abstract
The adsorption energies and the activation energy barriers for a series of reactions catalyzed by gold surfaces and obtained theoretically through density functional theory (DFT) based calculations were considered to clarify the role of the low coordinated gold atoms and the role of doping in the catalytic activity of gold. The effect of the surface steps was introduced by comparison of the activation energy barriers and of the adsorption energies on flat gold surfaces such as the Au(111) surface with those on stepped surfaces such as the Au(321) or the Au(110) surfaces. It is concluded that the presence of low coordinated atoms on the latter surfaces increases the adsorption energies of the reactants and decreases the activation energy barriers. Furthermore, the increasing of the adsorption energy of the reaction products can lead to lower overall reaction rates in the presence of low gold coordinated atoms due to desorption limitations. On the other hand, the effect of doping gold surfaces with other transition metal atoms was analyzed using the dissociation reaction of molecular oxygen as a test case. The calculations showed that increasing the silver content in some gold surfaces was related to a considerable increment of the reactivity of bimetallic systems toward the oxygen dissociation. Importantly, that increment in the reactivity was enhanced by the presence of low coordinated atoms in the catalytic surface models considered.
subject category
Chemistry
authors
Fajin, JLC; Cordeiro, MNDS; Gomes, JRB
our authors
José Luis Cagide Fajín
Post-doc Fellowship
José R. B. Gomes
Principal Researcheracknowledgements
Thanks are due to Fundacao para a Ciencia e Tecnologia (FCT), Lisbon, Portugal and to FEDER for financial support to REQUIMTE and to CICECO, projects PEst-C/EQB/LA0006/2011 and PEst-C/CTM/LA0011/2011, respectively. Programa Ciencia 2007 is also acknowledged. JLCF acknowledges FCT for the grant SFRH/BPD/64566/2009 co-financed by the Fundo Social Europeu (FSE).