Hydroformylation of Olefins by a Rhodium Single-Atom Catalyst with Activity Comparable to RhCl(PPh3)3

Homogeneous catalysts generally possess superior catalytic performance compared to heterogeneous catalysts. However, the issue of catalyst separation and recycling severely limits their use in practical applications. Single‐atom catalysts have the advantages of both homogeneous catalysts, such as “isolated sites”, and heterogeneous catalysts, such as stability and reusability, and thus would be a promising alternative to traditional homogeneous catalysts. In the hydroformylation of olefins, single‐atom Rh catalysts supported on ZnO nanowires demonstrate similar efficiency (TON≈40000) compared to that of homogeneous Wilkinson's catalyst (TON≈19000). HAADF‐STEM and infrared CO chemisorption experiments identified isolated Rh atoms on the support. XPS and XANES spectra indicate that the electronic state of Rh is almost metallic. The catalysts are about one or two orders of magnitude more active than most reported heterogeneous catalysts and can be reused four times without an obvious decline in activity. Rhodium single‐atom catalysts supported on ZnO nanowires display olefin hydroformylation efficiency comparable to that of homogeneous Wilkinson's catalyst.