Highly efficient N‐doped carbon supported FeSx‐Fe2O3 catalyst for hydrogenation of nitroarenes via pyrolysis of sulfurized N,Fe‐containing MOFs

Integrating MOFs as precursor, especially for employing N‐containing organic linkers, with sulfides is an effective method to prepare the highly efficient N‐doped carbon supported metal‐based catalysts for hydrogenation of nitroarenes. In this work, a N,Fe‐containing metal organic frameworks (MOFs; termed as MIL88‐HMTA) with spindle‐like structure was prepared via self‐assembly method, in which hexamethylenetetramine (HMTA) linker was introduced as N source. Subsequently, N‐doped carbon supported FeS x ‐Fe 2 O 3 catalyst (named FeS x ‐Fe 2 O 3 @CN) was fabricated upon the pyrolysis of sulfurized MIL88‐HMTA. Catalytic experiments reveal that the FeS x ‐Fe 2 O 3 @CN delivered excellent performance for hydrogenation of nitroarenes in comparison with those of catalyst without sulfidation process (Fe 2 O 3 @CN) and conventional MIL88 derived catalyst (Fe 2 O 3 @C). The XRD, TEM, SEM/EDX, Raman, UV, and XPS analyses have revealed that the developed FeS x ‐Fe 2 O 3 @CN catalyst exhibited outstanding catalytic efficiency was ascribed to synergistic effect between FeS x and Fe 2 O 3 species, abundant structural defects, more Fe‐N x species, and strengthened decomposition ability of hydrazine hydrate (N 2 H 4 ⋅H 2 O). Furthermore, the effect of sulfidation ratio (the mass ratio between thioacetamide and MIL88‐HMTA) towards preparation of the developed FeS x ‐Fe 2 O 3 @CN on the catalytic activity of hydrogenation reaction was also systematically performed. Notably, the optimized catalyst (denoted as FeS x ‐Fe 2 O 3 @CN‐ 8 ) exhibited unexpected performance and recyclability for hydrogenation of nitroarenes under mild condition. The pyrolysis of sulfurized N‐containing MOFs may present a facile approach for fabricating MOFs‐derived N‐doped carbon supported catalysts, which provides a potential application in heterogeneous catalytic reactions.