Bertini Marco, Ferrante Francesco, Gueci Laura, Prestianni Antonio, Duca Dario, Arena Francesco, Murzin Dmitry Yu
Dipartimento di Fisica e Chimica "Emilio Segrè", Università degli Studi di Palermo, Viale delle Scienze Ed. 17, Palermo I-90128, Italy.
Dipartimento di Ingegneria, Università degli Studi di Messina, Contrada di Dio, Messina I-98166, Italy.
J Chem Inf Model. 2025 May 26;65(10):4952-4967. doi: 10.1021/acs.jcim.5c00072. Epub 2025 May 2.
This study presents a graph-based approach to investigate the steady-state kinetics of the preferential CO oxidation process in H (PROX) occurring on a MnO model fragment with manganese centers at varying oxidation states, simulating the surface Mn(IV) active sites of a composite MnO-CeO 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 (Δ) 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 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/H PROX catalytic process on the manganese oxide fragments are discussed, highlighting their significance for future research and applications.
本研究提出了一种基于图形的方法，用于研究在具有不同氧化态锰中心的MnO模型片段上发生的H2中优先CO氧化过程（PROX）的稳态动力学，模拟先前在实验应用中使用的MnO-CeO复合催化剂的表面Mn(IV)活性位点。引入了一种新颖的建模方法，称为基于密度泛函理论（DFT）图形的动力学分析（DFT-GKA）。它利用自由活化能（Δ）值来表征在该复杂反应体系中假设处于准稳态的线性基元反应，这些值是通过结合热化学计算的密度泛函理论（DFT）确定的。该模型的实现使用了一种专门为高效处理分析所需的长列表而设计的Common Lisp代码。最后，讨论了与锰氧化物片段上的CO/H2 PROX催化过程相关的全面从头算DFT动力学描述符，强调了它们对未来研究和应用的重要性。
