CN115181568A - Synthesis of multilayer core-shell structure composite nano dual-mode luminescent material - Google Patents
Synthesis of multilayer core-shell structure composite nano dual-mode luminescent material Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 19
- 239000002131 composite material Substances 0.000 title claims description 13
- 230000015572 biosynthetic process Effects 0.000 title claims description 9
- 238000003786 synthesis reaction Methods 0.000 title claims description 9
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 122
- 239000004005 microsphere Substances 0.000 claims abstract description 49
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 239000002243 precursor Substances 0.000 claims abstract description 21
- 229910052691 Erbium Inorganic materials 0.000 claims abstract description 20
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 18
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 15
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 13
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- 238000000034 method Methods 0.000 claims abstract description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 12
- -1 rare earth ions Chemical class 0.000 claims abstract description 9
- 238000001354 calcination Methods 0.000 claims abstract description 8
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims abstract description 6
- 239000011248 coating agent Substances 0.000 claims abstract 5
- 238000000576 coating method Methods 0.000 claims abstract 5
- 230000007062 hydrolysis Effects 0.000 claims abstract 4
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 38
- 238000001035 drying Methods 0.000 claims description 22
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- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 6
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 5
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- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical group [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 3
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- 239000003960 organic solvent Substances 0.000 description 2
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
- C09K11/7794—Vanadates; Chromates; Molybdates; Tungstates
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Abstract
The invention discloses a multilayer core-shell structure nano luminescent material for down-converting red light and up-converting green light by rare earth and a preparation method thereof 3+ And Eu 3+ Uniformly coated on SiO 2 Coating SiO on the surface of the microsphere by a method of weak alkaline hydrolysis of tetraethoxysilane 2 Calcining the shell layer at high temperature to obtain a precursor SiO with a core-shell structure 2 @Gd 2 O 3 :Eu@SiO 2 (ii) a Coating the surface of the precursor with rare earth ions Gd by using a urea hydrolysis method 3+ 、Yb 3+ 、Er 3+ Continuously coating SiO by a method of alkalescent hydrolysis of tetraethoxysilane 2 Shell layer, dispersing the obtained product in H 2 Adding ammonium metavanadate into mixed solution of O and glycol to make VO 4 3+ With inner layer RE 3+ (RE=Gd 3+ ,Yb 3+ ,Er 3+ ) Combined, finally highObtaining SiO with a multilayer core-shell structure by warm calcination 2 @Gd 2 O 3 :Eu@SiO 2 @GdVO 4 :Yb,Er@SiO 2 And (4) microspheres. The prepared luminescent microsphere has the characteristics of uniform particle size, high luminescent intensity, good dispersibility and the like, saves rare earth resources, has low cost, and has the characteristics of environment-friendly preparation method, simple equipment, high conversion rate, easy industrial production and the like.
Description
Technical Field
The present invention belongs to a rare earth oxide-vanadate composite nano hairThe field of optical materials, and relates to SiO with a multilayer core-shell structure 2 @Gd 2 O 3 :Eu@SiO 2 @GdVO 4 :Yb,Er@SiO 2 Composite synthesis method of composite nano luminescent material (wherein Gd) 2 O 3 Eu is cubic phase, gdVO 4 Yb, er is a tetragonal phase structure), especially Gd with down-conversion (DC) red light cubic phase is synthesized by adopting a low-temperature, low-cost and environment-friendly method 2 O 3 Eu and green square phase GdVO of up-conversion (UC) 4 A method for preparing a core-shell structure nano-scale composite luminescent material of Yb and Er.
