Reduced NiGraf metal organic alloy in the hydrogenation of nitrobenzene to aniline: a computational analysis

Consisting of graphene oxide molecularly entrapped within jamborite nanoparticles, NiGraf (GO@Ni) is a versatile electrocatalyst for both hydrogen and oxygen evolution reactions involved in water electrolysis. Its reduced form obtained via reduction of jamborite-entrapped GO with thiophene (RGO@Ni) is a highly active and stable hydrogenation catalyst enabling the reduction of nitrobenzene to aniline at 35 °C in liquid phase using water as “on-solvent” reaction medium under biphasic conditions. Besides eliminating the need for organic solvent, the process has significant practical application potential for the synthesis of a compound produced worldwide at 7 million t/a rate. Here we report a computational study aimed at identifying a suitable reaction mechanism for the hydrogenation of nitrobenzene mediated by RGO@Ni. Results support a reaction mechanism that explains also the catalyst remarkable stability.