CN115181568B - Synthesis of multi-layer core-shell structure composite nano dual-mode luminescent material - Google Patents
Synthesis of multi-layer core-shell structure composite nano dual-mode luminescent material Download PDFInfo
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- 239000011258 core-shell material Substances 0.000 title claims abstract description 21
- 239000000463 material Substances 0.000 title claims abstract description 20
- 239000002131 composite material Substances 0.000 title claims description 12
- 230000015572 biosynthetic process Effects 0.000 title description 5
- 238000003786 synthesis reaction Methods 0.000 title description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 95
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 87
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 87
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 87
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 87
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 73
- 239000004005 microsphere Substances 0.000 claims abstract description 50
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 229910052691 Erbium Inorganic materials 0.000 claims abstract description 23
- 239000002243 precursor Substances 0.000 claims abstract description 22
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 18
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical group 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
- 239000004202 carbamide Substances 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 10
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims abstract description 6
- 238000001354 calcination Methods 0.000 claims abstract description 6
- 230000007062 hydrolysis Effects 0.000 claims abstract 7
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract 7
- 239000011248 coating agent Substances 0.000 claims abstract 3
- 238000000576 coating method Methods 0.000 claims abstract 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
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- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 239000012295 chemical reaction liquid Substances 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 9
- 229910002617 Gd(NO3)3·6H2O Inorganic materials 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910002538 Eu(NO3)3·6H2O Inorganic materials 0.000 claims description 4
- 230000002194 synthesizing effect Effects 0.000 claims description 4
- KUBYTSCYMRPPAG-UHFFFAOYSA-N ytterbium(3+);trinitrate Chemical compound [Yb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KUBYTSCYMRPPAG-UHFFFAOYSA-N 0.000 claims description 4
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- 239000011257 shell material Substances 0.000 description 6
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 6
- 239000011162 core material Substances 0.000 description 5
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052747 lanthanoid Inorganic materials 0.000 description 2
- 150000002602 lanthanoids Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
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- 230000009286 beneficial effect Effects 0.000 description 1
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- 238000005119 centrifugation Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
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- 238000000295 emission spectrum Methods 0.000 description 1
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- 239000011521 glass Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
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- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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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- C—CHEMISTRY; METALLURGY
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
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Abstract
The invention discloses a rare earth down-conversion red light-up-conversion green light multi-layer core-shell structure nano luminescent material and a preparation method thereof, wherein rare earth ions Gd 3+ and Eu 3+ are uniformly coated on the surface of SiO 2 microspheres by a urea homogeneous precipitation method, then SiO 2 shell layers are coated by a method of alkalescence hydrolysis of tetraethoxysilane, and a core-shell structure precursor SiO 2@Gd2O3:Eu@SiO2 is obtained after high-temperature calcination; and coating rare earth ions Gd 3+、Yb3+、Er3+ on the surface of the precursor by using a urea hydrolysis method, continuously coating a SiO 2 shell layer by using a method of alkalescence hydrolysis of tetraethoxysilane, dispersing the obtained product in a mixed solution of H 2 O and ethylene glycol, adding ammonium metavanadate to combine VO 4 3+ with an inner layer RE 3+(RE=Gd3+,Yb3+,Er3+), and finally calcining at high temperature to obtain the multi-layer core-shell structure SiO 2@Gd2O3:Eu@SiO2@GdVO4:Yb,Er@SiO2 microsphere. The prepared luminescent microsphere has the characteristics of uniform particle size, strong luminescence, 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 invention belongs to the field of rare earth oxide-vanadate composite nano luminescent materials, and relates to a composite synthesis method of a multi-layer core-shell structure SiO 2@Gd2O3:Eu@SiO2@GdVO4:Yb,Er@SiO2 composite nano luminescent material (wherein Gd 2O3: eu is a cubic phase, gdVO 4: yb and Er is a square phase structure), in particular to a method for synthesizing a core-shell structure nano composite luminescent material simultaneously having down-conversion (DC) red cubic phase Gd 2O3: eu and up-conversion (UC) green square phase GdVO 4: yb and Er by adopting a low-temperature, low-cost and environment-friendly method.
