Stoichiometric Selective Carbonylation of Methane to Acetic Acid by Chemical Looping

The conversion of methane to valuable products is one of the main challenges of modern chemistry. Acetic acid (AcOH) is a key chemical reagent in industry, produced nowadays by the carbonylation of methanol over homogeneous Rh and Ir catalysts. Here, we propose a stepwise chemical looping approach for the highly selective stoichiometric synthesis of AcOH by carbonylation of methane with CO using single-site Pt over isolated phosphotungstic anions on a titania support (Pt-HPW-TiO₂). The reaction proceeds by methane activation, which coincides with the reduction of initially oxidized Pt species in the presence of CO at 423 K and results in surface acetates attached to TiO₂. Subsequent hydrolysis by water at ambient temperature results in the synthesis of AcOH in a stoichiometric amount corresponding to 1.5 Pt. Spent Pt-HPW-TiO₂ is restored to the initial state by subsequent calcination in air. This approach provides an opportunity for the selective synthesis of AcOH (>99% in liquid phase) from methane, carbon monoxide, and air. A high concentration of AcOH (1.1 wt %) in an aqueous solution can be obtained at a high conversion of methane (4.5%).