Preparation of NaYF4:Yb^3+,Tm^3+@NaGdF4:Ce^3+,Eu3+double-jacket microtubes for dual-mode fluorescent anti-counterfeiting  

具有套管结构NaYF4:Yb^3+,Tm^3+@NaGdF4:Ce^3+,Eu^3+晶体的制备及在双模式荧光防伪中的应用

作　　者：Yin CHEN Shao-wen XIE Chao TONG Hai-hu TAN Li-jian XU Na LI Jian-xiong XU 陈殷;谢少文;童超;谭海湖;许利剑;李娜;许建雄(湖南工业大学生命科学与化学学院生物医用纳米材料与器件湖南省重点实验室,株洲412007;湖南工业大学冶金与材料工程学院电化学绿色冶金技术湖南省高等学校重点实验室,株洲412007)

机构地区：[1]Hunan Key Laboratory of Biomedical Nanomaterials and Devices,College of Life Sciences and Chemistry,Hunan University of Technology,Zhuzhou 412007,China [2]Key Laboratory of Electrochemical Green Metallurgy Technology of Hunan Higher Education Institutions,College of Metallurgy and Materials Engineering,Hunan University of Technology,Zhuzhou 412007,China

出　　处：《Transactions of Nonferrous Metals Society of China》2020年第12期3333-3346,共14页中国有色金属学报（英文版）

基　　金：Project(51874129)supported by the National Natural Science Foundation of China;Projects(2018JJ3115,2019JJ60049)supported by the Science Foundation of Hunan Province,China;Projects(19B153,19B158)supported by the Scientific Research Fund of Hunan Provincial Education Department,China。

摘　　要：Novel hydrophilic NaYF4:Yb^3+,Tm^3+@NaGdF4:Ce^3+,Eu^3+double-jacket microtubes(DJMTs)with upconversion/downconversion dual-mode luminescence were designed and prepared through epitaxial growth of NaGdF4:Ce^3+,Eu^3+shell onto the NaYF4:Yb^3+,Tm^3+microtube via poly(acrylic acid)(PAA)mediated hydrothermal method.It is demonstrated that PAA ligand played an important role in guiding the direct growth of NaGdF4:Ce^3+,Eu^3+shell onto the surface of NaYF4:Yb^3+,Tm^3+parent microtubes.The growth of NaGdF4:Ce^3+,Eu^3+shell experienced a crystal phase transition fromβ-NaGdF4 andβ-NaYF4 mixture toβ-NaYF4@NaGdF4 composite crystal,and morphology evolution from mixture ofβ-NaGdF4:Ce^3+,Eu^3+nanorods andβ-NaYF4:Yb^3+,Tm^3+microtubes to NaYF4:Yb^3+,Tm^3+@NaGdF4:Ce^3+,Eu^3+DJMTs.The formation mechanism of DJMTs was the dissolution−renucleation ofβ-NaGdF4:Ce^3+,Eu^3+nanorods and the growth ofβ-NaGdF4:Ce^3+,Eu^3+shell via the classical Ostwald ripening mechanism.The as-prepared DJMTs could exhibit blue upconversion and red downconversion luminescence,which was further made into environmentally benign luminescent inks for creating highly secured and fluorescent-based anti-counterfeiting patterns via inkjet printing.通过聚丙烯酸(PAA)调介的水热法在NaYF4:Yb^3+,Tm^3+微管上外延生长NaGdF4:Ce^3+,Eu^3+壳层,制备新型亲水性NaYF4:Yb^3+,Tm^3+@NaGdF4:Ce^3+,Eu^3+双模式荧光套管(DJMT)。研究表明,PAA配体在NaYF4:Yb^3+,Tm^3+微管表面形成NaGdF4:Ce^3+,Eu^3+壳层中起到重要的结构导向作用。NaYF4:Yb^3+,Tm^3+@NaGdF4:Ce^3+,Eu^3+双模式荧光双夹层微管的生长经历由β-NaGdF4和β-NaYF4两相混合物到β-NaYF4@NaGdF4复合晶体的晶相转变过程,同时,颗粒形貌由β-NaGdF4:Ce^3+,Eu^3+纳米棒与β-NaYF4:Yb^3+,Tm^3+微管的混合物演变为NaYF4:Yb^3+,Tm^3+@NaGdF4:Ce^3+,Eu^3+套管结构。DJMTs的生长机理遵循Ostwald熟化机制,生长过程中原位生成的β-NaGdF4:Ce^3+,Eu^3+纳米棒经过溶解−再成核以及表面沉积等过程,在NaYF4:Yb^3+,Tm^3+微管的表面附着β-NaGdF4:Ce^3+,Eu^3+壳层。制备的DJMT具有蓝色上转换和红色下转换荧光特性,可制成环保的荧光油墨,通过喷墨打印实现高度安全的荧光防伪图案的输出。

关 键 词：lanthanide-doped fluoride core-shell structure dual-mode luminescence inkjet printing anti- counterfeiting 

分 类 号：TQ422[化学工程]