Activation of H(2)O Tailored by Interfacial Electronic States at a Nanoscale Interface for Enhanced Electrocatalytic Hydrogen Evolution

[Image: see text] Despite the fundamental and practical significance of the hydrogen evolution reaction (HER), the reaction kinetics at the molecular level are not well-understood, especially in basic media. Here, with ZIF-67-derived Co-based carbon frameworks (Co/NCs) as model catalysts, we systematically investigated the effects of different reaction parameters on the HER kinetics and discovered that the HER activity was directly dependent not on the type of nitrogen in the carbon framework but on the relative content of surface hydroxyl and water (OH(–)/H(2)O) adsorbed on Co active sites embedded in carbon frameworks. When the ratio of the OH(–)/H(2)O was close to 1:1, the Co/NC nanocatalyst showed the best reaction performance under the condition of high-pH electrolytes, e.g., an overpotential of only 232 mV at a current density of 10 mA cm(–2) in the 1 M KOH electrolyte. We unambiguously identified that the structural water molecules (SWs) in the form of hydrous hydroxyl complexes absorbed on metal centers {OH(ad)·H(2)O@M(+)} were catalytic active sites for the enhanced HER, where M(+) could be transition or alkaline metal cations. Different from the traditional hydrogen bonding of water, the hydroxyl (hydroxide) groups and water molecules in the SWs were mainly bonded together via the spatial interaction between the p orbitals of O atoms, exhibiting features of a delocalized π-bond with a metastable state. These newly formed surface bonds or transitory states could be new weak interactions that synergistically promote both interfacial electron transfer and the activation of water (dissociation of O–H bonds) at the electrode surface, i.e., the formation of activated H adducts (H*). The capture of new surface states not only explains pH-, cation-, and transition-metal-dependent hydrogen evolution kinetics but also provides completely new insights into the understanding of other electrocatalytic reductions involving other small molecules, including CO(2), CO, and N(2).