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

[Display omitted] • Fe/Fe 3 C@NC hybrids fabricated by carbonization of NH 2 –MIL–101(Fe) octahedrons. • Fe/Fe 3 C@NC had large surface area, hierarchical pore structure, unique composition. • Fe/Fe 3 C@NC–750 exhibited best performance with tolerance to functional groups. • Direct and condensation routes were involved in catalytic transfer hydrogenation. 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/Fe 3 C@NC–T) via direct pyrolysis of the presynthesized NH 2 –MIL–101(Fe) octahedrons under nitrogen atmosphere, wherein tiny metallic Fe/Fe 3 C nanoparticles (NPs) were homogeneously inlaid in the N-doped porous carbon matrix. Among the various derived catalysts, Fe/Fe 3 C@NC–750 exhibited the best performance, with good tolerance to several different functional groups for the catalytic transfer hydrogenation of nitroarenes to anilines using N 2 H 4 ·H 2 O as the reductant under mild conditions. This performance was also superior to those of commercial catalysts (Fe, Fe 2 O 3 , and Fe 3 C) and Fe/Fe 3 C@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/Fe 3 C@NC–750. Moreover, the mechanism study revealed that both the direct route and the condensation route were involved in this catalytic reaction system. [ABSTRACT FROM AUTHOR]