Construction of Frustrated Lewis Pairs in Low‐Cost Silicate Minerals via H ₂ ‐Mediated Oxygen Vacancy Engineering for Efficient Photocatalytic CO ₂ Hydrogenation

ABSTRACT Frustrated Lewis pairs (FLPs) have attracted extensive attention in heterogeneous catalysis due to their distinctive ability to efficiently dissociate small molecules and accelerate reaction kinetics, yet challenges remain for low‐cost large‐scale applications. Herein, FLPs are first successfully fabricated in low‐cost silicate minerals, with the inherent surface hydroxyl groups (‐OH) of the latter serving as Lewis base (LB) sites. Simultaneously, H 2 ‐mediated deoxygenation induces oxygen vacancies (O V ), modulating the electronic states of adjacent Zn sites and transforms them into Lewis acid (LA) sites. Density functional theory (DFT) calculations are carried out to elucidate the optimal spatial distance between LA and LB sites and the charge transfer behavior, thereby furnishing atomic‐scale insights into the effective construction of FLPs. Coupled with in‐situ H 2 characterizations, the efficient dissociation of H 2 into H + and H − is directly visualized, thus affording abundant active hydrogen species for the subsequent reaction. Furthermore, FLPs can serve as shallow energy levels to facilitate the separation and migration of photogenerated carriers. The CO formation rate in photocatalytic reaction of the Zn 2 SiO 4 catalyst modified with FLPs is 2.3‐fold higher than that of the pristine FLPs‐free Zn 2 SiO 4 catalyst. This work provides a strategy for FLPs in low‐cost silicate minerals facilitating photocatalytic CO 2 hydrogenation.