Monomeric Copper(II) Sites Supported on Alumina Selectively Convert Methane to Methanol

Monomeric CuII sites supported on alumina, prepared using surface organometallic chemistry, convert CH4 to CH3OH selectively. This reaction takes place by formation of CH3O surface species with the concomitant reduction of two monomeric CuII sites to CuI, according to mass balance analysis, infrared, solid‐state nuclear magnetic resonance, X‐ray absorption, and electron paramagnetic resonance spectroscopy studies. This material contains a significant fraction of Cu active sites (22 %) and displays a selectivity for CH3OH exceeding 83 %, based on the number of electrons involved in the transformation. These alumina‐supported CuII sites reveal that C−H bond activation, along with the formation of CH3O‐ surface species, can occur on pairs of proximal monomeric CuII sites in a short reaction time. One plus one equals two: Methane is converted to methanol selectively by CuII sites generated on a γ‐alumina support using a surface organometallic chemistry and thermal molecular precursor approach. The activation of the material at high temperature under oxygen generates monomeric CuII sites. A large fraction of the sites formed are capable of partial oxidation of methane to methanol under mild conditions.