CN108410459A - 稀土掺杂纳米球型上转换发光化合物的制备方法 - Google Patents
稀土掺杂纳米球型上转换发光化合物的制备方法 Download PDFInfo
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 23
- 150000001875 compounds Chemical class 0.000 title claims abstract description 20
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 15
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- 238000002156 mixing Methods 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 30
- 229910052769 Ytterbium Inorganic materials 0.000 claims abstract description 11
- 229910052689 Holmium Inorganic materials 0.000 claims abstract description 7
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- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 7
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- FGDZQCVHDSGLHJ-UHFFFAOYSA-M rubidium chloride Chemical compound [Cl-].[Rb+] FGDZQCVHDSGLHJ-UHFFFAOYSA-M 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
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- 229910052688 Gadolinium Inorganic materials 0.000 description 3
- 229910052765 Lutetium Inorganic materials 0.000 description 3
- 229910052779 Neodymium Inorganic materials 0.000 description 3
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- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
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- HGWOWDFNMKCVLG-UHFFFAOYSA-N [O--].[O--].[Ti+4].[Ti+4] Chemical compound [O--].[O--].[Ti+4].[Ti+4] HGWOWDFNMKCVLG-UHFFFAOYSA-N 0.000 description 1
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- UZLYXNNZYFBAQO-UHFFFAOYSA-N oxygen(2-);ytterbium(3+) Chemical compound [O-2].[O-2].[O-2].[Yb+3].[Yb+3] UZLYXNNZYFBAQO-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及稀土掺杂纳米球型上转换化合物的制备方法，属于纳米上转换发光化合物领域。本发明化合物为TiO2:1％Ho,10％Yb,10％K。本发明的有益效果为：纳米尺寸的球型上转换发光材料尺寸小、可以应用于生物成像领域；球形发光材料更有利于涂屏且大大提高了显示屏的分辨率；具备其他纳米发光材料生物毒性小、稳定、发光时间长的优势。
Description
本申请为申请号为2016102275031、申请日为2016年4月13日、发明名称为“稀土掺杂纳米球型TiO2上转换化合物及其制备方法”的分案申请。
技术领域
本发明涉及纳米上转换发光化合物以及制备方法，特别是稀土掺杂纳米球型TiO2上转换化合物的制备方法。
背景技术
上转换发光，即反-斯托克斯发光(Anti-Stokes)，由斯托克斯定律而来。斯托克斯定律认为材料只能受到高能量的光激发，发出低能量的光，换句话说，就是波长短的频率高的激发出波长长的频率低的光。比如紫外线激发发出可见光，或者蓝光激发出黄色光，或者可见光激发出红外线。但是后来人们发现，其实有些材料可以实现与上述定律正好相反的发光效果，于是我们称其为反斯托克斯发光，又称上转换发光。因此上转换发光是将近红外光转换为可见光的过程，可通过双光子或三光子的吸收来完成发射光的波长小于激发光的波长。上转换材料在照明光源，显示显像，X射线增感屏，光学传感，印刷标识防伪，全固化短波长激光器以及生物标识等领域具有广泛的应用前景。
