Dual Polarization of Ni Sites at VO_x−Ni₃N Interface Boosts Ethanol Oxidation Reaction

Substituting thermodynamically favorable ethanol oxidation reaction (EOR) for oxygen evolution reaction (OER) engenders high‐efficiency hydrogen production and generates high value‐added products as well. However, the main obstacles have been the low activity and the absence of an explicit catalytic mechanism. Herein, a heterostructure composed of amorphous vanadium oxide and crystalline nickel nitride (VO x −Ni 3 N) is developed. The heterostructure immensely boosts the EOR process, achieving the current density of 50 mA cm −2 at the low potential of 1.38 V versus reversible hydrogen electrode (RHE), far surpassing the sluggish OER (1.65 V vs RHE). Electrochemical impedance spectroscopy indicates that the as‐fabricated heterostructure can promote the adsorption of OH − and the generation of the reactive species (O * ). Theoretical calculations further outline the dual polarization of the Ni site at the interface, specifically the asymmetric charge redistribution (interfacial polarization) and in‐plane polarization. Consequently, the dual polarization modulates the d‐band center, which in turn regulates the adsorption/desorption strength of key reaction intermediates, thereby facilitating the entire EOR process. Moreover, a VO x −Ni 3 N‐based electrolyzer, coupling hydrogen evolution reaction (HER) and EOR, attains 50 mA cm −2 at a low cell voltage of ≈1.5 V. This work thus paves the way for creating dual polarization through interface engineering toward broad catalysis.