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

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. © 2024 Wiley-VCH GmbH.