目前制备上转换发光材料，氧化物基质具有物理化学性能稳定，制备工艺简单，更适合生产和应用等优点。其中二氧化钛具有高折射率，良好的光学透明性和物理化学特性。但氧化物材料的不足之处是相对硫化物和氟化物来讲其声子能量高而影响了此材料的上转换发光效率。要想提高其发光效率可制成纳米材料。而目前大部分稀土掺杂氧化物的发明成果均不是纳米尺寸的。纳米尺寸的发光材料均为下转换发光材料，即为利用波长短的频率高的激发出波长长的频率低的光。如CN 200610135394.7公开了一种稀土掺杂二氧化钛纳米发光材料及其制备方法，选择的激发波长为460-470nm的绿色可见光,发射的波长为613-617nm。
因此，需要开发出纳米尺寸的上转换发光材料以使上转换材料的发光效率得以提高。
发明内容
本发明的目的在于克服现有技术的不足，制作出纳米级上转换发光材料。本发明提供稀土掺杂纳米球型TiO2上转换化合物，所述化合物的化学式为式I：TiO2:X％M,Y％Yb,Z％N(I)；
其中M为Y、Sc、La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu中的一种或多种；N为轻金属中的一种或多种；X、Y、Z的摩尔比满足下面的条件：1≤X≤l.8，Y＝10，0≤Z≤20。
优选地，X＝1.5，Z＝20。
优选地，M为Er、Ho、Eu、Tm中的一种或多种,N为Li、Na、K、Rb中的一种或多种。
本发明还保护包含所述的化合物的发光材料，当用发射峰在980nm的波长范围的光激发时，所述发光材料表现出在450nm—750nm的波长范围内的发光峰。
本发明还保护稀土掺杂纳米球型TiO2上转换发光化合物的制备方法，包含下列步骤：S1.将钛酸四丁酯和乙醇胺或二乙醇胺或三乙醇胺溶于无水乙醇，混合均匀得到溶液1；S2.将稀土硝酸盐或稀土氯化物和去离子水、无水乙醇混和均匀得到溶液2；S3.将溶液2在不断搅拌下逐滴加到溶液1中，并持续搅拌得到均匀、透明的溶胶3；S4.将溶胶3放入高压釜中加热得到生成物4，将所述生成物4清洗离心干燥获得发光粉末5，将获得的所述发光粉末5放入坩埚中退火冷却，获得所述上转换发光材料。
优选地，各组分摩尔配比为：
钛酸四丁酯：1；
乙醇胺或二乙醇胺或三乙醇胺：1～5；
稀土硝酸盐或稀土氯化物：0.01～0.1；
去离子水：0.5～5；
无水乙醇：1～30。
优选地，所述S2制备溶液2时加入轻金属氯化物。
优选地，所述所述轻金属氯化物为LiCl、KCl、NaCl、RbCl中的一种或多种。
优选地，所述所述轻金属氯化物摩尔配比为0.05～0.2。
优选地，稀土硝酸盐或稀土氯化物是指Y、Sc、La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu的硝酸盐或氯化物中的一种或多种。
本发明的优点和积极效果是：纳米尺寸的球型上转换发光材料首先该发明具备尺寸小的优势，可以应用于纳米光电器件；本发明还可以应用于生物成像领域，更具体地讲本发明可以通过细胞内吞作用进入细胞从而实现生物细胞成像，包括且不限于：体外细胞成像以及小动物活体成像等。其次，本发明为球形发光材料，因此更有利于涂屏从而大大提高了显示屏的分辨率。并且，本发明具备其他纳米发光材料生物毒性小、稳定、发光时间长的优势。
附图说明
图1、图2为本发明制备的发光材料的扫描电子显微镜照片；
图3为本发明制备的发光材料的X射线衍射谱图；
图4为本发明制备的发光材料在980nm激光激发无照明环境下拍摄的照片；
图5为本发明制备的发光材料在980nm激光激发有照明环境下拍摄的照片；
图6为本发明所制备的发光材料在980nm激光激发下的上转换发光光谱图。
具体实施方式
下面结合附图、通过具体实施例对本发明作进一步详述。以下实施例只是描述性的，不是限定性的，不能以此限定本发明的保护范围。实施例中所述实验方法如无特殊说明，均为常规方法；如无特殊说明，所述试剂和生物材料，均可从商业途径获得。
以下两表为本发明各实施例中所用试剂及实验仪器来源：
可以由下述实施例制备的发光化合物的化学式为：
TiO2:X％M,Y％Yb,Z％N(I)；
其中M为Y、Sc、La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu中的一种或多种；N为轻金属中的一种或多种；X、Y、Z的摩尔比满足下面的条件：1≤X≤l.8，Y＝10，0≤Z≤20。
其中，TiO2为发光化合物基质，M起发光作用，Yb起敏化作用，N起到加强发光化合物光强的作用。在下列实施例1-4中，M依次为Er、Ho、Eu、Tm，N为Li、K、Na、Rb为例进行描述。
实施例1
(1)量取浓度为0.966g/mL的钛酸四丁酯3.6mL，浓度为1.02g/mL的乙醇胺1.08mL混合均匀得到溶液1；
(2)0.18mL去离子水,7.2mL无水乙醇,浓度为0.01mol/L的15.3mL ErC13·6H2O，浓度为0.1mol/L的10.2mL硝酸镱，浓度为0.5mol/L的4.08mL LiCl，混和均匀制成溶液2；
(3)不断搅拌下,将溶液2逐滴滴入到溶液1中，并持续搅拌得到均匀、透明的掺杂TiO2溶胶；
