ABSTRACT
Direct chemical synthesis from methane and air under ambient conditions is attractive yet challenging. Low-valent organometallic compounds are known to activate methane, but their electron-rich nature seems incompatible with O2 and prevents catalytic air oxidation. We report selective oxidation of methane to methanol with an O2-sensitive metalloradical as the catalyst and air as the oxidant at room temperature and ambient pressure. The incompatibility between C-H activation and O2 oxidation is reconciled by electrochemistry and nanomaterials, with which a concentration gradient of O2 within the nanowire array spatially segregated incompatible steps in the catalytic cycle. An unexpected 220â¯000-fold increase of the apparent reaction rate constants within the nanowire array leads to a turnover number up to 52â¯000 within 24 h. The synergy between nanomaterials and organometallic chemistry warrants a new catalytic route for CH4 functionalization.