Computational design of core–shell tri-metallic Pd13−nNin@Pt42 (n = 0, 1, 12, and 13) nanoparticles for H2O adsorption and dissociation

Abstract

Density functional theory calculations are performed to investigate H2O adsorption and dissociation properties on the icosahedral Pd13−nNin@Pt42 (n = 0, 1, 12, and 13) tri-metallic core-shell nanoparticles. The adsorption of H2O adsorption on the vertex sites of Pd13−nNin@Pt42 (n = 0, 1, 12, and 13) nanoparticles, while the adsorption of OH on the bridge site (B1) is preferred, and H is easily absorbed on the vertex and bridge sites. In addition, the reaction pathways of H2O dissociation on the top of vertex atom (V1) and top of the edge atom (V2) sites of Pd13−nNin@Pt42 (n = 0, 1, and 12) nanoparticles, and V1 of the Ni13@Pt42 are analyzed to explore the H2O dissociation machanisms. It is found that the addition of Ni atoms in the core of the Pd13@Pt42 is unbeneficial for the breakage of the OH bond for H2O dissociation on the Pd13−nNin@Pt42 (n = 1 and 12) except Ni13@Pt42 nanoparticle. Moreover, for the Pd13−nNin@Pt42 (n = 0, 1, 12, and13) nanoparticles catalysts, the activity of H2O dissociation reaction follows the order of Ni13@Pt42 > Pd13@Pt42 > Pd12Ni1@Pt42 > Pd1Ni12@Pt42, illustrating that the Ni13@Pt42 is the strongest activity among of the Pd13−nNin@Pt42 (n = 0, 1, 12, and13) nanoparticles catalysts. Therefore, tuning the composition of Pd and Ni in the core of the Pd13−nNin@Pt42 nanoparticles catalysts, the activity of Pd13−nNin@Pt42 (n = 0, 1, 12, and 13) nanoparticles catalysts can be modulated effectively.