Promoted coke resistance of Ni by surface carbon for the dry reforming of methane

Dry reforming of methane (DRM) is an efficient process to transform methane and carbon dioxide to syngas. Nickel could show good catalytic activity for DRM, whereas the deactivation of nickel surfaces by the formation of inert carbon structures is inevitable. In this study, we carry out a detailed investigation of the evolution and catalytic performance of the carbon-covered surface structure on Ni(100) with a combined density functional theory and microkinetic modeling approach. The results suggest that the pristine Ni(100) surface is prone to carbon deposition and accumulation under reaction conditions. Further studies show that over this carbon-covered reconstructed Ni(100) surface, a carbon-based Mars-van-Krevelen mechanism would be favored, and the activity and coke resistance is promoted. This surface state and reaction mechanism were rarely reported before and would provide more insights into the DRM process under real reaction conditions and would help design more stable Ni catalysts. [Display omitted] •Pristine Ni(100) surface is prone to carbon deposition under reaction conditions•Carbon coverage of 0.5 monolayer is a threshold for surface deformation•A carbon-based MvK mechanism is favored over the carbon-covered Ni(100)•Activity and coke resistance are promoted over the carbon-covered surface Chemistry; Theoretical organic chemistry