Background
Because the rare earth element has a unique electronic layer structure, the rare earth compound has a plurality of excellent optical, electric and magnetic functions, and particularly the rare earth element has spectroscopy properties which are incomparable with common elements. The rare earth oxide and vanadate have high thermal stability, chemical stability and mechanical stability, so the rare earth oxide and vanadate can be widely applied to the fields of photoelectric communication, glass manufacturing industry, display illumination, catalysis, fluorescent probes and the like. The recent core-shell structure multi-level nano-material has properties of both core material and shell material, and can improve magnetic, optical, mechanical, thermal, electrical and catalytic properties thereof by adjusting and controlling the size and composition of the core and shell materials thereof, so as to be applied in various fields. The research of the rare earth oxide and vanadate core-shell structure multi-level nano/micron material has potential application prospect. At present, rare earth oxide and vanadate core-shell structure multimode luminescent materials have few reports, and mainly focus on synthesis of uniformly mixing multiple rare earth elements with UC and DC properties into the same material to prepare a dual-mode luminescent material. The synthesis mainly adopts organic template agent or organic solvent high-temperature hydrothermal synthesis, such as T, vairapeumulal, M, lakshmi, R.V. Kumar, S.K. J, M.A. Kumar,J. Lumin. 2020, 217, 116761；L. Wang, H. Chen, D. Zhang, D. Zhao, W. Qin, Mater. Lett. 2011, 65, 504-506；P. Kumar, J. Dwivedi, B. K. Gupta, J. Mater. Chem. C. 2014, 2, 10468-10475；A. K. Singh, S. K. Singh, B. K. Gupta, R. Prakash, S. B. Rai, Dalton. Trans.2013, 421065-1072, et alThe report of (1). These methods have the disadvantages of complicated synthesis method, no reutilization of raw materials, high raw material price and environmental pollution; and the rare earth elements with UC and DC properties are uniformly mixed into the same material to prepare the dual-mode luminescent material, so that the lanthanide elements have the defects of cross relaxation, reduction of the luminous intensity and the like, and the large-scale production and application are not facilitated. Respectively doping the rare earth elements with DC and UC properties into the inner layer or the outer layer of the core-shell structure, and using SiO in the middle 2 The shell is isolated to avoid the occurrence of cross relaxation between lanthanides to improve the luminous intensity. SiO 2 2 No toxicity, low cost, and use of SiO 2 As a nuclear material, resources can be saved; with SiO 2 As a shell material, the rare earth luminescent center can be protected from the interference of the environment, the light effect is improved, the concentration quenching among rare earth ions can be reduced, and the biocompatibility of a sample is improved. Thus developing a low-temperature, low-cost, environmentally friendly method for synthesizing SiO 2 The method for preparing the oxide and vanadate composite material with the nano/micron multilevel structure with the core-shell structure multimode luminescent performance as the core and shell materials has great significance.
Disclosure of Invention
The invention aims to provide SiO with no toxicity, low cost and adjustable particle size 2 Rare earth oxides and vanadate core-shell structures SiO as core and shell materials 2 @Gd 2 O 3 :Eu@SiO 2 @GdVO 4 :Yb,Er@SiO 2 The composite nanometer luminescent material has both down converted red light emitting and up converted green light emitting.
SiO of core-shell structure 2 @Gd 2 O 3 :Eu@SiO 2 @GdVO 4 :Yb,Er@SiO 2 The preparation method of the composite nano luminescent material comprises the following specific steps:
1. SiO 2 preparing microspheres: to a 100 mL round bottom flask was added 4 mL H 2 O, 35 mL of absolute ethyl alcohol, and adjusting the pH value to 8-9 by using ammonia water. Continuously stirring in an oil bath kettle to keep the temperature at 50 ℃, and then dropwise adding 1.7 mL of tetraethoxysilane. After the reaction is carried out for 6 to 8 hours, centrifugally separating the reaction liquid, and drying for 4 to 8 hours at 60 to 80 ℃ to obtain SiO with the diameter of 105nm 2 And (4) microspheres.
2. SiO 2 @Gd 2 O 3 :Eu@SiO 2 Preparing microspheres: 0.2g of the SiO prepared above is weighed 2 Putting microspheres into a 100 mL round-bottom flask, adding a certain amount of deionized H 2 Performing ultrasonic dispersion on O and absolute ethyl alcohol for 8 to 10 min, and adding a certain amount of Gd (NO) according to a molar ratio of 95 to 5 percent 3 ) 3 ·6H 2 O and Eu (NO) 3 ) 3 ·6H 2 Stirring for 5min, adding 0.3g of urea, stirring for 20-30 min to fully dissolve the urea, performing reflux reaction for 12-18 h at 85 ℃ in an oil bath pot, performing centrifugal separation on reaction liquid, and drying the obtained product for 4-8 h at the temperature of 60-80 ℃ to obtain a precursor SiO 2 @ RE. Then 0.2g of precursor SiO was weighed 2 @ RE white powder in a 100 mL beaker, a certain amount of deionized H was added 2 Ultrasonically dispersing O and absolute ethyl alcohol for 3-5min, adjusting the pH value to be 8-9, transferring the mixture into an oil bath pan, stirring, dropwise adding a certain amount of tetraethoxysilane, reacting at normal temperature for 3 h, then performing centrifugal separation, and putting the product into a muffle furnace to calcine at 900 ℃ for 4 h to obtain SiO 2 @Gd 2 O 3 :Eu@SiO 2 And (3) microspheres.
