Pd nanoflakes epitaxially grown on defect MoS2 nanosheets for enhanced nitroarenes hydrogenation to anilines

Hydrogenation of nitroarenes to anilines under mild conditions is attractive from both theoretical and practical viewpoints. Here, high-performance catalyst with layered Pd nanoparticles epitaxially growing on ultrathin MoS 2 nanosheets (Pd/MoS 2 ) were prepared. It shows surprisingly high catalytic activity, selectivity and stability for hydrogenation of various nitroarenes to corresponding anilines; the turnover frequency is one or two magnitudes higher than conventional Pd-based catalysts. Surface sulfur vacancies are formed on MoS 2 nanosheets with low formation energy barrier. These S vacancies provide efficient positions for adsorbing Pd atoms, which enables facile cleavage of N–O bond as result of strong interfacial electron interaction that decreases activation energy by 0.41 eV in comparison with conventional Pd catalysts. In situ spectroscopy and DFT calculation results reveal a dual-site mechanism, in which surface Pd sites adsorb and dissociate H 2 into active H*, and then readily reacts with nearby activated nitroarene to form aniline on interfacial Pd-MoS 2 sites.