Asymmetric Activation of the Nitro Group over a Ag/Graphene Heterointerface to Boost Highly Selective Electrocatalytic Reduction of Nitrobenzene

The electrocatalytic reduction of nitrobenzene to aniline normally faces high overpotential and poor selectivity because of its six-electron redox nature. Herein, a Ag nanoparticles/laser-induced-graphene (LIG) heterointerface was fabricated on polyimide films and employed as an electrode material for an efficient nitrobenzene reduction reaction (NBRR) via a onestep laser direct writing technology. The first-principles calculations reveal that Ag/LIG shows the lowest activation barriers for the NBRR, which could be attributed to the optimum adsorption of the H atom realized by the appropriate interaction between Ag/LIG heterointerfaces and nitrobenzene. As a result, the over-potential of the NBRR is reduced by 217 mV after silver loading, and Ag/LIG shows a high aniline selectivity of 93%. Furthermore, an electrochemical reduction of nitrobenzene in tandem with an electrochemical oxidative polymerization of aniline was designed to serve as an alternative method to remove nitrobenzene from the aqueous solution. This strategy highlights the significance of heterointerfaces for efficient electrocatalysts, which may stimulate the development of novel electrocatalysts to boost the electrocatalytic activity.