Exploring the structure of atom-precise silver-palladium bimetallic clusters prepared via improved single-pot co-reduction synthesis protocol.

Designing atom-precise bimetallic clusters with a relatively cost-effective and more abundant metal than Au (i.e., Ag) is desirable for the development of heterogeneous bimetallic cluster catalysts for industrial applications. Atom-precise Ag-based bimetallic clusters, which are analogs of the well-studied Au based clusters, are yet to be fully explored as catalysts. Establishing the Pd loading limit and the position of the Pd dopant in AgPd bimetallic clusters will further give an insight into the structure-activity relationships for these atom-precise AgPd heterogeneous catalysts. In this study, an improved single-pot co-reduction strategy was employed to prepare the bimetallic clusters, which were then characterized by mass spectrometry, x-ray photoelectron spectroscopy (XPS), and x-ray absorption spectroscopy (XAS) to identify the loading and position of the dopant metal. Our results show that only a single dopant Pd atom can be incorporated, and in comparison with monometallic Ag25 clusters, the absorption peaks of Ag24Pd1(SPhMe2)18 2- bimetallic clusters are blue shifted due to the incorporation of Pd. The XPS and XAS results show that the Ag24Pd1(SPhMe2)18 2- bimetallic clusters have multivalent Ag(0) and Ag(I) atoms and surprisingly show Pd(II) species with significant Pd-S bonding, despite the prevailing wisdom that the Pd dopant should be in the center of the cluster. The XAS results show that the singly doped Pd atom predominantly occupies the staple position, albeit we cannot unambiguously rule out the Pd atom in an icosahedral surface position in some clusters. We discuss the ramifications of these results in terms of possible kinetically vs thermodynamically controlled cluster formation.