Department of Chemistry, Chemical Theory Center, and Supercomputing Institute, University of Minnesota , Minneapolis, Minnesota 55455-0431, United States.
Department of Chemistry, King Abdulaziz University , Jeddah 21589, Saudi Arabia.
ACS Appl Mater Interfaces. 2017 Jun 14;9(23):19535-19540. doi: 10.1021/acsami.7b07055. Epub 2017 Jun 2.
Here we describe the synthesis of two Zr-based benzothiadiazole- and benzoselenadiazole-containing metal-organic frameworks (MOFs) for the selective photocatalytic oxidation of the mustard gas simulant, 2-chloroethyl ethyl sulfide (CEES). The photophysical properties of the linkers and MOFs are characterized by steady-state absorption and emission, time-resolved emission, and ultrafast transient absorption spectroscopy. The benzoselenadiazole-containing MOF shows superior catalytic activity compared to that containing benzothiadiazole with a half-life of 3.5 min for CEES oxidation to nontoxic 2-chloroethyl ethyl sulfoxide (CEESO). Transient absorption spectroscopy performed on the benzoselenadiazole linker reveals the presence of a triplet excited state, which decays with a lifetime of 9.4 μs, resulting in the generation of singlet oxygen for photocatalysis. This study demonstrates the effect of heavy chalcogen substitution within a porous framework for the modulation of photocatalytic activity.
在这里，我们描述了两种基于 Zr 的苯并噻二唑和苯并硒二唑的金属有机骨架（MOF）的合成，用于选择性光催化氧化模拟芥子气的 2-氯乙基乙基硫醚（CEES）。通过稳态吸收和发射、时间分辨发射和超快瞬态吸收光谱对连接体和 MOF 的光物理性质进行了表征。与含有苯并噻二唑的 MOF 相比，含有苯并硒二唑的 MOF 表现出更高的催化活性，CEES 氧化为无毒的 2-氯乙基乙基砜（CEESO）的半衰期为 3.5 分钟。对苯并硒二唑连接体进行的瞬态吸收光谱研究表明，存在三重态激发态，其衰减寿命为 9.4 μs，从而为光催化产生单线态氧。这项研究表明，在多孔骨架中进行重杂原子取代对于调节光催化活性具有重要意义。
