Acid-Stable Ru Atom Array for Converting Methanol to Methyl Formate at Commercially Viable Current Densities

Replacing the oxidation of water with the electrocatalytic oxidation of methanol is an attractive route to level the cost of H2 production with value-added chemicals; however, this reaction has been notoriously known for quickly poisoning electrocatalysts and/or sliding into complete oxidation, thereby producing CO2. Here, we report an acid-stable Ru metal atom array that is supported by MnO2 nanofibers (Ru-MAC/MnO2) for the electrocatalytic valorization of methanol to methyl formate (MF). The productivity of MF is 10 to 100 times higher than those reported in thermal- and photocatalytic processes at commercially viable current densities. Our experimental and simulation results demonstrate that the atom array possesses long-term electrochemical stability and prefers the MF pathway without generating *CO intermediates. The synergistic intersite metal–metal and metal–support electronic interactions endow Ru-MAC/MnO2 with outstanding structural stability toward large-current-density methanol electrolysis.