【作者】 周彬；

【导师】 魏长平；

【作者基本信息】 长春理工大学 ， 光学工程， 2010， 博士

【摘要】 稀土离子及有机配合物与介孔材料MCM-41形成的组装体,在催化、光开关、微传感器等领域有着广泛的应用,近年来受到众多研究者的关注。本文采用水热合成法在氨水体系室温条件下中合成了高度有序的介孔材料MCM-41,并将稀土离子、有机发光配合物等客体组装进MCM-41孔道中,制备出系列MCM41-水杨酸、MCM41-水杨酸与铽、MCM41-Eu(Bz)3、MCM41-Tb(Asal)3phen等样品。通过X射线衍射、红外光谱、氮气吸附脱附、差热-热失重、拉曼光谱等技术对样品结构进行了表征,并考察了其光致发光性能以及稀土离子与有机配体之间的能量传递,探讨了主体MCM-41与客体发光材料之间的相互影响。在MCM41-水杨酸体系中,水杨酸掺杂浓度为0.025g时发光最强。在MCM41-水杨酸与铽体系中,Tb3+对水杨酸的发光起到一定的敏化作用,Tb3+的发光强度与激发光强度有关,发射光强度与入射光强度呈非线性关系。在MCM-41与稀土二元有机配合物组装体MCM41-Eu(Bz)3体系中,组装体中主客体之间存在较强的相互作用,MCM-41的存在使Eu(Bz)3对激发光有更强的吸收,MCM41-Eu(Bz)3较Eu(Bz)3发光强度大幅度提高。在MCM-41与稀土三元有机配合物组装体MCM41-Tb(Asal)3phen体系中,MCM-41的表面晶格场对配体单重态和三重态能级有较大的影响,第二配体邻菲咯啉S1态吸收的能量向Tb3+转移的效率增加,使Tb3+荧光发射强度增强。当MCM-41骨架中掺杂Yb3+,再与发光客体Tb(Asal)3phen形成组装体MCM41/Yb-Tb(Asal)3phen,其发光强度比MCM41-Tb(Asal)3phen组装体提高了4倍,当Yb/Si=7.579x10-3时,发光强度最高。更多还原

【Abstract】 Rare earth ions and organic materials with mesoporous MCM-41 assembled into assemblies, which has important applications in catalytic converter, optical switching and micro-sensors fields, were caused attention by researchers in recent years.High ordered mesoporous material MCM-41 was synthesized in ammonia medium at room temperature, and the rare earth complexes were incorporated into the one-dimensional channels of MCM-41. A series of MCM41-salicylic acid, and MCM41-salicylic acid-Tb3+ MCM41-Eu(Bz)3, MCM41-Tb(Asal)3phen were prepared in the ammonia system. The structure and properties were characterized by XRD, IR, Raman, TG-DTA, N2 absorption-desorption, excitation and emission spectrum. The property of photoluminescence and energy transfer between rare earth ion and complexes as well as the relationship between the organic host and the inorganic optical guest were also studied.As doping concentration of 0.025g, salicylic acid was the most luminous. The concentration of Tb3+ played a sensitization role to salicylic acid, and shown anti-transfer phenomenon. The ourgoing light intensity and the incidence light intensity assume non-linear relationship. In mesoporous assembly body of MCM-41 and binary rare-earth organic complexes MCM41-Eu(Bz)3 systerm, Eu(Bz)3 can be bonded with the hydroxyl in the channel, thus the vibration energy of hydroxyl is reduced, then the luminescence of Eu3+ is enhanced effectively. Eu(Bz)3 has a stronger absorption of the excitated light in the assembly since the existence of MCM-41,MCM41-Eu(Bz)3 has a more excellent luminescence property than that of Eu(Bz)3.In mesoporous assembly body of MCM-41 and ternary rare-earth organic complexes MCM41-Tb(Asal)3phen system, the MCM-41 surface crystal field has great effect on matching only important state of body and triple state energy level, the efficiency of the energy that second matches body phen S1 state to Tb3+ increases, and makes the intensity of fluorescence launch of Tb3+ strengthen. When Yb3+ in the inorganic base material MCM-41 framework, Tb(Asal)3 phen and MCM-41 assembling experience and observe glowing object Tb (Asal)3 phen competes with the MCM-41 assembling queen, whose luminescence intensity in Tb (Asal) having improved four times. Luminescence intensity of the assembling body is strengthened, as Yb/Si=7.579×10-3, the luminescence intensity is maximal.更多还原