind the Ag metal.
Embodiment 3:
One, the preparation of Ag nano particle colloidal sol
Take by weighing 3.4mg Silver Nitrate (AgNO
3) be dissolved in the absolute ethyl alcohol of 17.6mL; After Silver Nitrate dissolves fully, take by weighing 40mgPVP, and under the environment of magnetic agitation, be dissolved in the Silver Nitrate ethanolic soln; Take by weighing the 3.8mg Peng Qinghuana and dissolve in the 10mL absolute ethyl alcohol, obtaining 10mL concentration is 1 * 10
-2The ethanol solution of sodium borohydride of mol/L; Under the environment of magnetic agitation, be 1.2: 1 ratio in the ratio of reductive agent and the amount of metal ion species, disposable adding 2.4mL1 * 10 in the Silver Nitrate ethanolic soln
-2The ethanol solution of sodium borohydride of mol/L continues reaction 10min afterwards, and promptly getting the 20mL silver content is 1 * 10
-3The Ag nano particle colloidal sol of mol/L.
Two, mix the preparation of the calcium titanate praseodymium fluorescent material of Ag nano particle
1) with the absolute ethyl alcohol is solvent, the Ca (NO of preparation 1mol/L
3)
2Ethanolic soln and 1 * 10
-2Pr (the NO of mol/L
3)
3Ethanolic soln;
2) press Pr
3+And Ca
2+Ratio be 1 * 10
-3: 1 ratio is with the Ca (NO of 50mL
3)
2Pr (the NO of ethanolic soln and 5mL
3)
3Ethanolic soln mixes, and obtains Pr
3+And Ca
2+Mixing solutions;
3) press metal and Ca
2+Molar ratio be 1 * 10
-4: 1 ratio adds the Ag nano particle colloidal sol that 5mL above-mentioned () prepares in mixed solution;
4) with rare nitric acid with above-mentioned 3) the pH value of the mixing solutions that obtains is adjusted to 4;
5) press chemical general formula CaTiO
3: Pr
3+The stoichiometric ratio of middle Ca and Ti is got the tetrabutyl titanate of 0.05mol, and tetrabutyl titanate is scattered in the absolute ethyl alcohol of 15mL, obtains the tetrabutyl titanate ethanolic soln;
6) under the situation of stirring at normal temperature; The tetrabutyl titanate ethanolic soln is added drop-wise to above-mentioned 4) in the mixing solutions that obtains; Reinforced finishing continues to stir until forming gel, then gel is put into dry 30h in 100 ℃ the baking oven; Afterwards dry thing is put in the High Temperature Furnaces Heating Apparatus insulation calcining 6h under 1200 ℃ of temperature, is chilled to take out to grind after the room temperature and obtains product.
The calcium titanate praseodymium of mixing the Ag metal of present embodiment preparation and do not mix the luminous spectrum of the cathode-ray exciting of calcium titanate praseodymium of Ag metal preparation with method as shown in Figure 3; Can know by Fig. 3, mix the luminous enhancing about 50% that the luminous ratio of calcium titanate praseodymium is not mixed the calcium titanate praseodymium of Ag metal behind the Ag metal.
Embodiment 4:
One, the preparation of Au nano particle colloidal sol
Take by weighing 4.12mg hydrochloro-auric acid (AuCl
3HCl4H
2O) be dissolved in the absolute ethyl alcohol of 8.42mL; After hydrochloro-auric acid dissolves fully, take by weighing 25mgPVP, and under the environment of magnetic agitation, be dissolved in the hydrochloro-auric acid ethanolic soln; Take by weighing the 17.6mg dissolution of ascorbic acid in the 10mL absolute ethyl alcohol, obtaining 10mL concentration is 1 * 10
-2The xitix ethanolic soln of mol/L; Under the environment of magnetic agitation, be 1.58: 1 ratio in the ratio of reductive agent and the amount of metal ion species, in the hydrochloro-auric acid ethanolic soln, add 1.58mL1 * 10
-2The xitix ethanolic soln of mol/L continues reaction 30min afterwards, and getting 10mLAu content is 1 * 10
-3The Au nano particle colloidal sol of mol/L.