Background
Because rare earth elements have unique electronic layer structures, rare earth compounds exhibit many excellent optical, electrical and magnetic functions, and in particular rare earth elements have spectral properties that are incomparable with those of common elements. The rare earth oxide and vanadate have high thermal stability, chemical stability and mechanical stability, so that the rare earth oxide and vanadate have wide application in the fields of photoelectric communication, glass manufacturing industry, display illumination, catalysis, fluorescent probes and the like. Recent core-shell structure multi-stage nano-materials can improve the magnetic, optical, mechanical, thermal, electric and catalytic properties of the core-shell structure multi-stage nano-materials by regulating the size and composition of the core and shell materials due to the properties of the core materials and the shell materials so as to be applied to 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, few reports of rare earth oxide and vanadate core-shell structure multimode luminescent materials are provided, and the synthesis of uniformly mixing various rare earth elements with UC and DC properties into the same material to prepare the dual-mode luminescent material is mainly focused on. The synthesis mainly adopts high-temperature hydrothermal synthesis of an organic template agent or an organic solvent, as reported in T. Vairapperumal, 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, 42, 1065-1072. and other documents. The methods have the advantages that the synthesis method is complex or the raw materials cannot be recycled, the raw materials are high in price, and the environment is polluted; and 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 cross relaxation between lanthanoids occurs, the luminescent intensity is reduced, and the like, which is not beneficial to large-scale production and application. Rare earth elements with DC and UC properties are respectively doped into an inner layer or an outer layer of the core-shell structure, and SiO 2 shell is used for isolating the rare earth elements in the middle to avoid cross relaxation between lanthanoids so as to improve luminous intensity. SiO 2 is nontoxic and low in cost, and SiO 2 is used as a core material, so that resources can be saved; siO 2 is used as a shell material, so that the rare earth luminous center can be protected from environmental interference, the light efficiency is improved, concentration quenching among rare earth ions can be reduced, and the biocompatibility of a sample is improved. Therefore, the method for developing the low-temperature, low-cost and environment-friendly method for synthesizing the nano/micron multi-level structure oxide and vanadate composite material with the multi-mode luminescence performance of the core-shell structure by taking SiO 2 as the core and shell material has great significance.
Disclosure of Invention
The invention aims to provide a synthesis method of a rare earth oxide and vanadate core-shell structure SiO 2@Gd2O3:Eu@SiO2@GdVO4:Yb,Er@SiO2 composite nano luminescent material which is nontoxic, low in cost and adjustable in particle size and is used as a core and shell material, and the material simultaneously has the functions of down-converting red light and up-converting green light emission.
The preparation method of the SiO 2@Gd2O3:Eu@SiO2@GdVO4:Yb,Er@SiO2 composite nano luminescent material with the core-shell structure comprises the following specific steps:
1. Preparation of SiO 2 microspheres: adding 4 mL H 2 O and 35 mL absolute ethyl alcohol into a 100 mL round-bottom flask, and adjusting the pH value to 8-9 by ammonia water. Stirring was continued in an oil bath to maintain the temperature at 50 ℃ and then 1.7 mL ethyl orthosilicate was added dropwise. And after reacting for 6-8 hours, centrifugally separating the reaction liquid, and drying at 60-80 ℃ for 4-8 hours to obtain the SiO 2 microsphere with the diameter of 105-nm.
