Chen Yana, Shen Zewen, Hu Yezi, Zhang Haotian, Yin Lisha, Zhao Guixia, Hai Guangtong, Huang Xiubing
College of Environmental Science and Engineering, North China Electric Power University, Beijing 102206, P. R. China.
Beijing Advanced Innovation Center for Materials Genome Engineering, Beijing Key Laboratory of Function Materials for Molecule & Structure Construction, School of Materials Science and Engineering, University of Science and Technology Beijing, Beijing 100083, P. R. China.
Nanoscale. 2025 Jan 29;17(5):2904-2911. doi: 10.1039/d4nr05302h.
Photocatalytic detoxification of sulfur mustards (, 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 (O) and superoxide radical anions (O˙) 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.
硫芥（双（2-氯乙基）硫醚，SM）的光催化解毒是保护生态环境和人类健康的有效方法。为了制备具有高性能的共价有机框架（COFs），用于将硫芥模拟物2-氯乙基乙基硫醚（CEES）选择性转化为无毒的2-氯乙基乙基亚砜（CEESO），合成了三种具有不同供体基团（R = H、OH和OMe）的卟啉基COFs。在这些COFs中，具有最强供电子能力的COF-OMe在各种浓度下对CEES均表现出更快、更高的解毒速率，在白色LED光照射下三小时内实现了CEES选择性氧化为无毒的CEESO，转化率达99.2%，选择性为100%。电荷转移和分离的促进以及有效产生的活性氧物种（ROS），包括单线态氧（O）和超氧阴离子自由基（O˙），被认为是其优异性能的原因。结果表明，供体增强的卟啉基COFs可作为多相光催化剂用于可见光驱动的有机转化和硫芥解毒。