Two, mix the preparation of the calcium titanate praseodymium fluorescent material of Au nano particle
1) with the absolute ethyl alcohol is solvent, the Ca (NO of preparation 1mol/L
3)
2Ethanolic soln is with the Pr (NO of deionized water preparation 0.1mol/L
3)
3The aqueous solution;
2) press Pr
3+And Ca
2+Ratio be 1 * 10
-3: 1 ratio is with the Ca (NO of 50mL
3)
2Pr (the NO of ethanolic soln and 0.5mL
3)
3Aqueous solution obtains Pr
3+And Ca
2+Mixing solutions;
3) press metal and Ca
2+Molar ratio be 5 * 10
-6: 1 ratio adds the Au nano particle colloidal sol that 0.25mL above-mentioned () prepares in mixed solution;
4) with rare nitric acid with above-mentioned 3) the pH value of the mixing solutions that obtains is adjusted to 5;
5) press chemical general formula CaTiO
3: Pr
3+The stoichiometric ratio of middle Ca and Ti is got the tetrabutyl titanate of 0.05mol, and tetrabutyl titanate is scattered in the absolute ethyl alcohol of 10mL, obtains the tetrabutyl titanate ethanolic soln;
6) under the situation of stirring at normal temperature; The tetrabutyl titanate ethanolic soln is added drop-wise to above-mentioned 4) in the mixing solutions that obtains; Reinforced finishing continues to stir until forming gel, then gel is put into dry 30h in 110 ℃ the baking oven; Afterwards dry thing is put in the High Temperature Furnaces Heating Apparatus insulation calcining 5h under 1300 ℃ of temperature, is chilled to take out to grind after the room temperature and obtains product.
The calcium titanate praseodymium of mixing the Au metal of present embodiment preparation and do not mix the luminous spectrum of the cathode-ray exciting of calcium titanate praseodymium of Au metal preparation with method as shown in Figure 4; Can know by Fig. 4, mix the luminous enhancing about 33% that the luminous ratio of calcium titanate praseodymium is not mixed the calcium titanate praseodymium of Au metal behind the Au metal.
Embodiment 5:
One, the preparation of Au nano particle colloidal sol
Take by weighing 4.12mg hydrochloro-auric acid (AuCl
3HCl4H
2O) be dissolved in the deionized water of 8.4mL; After hydrochloro-auric acid dissolves fully, take by weighing 14mg Trisodium Citrate and 6mg cetyl trimethylammonium bromide, and under the environment of magnetic agitation, be dissolved in the aqueous solution of chloraurate; Take by weighing the 1.9mg Peng Qinghuana and the 17.6mg xitix is dissolved into respectively in the 10mL deionized water, obtaining 10mL concentration is 5 * 10
-3The 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, be 1.58: 1 ratio in the ratio of reductive agent and the amount of metal ion species, adding 0.04mL sodium borohydride aqueous solution in the aqueous solution of chloraurate adds 1.56mL1 * 10 behind the stirring reaction 5min again in aqueous solution of chloraurate earlier
-2The aqueous ascorbic acid of mol/L continues reaction 30min afterwards, and getting 10mLAu content is 1 * 10
-3The Au nano particle colloidal sol of mol/L.