2. Preparation of SiO 2@Gd2O3:Eu@SiO2 microspheres: weighing 0.2 g of the prepared SiO 2 microsphere, adding a certain amount of deionized H 2 O and absolute ethyl alcohol into a 100mL round-bottom flask, then performing ultrasonic dispersion for 8-10 min, adding a certain amount of Gd (NO 3)3·6H2 O and Eu (NO 3)3·6H2 O, stirring 5 min), then adding 0.3 g urea, stirring 20-30 min to fully dissolve, performing reflux reaction at 85 ℃ in an oil bath for 12-18H, performing centrifugal separation on the reaction solution, drying the obtained product at 60-80 ℃ for 4-8H, obtaining precursor SiO 2 @ RE., then weighing 0.2 g precursor SiO 2 @RE white powder into a 100mL beaker, adding a certain amount of deionized H 2 O and absolute ethyl alcohol, performing ultrasonic dispersion for 3-5min, adjusting pH value, stirring in the oil bath, dripping a certain amount of tetraethoxysilane, performing centrifugal separation at normal temperature for 3-80 ℃ and then placing the obtained product into a 3742 ℃ of the microsphere, and performing centrifugal separation, and placing the obtained product into a 2@Gd2O3:Eu@SiO2 ℃ of the microsphere.
3. Preparation of SiO 2@Gd2O3:Eu@SiO2@GdVO4:Yb,Er@SiO2 microspheres: weighing 0.2 g of prepared SiO 2@Gd2O3:Eu@SiO2 microsphere into a 100 mL round-bottomed flask, adding a certain amount of deionized H 2 O and absolute ethyl alcohol, then performing ultrasonic dispersion for 10 min, sequentially adding 0.78 mmol Gd(NO3)3·6H2O、0.20 mmol Yb(NO3)3·6H2O、0.02 mmol Er(NO3)3·6H2O and 0.3 g of urea, stirring and dissolving, and then performing reflux reaction for 12H at 85 ℃ in an oil bath. And after the reaction is finished, centrifugally separating the obtained reaction liquid, and drying at 60 ℃ to obtain SiO 2@Gd2O3:Eu@SiO2@RE(RE=Gd3+,Yb3+,Er3+) microspheres.
Weighing SiO 2@Gd2O3:Eu@SiO2@RE(RE=Gd3+,Yb3+,Er3+) microsphere 0.2 g in a 100mL beaker, adding 4 mL H 2 O, 30 mL absolute ethyl alcohol and 0.6 mL ammonia water, performing ultrasonic dispersion, then dripping 100 mu L of tetraethoxysilane, reacting at normal temperature for 3 h, performing centrifugal separation, washing with water, washing with alcohol, and drying to obtain SiO2@Gd2O3:Eu@SiO2@RE(RE=Gd3+,Yb3+,Er3+)@SiO2 precursor microsphere.
And weighing the SiO2@Gd2O3:Eu@SiO2@RE(RE=Gd3+,Yb3+,Er3+)@SiO2 precursor microspheres 0.2g into a 100 mL round-bottomed flask, adding 15 mL H 2 O and 20 mL glycol, performing ultrasonic dispersion for 10 min, adding a certain amount of ammonium metavanadate, and performing reflux reaction for 6-12 hours at 100-125 ℃ in an oil bath. And after the reaction is finished, centrifugally separating the obtained brown yellow suspension, and drying at 60 ℃. And finally, placing the dried powder into a muffle furnace for calcining at 900 ℃ for 4 h to obtain the SiO 2@Gd2O3:Eu@SiO2@GdVO4:Yb,Er@SiO2 microsphere. (the water used in the invention is deionized water)
The preparation method of the material is environment-friendly, simple in equipment and simple in synthesis steps; the raw materials are low in cost, and expensive surfactant is not required to be used 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, b are XRD and TEM patterns, respectively, of a corresponding SiO 2@Gd2O3:Eu@SiO2@GdVO4:Yb,Er@SiO2 product of the example. FIGS. 1c and d are the XRD and TEM patterns, respectively, of the SiO 2@Gd2O3:Eu@SiO2@GdVO4:Yb,Er@SiO2 product corresponding to example two. The red line and the blue line in the XRD diagram are respectively a cubic Gd 2O3 standard card JCPDS No. 12-0797 and a square GdVO 4 standard card JCPDS No. 17-0260, and the samples obtained in the two embodiments are mixed phases of the cubic Gd 2O3 and the square GdVO 4 and have good crystallinity. TEM images show that the samples obtained in the two examples have clear multi-layer core-shell structure and better dispersibility.