3. SiO 2 @Gd 2 O 3 :Eu@SiO 2 @GdVO 4 :Yb,Er@SiO 2 Preparing microspheres: 0.2g of the SiO prepared is weighed 2 @Gd 2 O 3 :Eu@SiO 2 Putting microspheres into a 100 mL round-bottom flask, adding a certain amount of deionized H 2 Performing ultrasonic dispersion on O and absolute ethyl alcohol for 10 min, and then sequentially adding 0.78 mmol of Gd (NO) 3 ) 3 ·6H 2 O、0.20 mmol Yb(NO 3 ) 3 ·6H 2 O、0.02 mmol Er(NO 3 ) 3 ·6H 2 And O and 0.3g of urea are stirred and dissolved, and then are subjected to reflux reaction at 85 ℃ in an oil bath kettle for 12 hours. After the reaction is finished, centrifugally separating the obtained reaction liquid, and drying at 60 ℃ to obtain SiO 2 @Gd 2 O 3 :Eu@SiO 2 @RE(RE=Gd 3+ ,Yb 3+ ,Er 3+ ) And (3) microspheres.
Weighing SiO 2 @Gd 2 O 3 :Eu@SiO 2 @RE(RE=Gd 3+ ,Yb 3+ ,Er 3+ ) Microspheres 0.2g in a 100 mL beaker were added 4mL H 2 O, 30 mL of absolute ethyl alcohol and 0.6 mL of ammonia water, dropwise adding 100 mu L of ethyl orthosilicate after ultrasonic dispersion, reacting for 3 hours at normal temperature, centrifugally separating, washing with water, washing with alcohol, and drying to obtain SiO 2 @Gd 2 O 3 :Eu@SiO 2 @RE(RE=Gd 3+ ,Yb 3+ ,Er 3+ )@SiO 2 And (5) precursor microspheres.
Weighing the obtained SiO 2 @Gd 2 O 3 :Eu@SiO 2 @RE(RE=Gd 3+ ,Yb 3+ ,Er 3+ )@SiO 2 0.2g of precursor microspheres are put into a 100 mL round-bottom flask, and 15 mL of H is added 2 And O and 20 mL of ethylene glycol are subjected to ultrasonic dispersion for 10 min, then a certain amount of ammonium metavanadate is added, and the reflux reaction is carried out for 6 to 12 h at 100 to 125 ℃ in an oil bath kettle. And after the reaction is finished, performing centrifugal separation on the obtained brown yellow suspension, and drying at 60 ℃. Finally, placing the dried powder into a muffle furnace to be calcined for 4 hours at 900 ℃ to obtain SiO 2 @Gd 2 O 3 :Eu@SiO 2 @GdVO 4 :Yb,Er@SiO 2 And (3) microspheres. (all the water used in the patent of the invention is deionized water)
The preparation method of the material is environment-friendly, simple in equipment and simple and convenient in synthesis steps; the raw materials are low in price, and an expensive surfactant is not needed as a template agent; the method has the characteristics of no use of toxic and harmful organic solvents, no environmental pollution, energy conservation, high conversion rate, easy industrial production and the like, and is an ideal green process; the repeatability is good.
Description of the drawings:
FIGS. 1a and b are SiO diagrams corresponding to examples 2 @Gd 2 O 3 :Eu@SiO 2 @GdVO 4 :Yb,Er@SiO 2 XRD pattern and TEM pattern of the product. FIGS. 1c and d are SiO diagrams corresponding to the respective examples 2 @Gd 2 O 3 :Eu@SiO 2 @GdVO 4 :Yb,Er@SiO 2 XRD pattern and TEM pattern of the product. Red line and blue line in XRD pattern are cubic phase Gd 2 O 3 Standard card JCPDS No. 12-0797, and tetragonal GdVO 4 Standard card JCPDS No. 17-0260, it can be seen that samples obtained from both examples are cubic Gd 2 O 3 And tetragonal GdVO 4 The crystallinity is better. The TEM image shows that the samples obtained by the two examples have clear multilayer core-shell structures and better dispersity.
