Edge-Confined Rh2/MoS2 Dual-Atom Catalyst for Selective Activation of Nitro Group to Amino Group at Room Temperature

Selective hydrogenation of nitroarenes to produce functionalized anilines is highly important to synthesize fine and bulk chemicals, but it remains challenging to achieve high selectivity at room temperature. Here, we report that a steric-confinement Rh dual atom catalyst is constructed by anchoring dual Rh atoms on the edge Mo vacancies of thin-layered MoS₂ nanosheets (Rh₂/MoS₂ dual atom catalyst), which shows excellent catalytic conversion (100%) and selectivity (100%) for the selective hydrogenation of a family of nitroarene derivatives to functionalized anilines at room temperature. Extensive experimental characterizations and theoretical calculations indicate that the steric-confinement Rh₂ atoms, maintaining an exact metal–metal separation of 3.5 Å, facilitate spatially matched adsorption of the nitro group through a bidentate configuration. This significantly enhances the reactivity of nitro groups and drives the selective synthesis of functionalized anilines. The approach of employing bimetallic atoms to construct edge-confined active sites, as reported in this study, paves the way to develop highly selective catalysts for the targeted hydrogenation of nitroarenes.