Heteroatom number-dependent cluster frameworks in structurally comparable Pd–Au nanoclusters

Abstract

Investigating the impact of heteroatom alloying extents on regulating the cluster structures is crucial for the fabrication of cluster-based nanomaterials with customized properties. Herein, two structurally comparable Pd_xAu₁₂ (x = 1, 2) nanoclusters with a uniform surface environment but completely distinct kernel configurations were controllably synthesized and structurally determined. The single Pd-alloyed Pd₁Au₁₂ nanocluster retained an icosahedral metal framework, while the Pd₂Au₁₂ nanocluster with two Pd heteroatoms exhibited a unique toroidal configuration. The additional Pd heteroatom not only led to significant changes in the cluster frameworks but also profoundly affected their electrocatalytic CO₂ reduction performance. The Pd₁Au₁₂ nanocluster demonstrated enhanced catalytic performance, exhibiting a higher current density, a lower onset potential, and greater CO faradaic efficiency compared to the Pd₂Au₁₂ nanocluster. This work offers new insights into the customization of the structures and properties of gold nanoclusters by regulating the doping degree of Pd heteroatoms.