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Density functional theory calculations and a modified reaction model confirm that the initial high CO oxidation reactivity of a 13Ag-Ih nanoparticle from an icosahedron (Ih) structure is immediately diminished as the nanoparticle is transformed to an amorphous state by a reaction-driven structural change. The adsorption of O 2 and the formation of a four-center intermediate metastable state from coadsorbed CO and O 2 positively charge the 13Ag-Ih nanoparticle, and the repulsive force between the Ag atoms causes the reaction-driven structural change of the 13Ag-Ih nanoparticle. When one central Ag atom is substituted with a solute atom, a core-shell type of 12Ag-1X-Ih (X ) Pd, Pt, Au, Ni, or Cu) bimetallic nanoparticle is stabilized. Among them, we propose the 12Ag-1Pd nanoparticle as a robust and reactive Ag-based bimetallic nanoparticle for CO oxidation. The results show that the structural fluxionality accounts for the catalytic activity of small nanoparticles.

We report the geometric and electronic effects of amine (with one lone pair electron) and thiol (with two lone pair electrons) ligands on the structural transformation of Pt(55) nanoparticles (NPs) by first-principles calculation. Although a cuboctahedral (COh) structure is less stable than an icosahedral (Ih) structure by 1.36 eV for a bare Pt(55) NP, the activation barrier from the COh to the Ih structure is very high, by 1.97 eV, indicating that it would be difficult to observe the structural evolution of a COh structure to an Ih structure for a bare Pt(55) NP at ambient temperature. However, with the help of the adsorption of methylamine, the structural evolution from a COh structure to an Ih structure is accomplished by the Mackay transformation. This transformation is driven by a combination of both the external forces resulting from the adsorption of the ligand, which pull out the Pt atoms on the face sites of NPs in a radial direction, and the contraction forces in a tangential direction. As more methylamine is added, the Ih structure is observed to return to the original COh structure owing to the directional orbital hybridization that occurs between the Pt NPs and the methylamine. In contrast, such structural evolutions are not observed in the case of methylthiol because the sulfur (S) in the ligand has two lone pair electrons, leading to two Pt-S bonds. As a result, the radial-directed external force that the NPs experience because of the adsorption of methylthiols is much lower than that found in methylamine-ligated NPs. Furthermore, the adsorption of methylthiol leads to an expansion (not contraction) in the tangential direction, which does not qualify as a Mackay transformation. Thus, the Pt NPs ligated with methylthiol do not have a driving force strong enough to cause structural change. The methylthiol-stabilized Pt NPs retain their initial COh structure despite an abundance of ligand adsorption. From these results, we suggest that the NP structure can be controlled by varying the amount and species of ligands.

This report on the solid-to-liquid transition region of an Ag-Pd bimetallic nanocluster is based on a constant energy microcanonical ensemble molecular dynamics simulation combined with a collision method. By varying the size and composition of an Ag-Pd bimetallic cluster, we obtained a complete solid-solution type of binary phase diagram of the Ag-Pd system. Irrespective of the size and composition of the cluster, the melting temperature of Ag-Pd bimetallic clusters is lower than that of the bulk state and rises as the cluster size and the Pd composition increase. Additionally, the slope of the phase boundaries (even though not exactly linear) is lowered when the cluster size is reduced on account of the complex relations of the surface tension, the bulk melting temperature, and the heat of fusion. The melting of the cluster initially starts at the surface layer. The initiation and propagation of a five-fold icosahedron symmetry is related to the sequential melting of the cluster.

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