新型多光源钒基介孔有机-无机杂化发光材料研究

As a kind of complementary new materials, mesoporous organic-inorganic hybrid luminescent materials are extremely popular. But the current research exists the problem of the weak luminescence of host material, the lower luminous efficiency of hybrid luminescent materials and the understanding of sensitized luminescence mechanism between host and guest material is not clear. On the basis of the results obtained so far for the mesoporous silica hybrid luminescent materials, the present project is planned to develop new mesoporous YVO4:Eu3+ host material with high luminescence efficiency and structural stability. By applying a chemical self-assembly method, high-performance ternary multi-core rare earth complexes will be assembled with mesoporous YVO4:Eu3+ host material. Multi-source vanadium-based mesoporous organic-inorganic hybrid luminescent materials will also be constructed. Simultaneously,the structure and luminescent properties of the host, guest and host-guest phases will be investigated. The bonding and the sensitized luminescence energy transfer mechanisms of the host-guest interactions will be explored for the establishment of a new mesoporous organic-inorganic hybrid luminescent materials mechanism model. The successful implementation of the project will contribute to the scientific community with deep understanding of the new multi-source vanadium-based mesoporous organic-inorganic hybrid luminescent materials and promote interdisciplinary integration of organic chemistry, inorganic chemistry, the traditional luminescent materials and emerging mesoporous materials, with theoretical and practical significance.

介孔有机-无机杂化发光材料作为一种性能互补的新材料正倍受青睐，但目前的研究存在硅基主体材料发光较弱、杂化材料发光效率不高的问题，同时主客体之间敏化发光机理的认识还有待深入。本项目拟在硅基介孔杂化发光材料研究的基础上，制备具有高效发光和结构稳定的新型介孔YVO4:Eu3+主体材料，利用化学自组装技术把高性能的客体三元多核稀土配合物组装到介孔YVO4:Eu3+中，构建新型多光源钒基介孔有机-无机杂化发光材料。同时，研究主客体及组装材料的物相、结构和发光性能，揭示主客体之间的成键机理及敏化发光的能量转移机理，进而建立新型介孔杂化材料的机理模型，并以此为指导对杂化材料的各种现象做出合理解释，为新型多光源介孔杂化发光材料的研究提供理论依据。项目的成功实施将有助于深入对新型多光源钒基介孔杂化发光材料的认识，促进有机化学、无机化学、传统发光材料及新兴介孔材料的学科交叉融合，具有重要的学术意义。

作为一种性能互补和优化的交叉领域新材料，新型钒基多光源有机-无机杂化发光材料兼具有机材料、无机材料、介孔材料和发光材料的多重优点，但它的形貌控制和性能分析的研究工作在国内外还处于初始阶段，少见相关报道，尚需开展深入研究。本项目首先在传统硅基介孔主体材料制备的基础上，基于液相软化学法，进一步利用不同表面活性剂的模板导向作用及材料合成的各种实验因素调控ReVO4:Eu3＋主体材料的孔道结构，对介孔ReVO4:Eu3＋的形貌和结构进行系统研究，获得具有有序介孔孔道、结晶良好、结构稳定和兼具发光功能的介孔ReVO4:Eu3＋主体发光材料。其次，基于不同的有机配体，在配体中加入稀土荧光剂Eu3+ 和敏化剂Tb3+，同时利用介孔主体基质ReVO4:Eu3＋表面的Y3+与有机配体配位成键并协同Eu3+发光，构建结构和性能新颖的三元多核Eu3＋的稀土配合物(Eu,Tb)(aspirin)3phen、(Eu,Tb)(DBM)3phen、(Eu,Tb)(TTA)3phen和(Eu,Tb) (BA)3 phen。再次，基于浸渍法，在ReVO4:Eu3＋介孔中组装三元多核客体发光物质，应用介孔ReVO4:Eu3＋主体基质的纳米级孔道使客体分子之间相互隔离和均匀分布，制备和组装了结构稳定、孔道有序、结晶良好、粒径均一的杂化材料目标产物(Eu,Tb)(aspirin)3phen-ReVO4:Eu3+、(Eu,Tb)(DBM)3phen-ReVO4:Eu3+、(Eu,Tb)(TTA)3phen- ReVO4:Eu3+、和(Eu,Tb) (BA)3 phen ReVO4:Eu3+，最终实现了对多光源有机-无机杂化发光材料结构的调控和性能的复合。最后，本项目从材料和化学多学科交叉的角度，剖析了介孔主体材料的形成机理、多光源发光材料主客体之间相互作用的成键方式和自组装机理、主客体材料的发光机理、能量转移及传递的影响机理，初步构建了介孔杂化发光材料的机理模型，对杂化材料的各种现象做出了合理的解释，为新型多光源介孔杂化发光材料的研究提供理论依据。项目的成功实施丰富了对新型多光源钒基介孔杂化发光材料的认识，促进有机化学、无机化学、传统发光材料及新兴介孔材料的学科交叉融合，具有重要的学术意义和实用价值。