O2 adsorption and dissociation on the Pd13-nNin@Pt42 (n = 0, 1, 12, and 13) tri-metallic nanoparticles: A DFT study

Abstract

Density functional theory calculations are performed to investigate O2 adsorption and dissociation on the icosahedral Pd13-nNin@Pt42 (n=0, 1, 12, and 13) tri-metallic nanoparticles. The parallel adsorption of O2 on Pd13-nNin@Pt42 (n=0, 1, 12, and 13) is stronger than the vertical adsorption. The adsorption of O2 on the bridge site (B1) is favorable in the Pd13-nNin@Pt42 (n=0, 1, 12, and 13) nanoparticles, while the adsorption of O atom on the hollow site (H1) is preferred. The adsorption energies of O2 and O are strongly affected by the coordination number. Low coordination site shows strong adsorption of O2 and O on the Pd13-nNin@Pt42 (n=0, 1, 12, and 13) nanoparticles. The adsorption energies of O2 and O atoms are found to be correlated well with the d-band center of surface Pt. For the Pd13-nNin@Pt42 (n=0, 1, 12, and13) nanoparticles catalysts, the ORR activity follows the order of Ni13@Pt42>Pd13@Pt42>Pd12Ni1@Pt42>Pd1Ni12@Pt42, illustrating that the Ni13@Pt42 is the strongest ORR activity among the Pd13-nNin@Pt42 (n=0, 1, 12, and13) nanoparticles catalysts. Our results have important significance to understand the mechanism of O2 dissociation on the Pd13-nNin@Pt42 (n=0, 1, 12, and 13) tri-metallic nanoparticles.