Pt nanocluster electrocatalysts: preparation and origin of high oxygen reduction reaction activity.

We recently found that [Pt(CO)(PPh)] (Pt = platinum; CO = carbon monoxide; PPh = triphenylphosphine; = 1+ or 2+) is a Pt nanocluster (Pt NC) that can be synthesized with atomic precision in air. The present study demonstrates that it is possible to prepare a Pt-supported carbon black (CB) catalyst (Pt/CB) with 2.1 times higher oxygen reduction reaction (ORR) activity than commercial Pt nanoparticles/CB by the adsorption of [Pt(CO)(PPh)] onto CB and subsequent calcination of the catalyst.

Key factors for connecting silver-based icosahedral superatoms by vertex sharing.

Metal nanoclusters composed of noble elements such as gold (Au) or silver (Ag) are regarded as superatoms. In recent years, the understanding of the materials composed of superatoms, which are often called superatomic molecules, has gradually progressed for Au-based materials. However, there is still little information on Ag-based superatomic molecules.

Selective formation of [Au(SPh Bu)], [AuPd(SPh Bu)] and [AuPt(SCHPh)(SPh Bu)] by controlling ligand-exchange reaction.

To use atomically precise metal nanoclusters (NCs) in various application fields, it is essential to establish size-selective synthesis methods for the metal NCs. Studies on thiolate (SR)-protected gold NCs (Au (SR) NCs) revealed that the atomically precise Au (SR) NC, which has a different chemical composition from the precursor, can be synthesized size-selectively by inducing transformation in the framework structure of the metal NCs by a ligand-exchange reaction. In this study, we selected the reaction of [Au(SCHPh)] (SCHPh = 2-phenylethanethiolate) with 4--butylbenzenethiol ( BuPhSH) as a model ligand-exchange reaction and attempted to obtain new metal NCs by changing the amount of thiol, the central atom of the precursor NCs, or the reaction time from previous studies.

[AgPd(PPh)Cl]: A new family of synthesizable bi-icosahedral superatomic molecules.

Icosahedral noble-metal 13-atom nanoclusters (NCs) can form connected structures, which can be regarded as superatomic molecules, by vertex sharing. However, there have been very few reports on the superatomic molecules formed using silver (Ag) as the base element. In this study, we synthesized [AgPd(PPh)Cl] (Pd = palladium, PPh = triphenylphosphine, Cl = chloride), in which two icosahedral 13-atom NCs are connected, and elucidated its geometric and electronic structures to clarify what type of superatomic molecules can be synthesized.