Disproportionation of Silyl Formates, a Novel Strategy for Renewable Methanol Production

Clément Chauvier (1) , Arnaud Imberdis (1) , Pierre Thuéry (1) , Thibault Cantat (1)

1 LCMCE - Laboratoire de Chimie Moléculaire et de Catalyse pour l'Energie (ex LCCEF)

Methanol (CH$_3$OH) is a useful C1 building block employed in the chemical industry as precursor of important commodity chemicals such as formaldehyde, acetic acid or light olefins via the methanol-to-olefins (MTO) process. Nevertheless, the current methanol production methods is negatively impacted by the use of fossil resources. The production of CH$_3$OH would therefore strongly benefit from the advent of more sustainable processes like the six-electron reduction of CO$_2$ by hydrogenation, for example. An alternative strategy has recently emerged to generate CH$_3$OH from CO$_2$ via the intermediacy of formic acid (FA) as a C-H bond shuttle. At the onset, CO$_2$ is first reduced into FA by a relatively facile and intensively studied two-electron reduction (e.g. electroreduction). Subsequently, CH$_3$OH is produced by the disproportionation of FA. Under standard conditions, the competitive dehydrogenation and the targeted disproportionation of FA however display similar energy balances. To overcome this inextricable hurdle, we have thus sought a novel disproportionative route to methanol that suppresses the competing dehydrogenation pathway, while remaining attractive from the viewpoint of renewability. Towards that goal, we present a novel strategy based on the high-yielding catalytic disproportionation of silyl formates (HCO$_2$SiR$_3$) to methoxysilane (CH$_3$OSiR$_3$) and CO$_2$ followed by the release of free CH$_3$OH and the complete recycling of the silicon-containing byproducts generated throughout the process.

Domains: Material chemistry

Clément Chauvier, Arnaud Imberdis, Pierre Thuéry, Thibault Cantat. Disproportionation of Silyl Formates, a Novel Strategy for Renewable Methanol Production. International Conference On Phosphorus, Boron and Silicon (PBSi 2018), Dec 2018, Barcelona, Spain. ⟨cea-02340728⟩