Lattice distortion promotes dehydrogenation of layered double hydroxide for enhanced electrocatalytic oxidation activity

Abstract Nickel‐based layered double hydroxide (LDH) electrocatalyst has been explored for various small‐molecule electrooxidation reactions at the anode, but its efficiency is limited by the unsatisfactory dehydrogenation. In this work, we go beyond traditional compositional tuning and leverage the lattice distortion to promote the deprotonation process of LDH. The obtained curved c‐NiCo‐LDH electrocatalyst with lattice distortion can achieve above 90% faradaic efficiency of formate and a stable electrolysis at 300 mA cm −2 for 50 h during methanol oxidation reaction. A series of in situ electrochemical spectra unravel structural transformation process of LDH under operating conditions and establish a distortion‐performance relation, in which the tensile lattice distortion facilitates the formation of active Ni 3+ O species. Energetic analysis from theoretical calculations further supports enhanced dehydrogenation on the distorted unit of LDH and optimized Ni orbital electronic states for accelerated Ni 2+ OH and Ni 3+ O interconversions. This study establishes the groundwork of applying unconventional distortion to upgrade LDH for electrocatalysis, which can be extensible to other renewable energy conversions.