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Direct Synthesis of Methyl Formate from CO2 With Phosphine-Based Polymer-Bound Ru Catalysts.

ChemSusChem (2019-04-30)
Ruiyan Sun, Anna Kann, Heinrich Hartmann, Astrid Besmehn, Peter J C Hausoul, Regina Palkovits
ABSTRACT

Methyl formate was produced in one pot through the hydrogenation of CO2 to formic acid/formate followed by an esterification step. The route offers the possibility to integrate renewable energy into the fossil-based chemical value chain. In this work, a phosphine-polymer-anchored Ru complex was shown to be an efficient solid catalyst for the direct hydrogenation of CO2 to methyl formate. The 1,2-bis(diphenylphosphino)ethane-like polymer presented the highest activity with a turnover number (TON) of up to 3401 at 160 °C. The reaction parameters were systemically investigated to optimize the reaction towards the formation of methyl formate. This catalyst could be reused seven times without a significant decrease in activity. Evolution of the catalytic Ru center during the reaction was revealed, and a possible reaction mechanism was proposed.

MATERIALS
Product Number
Brand
Product Description

Sigma-Aldrich
4,4′-Dibromobiphenyl, 98%
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Allyl methyl sulfone, 96%