Suppressing Dehalogenation: Highly Chemoselective Hydrogenation of Halogenated Nitroarenes Enabled by a γ-Ray-Engineered Fe(III)-OH-Pt Interface

A gamma-ray irradiation-induced synchronous reduction-assembly strategy was proposed for the fabrication of a PtFe(OH)x/GO-Y bimetallic catalyst supported on graphene oxide (GO) for the chemoselective hydrogenation of halogenated nitroarenes under ambient conditions. This irradiation method facilely realized the in-situ reduction of Pt precursors and highly dispersed deposition on the GO surface, while simultaneously forming amorphous iron oxyhydroxides that uniformly distribute on the GO support. This process results in the formation of ∼2.5 nm Pt nanoparticles and the construction of a well-defined Fe(III)-OH-Pt synergistic interface as a real active moiety. Using NaBH4 as the hydrogen source, the catalyst achieved good reactivity toward the tandem hydrogenation of p-iodonitrobenzene (p-INB) and possesses good selectivity for the target product (p-iodoaniline, abbr. p-IAN), with a turnover frequency as high as 2058 h−1. Density functional theory calculations further corroborate that the high selectivity of this catalyst originates from the vertical adsorption configuration of the substrate molecule. Furthermore, the as-prepared PtFe(OH)x/GO-Y catalyst exhibited broad substrate compatibility and functional group tolerance in the tandem hydrogenation of various nitro compounds. This work highlights the potential of γ-ray irradiation for tuning metal particle size and constructing active interfacial sites, thereby offering an available strategy for the synthesis of functionalized anilines.