Chen, Enqi; Li, Xiyi; Wang, Chao; Xu, Youxun; Lan, Yang; Tang, Junwang; (2025) CO2 Promoted methanol conversion to methyl formate by photocatalysis. Chemical Engineering Journal , 510 , Article 161860. 10.1016/j.cej.2025.161860.

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Abstract

Methyl formate (MF), as an important precursor to numerous commercially significant compounds (e.g. dimethyl carbonate, methyl acetate, and ethyl glycol etc), is typically synthesised via the condensation reaction or carbonylation of methanol, requiring relatively high-value precursors (e.g. formic acid or dry CO) while with a low conversion or selectivity. Herein, palladium (Pd) and gold (Au) modified TiO2 (P25) was designed to use a very low-cost precursor methanol with the assistance of CO2 to synthesise MF under ambient conditions. Remarkably, a high conversion of methanol (98.1 %) and selectivity to MF (94.9 %) have been achieved under an optimised reaction condition using methanol as the major reactant. In this system, Au significantly enhances charge separation and transfer, and then Pd serves as a final hole acceptor, facilitating the oxidation of methanol to MF by PdAu-modified P25. This synergy boosts the MF formation rate by 15 times compared to single-metal-modified P25 under identical reaction conditions. Further studies reveal that formaldehyde is a pivotal intermediate in the formation of MF and employing CO2 as a reaction moderator inhibits the methanol over oxidation.

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