FIG. 2 is a diagram of the synthesis of SiO 2 @Gd 2 O 3 :Eu@SiO 2 @GdVO 4 :Yb,Er@SiO 2 The upconversion emission spectrogram of the sample shows that the synthesized sample has good upconversion luminescence performance, and the strongest emission peak is positioned at 552nm and is green emission.
FIG. 3 is a diagram of the synthesis of SiO 2 @Gd 2 O 3 :Eu@SiO 2 @GdVO 4 :Yb,Er@SiO 2 The down-conversion fluorescence spectrum of the sample shows that the synthesized sample has good down-conversion fluorescence performance, and the strongest emission peak is at 619nm and is red light emission.
FIG. 4 shows the synthesis of SiO 2 @Gd 2 O 3 :Eu@SiO 2 @GdVO 4 :Yb,Er@SiO 2 The CIE chromaticity coordinates of the sample and the luminescence photograph of the sample water dispersion liquid show that the sample has good luminescence properties of up-conversion green light and down-conversion red light.
The specific implementation mode is as follows:
example one
(1) To a 100 mL round bottom flask was added 4 mL H 2 O and 35 mL of absolute ethanol, and adjusting the pH value to be 8 to 9 by using ammonia water. Continuously stirring in an oil bath kettle to keep the temperature at 50 ℃, and then dropwise adding 1.7 mL of tetraethoxysilane. After the reaction is carried out for 6 to 8 hours, centrifugally separating the reaction liquid, washing with water and absolute ethyl alcohol for 3 times, drying at 60 to 80 ℃ for 4 to 8 hours to obtain SiO with the diameter of to 105nm 2 And (3) microspheres.
(2) Weighing 0.2g of SiO with the diameter of 105nm 2 Microspheres dispersed in 20 mL H 2 O and 15 mL of absolute ethanol, 0.3g of urea and 0.95 mmol of Gd (NO) 3 ) 3 ·6H 2 O and 0.05 mmol Eu (NO) 3 ) 3 ·6H 2 O, stirring at normal temperature for 30 min to dissolve, reacting in an oil bath at 85 ℃ for 12 hours, then performing centrifugal separation, washing with water and absolute ethyl alcohol for 3 times, and drying at 60 ℃ to obtain SiO 2 @ RE precursor. 0.2g of SiO are weighed 2 @ RE precursor, addInto 4 mL of H 2 O, 30 mL of absolute ethyl alcohol and 0.6 mL of ammonia water, dropwise adding 100 mu L of ethyl orthosilicate after ultrasonic dispersion, reacting for 3 hours at normal temperature, centrifuging, washing with water and absolute ethyl alcohol for 3 times, and drying at 60 ℃ to obtain SiO 2 @RE@SiO 2 And (3) precursor. Mixing SiO 2 @RE@SiO 2 Putting the precursor into a muffle furnace, heating from room temperature to 900 ℃ at a heating rate of 9 ℃/min, and calcining for 4 h to obtain SiO 2 @Gd 2 O 3 :Eu@SiO 2 And (3) microspheres.
(3) 0.2g of SiO are weighed 2 @Gd 2 O 3 :Eu@SiO 2 Microspheres in 100 mL round-bottom flask, 20 mL H was added 2 Performing ultrasonic dispersion on O and 15 mL of absolute ethyl alcohol for 10 min, and then sequentially adding 0.78 mmol of Gd (NO) 3 ) 3 ·6H 2 O、0.20 mmol Yb(NO 3 ) 3 ·6H 2 O、0.02 mmol Er(NO 3 ) 3 ·6H 2 Stirring and dissolving O and 0.3g of urea, carrying out reflux reaction at 85 ℃ in an oil bath for 12 hours, then carrying out centrifugal separation, washing with water and absolute ethyl alcohol for 3 times, and drying at 60 ℃ to obtain SiO 2 @Gd 2 O 3 :Eu@SiO 2 @RE（RE=Gd 3+ ,Yb 3+ ,Er 3+ ) And (3) microspheres. Taking SiO 2 @Gd 2 O 3 :Eu@SiO 2 @RE（RE=Gd 3+ ,Yb 3+ ,Er 3+ ) Microspheres 0.2g in a 100 mL beaker were added 4 mL H 2 O, 30 mL of absolute ethyl alcohol and 0.6 mL of ammonia water, dropwise adding 100 mu L of tetraethoxysilane after ultrasonic dispersion, reacting for 3 hours at normal temperature, then performing centrifugal separation, washing with water and absolute ethyl alcohol for 3 times, and drying at 60 ℃ to obtain SiO 2 @Gd 2 O 3 :Eu@SiO 2 @RE@SiO 2 （RE=Gd 3+ ,Yb 3+ ,Er 3+ ) And (5) precursor microspheres.
