title: Potential of ZrO clusters as replacement Pd catalyst.
abstract: Atomic clusters with specific size and composition and mimicking the chemistry of elements in the periodic table are commonly known as superatoms. It has been suggested that superatoms could be used to replace elements that are either scarce or expensive. Based on a photoelectron spectroscopy experiment of negatively charged ions, Castleman and co-workers [Proc. Natl. Acad. Sci. U.S.A. 107, 975 (2010)] have recently shown that atoms of Ni, Pd, and Pt which are well known for their catalytic properties, have the same electronic structure as their counterpart isovalent diatomic species, TiO, ZrO, and WC, respectively. Based on this similarity they have suggested that ZrO, for example, could be a replacement catalyst for Pd. Since catalysts are seldom single isolated atoms, one has to demonstrate that clusters of ZrO also have the same electronic structure as same sized Pd clusters. To examine if this is indeed the case, we have calculated the geometries, electronic structure, electron affinity, ionization potential, and hardness of Pdn and (ZrO)n clusters (n = 1-5). We further studied the reaction of these clusters in neutral and charged forms with H2, O2, and CO and found it to be qualitatively different in most cases. These results obtained using density functional theory with hybrid B3LYP functional do not support the view that ZrO clusters can replace Pd as a catalyst.
authors: Department of Physics, Virginia Commonwealth University, Richmond, Virginia 23284, USA.
authors: Swayamprabha
authors: S
authors: Behera
authors: Department of Physics, Virginia Commonwealth University, Richmond, Virginia 23284, USA.
authors: Nicholas
authors: N
authors: King
authors: Department of Chemistry, Virginia Commonwealth University, Richmond, Virginia 23284, USA and Department of Chemistry, Stanford University, Stanford, California 94305, USA.
authors: Devleena
authors: D
authors: Samanta
authors: Department of Physics, Virginia Commonwealth University, Richmond, Virginia 23284, USA.
authors: Puru
authors: P
authors: Jena