Bi1δ+-O-Ce3+ synergistic sites on rod ceria for unprecedentedly efficient transesterification

Heterogeneous catalysts for transesterification reaction are highly desirable, but normally suffer from low activity or severe deactivation. Here we report a Bi1-ceria catalyst for transesterification that exhibits catalytic activity of 2499 g1,2-BC gcat.−1 h-1 and stability for 800 h, in the synthesis of 1,2-butylene carbonates from 1,2-butanediol and dimethyl carbonate. Our study reveals that the constructed Bi1 does not serve as the conventional catalytic centre but regulates the acidity-basicity of the active sites through remote catalysis, realized by the induced delocalization of the f electron of Ce3+ and the remote propagation of electrons via the conductive lattice oxygen. The highly active sites lead to the Bi1 centred re-construction into BiOx during the reaction, which triggers tardily decline in catalytic activity. Nevertheless, the catalyst can be readily regenerated with thermal treatment by restoring the migrated oxygen. These findings open an avenue for the rational design of single-atom catalysts for transesterification reactions. Improving catalysts for producing carbonates remains a challenge due to limited activity and durability. This study shows a bismuth–ceria catalyst that enhances reaction steps through remote electronic effects and can be easily regenerated.