0.2g of SiO are weighed 2 @Gd 2 O 3 :Eu@SiO 2 @RE@SiO 2 （RE=Gd 3+ ,Yb 3+ ,Er 3+ ) Putting the precursor microspheres into a 100 mL round-bottom flask, and adding 15 mL H 2 And performing ultrasonic dispersion on O and 20 mL of glycol for 10 min, then adding 0.15 g of ammonium metavanadate, performing reflux reaction at 125 ℃ in an oil bath for 6 h, then performing centrifugal separation, washing with water and absolute ethyl alcohol for 3 times, and then drying at 60 ℃. Putting the dried sample into a muffleHeating the temperature in the furnace from room temperature to 900 ℃ at the heating rate of 9 ℃/min, and calcining for 4 h to obtain SiO 2 @Gd 2 O 3 :Eu@SiO 2 @GdVO 4 :Yb,Er@SiO 2 And (3) microspheres.
Example two
(1) To a 100 mL round bottom flask was added 4 mL H 2 O, 35 mL of absolute ethyl alcohol, and adjusting the pH value to 8-9 by using ammonia water. Continuously stirring in an oil bath kettle to keep the temperature at 50 ℃, and then dropwise adding 1.7 mL of tetraethoxysilane. After the reaction is carried out for 6 to 8 hours, centrifugally separating the reaction liquid, washing the reaction liquid with water and absolute ethyl alcohol for 3 times, drying the reaction liquid for 4 to 8 hours at 60 to 80 ℃ to obtain SiO with the diameter of 105nm 2 And (3) microspheres.
(2) Weighing 0.2g of SiO with the diameter of 105nm 2 Microspheres dispersed in 25 mL H 2 O and 10 mL of absolute ethanol, 0.3g of urea and 0.475 mmol of Gd (NO) 3 ) 3 ·6H 2 O and 0.025 mmol Eu (NO) 3 ) 3 ·6H 2 Stirring at normal temperature for 20 min to dissolve O, reacting in an oil bath at 85 ℃ for 18 hours, then performing centrifugal separation, washing 3 times with water and absolute ethyl alcohol, and drying at 80 ℃ to obtain SiO 2 @ RE precursor. 0.2g of SiO are weighed 2 @ RE precursor, 2 mL H 2 O, 30 mL of absolute ethyl alcohol and 0.6 mL of ammonia water, dropwise adding 100 mu L of ethyl orthosilicate after ultrasonic dispersion, reacting for 6 h at normal temperature, centrifuging, washing with water and absolute ethyl alcohol for 3 times, and drying at 80 ℃ to obtain SiO 2 @RE@SiO 2 And (3) precursor. Mixing SiO 2 @RE@SiO 2 Putting the precursor into a muffle furnace, heating from room temperature to 900 ℃ at the heating rate of 9 ℃/min, and calcining for 4 h to obtain SiO 2 @Gd 2 O 3 :Eu@SiO 2 And (3) microspheres.
(3) 0.2g of SiO are weighed out 2 @Gd 2 O 3 :Eu@SiO 2 Microspheres in 100 mL round-bottom flask, 20 mL H was added 2 Performing ultrasonic dispersion on O and 15 mL of absolute ethyl alcohol for 10 min, and then sequentially adding 0.78 mmol of Gd (NO) 3 ) 3 ·6H 2 O、0.20 mmol Yb(NO 3 ) 3 ·6H 2 O、0.02 mmol Er(NO 3 ) 3 ·6H 2 Stirring and dissolving O and 0.3g of urea, performing oil bath at 85 ℃ for reflux reaction for 12 hours, performing centrifugal separation, washing water and anhydrous alcoholDrying at 80 ℃ after 3 times to obtain SiO 2 @Gd 2 O 3 :Eu@SiO 2 @RE（RE=Gd 3+ ,Yb 3+ ,Er 3 + ) And (3) microspheres. Weighing SiO 2 @Gd 2 O 3 :Eu@SiO 2 @RE（RE=Gd 3+ ,Yb 3+ ,Er 3+ ) Microspheres 0.2g in a 100 mL beaker were added 4 mL H 2 O, 30 mL of absolute ethyl alcohol and 0.6 mL of ammonia water, dropwise adding 100 mu L of ethyl orthosilicate after ultrasonic dispersion, reacting for 3 hours at normal temperature, then performing centrifugal separation, washing with water and absolute ethyl alcohol for 3 times, and drying at 80 ℃ to obtain SiO 2 @Gd 2 O 3 :Eu@SiO 2 @RE@SiO 2 （RE=Gd 3+ ,Yb 3+ ,Er 3+ ) And (5) precursor microspheres.
