Dynamic Evolution and Reversibility of a Single Au25 Nanocluster for the Oxygen Reduction Reaction.

ABSTRACT

Ultrasmall metallic nanoclusters (NCs) protected by surface ligands represent the most promising catalytic materials; yet understanding the structure and catalytic activity of these NCs remains a challenge due to dynamic evolution of their active sites under reaction conditions. Herein, we employed a single-nanoparticle collision electrochemistry method for real-time monitoring of the dynamic electrocatalytic activity of a single fully ligand-protected Au25(PPh3)10(SC2H4Ph)5Cl22+ nanocluster (Au252+ NC) at a cavity carbon nanoelectrode toward the oxygen reduction reaction (ORR). Our experimental results and computational simulations indicated that the reversible depassivation and passivation of ligands on the surface of the Au252+ NC, combined with the dynamic conformation evolution of the Au259+ core, led to a characteristic current signal that involves "ON-OFF" switches and "ON" fluctuations during the ORR process of a single Au252+ NC. Our findings reinvent the new perception and comprehension of the structure-activity correlation of NCs at the atomic level.