Molecular Understanding\nof Heterogeneous Hydroformylation\non Rh<sub>1</sub>/CeO<sub>2</sub>: Morphology Effects

Heterogeneous\nhydroformylation enhances the separation\nprocess,\navoiding the use of phosphine ligands and reducing the loss of precious\nmetals. However, enhancing catalytic activity and elucidating reaction\nmechanisms remain challenging. In this work, we develop single-atom\ncatalysts (SACs) of Rh<sub>1</sub>/CeO<sub>2</sub> with different\nmorphologies and study their structure–performance relationships\nat the molecular level. The turnover frequency (TOF) of the Rh<sub>1</sub>/CeO<sub>2</sub>-Rod catalysts reaches 9386 h<sup>–1</sup> with a relatively high Rh loading (1.08 wt %), outperforming most\nreported SACs. The presence of oxygen atoms with dangling bonds and\nthe local stress surrounding the embedded Rh atoms are identified\nas the key factors behind the morphology effects. Our work deepens\nthe molecular understanding of the morphology effects underlying the\nenhancement of hydroformylation activity and paves the way for the\nfuture design of highly active heterogeneous hydroformylation SACs\nwith both high TOF and optimal Rh loading.