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

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 CO₂ photoreduction. Taking the V_o-Bi₂WO₆ 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 CO₂ 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 CO₂, suppressing competitive *H reduction to H₂. In situ electron paramagnetic resonance spectra also disclose BA oxidation proceeds via a more kinetically favorable pathway for *H production than H₂O oxidation. Benefiting from the synergistic enhancement in *H production and transfer, the photocatalyst achieves an impressive CO₂ 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.