Bonding and Electronic Interactions of Hydrogen with Gold Superatoms

• Published in: Journal of physical chemistry. C 2024-01, Vol.128 (1), p.19-30
• Main Authors: Maity, Subarna, Takano, Shinjiro, Masuda, Shinya, Tsukuda, Tatsuya
• Format: Article
• Language: English
• ISSN: 1932-7447; 1932-7455
• DOI: 10.1021/acs.jpcc.3c07090

Hydrogen in precious metals plays an important role in catalysis and energy storage. The interaction between gold and hydrogen has received particular attention in view of the “Au–H analogy” arising from similar electronegativities. Recent advances in the atomically precise synthesis and quantum chemical calculations of Au nanoclusters provide a good opportunity to gain a deeper understanding of the interaction between H and Au nanoclusters at the molecular level. In this Perspective, we present three types of the bonding and electronic interactions of H with chemically modified Au nanoclusters bearing Au superatoms (Au SAs) at the core: (1) hydrogen acts as a dopant in the Au SA by providing valence electrons to the SA orbitals; (2) hydrogen bridges the Au SAs via multiple Au–H–Au bonds by supplying electrons to the bonding orbitals between them; and (3) hydrogen acts as an electron-withdrawing ligand of the Au SA. The effects of hydrogen on the stabilities and physicochemical properties of the Au SAs are introduced. These emerging examples demonstrate that the interaction with hydrogen is a new approach to unlocking the potential of Au SAs as functional units.