苝酰亚胺桥键的有序介孔结晶膦酸钴的制备和光电性质及在光解水产氧方面的应用

Photocatalytic splitting of water utilizing solar energy is very important in solving the energy and environmental problems. The water oxidation half-reaction is a bottleneck restricting the onversion efficiency. Therefore, a key to this problem is to develop a high-efficiency water oxidation catalyst. This project will prepare ordered mesoporous crystalline cobalt phosphonate with perylene bisimide arranged periodically on the wall. The optimum preparation condition can be obtained by changing synthesis parameters. The influence of preparation parameters on the composition, microstructure, surface chemical state and oxygen evolution efficiency of photocatalyst will be discussed. Secondly, the effect of the surface structure, pore structure, and especially the regular arrangement of the perylene bisimide on improving the efficiency of photogenerated charge separation will be revealed. Thirdly, the relationship between oxygen evolution efficiency and the structure of the photocatalyst will be intensive studied. Finally, the highly efficient solar absorption, electron transfer, energy transform and catalytic mechanism will be elucidated combined with electric paramagnetic resonance. The goal of this project is to construct a high-efficient oxygen evolution photocatlyst. These studies will be of benefit to develop new water oxidation photocatalyst.

利用太阳能光解水在解决能源和环境危机方面具有重要意义，其中水的氧化反应是制约光解水效率的瓶颈，因此构筑高效的产氧光催化剂是突破瓶颈的关键。本项目拟以有机膦酸取代的苝酰亚胺为单体，缩聚制备苝酰亚胺在孔壁规则排列的有序介孔结晶磷酸钴，构筑新型光解水产氧催化剂。优化制备参数，获得制备光催化剂的最佳条件。重点研究制备参数对光催化剂的组成、微结构、表面化学态和光催化产氧性能的影响，揭示光催化剂的表面结构、孔结构，特别是苝酰亚胺的规则排列对提高光生载流子分离效率的作用，深入研究其产氧性能与光催化剂结构间的关系，结合电子顺磁共振等方法阐明光催化反应体系高效吸能、传能、转能的途径和机理，以期制备高效的光解水产氧催化剂，为开发新型产氧光催化剂提供研究思路。

本项目主要进行了三方面的研究：1）模拟绿色植物光合作用制备的有机-无机杂化材料光解水催化剂可以同时利用有机物性能易于调节和无机物机械强度高等优点。本项目制备了四类有机-无机光解水催化剂，得到了较好的光解水制氢性能材料。2）泡沫金属基底材料具有导电性好、比表面大，活性位点多的特点。以其为基底制备的电解水催化剂不仅可以大大降低了电解水所需的过电位，还可以显著提高电解水的催化性能。本项目制备了两个系列的泡沫金属基底的电解水催化剂，产氢和产氧达到100 mA/cm2电流密度所需的过电位可分别达到400 mV和300 mV。3）水相有机氧化还原液流电池由于其循环性好、无污染、可降解等优点，以及在原料上有实现大规模生产的可能性。现有的有机液流电池活性物质大都水溶性差，难以提高电流密度。本项目设计合成了四个系列的季铵盐类有机液流电池活性物质，大大提高了这类物质的水溶性，有利于得到高浓度、高电流密度的液流电池。这些研究可以为新动能转换研究提高一些经验和实践基础。