Superoxide Ion and Singlet Oxygen Photogenerated by Metalloporphyrin-Based Metal–Organic Frameworks for Highly Efficient and Selective Photooxidation of a Sulfur Mustard Simulant

The exploration of highly efficient materials for the degradation of chemical warfare agents has been a longstanding task for preventing human exposure. Herein, we report a series of metal–organic frameworks (MOFs) M-TCPP-La based on metallo-tetra(4-carboxyphenyl)porphyrin and LaIII, which were applied to selectively oxidize 2-chloroethyl ethyl sulfide (CEES, a sulfur mustard simulant) as heterogeneous photocatalysts. After irradiation from a commercial blue light-emitting diode (LED), both superoxide ion and singlet oxygen were generated by M-TCPP-La and involved in selective oxidization of CEES to 2-chloroethyl ethyl sulfoxide (CEESO). Notably, a very short half lifetime (2.5 min) was achieved using Fe-TCPP-La as the photocatalyst. In comparison to currently utilizing singlet oxygen and hydrogen peroxide as oxidizing agents, this work employing both singlet oxygen and superoxide ion represents a new and effective strategy of detoxification of mustard gas.