(4)将此溶液放入50mL高压釜的聚四氟乙烯的内衬中，于120℃加热6小时后自然冷却到室温，生成物离心后用去离子水清洗两遍、放入80℃电热恒温干燥箱中干燥；
(5)将获得的发光粉末放入坩埚中800℃退火4h，等冷却后研磨。
由实施例1方法制成的稀土掺杂纳米球型TiO2上转换发光化合物化学式为：TiO2:1.5％Er,10％Yb,20％Li。
实施例2
(1)称取浓度为0.966g/mL的钛酸四丁酯5mL，浓度为1.097g/mL的二乙醇胺6.8mL，混合得到混合溶液1；
(2)1.3mL去离子水,10mL无水乙醇,浓度为0.01mol/L的Ho(NO3)3·5H2O 14.2mL，浓度为0.1mol/L的Yb(NO3)3·5H2O 14.2mL，浓度为0.5mol/L的KCl 2.84mL，混和均匀制成溶液2；
(3)不断搅拌下,将溶液2逐滴滴入到溶液1中，并持续搅拌得到均匀、透明的掺杂TiO2溶胶；
(4)将此溶液放入高压釜的聚四氟乙烯的内衬中，于90℃加热3小时后自然冷却到室温，生成物离心后用去离子水清洗两遍、放入80℃电热恒温干燥箱中干燥；
(5)将获得的发光粉末放入坩埚中900℃退火2h，等冷却后研磨。
由实施例2方法制成的稀土掺杂纳米球型TiO2上转换发光化合物化学式为：TiO2:1％Ho,10％Yb,10％K。
实施例3
(1)称取浓度为0.966g/mL的钛酸四丁酯5mL，浓度为1.097g/mL的二乙醇胺1.36mL，混合得到混合溶液1；
(2)0.5mL去离子水,10mL无水乙醇,浓度为0.01mol/L的Eu(NO3)3·5H2O 17mL，浓度为0.1mol/L的Yb(NO3)35H2O 14.2mL，浓度为0.5mol/L的NaCl 1.42mL，混和均匀制成溶液2；
(3)不断搅拌下,将溶液2逐滴滴入到溶液1中，并持续搅拌得到均匀、透明的掺杂TiO2溶胶；
(4)将此溶液放入50mL高压釜的聚四氟乙烯的内衬中，于120℃加热3小时后自然冷却到室温，生成物离心后用去离子水清洗两遍、放入80℃电热恒温干燥箱中干燥；
(5)将获得的发光粉末放入坩埚中600℃退火4h，等冷却后研磨。
由实施例3方法制成的稀土掺杂纳米球型TiO2上转换发光化合物化学式为：TiO2:1.2％Eu,10％Yb,5％Na。
实施例4
(1)称取浓度为0.966g/mL的钛酸四丁酯5mL，浓度为1.125g/mL的三乙醇胺4mL，混合得到混合溶液1；
(2)0.5mL去离子水,10mL无水乙醇,浓度为0.01mol/L的Tm(NO3)3·5H2O 25.56mL，浓度为0.1mol/L的Yb(NO3)3·5H2O 10.2mL，浓度为0.5mol/L的RbCl 2.84mL，混和均匀制成溶液2；
(3)不断搅拌下,将溶液2逐滴滴入到溶液1中，并持续搅拌得到均匀、透明的掺杂TiO2溶胶；
(4)将此溶液放入50mL高压釜的聚四氟乙烯的内衬中，于120℃加热2小时后自然冷却到室温，生成物离心后用去离子水清洗两遍、放入80℃电热恒温干燥箱中干燥；
(5)将获得的发光粉末放入坩埚中750℃退火4h，等冷却后研磨。
由实施例4方法制成的稀土掺杂纳米球型TiO2上转换发光化合物化学式为：TiO2:1.8％Tm,10％Yb,10％Rb。
从图1、图2所示的实施例1所制备的发光材料扫描电子显微镜照片图可以看出,所制得的发光材料是直径在80nm左右,形貌为球型的纳米粒子。
从图3所示的实施例1所制备的发光材料的X射线衍射谱图可以看出,衍射峰对应于二氧化钛的金红石和锐钛矿相，还出现了氧化镱的衍射峰,由于掺杂的Er离子较少,未出现含Er化合物的衍射峰。
从图4、图5所示的实施例1所制备的发光材料在980nm激光照射下分别在无照明和有照明环境下拍摄的照片图可以看出,在980nm激光激发下样品发射出明亮的绿光。图4以及图5中灰色光斑为样品发射出明亮的绿光。
从图6所示的实施例1所制备的发光材料在980nm激光激发下的发光光谱图可以看出,在980nm激光激发下,样品在450nm—750nm波段范围内分别发射出绿色和红色上转换发光,分别对应于Er3+离子的跃迁,其中在560nm的绿色上转换发光最强。
Claims (1)
1.稀土掺杂纳米球型上转换发光化合物的制备方法，其特征在于，该化合物化学式为：TiO2:1％Ho,10％Yb,10％K，制备方法包括以下步骤：
(1)称取浓度为0.966g/mL的钛酸四丁酯5mL，浓度为1.097g/mL的二乙醇胺6.8mL，混合得到混合溶液1；
(2)1.3mL去离子水,10mL无水乙醇,浓度为0.01mol/L的Ho(NO3)3·5H2O 14.2mL，浓度为0.1mol/L的Yb(NO3)3·5H2O 14.2mL，浓度为0.5mol/L的KCl 2.84mL，混和均匀制成溶液2；
(3)不断搅拌下,将溶液2逐滴滴入到溶液1中，并持续搅拌得到均匀、透明的掺杂TiO2溶胶；
(4)将此溶液放入高压釜的聚四氟乙烯的内衬中，于90℃加热3小时后自然冷却到室温，生成物离心后用去离子水清洗两遍、放入80℃电热恒温干燥箱中干燥；
(5)将获得的发光粉末放入坩埚中900℃退火2h，等冷却后研磨，获得所述上转换发光材料。
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