0.2g of SiO are weighed 2 @Gd 2 O 3 :Eu@SiO 2 @RE(RE=Gd 3+ ,Yb 3+ ,Er 3+ )@SiO 2 Adding the precursor microspheres into a 100 mL round-bottom flask, and adding 15 mL H 2 And performing ultrasonic dispersion on O and 20 mL of glycol for 10 min, then adding 0.10 g of ammonium metavanadate, performing reflux reaction at 100 ℃ in an oil bath for 12 h, centrifuging, washing with water and absolute ethyl alcohol for 3 times, and drying at 60 ℃. Putting the dried sample into a muffle furnace, heating from room temperature to 900 ℃ at a heating rate of 9 ℃/min, and calcining for 4 h to obtain SiO 2 @Gd 2 O 3 :Eu@SiO 2 @GdVO 4 :Yb,Er@SiO 2 And (3) microspheres.
Claims (3)
1. SiO of multilayer core-shell structure capable of emitting down-conversion red light and up-conversion green light 2 @Gd 2 O 3 :Eu@SiO 2 @GdVO 4 :Yb,Er@SiO 2 The synthesis method of the composite nano luminescent material is characterized by comprising the following steps: (1) Synthesis of SiO with a nucleus diameter of about 105nm by the nanoribbon method 2 Microspheres prepared by hydrolyzing and coprecipitating rare earth ions (RE) with urea 3+ =Gd 3+ And Eu 3+ ) Deposited on SiO 2 Coating SiO with thickness of about 8 nm on the surface of the microsphere by using a hydrolysis method of tetraethoxysilane 2 Obtaining SiO from the shell 2 @RE@SiO 2 Microspheres; (2) Then utilizing urea hydrolysis coprecipitation method to make rare earth ion (RE) 3+ =Gd 3+ 、Yb 3+ And Er 3+ ) Deposited on SiO 2 @RE@SiO 2 SiO with the shell layer thickness of 8 nm on the surface of the microsphere 2 A shell layer; (3) Through VO 4 3- Ions and inner layer rare earth ions (RE) 3+ =Gd 3+ 、Yb 3+ And Er 3+ ) Combine to form GdVO 4 Calcination of Yb, er layer at 900 ℃ to obtain Gd with down-converted red light emission 2 O 3 Eu layer and GdVO for upconversion green light emission 4 Multilayer core-shell SiO of Yb, er layer 2 @Gd 2 O 3 :Eu@SiO 2 @GdVO 4 :Yb,Er@SiO 2 The composite nanometer luminescent material has the following specific technological conditions:
(1) To a 100 mL round bottom flask was added 4 mL H 2 O and 35 mL of absolute ethyl alcohol, adjusting the pH value to be 8 to 9 by using ammonia water, continuously stirring in an oil bath kettle to keep the temperature at 50 ℃, then dropwise adding 1.7 mL of tetraethoxysilane, reacting for 6 to 8 hours, then carrying out centrifugal separation on reaction liquid, washing with water and absolute ethyl alcohol for 3 times, drying at 60 to 80 ℃ for 4 to 8 hours, and obtaining SiO with the diameter of 105nm 2 Microspheres;
