Tailoring the Heterointerfaces of Earth-Abundant Transition-Metal Nanoclusters on Nickel Oxide Nanosheets for...

Evolving highly competent and economical electrocatalysts for alkaline water electrolysis is crucial in renewable hydrogen energy technologies. The slow hydrogen evolution reaction (HER)/oxygen evolution reaction (OER) kinetics under alkaline electrolytes, still, has troubled developments in high-performance green hydrogen production systems. Herein, we demonstrate the tailoring of the interface of earth-abundant transition-metal nanoclusters (MNCs), including iron (Fe), cobalt (Co), nickel (Ni), and copper (Cu) nanoclusters on nickel oxide nanosheets (M NCs|NiO NS) through metal-support interaction for enriched overall water splitting under an alkaline electrolyte. The strong metal-metal oxide interaction allows alteration of the binding capabilities of hydrogen ions (*H) and hydroxyl ions (*OH) on Ni electrodes. Specifically, the robust interaction between Fe and NiO reveals optimized binding of H* and OH* energies, facilitating the water-splitting reaction under an alkaline electrolyte. In addition, the improved HER/OER catalytic activity is attained with the Fe NCs|NiO NS with small overpotentials of ∼62.0 and ∼380.0 mV for the HER and OER, respectively, a high mass activity of ∼90.0 A g^-1, a turnover frequency of ∼5.94 s^-1, and long-lasting stability via offering abundant electrochemical active sites, three-dimensional (3D) morphologies, and high dispersion of nanoclusters that provide effective charge and mass transport processes. This study provides a promising strategy for the effective design of efficient bifunctional electrocatalysts based on earth-abundant materials for alkaline water electrolyzers.