American Chemical Society
jp1c08924_si_001.pdf (1.7 MB)

Factors Influencing Catalytic Activity of Size-Specific Triphenylphosphine-Ligated Gold Nanoclusters in the Electrocatalytic Hydrogen Evolution Reaction

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journal contribution
posted on 2021-12-22, 15:07 authored by Hanieh Mousavi, Yanting Yin, Shailendra Kumar Sharma, Christopher T. Gibson, Vladimir Golovko, Gunther G. Andersson, Cameron J. Shearer, Gregory F. Metha
Hydrogen production via electrocatalytic water splitting has attracted growing attention as an alternative renewable and clean energy source. Size-specific gold nanoclusters and complexes (AuNCs) can serve as models for investigating the catalytic behavior toward the hydrogen evolution reaction (HER) at the atomic level. This work is focused on exploring the factors influencing the catalytic activity of phosphine-ligated AuNCs as electrocatalysts for improving HER performance using Au101(PPh3)21Cl5, Au9(PPh3)8(NO3)3, and Au1(PPh3)Cl supported on reduced graphene oxide (rGO). Production of AuNC–rGO nanocomposites without agglomeration of the AuNCs was confirmed by transmission electron microscopy, X-ray photoelectron spectroscopy, and visible light absorbance. The weight loading of gold in the nanocomposite material was confirmed to be ≈5 wt % by thermogravimetric analysis and inductively coupled plasma mass spectrometry. Electrocatalytic performance of the AuNCs was determined through linear sweep voltammograms in 0.5 M sulfuric acid. Greater performance was observed for Au101NC–rGO, while Au9NC–rGO and Au1NC–rGO showed similar performance. The stability of each AuNC was determined through extended chronoamperometry experiments, and negligible reduction in performance was observed for Au101NC–rGO and Au9NC–rGO, while Au1NC–rGO was less stable. The variation in performance was attributed to a range of factors including catalyst size, electronic structure, and ligand density. This work provides guidelines to design highly efficient electrocatalysts using ligated metal clusters.