FIG. 2 is an up-conversion emission spectrum of a synthesized SiO 2@Gd2O3:Eu@SiO2@GdVO4:Yb,Er@SiO2 sample, from which it can be seen that the synthesized sample has good up-conversion luminescence properties, and the strongest emission peak is located at 552nm, which is the emission of green light.
FIG. 3 is a graph of down-conversion fluorescence spectrum of a synthesized SiO 2@Gd2O3:Eu@SiO2@GdVO4:Yb,Er@SiO2 sample, from which it can be seen that the synthesized sample has good down-conversion fluorescence performance, and the strongest emission peak is at 619nm, which is red light emission.
FIG. 4 is a photograph of CIE chromaticity coordinates of a sample of synthetic SiO 2@Gd2O3:Eu@SiO2@GdVO4:Yb,Er@SiO2 and luminescence of an aqueous dispersion of the sample, from which it can be seen that the sample has good luminescence properties of up-converting green light and down-converting red light.
The specific embodiment is as follows:
Example 1
(1) Adding 4 mL H 2 O and 35 mL absolute ethyl alcohol into a 100 mL round-bottom flask, and adjusting the pH value to 8-9 by ammonia water. Stirring was continued in an oil bath to maintain the temperature at 50 ℃ and then 1.7 mL ethyl orthosilicate was added dropwise. And 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, and drying the reaction liquid at 60 to 80 ℃ for 4 to 8 hours, thereby obtaining the SiO 2 microsphere with the diameter of 105 to nm.
(2) 0.2G of SiO 2 microsphere with the diameter of 105nm is weighed and dispersed in 20 mL H 2 O and 15 mL absolute ethyl alcohol, 0.3g of urea and 0.95 mmol Gd (NO 3)3·6H2 O and 0.05 mmol Eu (NO 3)3·6H2 O, after being dissolved by stirring 30 min at normal temperature, are reacted in an oil bath at 85 ℃ for 12 hours and then are centrifugally separated, water and absolute ethyl alcohol are washed for 3 times and then are dried at 60 ℃ to obtain a SiO 2 @RE precursor, 0.2g SiO 2 @RE precursor is weighed, 4 mL H 2 O, 30 mL absolute ethyl alcohol and 0.6 mL are added, 100 mu L of tetraethoxysilane are added after ultrasonic dispersion, after being reacted at normal temperature and 3 h, the mixture is centrifuged, water and absolute ethyl alcohol are washed for 3 times and then are dried at 60 ℃ to obtain the SiO 2@RE@SiO2 precursor, the SiO 2@RE@SiO2 precursor is put into a muffle furnace, and is heated up from room temperature to 900 ℃ at a speed of 9 ℃/min and calcined at a temperature of 4 h to obtain the SiO 2@Gd2O3:Eu@SiO2 microsphere.
(3) Weighing 0.2 g SiO 2@Gd2O3:Eu@SiO2 microsphere into a100 mL round bottom flask, adding 20 mL H 2 O and 15 mL absolute ethyl alcohol, then performing ultrasonic dispersion for 10 min, sequentially adding 0.78 mmol Gd(NO3)3·6H2O、0.20 mmol Yb(NO3)3·6H2O、0.02 mmol Er(NO3)3·6H2O and 0.3 g urea, stirring and dissolving, performing reflux reaction at 85 ℃ in an oil bath for 12 h, performing centrifugal separation, washing with water and absolute ethyl alcohol for 3 times, and drying at 60 ℃ to obtain SiO 2@Gd2O3:Eu@SiO2@RE（RE=Gd3+,Yb3+,Er3+) microsphere. Taking SiO 2@Gd2O3:Eu@SiO2@RE（RE=Gd3+,Yb3+,Er3+) microsphere 0.2 g in a100 mL beaker, adding 4 mL H 2 O, 30 mL absolute ethyl alcohol and 0.6 mL ammonia water, performing ultrasonic dispersion, then dripping 100 mu L of tetraethoxysilane, reacting at normal temperature for 3 h, performing centrifugal separation, washing with water and absolute ethyl alcohol for 3 times, and drying at 60 ℃ to obtain SiO2@Gd2O3:Eu@SiO2@RE@SiO2（RE=Gd3+,Yb3+,Er3+） precursor microsphere.
