Single MOF Based on Asymmetric Intramolecular Electron Compartments Enables Highly Efficient Photocatalytic CO ₂ Overall Reaction to Methanol

Abstract The development of single‐component photocatalysts that can achieve highly efficient photocatalytic CO 2 overall reactions (PCOR) to generate multielectron products remains a crucial challenge. Here, we present, for the first time, a novel strategy of constructing asymmetric “intramolecular electron compartments” (IEC) in single metal–organic frameworks (MOFs) that enables efficient PCOR to multielectron products. The resulting Cu‐MOF‐NK1(BF 4 − ) achieves a remarkable CH 3 OH production rate of 115.8 µmol g −1 h −1 (92.0% selectivity) without using any sacrificial agents and cocatalysts, making it one of the top‐performing single‐component PCOR catalysts reported to date. Notably, under simulating flue gas condition (15% CO 2 ), it remains the remarkable performance of 110.2 µmol g −1 h −1 with corresponding total electron assumption rate of 661.2 µmol g −1 h −1 , the highest value reported to date, setting a benchmark for low‐concentration CO 2 photocatalysts in overall reaction. Combined experimental and theoretical studies reveal new insights that the presence of asymmetric IEC within MOFs accounts for the enhanced accumulation of photogenerated electrons, thereby promoting the production of multielectron products. Our work not only develops a promising photocatalyst for converting CO 2 and H 2 O to methanol, but also establishes a universal design principle for constructing single‐component PCOR catalysts that enable multielectron reduction products.