Platinum-Catalysed Selective Aerobic Oxidation of Methane to Formaldehyde in the Presence of Liquid Water

Abstract

The aerobic, selective oxidation of methane to C1-oxygenates remains a challenge, due to the more facile, consecutive oxidation of formed products to CO2. Here, we report on the aerobic selective oxidation of methane under continuous flow conditions, over platinum-based catalysts yielding formaldehyde with a high selectivity (reaching 90 % for Pt/TiO2 and 65 % over Pt/Al2O3) upon co-feeding water. The presence of liquid water under reaction conditions increases the activity strongly attaining a methane conversion of 1–3 % over Pt/TiO2. Density-functional theory (DFT) calculations show that the preferential formation of formaldehyde is linked to the stability of the di-σ-hydroxy-methoxy species on platinum, the preferred carbon-containing species on Pt(111) at a high chemical potential of water. Our findings provide novel insights into the reaction pathway for the Pt-catalysed, aerobic selective oxidation of CH4.