Oxidative Strong Metal–Support Interaction Stabilized Single-Atom Catalysts for Heterogeneous Hydroformylation

The strong metal-support interaction (SMSI) is one of the most important concepts in heterogeneous catalysis, which plays a crucial role in modifying catalytic performance. However, the study of SMSI on single-atom catalysts (SACs), which are considered to bridge homogeneous and heterogeneous catalysis, remains preliminary. Here, to the best of our knowledge, we first report the oxidative SMSIs on SACs and utilize them to enhance hydroformylation activity and stability. The surface-adsorbed Rh single atoms tend to be encapsulated by ZrO₂ supports after calcination in air and can be re-exposed after reduction in H₂. The highest turnover frequency (TOF) of heterogeneous hydroformylation reaches 11,097 h^-1, surpassing previously reported SACs. The embedded Rh, generated through oxidative SMSI, also shows enhanced stability to resist metal leaching. Our work expands the conceptual boundaries of SMSIs and paves the way for the future design of highly active and stable heterogeneous hydroformylation catalysts.