Fe 2 Dimers for Non-Polar Diatomic O 2 Electroreduction.

Non-polar diatomic molecule activation is of great significance for catalysis. Despite the high atomic efficiency, the catalytic performance of single-atom catalysts is limited by insufficient receiving sites for diatomic molecule adsorption. Here, Fe 2 dimers were successfully synthesized through precisely regulating the metal loading on metal-organic frameworks. The unique role of metal dimers in activating diatomic O 2 molecules was explored. In alkaline electrolytes, the specific oxygen reduction reaction activity of Fe 2 dimers was 7 times higher than that of Fe 1 counterparts. The hydrogen atom transfer probes indicated a different activation mode for O 2 on Fe 1 and Fe 2 dimers, respectively. Theoretical calculation results revealed that Fe 2 dimers opened up a new reaction pathway by promoting the direct breaking of O=O bonds, thus avoiding the usual formation of *OOH intermediates, which helped explain the lower H 2 O 2 yield and higher specific activity.