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.
Bertini, M., Ferrante, F., Gueci, L., Prestianni, A., Duca, D., Arena, F., et al. (2025). Alternative Algebraic Perspectives on CO/H2 PROX over MnO2 Composite Catalysts. JOURNAL OF CHEMICAL INFORMATION AND MODELING, 65(10), 4952-4967 [10.1021/acs.jcim.5c00072].
Alternative Algebraic Perspectives on CO/H2 PROX over MnO2 Composite Catalysts
Bertini, Marco;Ferrante, Francesco;Gueci, Laura;Prestianni, Antonio;Duca, Dario
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2025-05-26
Abstract
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.File | Dimensione | Formato | |
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