In situ oxygen-induced zigzag graphene as metal-free catalyst for hydrogen activation in nitroarenes hydrogenation

Metal-free catalysts for hydrogenation reactions using molecular hydrogen (H2) are a major challenge in the field of catalysis. The Frustrated Lewis Pairs (FLPs) systems and heteroatom-doped carbon materials as metal-free catalysts are currently the mainstream research in hydrogenation reactions. Here, a series of oxygen-induced zigzag graphene (OZG) was constructed over thermal treatment of reduced graphene oxide (rGO) and applied as metal-free catalysts in nitrobenzene hydrogenation. The OZG-800 (thermal treatment at 800 °C) shows promising performance activity with 99.7% nitrobenzene conversion and 94.4% selectivity to aniline. The experimental results indicate that the zigzag edge and medium-strong acid sites formed by oxygen species may be the active centers in nitrobenzene hydrogenation. The density functional theory (DFT) calculations are in accord with experimental results that the zigzag edge and oxygen species play a critical role in H2 activation and dissociation. This work provides a promising route for the rational design of metal-free catalysts for hydrogenation.