Highly active iron oxide@N catalyst derived from the iron acetate/polyacrylonitrile threads: Driving nitroarene conversion to value‐added amines

Chemoselective reduction of nitroarenes to corresponding arylamines is a significant reaction in the chemical industry. However, in the presence of other reducible groups, including halogenated nitrobenzene, nitrobiphenyl, and nitroquinoline in the same molecule of nitroaromatics, the control of chemoselectivity remains challenging. Here, a facile fabrication of a heterogeneous iron‐based catalyst is reported as a potential alternative to precious metal catalysts for the chemoselective reduction of nitroarenes. The pyrolysis of iron acetate/polyacrylonitrile (PAN) template under an inert atmosphere furnishes active Fe3O4 nanoparticles (NPs) encapsulated in nitrogen‐doped (N‐doped) carbon layers, which can provide more catalytic active sites (Fe3O4/PAN@800). Notably, non‐precious iron oxide NPs supported on N‐doped carbon support prevent aggregation, thereby enhancing the catalytic activity. The sustainable and reusable Fe3O4/PAN@800 catalyst, having only 0.8% metal content as demonstrated by x‐ray photoelectron spectroscopy, delivers excellent yields of corresponding amines from differently functionalized nitroarenes. Hydrogenation of a series of structurally functionalized nitroarenes produced excellent yields of anilines, which serve as building blocks and intermediates for fine and bulk chemicals. Hydrogenation of 2‐chloro‐3‐nitropyridine, 2‐nitro‐1,1′‐biphenyl, ortho‐nitroaniline, and 4‐aminophenyl acrylonitrile yielded respective anilines up to 99%. The active sites of Fe3O4 have magnetic performance, hence, the catalyst can be easily recovered using a magnet and reused for at least five cycles without significant loss of catalytic activity. Therefore, the easily prepared, cost‐effective, and reusable Fe3O4/PAN@800 catalyst presented in this study shows potential for applications in the selective reduction of aromatic nitro compounds. Consequently, this study potentially establishes a guideline for the facile preparation of abundant transition‐non‐noble metal‐based reusable supported catalysts for various applications in the chemical industry. Highly active iron catalyst derived from the polyacrylonitrile threads.