A theoretical study of the water gas shift reaction mechanism on Cu(1Â 1Â 1) model system

The water gas shift (WGS) reaction is an important reaction system and has wide applications in several processes. However, the mechanism of the reaction is still in dispute. In this paper we have investigated the reaction mechanism on the model Cu(1 1 1) system using the density functional method and slab models. We have characterized the kinetics and the thermodynamics of the four reaction pathways containing 24 elementary steps and computed the reaction potential energy surfaces. Calculations show that the formate (HCOO) intermediate mechanism (CO + OH → HCOO → CO2 + H) and the associative mechanism (CO + OH → CO2 + H) are kinetically unlikely because of the high formation barrier. On the other hand, the carboxyl (HOCO) intermediate mechanism (CO + OH → HOCO → CO2 + H) and the redox mechanism (CO + O → CO2) are demonstrated to be feasible. Our calculations also indicate that surface oxygen atoms can reduce the barriers of both water dissociation and HOCO decomposition significantly. The calculated potential energy surfaces show that the water dissociation which produces OH groups is the rate-determining step at the initial stage of the reaction or in the absence of surface oxygen atoms. With the development of the reaction or in the presence of oxygen atoms on the surface, CO + OH → HOCO and CO + O → CO2 become the rate-limiting step for the carboxyl and redox mechanisms, respectively.