Activating Lattice Oxygen by Electrochemical De‐Lithiation for Efficient Benzyl Alcohol Oxidation

Abstract Electrocatalytic benzyl alcohol oxidation reaction (EBOR) is a feasible way to produce high‐value‐added benzaldehyde and benzoic acid. However, the performance of catalyst usually suffers from the high energy barrier for the O─O bonding step resulting in sluggish process. Herein, lattice oxygen activation strategy is proposed by the electrochemical de‐lithiation of LiNiO₂ to catalyze the EBOR through direct O─O bonding to significantly enhance the EBOR performance. The electrochemical de‐lithiation make the charge redistributed in Ni–O portion, leading to the lattice oxygen in LiNiO₂ activated, thereby reducing the energy barrier of the O─O coupling step by following lattice oxygen mechanism (LOM). The constructed de‐LiNiO₂ exhibits excellent EBOR catalytic activity featuring current densities of 100 and 400 mA cm⁻² at only 1.397 and 1.431 V, respectively, outperforming the currently reported analogous electrocatalysts. The formation of high‐valence Ni⁴⁺ after de‐lithiation leads to direct O–O coupling between lattice oxygen in de‐LiNiO₂ and oxygen‐containing intermediates in EBOR, favoring an energetically favorable LOM pathway, thereby enhancing the EBOR performance. This work provides a new strategy to enhance the electrocatalytic activity by changing the reaction mechanism rather than focusing on catalyst design, opening up a new path for the development of advanced biomass oxidation electrocatalysts.