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

Sinqobile V. L. Mahlaba, Nasseela Hytoolakhan Lal Mahomed, Alisa Govender, Junfeng Guo, Gerard M. Leteba, Pierre L. Cilliers, Eric van Steen

2022Angewandte Chemie International Edition19 citationsDOIOpen Access PDF

Abstract

Abstract The aerobic, selective oxidation of methane to C 1 ‐oxygenates remains a challenge, due to the more facile, consecutive oxidation of formed products to CO 2 . 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/TiO 2 and 65 % over Pt/Al 2 O 3 ) 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/TiO 2 . 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 CH 4 .

Topics & Concepts

FormaldehydeChemistryPlatinumAnaerobic oxidation of methaneCatalysisMethaneOxygenateDensity functional theoryInorganic chemistrySelectivityPhotochemistryOrganic chemistryComputational chemistryCatalytic Processes in Materials ScienceCatalysis and Oxidation ReactionsAdvanced Photocatalysis Techniques
Platinum‐Catalysed Selective Aerobic Oxidation of Methane to Formaldehyde in the Presence of Liquid Water | Litcius