Two, mix the preparation of the barium titanate praseodymium fluorescent material of Au nano particle
1) with the deionized water is solvent, the Ba (NO of preparation 2mol/L
3)
2The aqueous solution is with absolute ethyl alcohol preparation 1 * 10
-3Pr (the NO of mol/L
3)
3Ethanolic soln;
2) press Pr
3+And Ba
2+Ratio be 2 * 10
-3: 1 ratio is with the Ba (NO of 10mL
3)
2Pr (the NO of the aqueous solution and 40mL
3)
3Ethanolic soln mixes, and obtains Pr
3+And Ba
2+Mixing solutions;
3) press metal and Ba
2+Molar ratio be 1 * 10
-5: 1 ratio adds the Au nano particle colloidal sol that 0.2mL above-mentioned () prepares in mixed solution;
4) with Glacial acetic acid min. 99.5 with above-mentioned 3) the pH value of the mixing solutions that obtains is adjusted to 3;
5) press chemical general formula BaTiO
3: Pr
3+The stoichiometric ratio of middle Ba and Ti is got the tetrabutyl titanate of 0.02mol, and tetrabutyl titanate is scattered in the absolute ethyl alcohol of 20mL, obtains the tetrabutyl titanate ethanolic soln;
6) under the situation of stirring at normal temperature; The tetrabutyl titanate ethanolic soln is added drop-wise to above-mentioned 4) in the mixing solutions that obtains; Reinforced finishing continues to stir until forming gel, then gel is put into dry 30h in 100 ℃ the baking oven; Afterwards dry thing is put in the High Temperature Furnaces Heating Apparatus insulation calcining 4h under 1400 ℃ of temperature, is chilled to take out to grind after the room temperature and obtains product.
Embodiment 6:
One, the preparation of Pd nano particle colloidal sol
Take by weighing 0.53mg Palladous chloride (PdCl
22H
2O) be dissolved in the deionized water of 29.1mL; After Palladous chloride dissolves fully, take by weighing 11.0mgPVP and 4.0mg sodium lauryl sulphate, and under the environment of magnetic agitation, be dissolved in the palladium chloride aqueous solution; Take by weighing the 3.8mg Peng Qinghuana and dissolve in the 10mL deionized water, obtaining concentration is 1 * 10
-2The sodium borohydride reduction liquid of mol/L; Under the environment of magnetic agitation, be 3: 1 ratio in the ratio of reductive agent and the amount of metal ion species, in palladium chloride aqueous solution, add 0.9mL1 * 10 fast
-2The sodium borohydride aqueous solution of mol/L continues reaction 20min afterwards, and promptly getting 30mLPd content is 1 * 10
-4The Pd nano particle colloidal sol of mol/L.
Two, mix the preparation of the strontium titanates praseodymium fluorescent material of Pd nano particle
1) with the deionized water is solvent, the Sr (NO of preparation 1.5mol/L
3)
2The aqueous solution is with absolute ethyl alcohol preparation 5 * 10
-3Pr (the NO of mol/L
3)
3Ethanolic soln;
2) press Pr
3+And Sr
2+Ratio be 1 * 10
-2: 1 ratio is with the Sr (NO of 15mL
3)
2Pr (the NO of the aqueous solution and 45mL
3)
3Ethanolic soln mixes, and obtains Pr
3+And Sr
2+Mixing solutions;
3) press metal and Sr
2+Molar ratio be 5 * 10
-7: 1 ratio adds the Pd nano particle colloidal sol that 0.1125mL above-mentioned () prepares in mixed solution;
4) with rare nitric acid with above-mentioned 3) the pH value of the mixing solutions that obtains is adjusted to 1;
5) press chemical general formula SrTiO
3: Pr
3+The stoichiometric ratio of middle Sr and Ti is got the tetrabutyl titanate of 0.0225mol, and tetrabutyl titanate is scattered in the absolute ethyl alcohol of 10mL, obtains the tetrabutyl titanate ethanolic soln;
6) under the situation of stirring at normal temperature; The tetrabutyl titanate ethanolic soln is added drop-wise to above-mentioned 4) in the mixing solutions that obtains; Reinforced finishing continues to stir until forming gel, then gel is put into dry 24h in 120 ℃ the baking oven; Afterwards dry thing is put in the High Temperature Furnaces Heating Apparatus insulation calcining 3h under 1500 ℃ of temperature, is chilled to take out to grind after the room temperature and obtains product.
Should be understood that above-mentioned statement to preferred embodiment of the present invention is comparatively detailed, can not therefore 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 accompanying claims.
