CN104119901A - Titanate luminescent material cladding metal nanoparticle and preparation method thereof - Google Patents

Titanate luminescent material cladding metal nanoparticle and preparation method thereof Download PDF

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CN104119901A
CN104119901A CN201310150642.5A CN201310150642A CN104119901A CN 104119901 A CN104119901 A CN 104119901A CN 201310150642 A CN201310150642 A CN 201310150642A CN 104119901 A CN104119901 A CN 104119901A
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luminescent material
nagd
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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 belongs to the field of luminescent materials, and discloses a titanate luminescent material cladding a metal nanoparticle and a preparation method thereof. The chemical general formula of the luminescent material is NaGd1-xTiO4:Eux@My, wherein NaGd1-xTiO4:Eux is an outer shell, @ represents cladding, and M is an inner core, M is at least one selected from Ag, Au, Pt, Pd and Cu metal nanoparticles, 0<x<=0.05, y is the molar ratio of M to Ti, 0<y<=1*10<-2>. According to the provided titanate luminescent material cladding the metal nanoparticle, the core-shell structural luminescent material cladding the metal nanoparticle is formed by doping the M metal nanoparticle, the internal quantum efficiency of the luminescent material is improved, and the added metal nanoparticle gives play to effect of enhancing luminescent efficiency of the luminescent material.

Description

Titanate luminescent material of clad metal nano particle and preparation method thereof
Technical field
The present invention relates to field of light emitting materials, relate in particular to titanate luminescent material of a kind of clad metal nano particle and preparation method thereof.
Background technology
White light LEDs (1ight emitting diodes) has that efficiency is high, the life-span is long, volume is little, respond the advantage such as quick, pollution-free, energy-conservation has obtained paying attention to more and more widely.One of major way of realizing at present white light is blue GaN chip and yellow YAG:Ce phosphor combination generation white light.The shortcoming of the method is that colour rendering index is low.And utilize near ultraviolet LED chip and red, green, blue three primary colors fluorescent powder to be combined into white light LEDs, its luminous efficiency is high, colour temperature is adjustable and colour rendering index is high, has been widely studied, and has become the main flow of current development.The LED three primary colors fluorescent powder that therefore, can effectively be excited by purple light, near-ultraviolet light is just widely studied.
Titanate NaGdTiO 4at near ultraviolet band, also there is very strong absorption, be expected to become the rare earth ion doped fluorescent material substrate material of near ultraviolet excitated type.The luminescent properties that further improves this kind of material is the target of researchist's effort always.
Summary of the invention
Problem to be solved by this invention is to provide that a kind of luminous efficiency is higher, the titanate luminescent material of nontoxicity and the good clad metal nano particle of stability.
Technical scheme of the present invention is as follows:
A titanate luminescent material for clad metal nano particle, its chemical general formula is: NaGd 1-xtiO 4: Eu x@M y; Wherein, NaGd 1-xtiO 4: Eu xfor shell ,@is coated, and M is kernel; M is selected from least one in Ag, Au, Pt, Pd, Cu metal nanoparticle, and x is the mole number that Eu atom replaces Gd atom, 0 < x≤0.05, and y is the mol ratio of M and Ti, 0 < y≤1 * 10 -2; NaGd 1-xtiO 4: Eu xfor luminescent material, Eu exists with ionic species, and Eu is light emitting ionic center, and colon ": " represents Eu doping.
The titanate luminescent material of described clad metal nano particle, preferably, 0.005≤x≤0.03,1 * 10 -5≤ y≤5 * 10 -3.
