Regulating *H Dynamics via Photoinduced Oxygen Vacancy‐Lattice Oxygen Frustrated Lewis Pairs for Superior CO ₂ Photoreduction

Abstract Herein, we construct photoinduced oxygen vacancy‐lattice oxygen frustrated Lewis pairs (V o ‐O L FLPs) on metal oxide atomic layers, coupled with employing benzyl alcohol (BA) as an alternative *H source, to concurrently promote *H production and transfer, enabling efficient CO 2 photoreduction. Taking the V o ‐Bi 2 WO 6 atomic layers as examples, in situ solid‐state electron paramagnetic resonance and in situ X‐ray photoelectron spectroscopy elucidate photoinduced FLPs, composed of V o and O L , which respectively trap photogenerated electrons and holes to activate CO 2 and facilitate BA dehydrogenation. In situ Kelvin probe force microscopy and density of states calculations indicate V o suppresses the electron‐hole recombination by creating defect levels. Importantly, in situ Fourier‐transform infrared spectra, isotopic‐labeling experiments and theoretical calculations demonstrate the V o ‐O L FLPs mediate efficient *H transfer from BA to CO 2 , suppressing competitive *H reduction to H 2 . In situ electron paramagnetic resonance spectra also disclose BA oxidation proceeds via a more kinetically favorable pathway for *H production than H 2 O oxidation. Benefiting from the synergistic enhancement in *H production and transfer, the photocatalyst achieves an impressive CO 2 conversion rate of 3667.1 µmol g −1 h −1 with excellent 240 h stability, surpassing previously reported state‐of‐the‐art systems. This work offers atomic‐level insights for designing active sites to optimize *H dynamics.