Metal–Organic Framework with Dual Excitation Pathways as Efficient Bifunctional Catalyst for Photo‐assisted Li–O2 Batteries

Abstract Li–O 2 batteries (LOBs) have sparked significant interest due to their fascinating high theoretical energy density. However, the large overpotential for the formation and oxidation of Li 2 O 2 during charge and discharge process seriously hinders the further development and application of LOBs. In this work, metal–organic frameworks (MOFs) with different metal clusters (Fe, Ti, Zr) are successfully synthesized, and they are employed as the photoelectrodes for the photo‐assisted LOBs. The special dual excitation pathways of Fe‐MOF under illumination and the superior separation efficiency of photocarriers, which significantly enhance the activation of O 2 /Li 2 O 2 , improving the catalytic activity of oxygen reduction reaction and oxygen evolution reaction. Moreover, compared to traditional inorganic semiconductor crystals, Fe‐MOF exhibits large specific surface area and excellent O 2 adsorption ability. Therefore, the LOB with Fe‐MOF as the cathode exhibits large specific capacity, ultralow charge/discharge overpotential of 0.22 V at 0.05 mA cm −2 and excellent stability of 195 cycles under illumination. This study provides an environmentally friendly and highly efficient photocatalyst for LOBs, and a new strategy for designing photoelectrodes.