Molecular Understanding of Heterogeneous Hydroformylation on Rh1/CeO2: Morphology Effects

Abstract

Heterogeneous hydroformylation enhances the separation process, avoiding the use of phosphine ligands and reducing the loss of precious metals. However, enhancing catalytic activity and elucidating reaction mechanisms remain challenging. In this work, we develop single-atom catalysts (SACs) of Rh₁/CeO₂ with different morphologies and study their structure–performance relationships at the molecular level. The turnover frequency (TOF) of the Rh₁/CeO₂-Rod catalysts reaches 9386 h^–1 with a relatively high Rh loading (1.08 wt %), outperforming most reported SACs. The presence of oxygen atoms with dangling bonds and the local stress surrounding the embedded Rh atoms are identified as the key factors behind the morphology effects. Our work deepens the molecular understanding of the morphology effects underlying the enhancement of hydroformylation activity and paves the way for the future design of highly active heterogeneous hydroformylation SACs with both high TOF and optimal Rh loading.