Probing the Site-Specific Reactivity and Catalytic Activity of Ag (n = 15-20) Silver Clusters

Density functional theory calculations within the framework of generalized gradient approximation (GGA), meta-GGA, and local functionals were carried out to investigate the reactivity and catalytic activity of Ag (n = 15-20) clusters. Our results reveal that all the Ag clusters in this size range, except Ag₂₀, adsorb O₂ preferably in the bridged mode with enhanced binding energy as compared to the atop mode. The O₂ binding energies range from 0.77 to 0.29 in the bridged mode and from 0.36 to 0.15 eV in the atop mode of O₂ adsorption. The strong binding in the case of the bridged mode of O₂ adsorption is also reflected in the increase in O-O bond distance. Natural bond orbital charge analysis and vibrational frequency calculations reveal that enhanced charge transfer occurs to the O₂ molecule and there is significant red shift in the stretching frequency of O-O bond in the case of the bridged mode of O₂ adsorption on the clusters, thereby confirming the above results. Moreover, the simulated CO oxidation reaction pathways show that the oxidation of the CO molecule is highly facile on Ag₁₆ and Ag₁₈ clusters involving small kinetic barriers and higher heats toward CO₂ formation.