Selective Hydrogenation of Formamide to Methanol Over Supported Platinum Catalysts

Abstract

ABSTRACT The rising global energy demand, driven by population and economic growth, continues to be met largely by fossil fuels. Consequently, atmospheric CO 2 concentration has increased from ∼280 ppm in the pre‐industrial era to over 430 ppm today, motivating integrated capture‐and‐conversion strategies that valorize CO 2 as a feedstock. Amines are widely employed for post‐combustion CO 2 capture due to their low cost, rapid kinetics, and reversible carbamate formation. These amine–CO 2 adducts can be hydrogenated to formamides and subsequently to methanol under mild conditions (<150°C), regenerating the amine. However, selective C─N bond cleavage during the formamide hydrogenation for efficient release of methanol without sorbent deactivation remains a key challenge. Here, we demonstrate that 1 wt% Pt supported on TiO 2 (commercial P25) catalyzes the conversion of 4‐formylmorpholine to methanol with up to 62% yield and 95% selectivity at 150°C. In situ characterizations and DFT computations reveal that strong interaction between dispersed Pt and the support promotes selective C─N hydrogenolysis. The catalyst also exhibits excellent stability. These findings establish a robust heterogeneous platform for combined CO 2 capture and methanol synthesis, highlighting the critical role of support‐induced electronic effects in controlling bond scission.