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

Research output: Contribution to journalArticle

13 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

Fingerprint

Chalcogens
Pregnenolone Carbonitrile
Mustard Gas
sulfoxide
Metals
Absorption spectroscopy
Oxidation
Gases
Singlet Oxygen
Photocatalysis
Sulfides
Excited states
Catalyst activity
Substitution reactions
Modulation
Oxygen
benzo-1,2,3-thiadiazole

Keywords

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

ASJC Scopus subject areas

  • Materials Science(all)

Cite this

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; Bowman, David N.; Islamoglu, Timur; Asiri, Abdullah M.; Cramer, Christopher J.; Wasielewski, Michael R; Hupp, Joseph T; Farha, Omar K.

In: ACS Applied Materials and Interfaces, Vol. 9, No. 23, 14.06.2017, p. 19535-19540.

Research output: Contribution to journalArticle

Goswami, Subhadip ; Miller, Claire E. ; Logsdon, Jenna L. ; Buru, Cassandra T. ; Wu, Yi Lin ; Bowman, David N. ; Islamoglu, Timur ; Asiri, Abdullah M. ; Cramer, Christopher J. ; Wasielewski, Michael R ; Hupp, Joseph T ; Farha, Omar K. / Atomistic approach toward selective photocatalytic oxidation of a mustard-gas simulant : A case study with heavy-chalcogen-containing PCN-57 analogues. In: ACS Applied Materials and Interfaces. 2017 ; Vol. 9, No. 23. pp. 19535-19540.
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