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.
| Original language | English |
|---|---|
| Article number | 10 |
| Pages (from-to) | 4952-4967 |
| Number of pages | 16 |
| Journal | Journal of Chemical Information and Modeling |
| Volume | 65 |
| Issue number | 10 |
| DOIs | |
| Publication status | Published - 26 May 2025 |
| MoE publication type | A1 Journal article-refereed |
Funding
D.D. acknowledges financial support from the Conferenza dei Rettori delle Università Italiane (CRUI) and Università degli Studi di Palermo (UniPa) for Open Access Publishing. F.F., L.G. and F.A. acknowledge financial support under the National Recovery and Resilience Plan (PNRR), Mission 4, Component 2, Investment 1.1, Call for tender no. 104 published on 2.2.2022 by the Italian Ministry of University and Research (PRIN 2022), 2022EX89KF, funded by the European Union̄NextGenerationEŪProject Title “An integrated environmental sustainable approach for the valorization of wet AGROindustrial wastes to bioMEThane” (AGROMET)̄CUP B53D23005960006. D.D. acknowledges financial support from the Conferenza dei Rettori delle Università Italiane (CRUI) and Università degli Studi di Palermo (UniPa) for Open Access Publishing. F.F., L.G. and F.A. acknowledge financial support under the National Recovery and Resilience Plan (PNRR), Mission 4, Component 2, Investment 1.1, Call for tender no. 104 published on 2.2.2022 by the Italian Ministry of University and Research (PRIN 2022), 2022EX89KF, funded by the European Union─NextGenerationEU─Project Title “An integrated environmental sustainable approach for the valorization of wet AGROindustrial wastes to bioMEThane” (AGROMET)─CUP B53D23005960006.