Delocalized Orbitals Over Metal Clusters and Organic Linkers Enable Boosted Charge Transfer in Metal‐Organic Framework for Overall CO2 Photoreduction

Abstract The conversion of CO 2 to C 2 through photocatalysis poses significant challenges, and one of the biggest hurdles stems from the sluggishness of the multi‐electron transfer process. Herein, taking metal–organic framework (MOF, PFC‐98) as a model photocatalyst, we report a new strategy to facilitate charge separation. This strategy involves matching the energy levels of the lowest unoccupied node and linker orbitals of the MOF, thereby creating the lowest unoccupied crystal orbital (LUCO) delocalized over both the node and linker. This feature enables the direct excitation of electrons from photosensitive linker to the catalytic centers, achieving a direct charge transfer (DCT) pathway. For comparison, an isoreticular MOF (PFC‐6) based on analogue components but with far apart frontier energy level was synthesized. The delocalized LUCO caused the presence of an internal charge‐separated (ICS) state, prolonging the excited state lifetime and further inhibiting the electron‐hole recombination. The presence of ICS state prolongs the excited state lifetime and further inhibits the electron‐hole recombination. Moreover, it also induced abundant electrons accumulating at the catalytic sites, enabling the multi‐electron transfer process. As a result, the material featuring delocalized LUCO exhibits superior overall CO 2 photocatalytic performance with high C 2 production yield and selectivity.