Reduction of 4‐Nitrophenol Catalyzed by Gold Nanoclusters with Aggregation‐Induced‐Emission: Emission Intensity Correlated Activity and Mechanistic Exploration

Abstract

Thiolate‐protected Au nanoclusters (NCs) has developed as a promising class of model catalysts to achieve fundamental understanding of metal nano‐catalysis. In this work, using glutathione (GSH) protected Au NCs (Au@GSH NCs) with aggregation‐induced‐emission (AIE) characteristics as model catalyst for the hydrogenation of 4‐nitrophenol (4‐NP), photoluminescence (PL) intensity correlated catalytic activity of Au@GSH NCs was successfully mediated by the addition of Ag+ in the preparation or poor solvent in the reaction medium, showing a relationship of ‘as one falls, another rises.’ Au NCs with intense PL implied a dense packing of peripheral ligand which hampered the accessibility of active site and thus exhibited slowest catalytic reaction kinetics of the reduction of 4‐NP and vice versa. Based on this methodology, a case study of the effect of salt additives on the catalytic activity is carried out, different mechanisms are distinguished by the change in the PL intensity, and with the combination of diagnostic deuterium isotope experiments, it has been demonstrated that the proton from water solvent is involved in the reaction and that the proton transfer process is the rate‐determining step, the contribution of ionic additives to the hydrogen bonding network determines their effect on the reaction kinetics.