Electrochemical hydrogenative coupling of nitrobenzene into azobenzene over a mesoporous palladium–sulfur cathode

Azobenzene (AZO) and its derivatives are of great importance in the dyestuff and pharmaceutical industries; however, their sustainable synthesis is much slower than expected due to the lack of high-performance catalysts. In this work, we report a robust yet highly efficient catalyst of PdS mesoporous nanospheres (MNSs) with confined mesostructures and binary elemental composition that achieved sustainable electrosynthesis of value-added AZO by selective hydrogenative coupling of nitrobenzene (NB) feedstocks in H₂O under ambient conditions. Using a renewable electricity source and H₂O, binary PdS MNSs exhibited a remarkable NB conversion of 95.4%, impressive AZO selectivity of 93.4%, and good cycling stability in selective NB hydrogenation reaction (NBHR) electrocatalysis. Detailed mechanism studies revealed that the confined mesoporous microenvironment of PdS MNSs facilitated the hydrogenative coupling of key intermediates (nitrosobenzene and phenylhydroxylamine) into AZO and/or azoxybenzene (AOB), while their electron-deficient S sites stabilized the Pd-spillovered active H* and inhibited the over-hydrogenation of AZO/AOB into AN. By coupling with the anodic methanol oxidation reaction (MOR), the (-)NBHR‖MOR(+) two-electrode system exhibits much better NB-to-AZO performance in a sustainable and energy-efficient manner. This work thus paves the way for designing functional mesoporous metal alloy electrocatalysts applied in the sustainable electrosynthesis of industrial value-added chemicals.