Revisiting the activity origin of the PtAu24(SR)18 nanocluster for enhanced electrocatalytic hydrogen evolution by combining first-principles simulations with the experimental in situ FTIR technique

Thiolate-protected metal nanoclusters (NCs) have been widely used in various electrocatalytic reactions, yet the dynamic evolution of metal NCs during electrocatalysis has been rarely explored and the activity origin remains largely ambiguous. Herein, using a PtAu24(SCH3)(18) NC as a prototype model, we combined advanced first-principles calculations and attenuated total reflection surface-enhanced infrared spectroscopy (ATR-SEIRAS) to re-examine its active site and reaction dynamics in the hydrogen evolution reaction (HER). It has been previously assumed that the central Pt is the only catalytic center. However, differently, we observed the spontaneous desorption of thiolate ligands under moderate potential, and the dethiolated PtAu24 exhibits excellent HER activity, which is contributed not only by the central Pt atom but also by the exposed bridged Au sites. Particularly, the exposed Au exhibits high activity even comparable to Pt, and the synergistic effect between them makes dethiolated PtAu24 an extraordinary HER electrocatalyst, even surpassing the commercial Pt/C catalyst. Our predictions are further verified by electrochemical activation experiments and in situ FTIR (ATR-SEIRAS) characterization, where evident adsorption of Au-H* and Pt-H* bonds is monitored. This work detected, for the first time, the Au-S interfacial dynamics of the PtAu24 nanocluster in electrocatalytic processes, and quantitatively evaluated the essential catalytic role of the exposed Au sites that has been largely overlooked in previous studies.