Structural Evolution of Iron-Loaded Metal-Organic Framework Catalysts for Continuous Gas-Phase Oxidation of Methane to Methanol.

Abstract

Catalytic partial oxidation of methane presents a promising route to convert the abundant but environmentally undesired methane gas to liquid methanol with applications as an energy carrier and a platform chemical. However, an outstanding challenge for this process remains in developing a catalyst that can oxidize methane selectively to methanol with good activity under continuous flow conditions in the gas phase using O2 as an oxidant. Here, we report a Fe catalyst supported by a metal-organic framework (MOF), Fe/UiO-66, for the selective and on-stream partial oxidation of methane to methanol. Kinetic studies indicate the continuous production of methanol at a superior reaction rate of 5.9 × 10-2 μmolMeOH gFe-1 s-1 at 180 °C and high selectivity toward methanol, with the catalytic turnover verified by transient methane isotopic measurements. Through an array of spectroscopic characterizations, electron-deficient Fe species rendered by the MOF support is identified as the probable active site for the reaction.