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: | 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: | 17 Jul 2025 21:30 |
| URI: | https://orca.cardiff.ac.uk/id/eprint/118414 |
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