The present invention also provides the preparation method of the titanate luminescent material of above-mentioned clad metal nano particle, comprises the steps:
By the salts solution of M, trolamine titanium isopropoxide solution and dimethyl formamide hybrid reaction, make the TiO of nucleocapsid structure 2@M ycolloid; Again by centrifugal, washing with alcohol, dry TiO 2@M yafter colloid, obtain TiO 2@M ysolid; Wherein ,@represents TiO 2coated M; 20%～80% of the salts solution that the volume addition of dimethyl formamide is M, trolamine titanium isopropoxide solution and dimethyl formamide volume sum;
According to NaGd 1-xtiO 4: Eu x@M ythe stoichiometric ratio of middle element, measures Na, Gd and the Eu aqueous ethanolic solution of corresponding salt separately, and adds citric acid complexing agent and polyglycol surfactants, in 60～80 ℃ of stirring 2～6h, obtains colloidal sol, then under agitation adds TiO 2@M ysolid, then stir 2～12h, obtain precursor sol; Wherein, the mol ratio of citric acid and Na, Gd and Eu tri-metal ion species sums is 1～5:1, and the concentration of polyoxyethylene glycol is 0.05～0.20g/mL;
Precursor sol drying and volatilizing solvent is obtained to xerogel, grind xerogel, grind powder and be put under air atmosphere in 600～900 ℃ of pre-burnings 2～12 hours, grind pre-sintered sample after being cooled to room temperature; And then by the pre-sintered sample powder grinding in 900～1400 ℃ of calcining 1～8h, obtaining chemical general formula is NaGd 1-xtiO 4: Eu x@M ythe titanate luminescent material of clad metal nano particle;
Wherein, NaGd 1-xtiO 4: Eu xfor shell ,@is coated, and M is kernel; M is selected from least one in Ag, Au, Pt, Pd, Cu metal nanoparticle, and x is the mole number that Eu atom replaces Gd atom, 0 < x≤0.05, and y is the mol ratio of M and Ti, 0 < y≤1 * 10 -2.
The preparation method of the titanate luminescent material of described clad metal nano particle, preferably, the concentration of the salts solution of M is 5 * 10 -5mol/L～5 * 10 -3mol/L.
The preparation method of the titanate luminescent material of described clad metal nano particle, preferably, the concentration of described trolamine titanium isopropoxide solution is 0.22mol/L～2.5mol/L; In described trolamine titanium isopropoxide solution, solvent is Virahol, and solute is trolamine titanium isopropylate.
The preparation method of the titanate luminescent material of described clad metal nano particle, preferably, 25%～50% of the salts solution that the volume addition of dimethyl formamide is M, trolamine titanium isopropoxide solution and dimethyl formamide volume sum.
The preparation method of the titanate luminescent material of described clad metal nano particle, preferably, Na, Gd and Eu separately corresponding salt are respectively Na, Gd and Eu each self-corresponding nitrate or acetate; In aqueous ethanolic solution, the volume ratio of ethanol and water is 3～8:1;
Na, Gd and the Eu separately aqueous ethanolic solution of corresponding salt adopt with the following method and make:
Take respectively each self-corresponding oxide compound of Na, Gd and Eu, carbonate is raw material, is dissolved in nitric acid, and the mixing solutions that the volume ratio that then adds second alcohol and water is 3～8:1, obtains Na, Gd and the Eu aqueous ethanolic solution of corresponding salt separately; Or,
Take respectively each self-corresponding acetate of Na, Gd and Eu, nitrate is raw material, and the mixing solutions that the volume ratio that is dissolved in second alcohol and water is 3～8:1, obtains Na, Gd and the Eu aqueous ethanolic solution of corresponding salt separately.
The preparation method of the titanate luminescent material of described clad metal nano particle, preferably, described pre-burning and calcination process are all to carry out in retort furnace or high temperature box furnace.
The preparation method of the titanate luminescent material of described clad metal nano particle, preferably, 0.005≤x≤0.03,1 * 10 -5≤ y≤5 * 10 -3.
The titanate luminescent material of clad metal nano particle provided by the invention, quote doping M metal nanoparticle, to form the nucleocapsid structure luminescent material of clad metal nano particle, improved its internal quantum efficiency, the metal nanoparticle adding, can play the luminous efficiency that has strengthened luminescent material; And the prepared praseodymium titanate luminescent material stability of mixing is better.
