Synergistic Effect of Boron and Oxygen Coordination on Ruthenium Clusters for Industrial Water Splitting in Alkaline Medium

Abstract The alteration in the coordination environment of metal atoms can manipulate their electronic structure and regulate the electrocatalytic hydrogen evolution activity. In this work, synchrotron radiation tests prove that the boron (B) and oxygen (O) elements co‐coordinate with ruthenium clusters (Ru C ) on the surface of B–O modified reduced graphene oxide. The electrochemical tests demonstrate that this unique structure electrocatalyst presents an overpotential of 12 mV in 1 M KOH condition and for over 120 h at the current of −1 A cm −2 , indicating potential practical applications. The quasi in‐situ X‐ray photoelectron spectroscopy and in‐situ infrared spectroscopy confirmed that the B–O diatomic coordination can modulate the synergy between the substrate and the Ru C catalytic site, enhancing the intrinsic catalytic activity and ion migration efficiency. The first principles calculation further proves that B–O diatomic coordination will reduce the desorption barrier of H* and construct a complete hydrogen migration path. This study discloses the significance of the synergistic effect of two anions to enhance the catalytic activity of the catalyst by altering the coordination environment of ruthenium clusters.