Dual‐Functional Frustrated Lewis Pairs‐Regulated GaOOH/Ga 2 O 3 Heterojunctions: Targeted Molecular Activation for Boosted Photocatalytic Tandem CO 2 Hydrogenation

ABSTRACT Frustrated Lewis pairs (FLPs) possess spatially segregated Lewis active sites, enabling exceptional performance in small‐molecule activation and establishing them as a unique and promising catalytic platform. Nevertheless, most reported FLP‐based catalysts are plagued by limited molecular activation specificity, as they are merely capable of activating a single type of substrate molecule. In this work, we rationally design and fabricate a dual‐functional FLPs catalyst based on defective GaOOH/Ga 2 O 3 heterojunctions. Combined experimental characterizations and density functional theory calculations collectively corroborate the formation of intrinsic FLPs in both defective GaOOH and Ga 2 O 3 components. The GaOOH/Ga 2 O 3 heterojunction (Ga‐350) delivers remarkable synergistic effects toward CO 2 hydrogenation. Within this heterojunction, Ga 2 O 3 exhibits superior activity for heterolytic H 2 cleavage, while GaOOH preferentially activates CO 2 molecules. The resultant active hydrogen species migrate to the adsorbed CO 2 intermediates and subsequently drive the tandem photocatalytic reaction. Integrated with dual‐functional FLPs and a type‐II heterojunction, the Ga‐350 exhibited outstanding CO 2 ‐to‐CO conversion activity that not only surpassed that of pristine GaOOH and Ga 2 O 3 , but also exceeded those of the Al‐based and In‐based FLP counterparts prepared under identical calcination conditions. This work offers an instructive strategy for the rational design of dual‐functional FLPs materials toward targeted small‐molecule activation and efficient photocatalytic CO 2 conversion.