Dataset for Modified Energy Span Analysis of Catalytic Parallel Pathways and Selectivity

Mechanistic modeling provides vital insights into catalytic reactions. To analyze complex reaction networks with parallel pathways, we leverage the graph theory approach of the Energy Span Model (ESM) to develop a modified energy span analysis (MESA). A new method of cycle plots is proposed to perform reaction pathways analysis visually. We demonstrate this method on two published models: one describing carbon monoxide oxidation and the other simulating ethylene conversion to propanal via hydroformylation or ethane via hydrogenation. Fundamental insights explain kinetic observables, such as a reactant’s negative reaction order. General principles are revealed, such as rate-determining surface species being outside the primary reaction flux cycle and pathway selectivity being a purely kinetic property when reaction conditions are not near equilibrium. Finally, we demonstrate MESA’s consistency with published microkinetic modeling results, highlighting this technique’s extension of the ESM to heterogeneous catalysts using collision theory to describe adsorption steps and concentration effects.机理建模可为催化反应研究提供至关重要的机制洞察。为分析包含平行反应路径的复杂反应网络，我们借助能量跨度模型（Energy Span Model，ESM）的图论分析框架，开发了改进型能量跨度分析（Modified Energy Span Analysis，MESA）。本文提出一种全新的循环图分析法，可实现反应路径的可视化分析。我们在两篇已发表的模型体系中验证了该方法：其一为一氧化碳氧化模型，其二为模拟乙烯分别经氢甲酰化反应生成丙醛、经加氢反应生成乙烷的模型。本研究通过基础机制阐释了诸多动力学可观测现象，例如反应物的负反应级数。研究同时揭示了若干通用规律：当反应条件未接近平衡态时，速率决定型表面物种并不处于主反应通量循环之内，且反应路径选择性仅为纯动力学属性。最后，我们验证了MESA与已发表的微观动力学建模结果具有一致性，并着重展示了该技术将ESM拓展至多相催化体系的应用场景——该方法借助碰撞理论描述吸附步骤与浓度效应。