Carbon matrix anchored Rh1Co single-atom alloy catalyst for robust hydroformylation with wide substrate generality

A novel Rh₁Co single-atom alloy (SAA) catalyst, in which Rh species are atomically dispersed on Co nanoparticles that are anchored by N-doped carbon (N-C) matrix for hydroformylation of olefins. The Rh₁Co SAA/N-C catalyst exhibits high activity towards the hydroformylation of 1-hexene, achieving both nearly 100% conversion and selectivity as well as good cycle stability. It also shows extremely wide substrate generality for at least 17 different types of olefins. A synergistic catalytic mechanism of the Rh₁Co SAA/N-C catalyst was discovered that H₂ is dissociated on Co sites and Co-H species are facilitated to be generated, CO is also adsorbed and inserted on Co sites that promote the C-C coupling, while the Rh-Co dual sites are beneficial to the co-adsorption of 1-hexene. Theoretical calculations reveal the Rh₁Co SAA/N-C catalyst shows a lower rate-determining energy barrier of CO insertion due to the optimized charge distribution of the precursor of CO insertion at Co sites.