MOF-derived N-doped carbon composites embedded with Fe/Fe3C nanoparticles as highly chemoselective and stable catalysts for catalytic transfer hydrogenation of nitroarenes

Abstract Owing to the competitive hydrogenation of reducible functionalized groups and the complexity of the reaction mechanism, the selective catalytic hydrogenation of nitroarene compounds to value-added amine products is challenging. Herein, we designed and prepared a series of highly efficient iron-based nanocomposites (Fe/Fe3C@NC–T) via direct pyrolysis of the presynthesized NH2–MIL–101(Fe) octahedrons under nitrogen atmosphere, wherein tiny metallic Fe/Fe3C nanoparticles (NPs) were homogeneously inlaid in the N-doped porous carbon matrix. Among the various derived catalysts, Fe/Fe3C@NC–750 exhibited the best performance, with good tolerance to several different functional groups for the catalytic transfer hydrogenation of nitroarenes to anilines using N2H4·H2O as the reductant under mild conditions. This performance was also superior to those of commercial catalysts (Fe, Fe2O3, and Fe3C) and Fe/Fe3C@C–750 without N doping. The synergistic catalysis between the Fe-based NP and N dopant mainly contributed to the excellent catalytic performance of Fe/Fe3C@NC–750. Moreover, the mechanism study revealed that both the direct route and the condensation route were involved in this catalytic reaction system.