Selective Photooxidation of a Mustard-Gas Simulant Catalyzed by a Porphyrinic Metal-Organic Framework

Yangyang Liu; Ashlee J Howarth; Joseph T Hupp; Omar K Farha

doi:10.1002/anie.201503741

Selective Photooxidation of a Mustard-Gas Simulant Catalyzed by a Porphyrinic Metal-Organic Framework

Angew Chem Int Ed Engl. 2015 Jul 27;54(31):9001-5. doi: 10.1002/anie.201503741. Epub 2015 Jun 17.

Authors

Yangyang Liu¹, Ashlee J Howarth¹, Joseph T Hupp², Omar K Farha^{3

4}

Affiliations

¹ Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, IL 60208-3113 (USA).
² Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, IL 60208-3113 (USA). j-hupp@northwestern.edu.
³ Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, IL 60208-3113 (USA). o-farha@northwestern.edu.
⁴ Department of Chemistry, Faculty of Science, King Abdulaziz University, Jeddah (Saudi Arabia). o-farha@northwestern.edu.

PMID: 26083551
DOI: 10.1002/anie.201503741

Abstract

The photooxidation of a mustard-gas simulant, 2-chloroethyl ethyl sulfide (CEES), is studied using a porphyrin-based metal-organic framework (MOF) catalyst. At room temperature and neutral pH value, singlet oxygen is generated by PCN-222/MOF-545 using an inexpensive and commercially available light-emitting diode. The singlet oxygen produced by PCN-222/MOF-545 selectively oxidizes CEES to the comparatively nontoxic product 2-chloroethyl ethyl sulfoxide (CEESO) without formation of the highly toxic sulfone product. In comparison to current methods, which utilize hydrogen peroxide as an oxidizing agent, this is a more realistic, convenient, and effective method for mustard-gas detoxification.

Keywords: chemical warfare agents; heterogeneous catalysis; metal-organic frameworks; photooxidation; singlet oxygen.