Electron‐Donating Cu Atoms Induced High Proton Supply and Anti‐Poisoning Ruthenium Clusters for Superior Direct Seawater Hydrogen Production

Abstract Direct seawater hydrogen production via electrolysis would be a transformative technology for large‐scale pathways for future sustainable energy systems. However, prohibiting the formation of insoluble hydroxides and promoting proton supply at the electrode‐seawater interface are extremely desirable but remain challenging. Herein, inspired by the dual‐metal pair sites in natural enzyme, the de novo design of an efficient, robust, and precise electron‐donating Cu‐modulated ruthenium clusters on porous carbon matrix (Cu@Ru nc ‐C) is reported as a high proton supply and anti‐poisoning cathode material for superior direct seawater hydrogen production. Benefitting from the unique Cu@Ru nc pair sites, the cathode exhibits particularly high hydrogen evolution activities with ultralow overpotentials to reach a high current density of 300 mA cm −2 in both alkaline (115 mV) and seawater (459 mV) electrolytes, and notably, the cathode can maintain superior long‐lasting stability in seawater electrolysis. The mechanism exploration demonstrates that the ruthenium cathode with Cu@Ru nc pair sites exhibits low oxophilic and fast proton‐transferring local reaction environments to prohibit the formation of insoluble precipitates and provide efficient proton supply within the electrode‐seawater interface. It is expected that the proposed bioinspired regulation strategy offers a new pathway for constructing efficient, robust, and selective cathode materials for scalable seawater hydrogen production.