Ag‐based bimetallic clusters as catalysts for p‐nitrophenol reduction by glycerol: A DFT investigation

Abstract

Reducing p‐nitrophenol (PNP) to p‐aminophenol is an industrially relevant synthesis. Nevertheless, only a few heterogeneous catalysts have been evaluated for the reduction of PNP by glycerol. Appropriate quantum computational studies can screen potential catalysts for this crucial green reaction. The present research investigates the catalytic activities of Pd@Ag and Ni@Ag core‐shell nanogeometries toward PNP reduction by glycerol through density functional theory (DFT) calculations. The central atom of a geometry‐optimized 13‐atom Ag cluster was replaced by Pd and Ni atoms to create the core‐shell morphologies. The interaction energies of PNP and glycerol with each of the (metal/bimetallic) clusters were evaluated by DFT calculations to find the best PNP and glycerol molecule orientation with the respective bimetallic cluster. Electrostatic potential surface and natural bond orbital analyses were performed to study the charge distribution and transfer between atomic orbitals. The frequencies of vibrational modes in isolated PNP/glycerol structures were compared to those when these molecules were in the presence of the different metal clusters to infer the effect of the interactions. All performed analyses indicated improved catalytic activity toward PNP reduction by glycerol upon Ni‐doping of the Ag13 cluster.