Process‐Driven Protonation in Benzothiadiazole‐Integrated Covalent Organic Frameworks: Activation of Peroxymonosulfate for Pollutant Oligomerization via Dominant Electron Transfer Process

ABSTRACT Traditional peroxymonosulfate (PMS) activation typically follows a static, catalyst‐centered paradigm, constrained by radical‐mediated pathways with limited selectivity and incomplete mineralization. Going beyond this convention, we established a process‐driven protonation strategy that steers PMS activation toward a dominant electron transfer process (ETP), enabling selective pollutant oligomerization. By developing benzothiadiazole‐integrated covalent organic frameworks (BT‐COFs) as a model platform, it was demonstrated that PMS addition intrinsically acidifies the reaction medium, triggering in situ framework protonation at specific nitrogen sites. This self‐induced protonation acts as a molecular switch, reorganizing the interfacial electronic structure and generating a polarized catalytic interface that facilitates directional electron transfer rather than radical generation. Consequently, the complete bisphenol A (BPA) removal within 5 min ( k obs = 1.68 min −1 ) was achieved through an ETP‐directed oligomerization pathway, wherein the dynamic catalytic interface remains accessible through simple regeneration, maintaining excellent stability and robustness in complex water matrices. This work redefines the role of PMS as an active interfacial regulator and provides a dynamic, process‐adaptive conceptual framework for designing intelligent metal‐free systems for sustainable environmental remediation.