The 0.2 g SiO2@Gd2O3:Eu@SiO2@RE@SiO2（RE=Gd3+,Yb3+,Er3+） precursor microsphere is weighed into a 100mL round bottom flask, 15 mL H 2 O and 20mL glycol are added, then ultrasonic dispersion is carried out for 10 min, then 0.15 g ammonium metavanadate is added, centrifugal separation is carried out after oil bath reflux reaction for 6 h at 125 ℃, and water and absolute ethyl alcohol are washed for 3 times, and then 60 ℃ is dried. And (3) placing the dried sample into a muffle furnace, heating to 900 ℃ from room temperature at a heating rate of 9 ℃ per minute, and calcining for 4h to obtain the SiO 2@Gd2O3:Eu@SiO2@GdVO4:Yb,Er@SiO2 microsphere.
Example two
(1) Adding 4 mL H 2 O and 35 mL absolute ethyl alcohol into a 100 mL round-bottom flask, and adjusting the pH value to 8-9 by ammonia water. Stirring was continued in an oil bath to maintain the temperature at 50 ℃ and then 1.7 mL ethyl orthosilicate was added dropwise. And 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, and drying the reaction liquid at 60 to 80 ℃ for 4 to 8 hours, thereby obtaining the SiO 2 microsphere with the diameter of 105 to nm.
(2) 0.2G of SiO 2 microsphere with the diameter of 105nm is weighed and dispersed in 25 mL H 2 O and 10 mL absolute ethyl alcohol, 0.3g of urea and 0.475 mmol Gd (NO 3)3·6H2 O and 0.025 mmol Eu (NO 3)3·6H2 O, after being dissolved by stirring at normal temperature for 20 min, are reacted in an oil bath at 85 ℃ for 18 hours and then are centrifugally separated, water and absolute ethyl alcohol are washed for 3 times and then are dried at 80 ℃ to obtain a SiO 2 @RE precursor, 0.2g SiO 2 @RE precursor is weighed, 2 mL H 2 O, 30 mL absolute ethyl alcohol and 0.6 mL are added, 100 mu L of tetraethoxysilane are added after ultrasonic dispersion, 6h is reacted at normal temperature and then are centrifugally separated, water and absolute ethyl alcohol are washed for 3 times and then are dried at 80 ℃ to obtain the SiO 2@RE@SiO2 precursor, the SiO 2@RE@SiO2 precursor is put into a muffle furnace, and is calcined at 900 ℃ from room temperature to 900 ℃ at a speed of 9 ℃ and a temperature rising speed of h, so as to obtain the SiO 2@Gd2O3:Eu@SiO2 microsphere.
(3) Weighing 0.2 g SiO 2@Gd2O3:Eu@SiO2 microsphere into a 100 mL round bottom flask, adding 20 mL H 2 O and 15 mL absolute ethyl alcohol, then performing ultrasonic dispersion for 10min, sequentially adding 0.78 mmol Gd(NO3)3·6H2O、0.20 mmol Yb(NO3)3·6H2O、0.02 mmol Er(NO3)3·6H2O and 0.3 g urea, stirring and dissolving, performing reflux reaction at 85 ℃ in an oil bath for 12h, performing centrifugal separation, washing with water and absolute ethyl alcohol for 3 times, and drying at 80 ℃ to obtain SiO2@Gd2O3:Eu@SiO2@RE（RE=Gd3+,Yb3+,Er3 +） microsphere. Weighing SiO 2@Gd2O3:Eu@SiO2@RE（RE=Gd3+,Yb3+,Er3+) microsphere 0.2 g in a 100 mL beaker, adding 4mL H 2 O, 30 mL absolute ethyl alcohol and 0.6 mL ammonia water, performing ultrasonic dispersion, then dripping 100 mu L of tetraethoxysilane, reacting at normal temperature for 3h, performing centrifugal separation, washing with water and absolute ethyl alcohol for 3 times, and drying at 80 ℃ to obtain SiO2@Gd2O3:Eu@SiO2@RE@SiO2（RE=Gd3+,Yb3+,Er3+） precursor microsphere.