Preparation method of the present invention, due to adding of dimethyl formamide (DMF), is reduced into metal simple-substance M metal ion, and trolamine titanium isopropylate (TTEAIP) is slowly hydrolyzed and forms TiO on metal core surface 2shell makes TiO 2@M y, with TiO 2@M yfor titanium source, adopt high temperature solid-state method, the compound preparation corresponding with Na, Gd and Eu is coated with the titanate fluorescent powder of metal nanoparticle, i.e. NaGd 1-xtiO 4: Eu x@M y; The method technique is simple, equipment requirements is low, pollution-free, be easy to control, be suitable for suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is luminescent material and the luminescent spectrum comparison diagram of comparative example luminescent material under wavelength 281nm excites of embodiment 2 preparations; Wherein curve 1 is the NaGd of the clad metal nano particle Ag that makes of embodiment 2 0.8tiO 4: Eu 0.2@Ag 5 * 10-4the luminescent spectrum of luminescent material; Curve 2 is not NaGd of clad metal nano particle Ag of comparative example 0.8tiO 4: Eu 0.2the luminescent spectrum of luminescent material.
Embodiment
The difference that illustrates titanate luminescent material by a plurality of embodiment below forms and preparation method thereof, with and the aspect such as performance.
Embodiment 1
Sol-gel method is prepared NaGd 0.995tiO 4: Eu 0.005@Au 1 * 10-2:
TiO 2@Au 1 * 10-2preparation: take 10.3mg hydrochloro-auric acid (AuCl 3hCl4H 2o) be dissolved in deionized water, obtain 20mL5 * 10 -3mol/L chlorauric acid solution; Pipette the trolamine titanium isopropylate of 5mL4.3mol/L, by isopropanol to 1mol/L.Pipette 10mL5 * 10 -3the aqueous isopropanol of the trolamine titanium isopropylate of mol/L chlorauric acid solution and 5mL1mol/L, stirs; Then the dimethyl formamide that adds 15mL, stirs after 15min under room temperature, adopts condensation reflux unit to carry out heated and stirred, and Heating temperature is 140 ℃, and solution to light brown, then during to dark-brown, stops heating via colourless, is cooled to room temperature, obtains TiO 2@Au 1 * 10-2colloid.Then through centrifugal, washing with alcohol, is dried and obtains TiO 2@Au 1 * 10-2solid, wherein y is 1 * 10 -2.
NaGd 0.995tiO 4: Eu 0.005@Au 1 * 10-2preparation: take 0.3281g CH 3cOONa, 1.3306gGd (CH 3cOO) 3with 0.0066g Eu (CH 3cOO) 3be placed in container, then adding 50mL volume ratio is the mixing solutions of the second alcohol and water of 4:1, adds 1.5369g citric acid and 2.5g polyoxyethylene glycol 100 under 80 ℃ of stirring in water bath conditions, stirs and obtains the colloidal sol of homogeneous transparent in 2 hours, and then add TiO 2@Au 1 * 10-2powder 0.3195g, continues to stir 2h, obtains precursor sol.
Precursor sol dry 20h solvent flashing at 70 ℃ is obtained to xerogel, then by the xerogel grind into powder obtaining, put into high temperature box furnace calcining at constant temperature 12h at 600 ℃, then in 1200 ℃ of calcining 6h, be cooled to room temperature and obtain NaGd 0.995tiO 4: Eu 0.005@Au 1 * 10-2luminescent material.
Embodiment 2
Sol-gel method is prepared NaGd 0.8tiO 4: Eu 0.2@Ag 5 * 10-4:
TiO 2@Ag 5 * 10-4preparation: take 3.4mg Silver Nitrate (AgNO 3) be dissolved in deionized water, obtain 20mL1 * 10 -3mol/L silver nitrate solution; Pipette the trolamine titanium isopropylate of 10mL4.3mol/L, by isopropanol to 0.22mol/L.Pipette 2mL1 * 10 -3the aqueous isopropanol of the trolamine titanium isopropylate of mol/L silver nitrate solution and 18mL0.22mol/L, stirs; Then the dimethyl formamide that adds 10mL, stirs after 15min under room temperature, adopts condensation reflux unit to carry out heated and stirred, and Heating temperature is 140 ℃, and solution to light brown, then during to dark-brown, stops heating via colourless, is cooled to room temperature, obtains TiO 2@Ag 5 * 10-4colloid.Then through centrifugal, washing with alcohol, is dried and obtains TiO 2@Ag 5 * 10-4solid, wherein y is 5 * 10 -4.
