The search for active, inexpensive, and stable heterogeneous catalysts for organic transformation still remains challenging in both academia and industry. Herein, we present the facile fabrication of non-noble cobalt nanocomposites on N-doped hierarchical porous carbon derived from naturally renewable biomass together with Earth-abundant and low-cost cobalt salts. The whole preparation process is operationally simple and straightforward, cost-effective and environmentally benign and can be used in mass production for practical applications. The most active cobalt nanocomposite catalyst, that is, CoO_x@NC-800, demonstrated outstanding activity and excellent selectivity for the hydrogenation of functionalized nitroarenes to aniline derivatives with molecular hydrogen in water as a green medium. It also showed high activity for the direct and expedient synthesis of imines from the reductive amination of nitroarenes and aldehydes with excellent selectivity and good tolerance to a variety of functional groups. More importantly, a new straightforward one-pot cascade synthesis of benzimidazole was developed from the reductive amination of ortho-amino substituted nitrobenzene with aldehyde followed by sequential cyclization in a green and sustainable manner, further highlighting the utility of the catalyst. In addition, the catalyst can be easily separated for successive reuses without a significant loss in both activity and selectivity.

A heterogeneous nanocomposite of Fe–Fe₃C nanoparticles and Fe–N_x sites on N-doped porous carbon allows for efficient synthesis of quinolines and quinazolinones via oxidative coupling of amines and aldehydes in aq. solution using H₂O₂ as the oxidant.

The development of abundantly available base metal catalysts for organic transformations remains an important goal of chemical research. Herein, we report the first facile fabrication of active, inexpensive, and reusable cobalt nanoparticles (NPs) coated with a N,P-codoped carbon shell derived from naturally renewable biomass and earth-abundant, low-cost cobalt salt and PPh₃. The entire process is operationally simple, straightforward, cost-effective and environmentally benign and can be used in mass production for practical application. The resultant catalysts allow for highly efficient and selective transfer hydrogenation of functionalized nitroarenes to the corresponding anilines using formic acid or ammonium formate as the hydrogen donor. Uniformly incorporated N and P into the carbon lattices exhibited synergistic effects with the encapsulated Co NPs to engineer the structure and composition of the catalyst, thereby substantially boosting the catalytic efficiency. The most active catalyst Co@NPC-800 exhibited outstanding activity and exclusive selectivity for the reduction of functionalized nitroarenes to anilines, especially those decorated with readily reducible functional groups. The catalyst demonstrated high stability and can be easily separated by using an external magnet for successive reuses without significant loss in both activity and selectivity.