Constructing matched sub-nanometric cobalt clusters with multiple oxidation and metallic states for efficient propane dehydrogenation

Modulating unique microenvironment including both oxidation and metallic states on sub-nanocluster metal catalysts remains challenging, since designing heterogeneous catalysis within controllable oxidation state is necessary for achieving optimum performance. Here we construct stable sub-nano-Co clusters, which shows different microenvironment with the reported sub-nanocluster catalysts and reported Co-based catalysts. The coexistence of both ionic bonds of Co-O and metallic bonds of Co-Co shows features of multiple oxidation and metallic states, which changes the electronic orbital configuration of the individual Co atom in clusters. The specific microenvironment within low oxidation state and high electron density promotes combination of empty and filled host orbitals to yield high electron transfer between metal and propane, which exhibits higher reactivity than the reported Co-based and other non-noble metals catalysts. The desired reactivity offers the possibility for the exploitation of highly efficient non-noble metal catalysts for propane dehydrogenation in industrial applications. Designing heterogeneous catalysts with modulated microenvironments is important for optimum performance. Here, cobalt sub-nanoclusters with Co-O and Co-Co bonds show multiple oxidation and metallic states for propane dehydrogenation.