Superoxide Ion and Singlet Oxygen Photogenerated by Metalloporphyrin-Based Metal−Organic Frameworks for Highly Efficient and Selective Photooxidation of a Sulfur Mustard Simulant
Zi-Hao Long, Dong Luo, Kun Wu, Zi-Ye Chen, Ming-Min Wu, Xiao-Ping Zhou,* and Dan Li
ABSTRACT: 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) MTCPP-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.
KEYWORDS: metal−organic framework, metalloporphyrin, superoxide ion, singlet oxygen, photocatalyst, chemical warfare agents
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