Corrosion-driven interfacial reconstruction enables selective two-carbon ethanol oxidation at industrial current density.

Abstract

The sluggish kinetics of the anodic oxygen evolution reaction (OER) severely limit the energy efficiency of conventional water electrolysis. Replacing OER with thermodynamically favorable small-molecule oxidation offers a promising strategy to reduce energy consumption while enabling value-added chemical production. Here, we report a corrosion-driven interfacial reconstruction strategy to in situ construct a self-supported nickel-iron layered double hydroxide/iron oxyhydroxide (NiFe-LDH/FeOOH) heterostructure on iron foam for efficient ethanol electrooxidation (EOR). The hierarchically assembled nanosheet architecture, coupled with a strongly coupled heterointerface, enables abundant accessible active sites and promotes interfacial charge redistribution. As a result, the catalyst delivers a high current density exceeding 400 mA -2 at 1.5 V along with a high Faradaic efficiency of 92.21% over 3 days, underscoring great potential for EOR at industrial current density. Operando spectroscopic analyses reveal a selective C2 oxidation pathway via acetaldehyde intermediates. Density functional theory (DFT) calculations further demonstrate that interfacial electronic coupling lowers the energy barrier of the rate-determining CH3CH2O to CH3CHO step. This work highlights the critical role of heterointerface engineering in regulating both electronic structure and reaction pathways, providing a viable strategy for coupling energy-efficient hydrogen production with selective biomass upgrading.