Numerical investigation of the reaction kinetics of dry reforming of methane over the yolk-shell and single-atom alloy catalysts

Dry reforming of methane (DRM) over Ni-based supported catalysts has been widely studied due to Ni's low cost and high activity. Despite their excellent performance, side reactions such as methane decomposition and Boudouard reaction can cause severe coke formation leading to catalyst deactivation. Our recent work reported that both yolk-shell morphology and Pt-Ni interaction in single-atom-alloy (SAA) structures could maintain the DRM activity. However, the effect of morphology and Pt-Ni interaction could not be elucidated. In this work, we studied the reaction kinetics of DRM by proposing a detailed elementary reaction mechanism with 12 surface species and 17 elementary steps over the Ptx-NiCe@SiO2 and Pt0.25-NiCe/SiO2WI catalysts. Due to the different DRM activity over the wet-impregnated and yolk-shell structures, we examined multiple reaction models to explain the effect of morphology and Pt-Ni interaction on the DRM activity. Our results show that the reverse Boudouard reaction and dissociative adsorption of CO2 and CH4 are the rate-limiting steps. The desorption of CO* and H* is also critical to products yield and selectivity. Compared with Pt0.25-NiCe/SiO2WI catalyst, the C* removal followed by the fast CO* desorption is more favored on Pt0.25-NiCe@SiO2 SAA, suggesting the reverse Boudouard reaction prevents the catalyst deactivation by coking. The high O* and low H* coverages are observed on Pt0.25-NiCe@SiO2 SAA due to the confined yolk-shell morphology and enhanced Pt-Ni interaction in SAA structures, respectively. Both these effects can lead to facile C* removal in the Pt0.25-NiCe@SiO2 SAA catalyst leading to a stable DRM activity.