Recently, the team of Professor Liu Yongdi from our School of Resources and Environmental Engineering has made important progress in the field of persulfate-based advanced oxidation technology, and the relevant research results, titled Process-Driven Protonation in Benzothiadiazole-Integrated Covalent Organic Frameworks: Activation of Peroxymonosulfate for Pollutant Oligomerization via Dominant Electron Transfer Process, were published in Angewandte Chemie International Edition.
The traditional peroxymonosulfate (PMS) activation process usually follows a catalyst-centered static mode, which is limited by the free radical-mediated reaction pathway, resulting in limited selectivity and incomplete mineralization. Breaking through this traditional framework, this study established a process-driven protonation strategy, which guides PMS activation to the dominant electron transfer process (ETP), thus realizing the selective oligomerization of pollutants. By developing benzothiadiazole-integrated covalent organic frameworks (BT-COFs) as a model platform, the study confirmed that the addition of PMS inherently acidifies the reaction medium, thus triggering in-situ protonation of the frameworks at specific nitrogen sites. This self-induced protonation acts like a molecular switch, reorganizing the interfacial electronic structure and forming a polarized catalytic interface, which promotes directed electron transfer rather than free radical generation. Through the ETP-oriented oligomerization pathway, complete removal of the pollutant bisphenol A can be achieved within 5min (kobs=1.68min-1), and the dynamic catalytic interface can be regenerated through a simple process, exhibiting excellent stability in complex aqueous media. This study gives PMS a new definition as an active interface regulator, and provides a dynamic, process-adaptive new paradigm for the design of intelligent metal-free systems for sustainable environmental remediation.
East China University of Science and Technology is the sole corresponding unit of the paper, with doctoral student Xiang Caixin as the first author, and Professor Liu Yongdi and Professor Lei Juying as the corresponding authors. This research work has received careful guidance from Professor Zhang Jinlong and Associate Professor Zhou Liang, and was supported by projects such as the National Natural Science Foundation of China.
Original link: https://onlinelibrary.wiley.com/doi/abs/10.1002/ange.4772250
