Porous coordination polymer-stabilized rhodium single-atom catalyst for regioselective hydroformylation

Abstract

The selective hydroformylation of olefins represents one of the most significant reactions in chemical production. In this work, a porous coordination polymer-supported rhodium single-atom catalyst was constructed for olefin hydroformylation. The Rh-based catalyst features rhodium atoms anchored in a single-atom form within the polymer framework, exhibiting high catalytic activity in the hydroformylation of styrene. Notably, the electronic and spatial effects conferred by the phosphorus-functionalized polymer support synergistically contribute to the preferential formation of iso-aldehydes over the Rh/Zr-HTP catalyst during hydroformylation (i/n ratio = 7.5). Detailed characterization revealed that the formation of an HRh(CO)₃(P-frame) intermediate under reaction conditions facilitates the generation of iso-aldehydes. Furthermore, the catalyst demonstrated high efficiency, exceptional stability, and facile recyclability.