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.