Alternative Algebraic Perspectives on CO/H₂ PROX over MnO₂ Composite Catalysts

This study presents a graph-based approach to investigate the steady-state kinetics of the preferential CO oxidation process in H₂ (PROX) occurring on a MnO₂ model fragment with manganese centers at varying oxidation states, simulating the surface Mn(IV) active sites of a composite MnO₂−CeO₂ catalyst previously used in experimental applications. A novel modeling approach, termed DFT graph-based kinetic analysis (DFT-GKA), is introduced. It utilizes free activation energy (ΔG) values to characterize linear elementary events, supposed at pseudosteady-state, in this complex reaction system, as determined through density functional theory (DFT) integrated by thermochemical calculations. The implementation of this model is achieved using a homemade Common Lisp code, specifically designed for efficient manipulation of long lists essential for the analysis. Finally, the comprehensive ab initio DFT kinetic descriptors related to the CO/ H₂ PROX catalytic process on the manganese oxide fragments are discussed, highlighting their significance for future research and applications.