Synergistic enhancement of electrocatalytic nitroarene hydrogenation over Mo(2)C@MoS(2) heteronanorods with dual active-sites.

Electrocatalytic hydrogenation (ECH) enables the sustainable production of chemicals under ambient conditions, in which catalysts catering for the different chemisorption of reactants/intermediates are desired but still challenging. Here, Mo(2)C@MoS(2) heteronanorods with dual active-sites are developed to accomplish efficient nitroarene ECH according to our theoretical prediction that the binding of atomic H and nitro substrates would be synergistically strengthened on Mo(2)C-MoS(2) interfaces. They afford high faradaic efficiency (>85%), yield (>78%) and selectivity (>99%) for the reduction of 4-nitrostyrene (4-NS) to 4-vinylaniline (4-VA) in neutral electrolytes, outperforming not only the single-component counterparts of Mo(2)C nanorods and MoS(2) nanosheets, but also recently reported noble-metals. Accordingly, in situ Raman spectroscopy combined with electrochemical tests clarifies the rapid ECH of 4-NS on Mo(2)C-MoS(2) interfaces due to the facilitated elementary steps, quickly refreshing active sites for continuous electrocatalysis. Mo(2)C@MoS(2) further confirms efficient and selective ECH toward functional anilines with other well-retained reducible groups in wide substrate scope, underscoring the promise of dual-site engineering for exploring catalysts.