Visible Light‐Switchable Lattice Oxygen Sites for Selective C−H and C(O)−C Bond Electrooxidation

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.