(2) Weighing 0.2g of SiO with the diameter of 105nm 2 Microspheres dispersed in 20 mL H 2 O and 15 mL of absolute ethanol, 0.3g of urea and 0.95 mmol of Gd (NO) 3 ) 3 ·6H 2 O and 0.05 mmol Eu (NO) 3 ) 3 ·6H 2 O, stirring at normal temperature to dissolve, reacting in 85 ℃ oil bath for 12 hours, centrifuging, washing with water and absolute ethyl alcohol for 3 times, drying at 60 ℃, weighing 0.2g of dried sample, adding 4 mL of H 2 O, 30 mL of absolute ethyl alcohol and 0.6 mL of ammonia water, dropwise adding 100 mu L of tetraethoxysilane after ultrasonic dispersion, reacting for 3 hours at normal temperature, centrifugally separating, washing with water and absolute ethyl alcohol for 3 times, and drying to obtain SiO 2 @RE@SiO 2 The precursor is calcined for 4 hours at 900 ℃ in a muffle furnace to obtain SiO 2 @Gd 2 O 3 :Eu@SiO 2 Microspheres;
(3) 0.2g of SiO are weighed 2 @Gd 2 O 3 :Eu@SiO 2 Microspheres in 100 mL round-bottom flask, 20 mL H was added 2 Performing ultrasonic dispersion on O and 15 mL of absolute ethyl alcohol for 10 min, and then sequentially adding 0.78 mmol of Gd (NO) 3 ) 3 ·6H 2 O、0.20 mmol Yb(NO 3 ) 3 ·6H 2 O、0.02 mmol Er(NO 3 ) 3 ·6H 2 Stirring and dissolving O and 0.3g of urea, carrying out reflux reaction at 85 ℃ in an oil bath for 12 h, then carrying out centrifugal separation, washing with water and absolute ethyl alcohol for 3 times, and drying at 60 ℃ to obtain SiO 2 @Gd 2 O 3 :Eu@SiO 2 @RE (RE=Gd 3+ ,Yb 3+ ,Er 3+ ) Microspheres; 0.2g of SiO are weighed 2 @Gd 2 O 3 :Eu@SiO 2 @RE (RE=Gd 3+ ,Yb 3+ ,Er 3+ ) Microspheres were placed in a 100 mL beaker and 4 mL H was added 2 O, 30 mL of absolute ethyl alcohol and 0.6 mL of ammonia water, dropwise adding 100 mu L of tetraethoxysilane after ultrasonic dispersion, reacting for 3 hours at normal temperature, centrifuging, washing with water and absolute ethyl alcohol for 3 times, and drying at 60 ℃ to obtain SiO 2 @Gd 2 O 3 :Eu@SiO 2 @RE@SiO 2 (RE=Gd 3+ ,Yb 3+ ,Er 3+ ) Precursor microspheres; 0.2g of SiO are weighed 2 @Gd 2 O 3 :Eu@SiO 2 @RE@SiO 2 (RE=Gd 3+ ,Yb 3+ ,Er 3+ ) Putting the precursor microspheres into a 100 mL round-bottom flask, and adding 15 mL H 2 Performing ultrasonic dispersion on O and 20 mL of ethylene glycol for 10 min, then adding 0.15 g of ammonium metavanadate, performing reflux reaction at 125 ℃ in an oil bath for 6 h, centrifuging, washing with water and absolute ethyl alcohol for 3 times, then drying at 60 ℃, finally putting the dried powder into a muffle furnace, heating from room temperature at the heating rate of 9 ℃ per min to 900 ℃ and calcining for 4 h to obtain SiO 2 @Gd 2 O 3 :Eu@SiO 2 @GdVO 4 :Yb,Er@SiO 2 And (3) microspheres.
2. The multilayer core-shell structure of claim 1 comprising SiO that down-convert red and up-convert green light 2 @Gd 2 O 3 :Eu@SiO 2 @GdVO 4 :Yb,Er@SiO 2 The synthesis method of the composite nano luminescent material is characterized by comprising the following steps: siO used 2 The diameter of the core is about 105 nm; siO 2 2 Depositing rare earth ions (RE) on the surface of the microsphere 3+ =Gd 3+ And Eu 3+ ) The rear surface is coated with SiO with the thickness of about 8 nm 2 Shell layer for avoiding rare earth ions (RE) with subsequent coating 3+ =Gd 3+ 、Yb 3+ And Er 3+ ) Cross relaxation occurs and fluorescence is quenched.
