Atomistic approach toward selective photocatalytic oxidation of a mustard-gas simulant: A case study with heavy-chalcogen-containing PCN-57 analogues

Goswami, Subhadip, Miller, Claire E., Logsdon, Jenna L., Buru, Cassandra T., Wu, Yi-Lin ORCID: https://orcid.org/0000-0003-0253-1625, Bowman, David N., Islamoglu, Timur, Asiri, Abdullah M., Cramer, Christopher J., Wasielewski, Michael R., Hupp, Joseph T. and Farha, Omar K. 2017. Atomistic approach toward selective photocatalytic oxidation of a mustard-gas simulant: A case study with heavy-chalcogen-containing PCN-57 analogues. ACS Applied Materials and Interfaces 9 (23) , pp. 19535-19540. 10.1021/acsami.7b07055

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Abstract

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.

Item Type:	Article
Date Type:	Published Online
Status:	Published
Schools:	Chemistry
Publisher:	American Chemical Society
ISSN:	1944-8244
Date of First Compliant Deposit:	16 January 2019
Date of Acceptance:	31 May 2017
Last Modified:	06 Nov 2023 20:48
URI:	https://orca.cardiff.ac.uk/id/eprint/118414

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