Theoretical study of CO oxidation on cationic, neutral, and anionic AuM dimers (M = Pd and Ag).

The CO and O2 adsorption as well as CO oxidation on cationic, neutral, and anionic AuM dimers (M = Pd, Ag) are studied by density functional calculations. Our results show that CO and O2 are adsorbed more stably on AuPd dimers than on AuAg dimers with corresponding charge state. O2 is favorable to be adsorbed on Pd atom in AuPd(+), AuPd and AuPd(-) dimers. CO is adsorbed on Pd in AuPd and AuPd(-), while it is favorable to be adsorbed on Au in AuPd(+). For AuAg dimers, O2 is adsorbed on Ag in AuAg and AuAg(-), and it is adsorbed on Au in AuAg(+). CO is adsorbed on Ag in AuPd(-), while it is adsorbed on Au in AuAg and AuAg(+). The CO oxidation reaction is explored along two possible pathways: path-1 involves CO attacking the initial complexes of AuM dimers and O2, and path-2 is related to O2 interacting with the complexes of AuM dimers and CO. The charge state of AuM dimers has a substantial effect on CO oxidation. The reaction on AuPd(-) prefers path-1, and AuPd(+) mediated reaction proceeds along path-2, while CO oxidation on AuPd is difficult along both paths. For AuAg, both pathways are viable for AuAg(-) mediated reactions, while AuAg and AuAg(+) mediated reactions prefer path-2. Moreover, the energy barriers of CO oxidation on neutral AuAg is comparable with those on AuPd in all charge states while the energy barriers for AuAg(-) and AuAg(+) are considerably lower than those for all AuPd dimmers, indicating the impurity atom also plays a significant role in the catalytic activity. Furthermore, AuAg(-) is proposed to be the most active species due to the lowest barrier involved in the reaction.