Platinum‐Grafted Twenty‐Five Atom Gold Nanoclusters for Robust Hydrogen Evolution

• Published in: Small (Weinheim an der Bergstrasse, Germany) Germany), 2024-06, Vol.20 (23), p.e2308610-n/a
• Main Authors: Mymoona, Paloli, Rival, Jose V., Nonappa, Shibu, Edakkattuparambil Sidharth, Jeyabharathi, Chinnaiah
• Format: Article
• Language: English
• Subjects: electrocatalysis; Electrochemical activation; Electroless plating; Gold; Grafting; Green hydrogen; Hydrogen; hydrogen evolution reaction; Hydrogen evolution reactions; Nanoclusters; Platinum; Positron emission; precision nanoclusters; Robustness; Self-assembly; supramolecular assembly; Thiols; Underpotential deposition
• ISSN: 1613-6810; 1613-6829
• DOI: 10.1002/smll.202308610

A robust hydrogen evolution is demonstrated from Au25(PET)18]− nanoclusters (PET = 2‐phenylethanethiol) grafted with minimal platinum atoms. The fabrication involves an electrochemical activation of nanoclusters by partial removal of thiols, without affecting the metallic core, which exposes Au‐sites adsorbed with hydrogen and enables an electroless grafting of platinum. The exposed Au‐sites feature the (111)‐facet of the fcc‐Au25 nanoclusters as assessed through lead underpotential deposition. The electrochemically activated nanoclusters (without Pt loading) show better electrocatalytic reactivity toward hydrogen evolution reaction than the pristine nanoclusters in an acidic medium. The platinum‐grafted nanocluster outperformed with a lower overpotential of 0.117 V vs RHE (RHE = Reversible Hydrogen Electrode) compared to electrochemically activated nanoclusters (0.353 V vs RHE ) at 10 mA cm−2 and is comparable with commercial Pt/C. The electrochemically activated nanoclusters show better reactivity at higher current density owing to the ease of hydrogen release from the active sites. The modified nanoclusters show unique supramolecular self‐assembly characteristics as observed in electron microscopy and tomography due to the possible metallophilic interactions. These results suggest that the post‐surface modification of nanoclusters will be an ideal tool to address the sustainable production of green hydrogen. Active platinum grafting! Adsorbed hydrogen enables electroless‐grafting of Pt on [Au25(PET)18]− nanoclusters with minimal platinum loading scales scaling the reactivity of hydrogen evolution reaction closer to benchmark Pt/C.