Abstract Analysis of apparent activation energy is presented for different heterogeneous catalytic reactions with parallel reaction routes. In the case of kinetic coupling between catalytic cycles the activation energy in a particular route depends not only on the activation energies of the elementary steps comprising this route, but also on the frequency of the steps in a parallel route. Expressions were derived for coupling between routes through irreversible adsorption of the substrate, quasi-equilibrated binding as well as different substrate adsorption modes. Theoretical analysis of the apparent activation energy was extended for the reaction network with two routes possessing mechanistically different rate determining steps (i.e. monomolecular vs bimolecular). For structure sensitive reactions an expression for the apparent activation energy for parallel reactions was developed for cases with a continuous distribution of active centers and a cubo-octahedral representation of the metal clusters. A comparison between the theoretical analysis and experimental data on transformations of furfural to furfuryl alcohol and furan on ruthenium clusters shows applicability of the developed theoretical framework. Graphic Abstract

中文翻译：

---

结构敏感性对平行多相催化反应表观活化能的影响

摘要 对具有平行反应路线的不同多相催化反应进行了表观活化能分析。在催化循环之间的动力学耦合的情况下，特定路线中的活化能不仅取决于构成该路线的基本步骤的活化能，还取决于平行路线中步骤的频率。通过底物的不可逆吸附、准平衡结合以及不同的底物吸附模式，推导出路线之间的耦合表达式。对反应网络的表观活化能的理论分析扩展到具有机械不同速率确定步骤（即单分子与双分子）的两条路线。对于结构敏感反应，针对具有连续分布的活性中心和金属簇的立方八面体表示的情况，开发了平行反应的表观活化能表达式。糠醛向糠醇和呋喃在钌簇上的转化的理论分析和实验数据之间的比较显示了所开发的理论框架的适用性。图形摘要