The 0.2 g SiO2@Gd2O3:Eu@SiO2@RE(RE=Gd3+,Yb3+,Er3+)@SiO2 precursor microsphere is weighed into a 100mL round bottom flask, 15 mL H 2 O and 20 mL glycol are added, then ultrasonic dispersion is carried out for 10 min, then 0.10 g ammonium metavanadate is added, oil bath is carried out for 100 ℃ reflux reaction for 12 h, centrifugation is carried out, water and absolute ethyl alcohol are washed for 3 times, and then 60 ℃ drying is carried out. And (3) placing the dried sample into a muffle furnace, heating to 900 ℃ from room temperature at a heating rate of 9 ℃ per minute, and calcining for 4 h to obtain the SiO 2@Gd2O3:Eu@SiO2@GdVO4:Yb,Er@SiO2 microsphere.
Claims (3)
1. A synthetic method of a SiO 2@Gd2O3:Eu@SiO2@GdVO4:Yb,Er@SiO2 composite nano luminescent material with a multilayer core-shell structure capable of emitting down-converted red light and up-converted green light is characterized in that: (1) By means ofSynthesizing SiO 2 microsphere with a core diameter of 105nm by a method, depositing rare earth ions Gd 3+ and Eu 3+ on the surface of the SiO 2 microsphere by a urea hydrolysis coprecipitation method, and coating a SiO 2 shell layer with a thickness of 8nm by an ethyl orthosilicate hydrolysis method to obtain the SiO 2@RE@SiO2 microsphere; (2) Then, rare earth ions Gd 3+、Yb3+ and Er 3+ are deposited on the surface of the SiO 2@RE@SiO2 microsphere by utilizing a urea hydrolysis coprecipitation method, and SiO 2 shell layers with the thickness of 8nm are coated; (3) The GdVO 4:Yb and Er layers are formed by combining VO 4 3- ions with inner rare earth ions Gd 3+、Yb3+ and Er 3+, gdVO 4:Yb and Er layers are obtained by calcining at 900 ℃ to obtain the multi-layer core-shell structure SiO 2@Gd2O3:Eu@SiO2@GdVO4:Yb,Er@SiO2 composite nano luminescent material with down-conversion red light emission Gd 2O3:Eu layers and up-conversion green light emission, and the specific process conditions are as follows:
(1) Adding 4mL of H 2 O and 35mL of absolute ethyl alcohol into a 100mL round-bottom flask, regulating the pH value to 8-9 by ammonia water, continuously stirring in an oil bath kettle to keep the temperature at 50 ℃, then dropwise adding 1.7mL of tetraethoxysilane, centrifugally separating reaction liquid after reacting for 6-8 hours, washing water and absolute ethyl alcohol for 3 times, and drying at 60-80 ℃ for 4-8 hours to obtain SiO 2 microspheres with the diameter of 105 nm;
(2) 0.2g of SiO 2 microsphere with the diameter of 105nm is weighed and dispersed in 20mL of H 2 O and 15mL of absolute ethyl alcohol, 0.3g of urea and 0.95mmol of Gd (NO 3)3·6H2 O and 0.05mmol of Eu (NO 3)3·6H2 O are added, stirred and dissolved at normal temperature, reacted in an oil bath at 85 ℃ for 12 hours, centrifugally separated, washed by water and absolute ethyl alcohol for 3 times and dried at 60 ℃, 0.2g of dried sample is weighed, 4mL of H 2 O, 30mL of absolute ethyl alcohol and 0.6mL of ammonia water are added, 100 mu L of tetraethoxysilane is added after ultrasonic dispersion, centrifugally separated after reaction for 3 hours at normal temperature, washed by water and absolute ethyl alcohol for 3 times and dried to obtain a precursor of SiO 2@Gd3+,Eu3+@SiO2, and then the precursor is calcined at 900 ℃ for 4 hours in a muffle furnace to obtain SiO 2@Gd2O3:Eu@SiO2 microsphere;
