基于荧光素类光敏剂的单分子光催化水分解产氢体系的设计探索

项目名称： 基于荧光素类光敏剂的单分子光催化水分解产氢体系的设计探索

项目编号： No.21503126

项目类型： 青年科学基金项目

立项/批准年度： 2016

项目学科： 数理科学和化学

项目作者： 张伟

作者单位： 陕西师范大学

项目金额： 21万元

中文摘要： 探寻高效高稳定性的光催化水分解体系是当前和未来光催化研究的核心问题。均相光催化水分解体系由于诸多优点倍受重视。针对均相光催化水分解过程中存在的低电荷传递效率问题，提出构建吸光单元和催化单元组成的非共轭单分子高效光解水均相体系，设计制备通过烷基硫醇中巯基作为配体的桥联单分子光催化体系，研究荧光素类光敏剂与过渡金属配合物催化分子之间桥联位置、桥联方式、桥联分子结构对体系光催化效率的影响，揭示决定单分子体系中电荷转移效率的关键因素；进而通过设计双光敏剂、多光敏剂分子与单催化分子的桥联体，研究激发电荷供体数量对体系催化活性的影响，阐明激发电荷密度对氢气生成速度的影响机制，最终发展一类具有高效率的单分子新型均相光催化水分解催化体系。该项目致力于认识均相光解水制氢的分子催化机理和探索提高均相光催化体系产氢效率的新途径，具有重要的理论与实际研究意义。

中文关键词： 水分解；光催化制氢；荧光素；单分子；均相催化

英文摘要： Developing highly efficient and stable photocatalytic water splitting (PWS) systems is of great importance in the area of photocatalytic research. Homogeneous PWS systems have attracted extensive attention in the past few decades. In this proposal, we proposed the constructing of single molecular homogeneous PWS systems for H2 production. Through inter molecular chemical bonding, we planned to modify xanthene dye photosensitizers by grafting alkanes with mercapto groups chelating with transition metal cations. By studying the effects from the grafting position as well as the structure of connecting molecule, we aimed at uncovering the decisive factor that limiting the charger transfer efficiency in single molecular PWS systems. Subsequently, single molecules with double/multiple photosensitizer units will be designed towards understanding the relationship between the system efficiency and the activated charge density on the proton reduction center, and thus towards developing much improved PWS hydrogen production systems. This proposal is significant theoretically and practically as we committed to understand the mechanism inside homogeneous PWS and explore novel systems with remarkably improved efficiency.

英文关键词： water splitting;photocatalytic hydrogen production;xanthene dye;single molecular;homogeneous catalysis