Claims (10)
1. titanate luminescent material, its chemical general formula is:
M
1TiO
3XPryM
2Wherein, M
1At least a among Ca, Sr or the Ba, M
2At least a in Ag, Au, Pt or the Pd nano particle, the x value is 5 * 10
-5～1 * 10
-2, the y value is 5 * 10
-7～1 * 10
-4
2. the preparation method of a titanate luminescent material is characterized in that, comprises the steps:
According to chemical general formula M
1TiO
3XPryM
2In the stoichiometric ratio of each element, M is provided
2Nano particle colloidal sol, source compound and the M of Pr
1Source compound; Wherein, M
1At least a among Ca, Sr or the Ba, M
2At least a in Ag, Au, Pt or the Pd nano particle, the x value is 5 * 10
-5～1 * 10
-2, the y value is 5 * 10
-7～1 * 10
-4
Source compound and M with said Pr
1Source compound be dissolved in respectively in ethanol or the water, be configured to contain the Pr ion solution and contain M
1Ion solution;
With the Pr ion solution of above-mentioned configuration, according to 5 * 10
-5: 1～1 * 10
-2: 1 mol ratio, add to and contain M
1In the ion solution; Add said M subsequently successively
2Nano particle colloidal sol and acid solution, and make the pH value of this mixing solutions be adjusted to 1～6, wherein, M
2With M
1The ionic mol ratio is 5 * 10
-7: 1～1 * 10
-4: 1;
According to chemical general formula M
1TiO
3XPryM
2Middle Ti and M
1Stoichiometric ratio, toward above-mentioned mixed solution and dripping tetrabutyl titanate ethanolic soln, stir, make gel;
Said gel is after drying treatment and calcination processing, and cooling, grinding obtain said titanate luminescent material.
3. the preparation method of titanate luminescent material according to claim 2 is characterized in that, said M
2Nano particle colloidal sol adopt following step to make:
With M
2Source compound be dissolved in ethanol or the water, be configured to M
2Ion solution;
Under the state that stirs, toward above-mentioned M
2Add surface treatment agent in the ion solution, make and contain M
2Ionic mixing solutions, and the M that this surface treatment agent is finally being obtained
2Content in the nano particle colloidal sol is 5 * 10
-4G/mL～4 * 10
-3G/mL;
Toward the above-mentioned M that contains
2Add reductant solution in the ionic mixing solutions, stir, make said M
2Nano particle colloidal sol; Wherein, in the reductant solution, reductive agent and M
2The ionic mol ratio is 0.5: 1～4.8: 1.
4. the preparation method of titanate luminescent material according to claim 3 is characterized in that, said M
2Source compound be a kind of in Silver Nitrate, hydrochloro-auric acid, Platinic chloride or the Palladous chloride.
5. the preparation method of titanate luminescent material according to claim 3; It is characterized in that said surface treatment agent is at least a in Vilaterm arsenic pyrrolidone, Trisodium Citrate, cetyl trimethylammonium bromide, sodium lauryl sulphate, the sodium laurylsulfonate.
6. the preparation method of titanate luminescent material according to claim 3 is characterized in that, in the said reductant solution, reductive agent is Hydrazine Hydrate 80, xitix, Peng Qinghuana; Solvent is ethanol or water.
7. the preparation method of titanate luminescent material according to claim 2 is characterized in that, the source compound of said Pr and M
1Source compound be respectively separately corresponding nitrate salt.
8. the preparation method of titanate luminescent material according to claim 2 is characterized in that, said acid solution is nitric acid or Glacial acetic acid min. 99.5.
9. the preparation method of titanate luminescent material according to claim 2 is characterized in that, during said drying treatment, drying temperature is 80～120 ℃, and be 24～36h time of drying.
10. according to the preparation method of the described titanate luminescent material of claim 2, it is characterized in that said calcination processing is, calcining temperature is 900～1500 ℃, and calcination time is 3～8h.
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