LAUSR

The development of bifunctional, highly active and stable non‐noble‐metal catalysts is important for synthetic chemistry. In this study, a highly dispersed Co catalyst stabilized on the mesoporous N‐doped carbon layers was prepared by adsorption and pyrolysis of cobalt complex on dendritic fibrous silica nanospheres (KCC‐1@Co−N−C−T). The characterizations of HAADF‐STEM, XRD and XPS together with the KSCN poisoning tests determine the absence of Co0 or CoOx nanoparticles and suggest that the Co−Nx species are the active sites. The formation of Co−Nx species results from the properties of N‐rich cobalt‐phenanthroline complex and dendritic fibrous silica supports, increasing the original spatial distance between Co atoms and thus preventing them from aggregation. The KCC‐1@Co−N−C‐800 catalyst showed excellent activity and selectivity for the oxidative dehydrogenation (ODH) of saturated N‐heterocycles and base‐free catalytic transfer hydrogenation (CTH) of unsaturated N‐heterocycles.