Frustrated Lewis Pairs on Porous Ceria Nanorods Drive Low-Temperature Dimethyl Carbonate Hydrogenation to Methanol.

Abstract

The hydrogenation of dimethyl carbonate (DMC) to CH₃OH represents an important reaction for advancing the circular carbon economy. However, its practical application remains hindered by the challenge of achieving high catalytic activity under mild conditions. Herein, we demonstrate that frustrated Lewis pairs (FLPs) constructed on porous CeO₂ nanorods serve as active sites for efficient low-temperature DMC hydrogenation. These FLPs sites, composed of adjacent two Ce³⁺ (Lewis acid centers) and lattice O^2- (Lewis base sites), exhibit a bidentate adsorption configuration that simultaneously engages both oxygen atoms of the C-O-C group in DMC. This binding mode promotes DMC activation and suppresses CO₂ formation. Coupled with efficient H₂ dissociation and subsequent *H spillover from Pd clusters, the FLPs sites deliver a CH₃OH production rate of 18.1 mmol g_cat^-1 h^-1 with >90% selectivity at 80 °C, outperforming state-of-the-art catalysts that typically require temperatures above 160 °C. This work highlights the potential of designing FLPs for driving hydrogenation.