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Oxygen dissociation on palladium and gold core/shell nanoparticles
Author(s) -
Staykov Aleksandar,
Derekar Durgesh,
Yamamura Keisuke
Publication year - 2016
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.25217
Subject(s) - palladium , dissociation (chemistry) , nanoparticle , catalysis , chemistry , colloidal gold , oxygen , adsorption , chemical physics , chemical engineering , inorganic chemistry , materials science , nanotechnology , organic chemistry , engineering
Oxygen dissociation reaction on gold, palladium, and gold‐palladium core/shell nanoparticles was investigated with plane wave basis set, density functional theory. Bader population analysis of charge and electron distribution was employed to understand the change of catalytic activity as a function of the nanopaticle composition. The nanoparticles’ electronic properties were investigated and the degree of core/shell charge polarization was estimated for each composition. It was found that surface polarization plays an important role in the catalysis of the initial step of electrophile reactions such as oxygen dissociation. We have investigated the O 2 adsorption energy on each nanoparticle and the activation barrier for the oxygen dissociation reaction as a function of the nanoparticle structure. Furthermore, we have investigated the influence of surface geometry, that is., surface bond lengths on the catalytic activity. We have compared the electronic and the geometry effects on the oxygen activation and dissociation. Our design rules for core/shell nanoparticles offer an effective method for control of the surface catalytic activity. Palladium and gold are often used as catalysts in synthetic chemistry. First‐principles calculations elucidate the mechanisms that control the surface reactivity of gold, palladium, and gold‐palladium core shell nanoparticles in oxygen dissociation reactions. Oxygen dissociation is promoted on the gold surface of gold/palladium core‐shell nanoparticles by favorable electron transfer from the core to the shell. Such core‐shell electronic effects can be used for fine‐tuning the nanoparticles catalytic activity.