Photocatalytic detoxification of a sulfur mustard simulant using donor-enhanced porphyrin-based covalent-organic frameworks

Photocatalytic detoxification of sulfur mustards (e.g., bis (2-chloroethyl) sulfide, SM) is an effective approach for protecting the ecological environment and human health. In order to fabricate COFs with high performance for the selective transformation of the SM simulant 2-chloroethyl ethyl sulfide (CEES) to nontoxic 2-chloroethyl ethyl sulfoxide (CEESO), three porphyrin-based COFs with different donor groups (R = H, OH, and OMe) were synthesized. Among these COFs, COF-OMe, which possesses the strongest electron-donating ability, demonstrated a faster and higher detoxification rate of CEES at various concentrations, achieving selective oxidation of CEES to non-toxic CEESO with 99.2% conversion and 100% selectivity using white LED light irradiation within three hours. The facilitated charge transfer and separation as well as efficaciously produced reactive oxygen species (ROS), including singlet oxygen (¹O₂) and superoxide radical anions (O₂˙^-) are supposed to contribute to the excellent performance. The results demonstrated that the donor-enhanced porphyrin-based COFs could act as heterogeneous photocatalysts for visible light driven organic transformation and detoxification of sulfur mustards.