A research team led by Tiannan Ye and Jiesheng Chen at the Frontiers Science Center for Transformative Molecules, Shanghai Jiao Tong University, has published their latest research findings titled “Ordered single active sites for cascade hydrogenation and hydroformylation reactions” in the journal Nature Catalysis.

Article abstract:

Metal single-atom catalysts offer improved activity and selectivity due to their unique electronic and coordination properties compared with bulk metals. However, many single-atom catalysts suffer from randomly dispersed active sites and limited electron-donating ability due to bonding with electronegative elements or less reactive metals. Here we demonstrate that Mg-rich intermetallic Mg29TM4 (TM = Pd, Rh, Ir, Pt) nanocatalysts overcome these limitations. These materials feature periodically dispersed, electron-rich single-atom sites of noble metals within a uniform chemical environment. Mg29TM4 exhibits high activity and selectivity in C2H2 semihydrogenation (Mg29Pd4) and olefin hydroformylation (Mg29Rh4), with Mg29Rh4 achieving high regioselectivity for branched aldehydes (branched:linear > 200:1). Kinetic and density functional theory studies suggest that the Mg–TM ensemble enables precise control over carbon–carbon multiple bond adsorption and activation, enhancing both activity and selectivity. Furthermore, the ternary Mg29Pd1.3Rh2.7 catalyst, with its synergistic Mg–Pd and Mg–Rh dual single-atom sites, efficiently catalyses a cascade reaction involving phenylacetylene hydrogenation followed by hydroformylation.