NaGd 0.8tiO 4: Eu 0.2@Ag 5 * 10-4preparation: take 0.3400g NaNO 3, 1.0983g Gd (NO 3) 3with 0.2704g Eu (NO 3) 3be placed in container, then adding 50mL volume ratio is the mixing solutions of the second alcohol and water of 3:1, adds 3.8424g citric acid and 5g PEG20000 under 80 ℃ of stirring in water bath conditions, stirs and obtains the colloidal sol of homogeneous transparent in 4 hours, and then add TiO 2@Ag 5 * 10-4powder 0.3195g, continues to stir 6h, obtains precursor sol.
Precursor sol dry 10h solvent flashing at 100 ℃ is obtained to xerogel, then by the xerogel grind into powder obtaining, put into retort furnace calcining at constant temperature 6h at 800 ℃, then in 1000 ℃ of calcining 4h, be cooled to room temperature and obtain NaGd 0.8tiO 4: Eu 0.2@Ag 5 * 10-4luminescent material.
Fig. 1 is luminescent material and the luminescent spectrum comparison diagram of comparative example luminescent material under wavelength 281nm excites of embodiment 2 preparations; Wherein curve 1 is the NaGd of the clad metal nano particle Ag that makes of embodiment 2 0.8tiO 4: Eu 0.2@Ag 5 * 10-4the luminescent spectrum of luminescent material; Curve 2 is not NaGd of clad metal nano particle Ag of comparative example 0.8tiO 4: Eu 0.2the luminescent spectrum of luminescent material.
As can be seen from Figure 1, the emission peak at 618nm place, after clad metal nano particle, the luminous intensity of luminescent material has strengthened 27% compared with comparative example luminescent material.
Embodiment 3
Sol-gel method is prepared NaGd 0.5tiO 4: Eu 0.5@Pt 5 * 10-3:
TiO 2@Pt 5 * 10-3preparation: take 25.9mg Platinic chloride (H 2ptCl 66H 2o) be dissolved in deionized water, obtain 10mL2.5 * 10 -3mol/L platinum acid chloride solution; Pipette the trolamine titanium isopropylate of 5mL4.3mol/L, by isopropanol to 0.5mol/L.Pipette 8mL2.5 * 10 -3the aqueous isopropanol of the trolamine titanium isopropylate of mol/L platinum acid chloride solution and 16mL0.5mol/L, stirs; Then the dimethyl formamide that adds 6mL, stirs after 15min under room temperature, adopts condensation reflux unit to carry out heated and stirred, and Heating temperature is 140 ℃, and solution to light brown, then during to dark-brown, stops heating via colourless, is cooled to room temperature, obtains TiO 2@Pt 5 * 10-3colloid.Then through centrifugal, washing with alcohol, is dried and obtains TiO 2@Pt 5 * 10-3solid, wherein y is 5 * 10 -3.
NaGd 0.5tiO 4: Eu 0.5@Pt 5 * 10-3preparation: then take 0.1240g Na 2o, 0.3625g Gd 2o 3, 0.3519g Eu 2o 3by 2mL concentrated nitric acid and 3mL deionized water heating for dissolving in container, after cooling, adding 50mL volume ratio is the mixing solutions of the second alcohol and water of 3:1, under 80 ℃ of stirring in water bath conditions, add 7.6848g citric acid and 2.75g Macrogol 200, stir and obtain the colloidal sol of homogeneous transparent in 1 hour, and then add TiO 2@Pt 5 * 10-3powder 0.3195g, continues to stir 12h, obtains precursor sol.
