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A thermodynamically consistent surface reaction mechanism for CO oxidation on Pt

机译:CO在Pt上氧化的热力学一致表面反应机理

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摘要

The thermodynamic inconsistency of catalytic combustion reaction mechanisms has been a long-standing, fundamental, and practical problem. Here, we develop a thermodynamically consistent catalytic reaction mechanism for CO oxidation on Pt. First, we propose a modification of the bond index of the unity bond index-quadratic exponential potential (UBI-QEP) semiempirical framework for calculation of the activation energy of the Langmuir-Hinshelwood-type bimolecular surface reaction between co-adsorbed CO~* and O~*. Thermodynamic consistency is then ensured in the reaction mechanism by combining the semiempirical UBI-QEP theory, statistical mechanics, and constraint-based optimization against experimental data. Atmospheric pressure ignition and ultrahigh vacuum molecular beam experiments are selected as targets for optimization. The optimized mechanism is validated against redundant experiments, including temperature-programmed desorption, temperature-programmed reaction, and molecular beam experiments. Our microkinetic model is able to capture multiple types of data while being thermodynamically consistent over a wide range of conditions.
机译:催化燃烧反应机理的热力学不一致一直是一个长期的,基本的和实际的问题。在这里,我们开发了一种在Pt上氧化CO的热力学一致催化反应机理。首先,我们提出了对整体键指数-二次指数势(UBI-QEP)半经验框架的键指数的修正,以计算共吸附CO〜*和-之间的L​​angmuir-Hinshelwood型双分子表面反应的活化能。哦〜*然后,通过结合半经验的UBI-QEP理论,统计力学和针对实验数据的基于约束的优化,可以确保反应机理中的热力学一致性。选择大气压点火和超高真空分子束实验作为优化目标。针对冗余实验验证了优化的机理,这些实验包括程序升温脱附,程序升温反应和分子束实验。我们的微动力学模型能够捕获多种类型的数据,同时在广泛的条件下具有热力学一致性。

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