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

Subhadip Goswami, Claire E. Miller, Jenna L. Logsdon, Cassandra T. Buru, Yi-Lin Wu, David N. Bowman, Timur Islamoglu, Abdullah M. Asiri, Christopher J. Cramer, Michael R. Wasielewski, Joseph T. Hupp, Omar K. Farha*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

43 Scopus citations

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.

Original languageEnglish (US)
Pages (from-to)19535-19540
Number of pages6
JournalACS Applied Materials and Interfaces
Volume9
Issue number23
DOIs
StatePublished - Jun 14 2017

Keywords

  • chemical warfare agents
  • metal-organic framework
  • photocatalysis
  • sulfur mustard
  • transient absorption

ASJC Scopus subject areas

  • Materials Science(all)

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