The reaction pathways connecting methanol to methane and formaldehyde are among the most emblematic in chemistry because of their outstanding interest in the fields of energy, synthesis, and bio- and geo-chemistry. Despite of its fundamental nature, the one-pot synthesis of formaldehyde and methane stemming from methanol has never been reported before. Here we present a study, based on ab initio molecular dynamics and free-energy methods, in which the simultaneous oxidation and reduction (i.e., the disproportionation) of liquid methanol into methane and formaldehyde has been achieved at ambient temperature through the application of a static electric field. Because strong electric fields can be generated in the proximity of field emitter tips, this finding shows that the challenge of experimentally disproportionating methanol into formaldehyde and methane could be attempted. We show that the methanol "solvent" molecules play a major role in this process and that the chemical pathway connecting methanol to the detected products in the bulk liquid phase is very different from its reproduced gas-phase counterpart. Finally, we demonstrate that switching on an external electric field drastically modifies the reaction network of methanol, lowering some activation barriers, stabilizing the methane and formaldehyde products, and opening otherwise difficult-to-achieve chemical routes.

CNR IPCF Viale Ferdinando Stagno d'Alcontres 37 98158 Messina Italy Email

Institute of Biophysics Czech Academy of Sciences Královopolská 135 61265 Brno Czech Republic Email

Sorbonne Universités Université Pierre et Marie Curie Paris 06 Institut de Minéralogie de Physique des Matériaux et de Cosmochimie CNRS Muséum national d'Histoire naturelle Institut de Recherche pour le Développement Unité Mixte de Recherche 7590 F 75005 Paris France Email ; Email ; Email

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