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

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 (CO₃ ^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 CO₃ ^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.