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Atomistic Approach toward Selective Photocatalytic Oxidation of a Mustard-Gas Simulant: A Case Study with Heavy-Chalcogen-Containing PCN-57 Analogues

TitleAtomistic Approach toward Selective Photocatalytic Oxidation of a Mustard-Gas Simulant: A Case Study with Heavy-Chalcogen-Containing PCN-57 Analogues
Publication TypeJournal Article
Year of Publication2017
AuthorsGoswami S., Miller C.E, Logsdon J.L, Buru C.T, Wu Y.L, Bowman D.N, Islamoglu T., Asiri A.M, Cramer C.J, Wasielewski M.R, Hupp J.T, Farha O.K
JournalACS Appl Mater Interfaces
Volume9
Issue23
Pagination19535-19540
Date PublishedJun 14
ISBN Number1944-8244 (Linking)
Accession Number28562000
KeywordsCHEMICAL WARFARE AGENTS, metal-organic framework, photocatalysis, Sulfur Mustard, transient absorption
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 mus, 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.

URLhttps://www.ncbi.nlm.nih.gov/pubmed/28562000
DOI10.1021/acsami.7b07055
Short TitleAtomistic Approach toward Selective Photocatalytic Oxidation of a Mustard-Gas Simulant: A Case Study with Heavy-Chalcogen-Containing PCN-57 Analogues

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