Precursor sol dry 6h solvent flashing at 150 ℃ is obtained to xerogel, then by the xerogel grind into powder obtaining, put into high temperature box furnace calcining at constant temperature 2h at 900 ℃, then in 1400 ℃ of calcining 1h, be cooled to room temperature and obtain NaGd 0.5tiO 4: Eu 0.5@Pt 5 * 10-3luminescent material.
Embodiment 4
Sol-gel method is prepared NaGd 0.7tiO 4: Eu 0.3@Pd 1 * 10-5:
TiO 2@Pd 1 * 10-5preparation: take 0.22mg Palladous chloride (PdCl 22H 2o) be dissolved in deionized water, obtain 20mL5 * 10 -5mol/L palladium chloride solution; Pipette the trolamine titanium isopropylate of 10mL4.3mol/L, by isopropanol to 2.5mol/L.Pipette 5mL5 * 10 -5the aqueous isopropanol of the trolamine titanium isopropylate of mol/L palladium chloride solution and 10mL2.5mol/L, stirs; Then the dimethyl formamide that adds 5mL, stirs after 15min under room temperature, adopts condensation reflux unit to carry out heated and stirred, and Heating temperature is 140 ℃, and solution to light brown, then during to dark-brown, stops heating via colourless, is cooled to room temperature, obtains TiO 2@Pd 1 * 10-5colloid.Then through centrifugal, washing with alcohol, is dried and obtains TiO 2@Pd 1 * 10-5solid, wherein y is 1 * 10 -5.
NaGd 0.7tiO 4: Eu 0.3@Pd 1 * 10-5preparation: take 0.2119g Na 2cO 3, 0.6923g Gd 2(CO 3) 3with 0.2903g Eu 2(CO 3) 3by the rare nitric acid heating for dissolving of 5mL in container, after cooling, adding 50mL volume ratio is the mixing solutions of the second alcohol and water of 3:1, adds 5.3793g citric acid and 8.75g Macrogol 2000 under 65 ℃ of stirring in water bath conditions, stirs the colloidal sol that obtains homogeneous transparent for 6 hours.And then add TiO 2@Pd 1 * 10-5powder 0.3195g, continues to stir 4h, obtains precursor sol.Precursor sol dry 8h solvent flashing at 100 ℃ is obtained to xerogel, then by the xerogel grind into powder obtaining, put into high temperature box furnace calcining at constant temperature 4h at 850 ℃, then in 900 ℃ of calcining 8h, be cooled to room temperature and obtain NaGd 0.7tiO 4: Eu 0.3@Pd 1 * 10-5luminescent material.
Embodiment 5
Sol-gel method is prepared NaGd 0.9tiO 4: Eu 0.1@Cu 1 * 10-4:
TiO 2@Cu 1 * 10-4preparation: take in the ethanol that 1.6mg cupric nitrate is dissolved into 16mL, obtain 20mL4 * 10 -4mol/L copper nitrate solution; Pipette the trolamine titanium isopropylate of 5mL4.3mol/L, by isopropanol to 2mol/L.Pipette 2mL4 * 10 -4the aqueous isopropanol of the trolamine titanium isopropylate of mol/L copper nitrate solution and 4mL2mol/L, stirs; Then the dimethyl formamide that adds 24mL, stirs after 15min under room temperature, adopts condensation reflux unit to carry out heated and stirred, and Heating temperature is 140 ℃, and solution to light brown, then during to dark-brown, stops heating via colourless, is cooled to room temperature, obtains TiO 2@Cu 1 * 10-4colloid.Then through centrifugal, washing with alcohol, is dried and obtains TiO 2@Cu 1 * 10-4solid, wherein y is 1 * 10 -4.
NaGd 0.9tiO 4: Eu 0.1@Cu 1 * 10-4preparation: take 0.3281g CH 3cOONa, 1.2036gGd (CH 3cOO) 3with 0.1316g Eu (CH 3cOO) 3be placed in container, then adding 50mL volume ratio is the mixing solutions of the second alcohol and water of 4:1, adds 6.9163g citric acid and 2.5g PEG 20000 under 60 ℃ of stirring in water bath conditions, stirs the colloidal sol that obtains homogeneous transparent for 3 hours.And then add TiO 2@Cu 1 * 10-4powder 0.3514g, continues to stir 12h, obtains precursor sol.
