Construction of Efficient S‐Scheme WO ₃ /COFTB Heterojunction Photocatalyst for Round‐The‐Clock Elimination of Antibiotic Ciprofloxacin via Photoinduced Electron Storage Coupled With Peroxidase‐Like Mechanism

Developing round‐the‐clock photocatalysts with sustained high‐efficiency performance remains one of the most challenging frontiers in environmental remediation. Herein, we propose a strategy of construction of highly efficient round‐the‐clock photocatalysts through a mechanism based on photo‐induced electron storage coupled with peroxidase‐like activity. Based on this strategy, a novel S‐scheme WO 3 /COFTB heterojunction was successfully developed by integrating bipyridine‐based covalent organic framework (COFTB) with hexagonal WO 3 for the round‐the‐clock degradation of organic contaminants. Under illumination, the WO 3 /COFTB heterojunction efficiently generates H 2 O 2 in situ from water and air. WO 3 acts as an electron transfer station in COFTBW, enabling efficient ciprofloxacin (CIP) degradation under both light irradiation (99.32%, 60 min) and dark conditions (92.95%, 60 min). The S‐scheme charge transfer mechanism in COFTBW is revealed, where the heterojunction structure facilitates photoinduced carrier separation and transfer, thereby boosting photocatalytic efficiency. In darkness, the stored electrons in WO 3 migrate to COFTB, triggering direct O 2 reduction and subsequent H 2 O 2 activation to generate ROS, which drive pollutant degradation in the absence of light. This study provides a novel design strategy for round‐the‐clock photocatalysts through the synergistic coupling of multiple mechanisms, allowing the construction of an energy‐efficient and robust photocatalytic system capable of effective round‐the‐clock degradation of pollutants.