State Key Laboratory of Crystal Materials, Shandong University, Jinan 250100, PR China.
State Key Laboratory of Crystal Materials, Shandong University, Jinan 250100, PR China.
J Colloid Interface Sci. 2021 Nov 15;602:300-306. doi: 10.1016/j.jcis.2021.05.087. Epub 2021 May 18.
Porphyrin is an important photosensitizer for singlet oxygen (O) formation. However, porphyrin derivatives still display low efficiency and difficult recovery. In this work, an Ag-based MOFs (AgTPyP; TPyP, 5,10,15,20-tetra(4-pyridyl) porphyrin) is synthesized. Compared with ligand TPyP, AgTPyP shows nearly 100% conversion and selectivity in the photocatalytic selective oxidation of sulfides to sulfoxides and obvious photodynamic therapeutic effect under visible light. Combined characterizations suggest that O is the only active oxygen species, which is due to the large exciton binding energy and narrow energy gap between the lowest excited singlet state (S) and the lowest triplet state (T) induced by the presence of Ag ion. The selectivity and conversion efficiency of five-cycle experiments do not decrease, indicating the excellent stability of AgTPyP. This work provides an alternative approach to simultaneously enhance the exciton effect of porphyrin and stabilize Ag-based photocatalysts.
卟啉是单线态氧(O)形成的重要光敏剂。然而,卟啉衍生物仍显示出低效率和难以回收的问题。在这项工作中,合成了一种基于 Ag 的 MOFs(AgTPyP;TPyP,5,10,15,20-四(4-吡啶基)卟啉)。与配体 TPyP 相比,AgTPyP 在光催化选择性氧化硫化物为亚砜和可见光下明显的光动力治疗效果方面表现出近 100%的转化率和选择性。综合表征表明,O 是唯一的活性氧物种,这是由于 Ag 离子的存在导致激子结合能大和最低激发单线态(S)和最低三重态(T)之间的能隙变窄。五轮实验的选择性和转化率没有降低,表明 AgTPyP 具有优异的稳定性。这项工作提供了一种同时增强卟啉的激子效应和稳定基于 Ag 的光催化剂的替代方法。