Structure of V-doped Pdn (n = 2–12) clusters and their ability for H2 dissociation

The structure and stability of V-doped Pdn (n = 2–12) clusters as well as their ability for hydrogen dissociation are analyzed using a successive growth algorithm coupled with density functional theory (DFT) computations. From the structural point of view, the lowest energy structures of these clusters are three-dimensional with exohedral geometries for n = 2–7 whereas endohedral for n = 8 onward. From their second-order energy differences, Pd4V and Pd10V are found to be the most stable ones. Among the PdnV(H2) complexes, Pd6V–2H possesses the highest stability, as it is supported by the chemisorption energy, the vertical ionization potential (VIP), and the vertical electron affinity (VEA), respectively. Most importantly, the hydrogen dissociation pathway on PdnV clusters with n = 3, 4 and 10–12 shows that these clusters are rigid and suitable to dissociate H2 while for n = 5–9 the structure of the clusters changes. The H2 dissociation process on PdnV clusters with n = 8, 10, and 11 carries out barrierless. © 2018 Hydrogen Energy Publications LLC

DFT; H2; Hydrogen dissociation; PdnV clusters Binary alloys; Density functional theory; Electron affinity; Hydrogen; Ionization potential; Palladium alloys; Chemisorption energy; Dissociation process; Hydrogen dissociation; Lowest energy structure; PdnV clusters; Second-order energies; Vertical electron affinities; Vertical ionization potentials; Dissociation

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