Theoretically predicted CO adsorption and dissociation on Ru-doped Co(1 0 0) surfaces.

[Display omitted] • CO adsorption at lowest coverage is enhanced due to the short-range electronic effect of Ru on adsorbed CO molecular. • CO dissociation barrier depends on the adsorption site and the Ru content. • The amount of saturated adsorbed CO is increased while that of dissociated CO is decreased on the Ru-doped Co(1 0 0) surfaces at high coverage. • The adsorption model is preferred than substitution model for CO activation, as reflected by more CO molecular states for the subsequent H-assisted dissociation. CO adsorption and dissociation on Ru-doped Co(1 0 0) surfaces at different CO coverage compared to clean surface were investigated based on spin-polarized density functional theory (DFT), in order to explore the effect of the initial step of Ru promoter on CO activation in cobalt-based Fischer-Tropsch synthesis (FTS). The results show that CO adsorption is highly site-dependent, the adsorption strength of CO at different types of adsorption sites is determined by the interaction between the adsorbed CO molecule and Ru-doped Co(1 0 0) surfaces. CO dissociation is promoted at hollow sites but inhibited at top and bridge sites above the Ru atoms. In addition, the amount of saturated adsorbed CO is increased while the amount of dissociated CO is decreased on the Ru-doped Co(1 0 0) surfaces at high coverage. Combining the experimental results, it is concluded that the adsorption model is preferred than substitution model for CO activation, because the increased CO molecular states in adsorption model is facile for the subsequent H-assisted dissociation on Co surface. The present work suggests that the addition of Ru promoter can improve the CO activation on Co(1 0 0) surface and pave the way for experimental research. [ABSTRACT FROM AUTHOR]