Department of Chemistry, Tsinghua University, Beijing, 100084, P. R. China.
Anhui Provincical Key Laboratory for Degradation and Monitoring of Pollution of the Environment, Fuyang Normal College, Fuyang, 236037, P. R. China.
Adv Mater. 2019 Feb;31(7):e1806626. doi: 10.1002/adma.201806626. Epub 2018 Dec 27.
A full-spectrum (300-700 nm) responsive porphyrin supramolecular photocatalyst with a theoretical solar spectrum efficiency of 44.4% is successfully constructed. For the first time, hydrogen and oxygen evolution (40.8 and 36.1 µmol g h ) is demonstrated by a porphyrin photocatalyst without the addition of any cocatalysts. The strong oxidizing performance also presents an efficient photodegradation activity that is more than ten times higher than that of g-C N for the photodegradation of phenol. The high photocatalytic reduction and oxidation activity arises from a strong built-in electric field due to molecular dipoles of electron-trapping groups and the nanocrystalline structure of the supramolecular photocatalyst. The appropriate band structure of the supramolecular photocatalyst adjusted via the highest occupied molecular orbital and lowest unoccupied molecular orbital energy levels of the porphyrin gives rise to thermodynamic driving potential for H and O evolution under visible light irradiation. Controlling the energy band structure of photocatalysts via the ordered assembly of structure-designed organic molecules could provide a novel approach for the design of organic photocatalysts in energy and environmental applications.
成功构建了一种具有全光谱（300-700nm）响应能力的卟啉超分子光催化剂，其理论太阳光光谱效率为 44.4%。首次在没有添加任何助催化剂的情况下，通过卟啉光催化剂实现了氢和氧的析出（40.8 和 36.1µmol g h）。强氧化性能还呈现出高效的光降解活性，对于苯酚的光降解，其活性比 g-C3N 高十倍以上。高的光催化还原和氧化活性源于电子捕获基团的分子偶极和超分子光催化剂的纳米晶结构引起的强内置电场。通过卟啉的最高占据分子轨道和最低未占据分子轨道能级对超分子光催化剂的能带结构进行适当调整，在可见光照射下为 H 和 O 的析出提供了热力学驱动力。通过结构设计的有机分子的有序组装来控制光催化剂的能带结构，为在能源和环境应用中设计有机光催化剂提供了一种新方法。
