Ni‐CeO2 Heterostructure Promotes Hydrogen Evolution Reaction via Tuning of the O‐H Bonding Length of Adsorbed Water at the Electrolyte/electrode Interface

Understanding the properties and structure of reactant water molecules at the electrolyte solution/electrode interface is relevant to know the mechanisms of hydrogen evolution reaction (HER). However, this approach has rarely been implemented due to the elusive local microenvironment in the vicinity of the catalyst. Taking the Ni-CeO2 heterostructure immobilized onto carbon paper (Ni-CeO2/CP) as a model, the dynamic behavior of adsorbed intermediates during the reaction was measured by in situ surface-enhanced infrared absorption spectroscopy with the attenuated total reflection configuration (ATR-SEIRAS). Theoretical calculations are also combined to comprehend the potential causes of increased HER activity. The results show that the O-H bond of adsorbed water at the electrolyte solution/electrode interface becomes longer for promoting the dissociation of water and accelerating the kinetically slow Volmer step. In addition, forming the Ni-CeO2 heterostructure interface optimizes the hydrogen adsorption Gibbs free energy, thus increasing HER activity. Therefore, the Ni-CeO2/CP electrode exhibits remarkably low HER overpotentials of 37 and 119 mV at 10 and 100 mA cm-2, which are close to commercial Pt/C (16 and 102.6 mV, respectively).