3. The multilayer core-shell structure of claim 1 of SiO red down-converted and green up-converted from a multilayer core-shell structure 2 @Gd 2 O 3 :Eu@SiO 2 @GdVO 4 :Yb,Er@SiO 2 The synthesis method of the composite nano luminescent material is characterized by comprising the following steps: hydrolyzing rare earth ion (RE) with urea 3+ =Gd 3+ 、Yb 3+ And Er 3+ ) Deposition to SiO 2 @Gd 2 O 3 :Eu@SiO 2 After the surface of the microsphere, siO with the thickness of about 8 nm is coated firstly 2 A shell layer, and then GdVO is substituted by ammonium metavanadate 4 Yb and Er coated on SiO 2 @Gd 2 O 3 :Eu@SiO 2 Obtaining a multilayer core-shell structure product on the surface of the microsphere.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101074374A (en) * | 2006-05-19 | 2007-11-21 | 中国科学院理化技术研究所 | Rare-earth nano-fluorescent grain with core-shell structure, its production and use |
| US20080290318A1 (en) * | 2005-04-26 | 2008-11-27 | Van Veggel Franciscus C J M | Production of Light from Sol-Gel Derived Thin Films Made with Lanthanide Doped Nanoparticles, and Preparation Thereof |
| CN101941676A (en) * | 2010-08-26 | 2011-01-12 | 吉林大学 | Method for preparing Ln2O3:RE<3+> and Ln2O3:RE<3+>@SiO2 monodisperse rare earth nano particles |
| US20110127445A1 (en) * | 2006-10-17 | 2011-06-02 | National University Of Singapore | Upconversion fluorescent nano-structured material and uses thereof |
| CN103756668A (en) * | 2014-01-08 | 2014-04-30 | 上海大学 | Core-shell type rare earth up-conversion composite nanoparticle and preparation method thereof |
| CN106939162A (en) * | 2016-01-04 | 2017-07-11 | 内蒙古大学 | SiO2The synthetic method of@Tb (phen-Si) L nuclear shell structure nano luminescent composites |
| CN109158062A (en) * | 2018-09-19 | 2019-01-08 | 新疆维吾尔自治区产品质量监督检验研究院 | Silicon dioxide colloid compound rare-earth core-shell type microballoon and preparation method thereof |
| CN112300788A (en) * | 2020-11-02 | 2021-02-02 | 中山大学 | Core-point shell structure photomagnetic nanoprobe and preparation method and application thereof |
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080290318A1 (en) * | 2005-04-26 | 2008-11-27 | Van Veggel Franciscus C J M | Production of Light from Sol-Gel Derived Thin Films Made with Lanthanide Doped Nanoparticles, and Preparation Thereof |
| CN101074374A (en) * | 2006-05-19 | 2007-11-21 | 中国科学院理化技术研究所 | Rare-earth nano-fluorescent grain with core-shell structure, its production and use |
| US20110127445A1 (en) * | 2006-10-17 | 2011-06-02 | National University Of Singapore | Upconversion fluorescent nano-structured material and uses thereof |
| CN101941676A (en) * | 2010-08-26 | 2011-01-12 | 吉林大学 | Method for preparing Ln2O3:RE<3+> and Ln2O3:RE<3+>@SiO2 monodisperse rare earth nano particles |
| CN103756668A (en) * | 2014-01-08 | 2014-04-30 | 上海大学 | Core-shell type rare earth up-conversion composite nanoparticle and preparation method thereof |
| CN106939162A (en) * | 2016-01-04 | 2017-07-11 | 内蒙古大学 | SiO2The synthetic method of@Tb (phen-Si) L nuclear shell structure nano luminescent composites |
| CN109158062A (en) * | 2018-09-19 | 2019-01-08 | 新疆维吾尔自治区产品质量监督检验研究院 | Silicon dioxide colloid compound rare-earth core-shell type microballoon and preparation method thereof |
| CN112300788A (en) * | 2020-11-02 | 2021-02-02 | 中山大学 | Core-point shell structure photomagnetic nanoprobe and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| HE BAI ET AL.: "High-efficient fabrication of core-shell structured SiO2@GdPo4:Tb@SiO2 nanoparticles with improved luminescence", ROYAL SOCIETY OPEN SCIENCE, vol. 7, no. 5, pages 192235 * |
| 杨云江: "双模多层核壳结构稀土复合发光微球的制备、表征及其荧光防伪应用研究", 中国优秀硕士学位论文全文数据库 工程科技I辑, no. 01, pages 020 - 875 * |
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