文献类型：期刊文献

英文题名：On the importance of thermodynamic consistency to DFT-based microkinetic analysis of complex heterogeneous reactions with multiple pathways

作者：Zhang, Jing-Peng[1];Zhou, Ning[1];Lei, Ming[1];Chen, De[2];Zhou, Xing-Gui[1];Zhu, Yi-An[1]

机构：[1]East China Univ Sci & Technol, Sch Chem Engn, State Key Lab Green Chem Engn & Ind Catalysis, UNILAB, Shanghai 200237, Peoples R China;[2]Norwegian Univ Sci & Technol, Dept Chem Engn, N-7491 Trondheim, Norway

年份：2025

卷号：317

外文期刊名：CHEMICAL ENGINEERING SCIENCE

收录：;EI(收录号：20252618659103);WOS:【SCI-EXPANDED(收录号:WOS:001521005000003)】；

基金：This work is supported by the National Key Research and Development Program of China (No. 2024YFA1509901) and the National Natural Science Foundation of China (No. 22073027), and the research council of Norway through the innovation project for the industrial sector (340988, with Yara International).

语种：英文

外文关键词：Thermodynamic consistency; Thermodynamic constraints; Complex reaction network; Independent pathway

摘要：Thermodynamic consistency is of vital importance for the DFT-based microkinetic analysis of heterogeneous catalytic reactions, especially when a reactor model is considered. In this work, thermodynamic consistency in the complex reactions consisting of multiple reaction pathways is ensured by imposing thermodynamic constraints on a set of independent pathways identified through linear algebra algorithms. It is required that any linear combination of elementary steps leading to the overall reaction be consistent with the overall reaction thermodynamics, and the change in the activation energies for the forward and reverse reactions of elementary steps (or the enthalpy and entropy of activation, and the Gibbs free energy barrier) be minimized as small as possible. We further demonstrate that as long as the thermodynamic constraints are satisfied on the independent pathways, the thermodynamic properties of reaction intermediates and transition states can be uniquely determined. Then, the dry methane reforming reaction over Ni(111) is used as an example to show the importance of thermodynamic consistency to the thermodynamics and kinetics of the reaction. It is found that the three thermodynamically consistent methods proposed can help to predict with much better accuracy the equilibrium conversion at the outlet of the PFR reactor, kinetic parameters, as well as DRC, and the incorporation of scaling relations into the correction of the electronic energies of the reaction intermediates and transition states makes the best predication of the activation energy for the overall reaction.