Dynamic Geminal‐Atom Coordination for Highly Efficient Photo‐Fenton Catalysis

ABSTRACT Understanding and leveraging non‐reactive species in natural environments to modulate the active centers of geminal‐atom catalysts (GACs) is crucial for enhancing their catalytic performance. Here, we develop a two‐coordinated copper geminal‐atom catalyst and reveal that the ubiquitous yet inert carbonate ions (CO 3 2− ) in seawater dynamically reorganize the coordination environment of active copper sites, thereby enhancing photo‐Fenton reactivity. Control experiments, in situ spectroscopy and theoretical modeling demonstrate that CO 3 2− induces reversible coordination transformations that modulate the electronic structure and facilitate interfacial charge transfer, resulting in a 17‐fold increase in hydroxyl radical production. This effect enables efficient degradation of diverse marine pollutants, including effective Chlorella decomposition under natural sunlight. Life‐cycle and technoeconomic assessments further demonstrate the environmental benefits and economic feasibility of this approach. Overall, this work establishes a generalizable strategy for active geminal‐atom catalysts via environmentally abundant species, offering mechanistic insights and scalable pathways toward large‐scale and sustainable aquatic pollution remediation.