A Multisite Microkinetic Framework for Describing Interfacial Kinetics in Dry Methane Reforming (DRM) over Ni-CeO2Catalysts

Document Type

Article

Publication Date

2-6-2026

Abstract

Oxide-supported Ni catalysts are widely employed for the dry reforming of methane (DRM), where the metal–support interface plays a pivotal role in mediating interfacial O-transport and H-spillover reactions. In this work, a multisite microkinetic model is developed for the Ni-CeO2 system to elucidate how interfacial processes govern the overall DRM activity and/or selectivity. Kinetic parameters for the model are obtained from density functional theory (DFT), and they are adjusted to ensure thermodynamic consistency, while geometric parameters are derived from an assumed catalyst model. Analyses of reaction orders reveal mixed dependencies of DRM rate on CH4 and CO2 pressures, depending on the prevailing kinetic regime. Global sensitivity analysis (Sobol) identifies the Ni nanoparticle radius (rm) as a dominant geometric parameter controlling the overall rate. Degree of rate control (DRC) analysis shows that CH4 activation is rate-determining for small Ni nanoparticles, while O-transport becomes limiting at a larger rm, indicating a transition to deactivation-prone regimes. The model captures this transition without explicitly incorporating coking pathways, demonstrating its robustness in representing interfacial effects. This multisite model establishes a mechanistic framework for examining transport across metal–support boundaries and serves as a predictive tool for studying interface-mediated reaction systems.

Publication Source (Journal or Book title)

ACS Catalysis

First Page

2535

Last Page

2549

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