Cobalt Entrapped in N,S‐Codoped Porous Carbon: Catalysts for Transfer Hydrogenation with Formic Acid

: Catalysts with Co nanoparticles (NPs) entrapped in N,S-codoped carbon shells were successfully fabricated by pyrolysis of porous organic polymers (POPs) with cobalt salts. The encapsulated structure consisting of Co NPs and N,S-codoped carbon layers was verified by TEM, XRD, and X-ray photoelectron spectroscopy. The catalysts displayed excellent activity and stability for the catalytic transfer hydrogenation (CTH) of nitrobenzene with formic acid under base-free conditions. Furthermore, the resultant catalysts allowed for highly efficient and selective transfer hydrogenation of various functionalized nitroarenes to the corresponding anilines. Through control experiments, the covered Co NPs were identified as active sites for CTH. The incorporation of S into the N-doped carbon lattice promoted the electron transfer from metallic cobalt NPs to their shells, which played a significant role in the acceleration of CTH. Moreover, the Co-NSPC-850 catalyst pyrolyzed at 850 °C showed excellent stability in the recycling experiments.