Ordered Porous Nitrogen‐Doped Carbon Matrix with Atomically Dispersed Cobalt Sites as an Efficient Catalyst for Dehydrogenation and Transfer Hydrogenation of N‐Heterocycles

Single‐atom catalysts (SACs) have been explored widely as potential substitutes for homogeneous catalysts. Isolated cobalt single‐atom sites were stabilized on an ordered porous nitrogen‐doped carbon matrix (ISAS‐Co/OPNC). ISAS‐Co/OPNC is a highly efficient catalyst for acceptorless dehydrogenation of N‐heterocycles to release H 2 . ISAS‐Co/OPNC also exhibits excellent catalytic activity for the reverse transfer hydrogenation (or hydrogenation) of N‐heterocycles to store H 2 , using formic acid or external hydrogen as a hydrogen source. The catalytic performance of ISAS‐Co/OPNC in both reactions surpasses previously reported homogeneous and heterogeneous precious‐metal catalysts. The reaction mechanisms are systematically investigated using first‐principles calculations and it is suggested that the Eley–Rideal mechanism is dominant.