Selective Electrocatalytic Hydrogenation of Nitroarenes on Interlayer-Expanded MoS2

As a promising route to hydrogenate organic compounds at ambient conditions, electrocatalytic hydrogenation (ECH) urgently demands noble-metal-free electrocatalysts with satisfactory activity and selectivity. Here, molybdenum disulfide intercalated by dimethylamine (MoS2-DMA) demonstrates its superiority associated with the engineered interlayer chemistry in the ECH of nitroarenes to anilines. The in situ intercalation by DMA cations leads to the phase transition from semiconducting 2H to metallic 1T and the formation of abundant sulfur vacancies, which is beneficial for activating nitro groups and stabilizing chemisorbed H intermediate toward fast hydrogenation. In a wide potential range of −0.08 to −0.48 V (vs reversible hydrogen electrode (RHE)), MoS2-DMA affords the excellent ECH performance of p-nitrostyrene to p-aminostyrene with high Faradic efficiency (>90%), yield (>90%), and selectivity (>99%), outperforming typical MoS2. The good efficiency of such intercalated MoS2 within a broad substrate scope further verifies the promise of interlayer engineering for exploiting cost-efficient catalysts in an electrochemical refinery.