(3) Weighing 0.2g of SiO 2@Gd2O3:Eu@SiO2 microsphere into a 100mL round bottom flask, adding 20mL of H 2 O and 15mL of absolute ethyl alcohol, performing ultrasonic dispersion for 10min, sequentially adding 0.78mmol Gd(NO3)3·6H2O、0.20mmol Yb(NO3)3·6H2O、0.02mmol Er(NO3)3·6H2O and 0.3g of urea, stirring for dissolution, performing reflux reaction at 85 ℃ in an oil bath for 12H, performing centrifugal separation, washing with water and absolute ethyl alcohol for 3 times, and drying at 60 ℃ to obtain SiO 2@Gd2O3:Eu@SiO2@Gd3+,Yb3+,Er3+ microsphere; weighing 0.2g of SiO 2@Gd2O3:Eu@SiO2@Gd3+,Yb3+,Er3+ microsphere in a 100mL beaker, adding 4mL of H 2 O, 30mL of absolute ethyl alcohol and 0.6mL of ammonia water, performing ultrasonic dispersion, then dropwise adding 100 mu L of tetraethoxysilane, reacting at normal temperature for 3H, centrifuging, washing with water and absolute ethyl alcohol for 3 times, and drying at 60 ℃ to obtain SiO 2@Gd2O3:Eu@SiO2@Gd3+,Yb3+,Er3+@SiO2 precursor microsphere; and weighing 0.2g SiO2@Gd2O3:Eu@SiO2@Gd3+,Yb3+,Er3+@SiO2 precursor microspheres in a 100mL round-bottom flask, adding 15mL of H 2 O and 20mL of ethylene glycol, performing ultrasonic dispersion for 10min, adding 0.15g of ammonium metavanadate, performing reflux reaction at 125 ℃ in an oil bath for 6H, centrifuging, washing with water and absolute ethyl alcohol for 3 times, drying at 60 ℃, and finally placing the dried powder in a muffle furnace, heating to 900 ℃ from room temperature at a heating rate of 9 ℃/min, and calcining for 4H to obtain the SiO 2@Gd2O3:Eu@SiO2@GdVO4:Yb,Er@SiO2 microspheres.
2. The method for synthesizing the SiO 2@Gd2O3:Eu@SiO2@GdVO4:Yb,Er@SiO2 composite nano luminescent material with the multilayer core-shell structure capable of emitting down-converted red light and up-converted green light, which is characterized in that: the diameter of the SiO 2 core used is 105nm; the SiO 2 microsphere surface is deposited with rare earth ions Gd 3+ and Eu 3+, and then the surface is coated with a SiO 2 shell layer with the thickness of 8nm, so as to avoid fluorescence quenching caused by cross relaxation phenomenon with the rare earth ions Gd 3+、Yb3+ and Er 3+ coated subsequently.
3. The method for synthesizing the SiO 2@Gd2O3:Eu@SiO2@GdVO4:Yb,Er@SiO2 composite nano luminescent material with the multilayer core-shell structure capable of emitting down-converted red light and up-converted green light, which is characterized in that: after rare earth ions Gd 3+、Yb3+ and Er 3+ are deposited on the surface of SiO 2@Gd2O3:Eu@SiO2 microsphere by urea hydrolysis, siO 2 shell layer with the thickness of 8nm is coated, and GdVO 4:Yb and Er are coated on the surface of SiO 2@Gd2O3:Eu@SiO2 microsphere by ammonium metavanadate substitution reaction to obtain the multilayer core-shell structure product.
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