Precursor sol dry 15h solvent flashing at 80 ℃ is obtained to xerogel, then by the xerogel grind into powder obtaining, put into high temperature box furnace calcining at constant temperature 3h at 900 ℃, then in 1300 ℃ of calcining 3h, be cooled to room temperature and obtain NaGd 0.9tiO 4: Eu 0.1@Cu 1 * 10-4luminescent material.
Embodiment 6
Sol-gel method is prepared NaGd 0.99tiO 4: Eu 0.01@(Ag 0.5/ Au 0.5) 1.25 * 10-3:
TiO 2@(Ag 0.5/ Au 0.5) 1.25 * 10-3preparation: take 6.2mg hydrochloro-auric acid (AuCl 3hCl4H 2o) and 2.5mg AgNO 3be dissolved in the deionized water of 28mL, the total metal concentration that obtains 30mL is 1 * 10 -3(hydrochloro-auric acid and silver nitrate solution concentration are respectively 0.5 * 10 to the mixing solutions of mol/L hydrochloro-auric acid and Silver Nitrate -3mol/L); Pipette the trolamine titanium isopropylate of 2mL4.3mol/L, by isopropanol to 0.4mol/L.Pipette 5mL1 * 10 -3the trolamine titanium isopropylate of the mixing solutions of mol/L hydrochloro-auric acid and Silver Nitrate and 10mL0.4mol/L, stirs; Then the dimethyl formamide that adds 10mL, stirs after 15min under room temperature, adopts condensation reflux unit to carry out heated and stirred, and Heating temperature is 140 ℃, and solution to light brown, then during to dark-brown, stops heating via colourless, is cooled to room temperature, obtains TiO 2@(Ag 0.5/ Au 0.5) 1.25 * 10-3colloid.Then through centrifugal, washing with alcohol, is dried and obtains TiO 2@(Ag 0.5/ Au 0.5) 1.25 * 10-3solid, wherein y is 1.25 * 10 -3.
NaGd 0.99tiO 4: Eu 0.01@(Ag 0.5/ Au 0.5) 1.25 * 10-3preparation: take 0.3400g NaNO 3, 1.3592gGd (NO 3) 3with 0.0135g Eu (NO 3) 3be placed in container, then adding 50mL volume ratio is the mixing solutions of the second alcohol and water of 3:1, adds 3.0739g citric acid and 10g Macrogol 4000 under 70 ℃ of stirring in water bath conditions, stirs the colloidal sol that obtains homogeneous transparent for 4 hours.And then add TiO 2@(Ag 0.5/ Au 0.5) 1.25 * 10-3powder 0.3195g, continues to stir 6h, obtains precursor sol.
Precursor sol dry 12h solvent flashing at 100 ℃ is obtained to xerogel, then by the xerogel grind into powder obtaining, put into retort furnace calcining at constant temperature 3h at 800 ℃, then in 1200 ℃ of calcining 5h, be cooled to room temperature and obtain NaGd 0.99tiO 4: Eu 0.01@(Ag 0.5/ Au 0.5) 1.25 * 10-3luminescent material.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any modifications of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.

Claims (10)

1. a titanate luminescent material for clad metal nano particle, is characterized in that, its chemical general formula is: NaGd 1-xtiO 4: Eu x@M y; Wherein, NaGd 1-xtiO 4: Eu xfor shell ,@is coated, and M is kernel; M is selected from least one in Ag, Au, Pt, Pd, Cu metal nanoparticle, and x is the mole number that Eu atom replaces Gd atom, 0 < x≤0.05, and y is the mol ratio of M and Ti, 0 < y≤1 * 10 -2.
2. the titanate luminescent material of clad metal nano particle according to claim 1, is characterized in that, 0.005≤x≤0.03,1 * 10 -5≤ y≤5 * 10 -3.
