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

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18 Citations (Scopus)

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
Pages (from-to)19535-19540
Number of pages6
JournalACS Applied Materials and Interfaces
Volume9
Issue number23
DOIs
Publication statusPublished - Jun 14 2017

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Keywords

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

ASJC Scopus subject areas

  • Materials Science(all)

Cite this

Goswami, 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. (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), 19535-19540. https://doi.org/10.1021/acsami.7b07055