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Lattice‐oxygen is highly oxidizable, ideal for electrocatalytic C−H oxidation but insufficient alone for C(O)−C bond cleavage due to the non‐removable nature of lattice sites. Here, we present a visible light‐assisted electrochemical method of in‐situ formulating removable lattice‐oxygen sites in a nickel‐oxyhydroxide (ESE‐NiOOH) electrocatalyst. This catalyst efficiently converts aromatic alcohols and carbonyls with C(O)−C fragments from lignin and plastics into benzoic acids (BAs) with high yields (83–99%). Without light irradiation, ESE‐NiOOH’s intrinsic lattice‐oxygen is non‐removable and inert for C(O)−C bond cleavage. In‐situ characterizations show light‐induced lattice‐oxygen removal and regeneration via OH– refilling. Theoretical calculations identify the nucleophilic oxygen attack on ketone‐derived carbanion as a rate‐determining step, which can be remarkably facilitated by removable lattice‐oxygen to activate α‐C−H bonds. As a proof‐of‐concept, an “electrochemical funnel” strategy is developed for high‐efficiency upgrading aromatic mixtures with C(O)−C moieties into BA with up to 94% yield. This in‐situ removal‐regeneration approach for lattice sites opens an avenue for the tailored design of interfacial electrocatalysts to selectively upcycle waste carbon sources into valuable products.
Wang et al. (Mon,) studied this question.