卟啉/酞菁类大环配合物的制备及其敏化制氢效能研究

Production of hydrogen (H2) by water splitting (electrochemical, photochemical, or thermal) offers an obviously excellent way to capture solar energy and provide "greener" energy for the future. H2 is not only a fuel itself but also can be processed to produce other fuels (Fischer-Tropsch reactions). As a consequence, it is an essential material for the organic chemical industry and for producing fertilizers by the Haber-Bosch process. Catalysts are a crucial issue for H2 production. Associated with their well known intense absorption, electrochemical, photochemical, and thermal stability, phthalocyanine derivatives have been among the excellent catalyst candidates for solar conversion and water splitting. The present project will be started from the preparation of a series of macrocyclic photosensitizers to studying the relationship between the molecular structure and the efficiency of photocatalytic hydrogen evolution and finally towards constructing efficient and stable dye-sensitized semiconductor photocatalytic hydrogen evolution systems. By means of such kind of typical green energy technologies, effective ways to solve the problem of energy shortages are expected. This is believed to be of significant theoretical importance and able to lead to a great deal of economic and social benefits.

染料敏化半导体制氢技术是当今世界新能源技术的主要发展方向之一，对各国未来新能源产业的形成和发展具有引领作用。在借鉴国内外染料敏化纳米晶太阳能电池的研究成果的基础上，结合申请者所在课题组的最新进展，基于大环配合物分子结构上的多变性、易裁剪性，络合金属原子种类的多样性及其对光、热的高稳定性，本项目将通过对卟啉、酞菁类大环配合物的化学修饰制备系列大环光敏剂，研究其分子结构、聚集形态和负载方式等与产氢效率之间的关系，构建高效、稳定的染料敏化半导体光催化产氢体系。该体系是一种典型的绿色新能源技术，是现代高新技术的交叉与结合，可望为解决能源短缺等难题提供行之有效的途径，具有重要的理论价值，蕴含着极大的经济和社会效益。

经过两年来的不懈努力，课题按计划进展顺利，各项研究任务得以落实和执行。根据本领域的最新进展，设计合成了系列卟啉、酞菁类化合物，在研究其结构、谱学和电化学性质等物化特性的基础上，采用化学键合、分子自组装等方式修饰相关的半导体或其复合物，探讨了敏化半导体的光电化学转化过程中的关键物理化学问题，如染料的能带结构、光吸收、端配体中给电子基团的性质及敏化中心与半导体的结合方式等对体系的光电子注入、载流子复合和产氢效率的影响及其作用机制等，结合理论计算总结染料结构与性能的关系，探索了构筑具有宽光谱（可见/近红外光）响应、定向的能量和电荷转移通道和高量子效率的敏化半导体产氢体系的新思路，项目进行中获得了一些具有重要理论意义的实验结果，部分已发表在各类国际期刊上。该体系是一种典型的绿色新能源技术，具有重要的理论价值，蕴含着极大的经济和社会效益。