3. the titanate luminescent material of clad metal nano particle according to claim 1, is characterized in that, comprises a kind of in following luminescent material:
NaGd 0.995TiO 4:Eu 0.005@Au 1×10ˉ2；NaGd 0.8TiO 4:Eu 0.2@Ag 5×10ˉ4；NaGd 0.5TiO 4:Eu 0.5@Pt 5×10ˉ3；NaGd 0.7TiO 4:Eu 0.3@Pd 1×10ˉ5；NaGd 0.9TiO 4:Eu 0.1@Cu 1×10ˉ4；NaGd 0.99TiO 4:Eu 0.01@(Ag 0.5/Au 0.5) 1.25×10ˉ3。
4. a preparation method for the titanate luminescent material of clad metal nano particle, is characterized in that, comprises the steps:
By the salts solution of M, trolamine titanium isopropoxide solution and dimethyl formamide hybrid reaction, make the TiO of nucleocapsid structure 2@M ycolloid; Again by centrifugal, washing with alcohol, dry TiO 2@M yafter colloid, obtain TiO 2@M ysolid; Wherein ,@represents TiO 2coated M; 20%～80% of the salts solution that the volume addition of dimethyl formamide is M, trolamine titanium isopropoxide solution and dimethyl formamide volume sum;
According to NaGd 1-xtiO 4: Eu x@M ythe stoichiometric ratio of middle element, measures Na, Gd and the Eu aqueous ethanolic solution of corresponding salt separately, and adds citric acid complexing agent and polyglycol surfactants, in 60～80 ℃ of stirring 2～6h, obtains colloidal sol, then under agitation adds TiO 2@M ysolid, then stir 2～12h, obtain precursor sol; Wherein, the mol ratio of citric acid and Na, Gd and Eu tri-metal ion species sums is 1～5:1, and the concentration of polyoxyethylene glycol is 0.05～0.20g/mL;
Precursor sol drying and volatilizing solvent is obtained to xerogel, grind xerogel, grind powder and be put under air atmosphere in 600～900 ℃ of pre-burnings 2～12 hours, grind pre-sintered sample after being cooled to room temperature; And then by the pre-sintered sample powder grinding in 900～1400 ℃ of calcining 1～8h, obtaining chemical general formula is NaGd 1-xtiO 4: Eu x@M ythe titanate luminescent material of clad metal nano particle;
Wherein, NaGd 1-xtiO 4: Eu xfor shell ,@is coated, and M is kernel; M is selected from least one in Ag, Au, Pt, Pd, Cu metal nanoparticle, and x is the mole number that Eu atom replaces Gd atom, 0 < x≤0.05, and y is the mol ratio of M and Ti, 0 < y≤1 * 10 -2.
5. the preparation method of the titanate luminescent material of clad metal nano particle according to claim 4, is characterized in that, the concentration of the salts solution of M is 5 * 10 -5mol/L～5 * 10 -3mol/L; The concentration of described trolamine titanium isopropoxide solution is 0.22mol/L～2.5mol/L.
6. according to the preparation method of the titanate luminescent material of the clad metal nano particle described in claim 4 or 5, it is characterized in that, in described trolamine titanium isopropoxide solution, solvent is Virahol.
7. the preparation method of the titanate luminescent material of clad metal nano particle according to claim 4, it is characterized in that 25%～50% of the salts solution that the volume addition of dimethyl formamide is M, trolamine titanium isopropoxide solution and dimethyl formamide volume sum.
8. the preparation method of the titanate luminescent material of clad metal nano particle according to claim 4, is characterized in that, Na, Gd and Eu separately corresponding salt are respectively Na, Gd and Eu each self-corresponding nitrate or acetate; In aqueous ethanolic solution, the volume ratio of ethanol and water is 3～8:1.
9. the preparation method of the titanate luminescent material of clad metal nano particle according to claim 4, is characterized in that, in aqueous ethanolic solution, the volume ratio of ethanol and water is 3～8:1.
10. the preparation method of the titanate luminescent material of clad metal nano particle according to claim 4, is characterized in that, 0.005≤x≤0.03,1 * 10 -5≤ y≤5 * 10 -3.
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Application publication date: 20141029