Abstract Periodic density function theory (DFT) and kinetic Monte Carlo (kMC) method are carried out to investigate CO dissociation process on the Mn-doped Fe(100) surface. The energetics information of relevant atomistic processes and adsorption features of relevant species are obtained from DFT calculations. Subsequently, kMC simulations are performed with DFT results employed as database. Simulations show that the energy barriers for CHO and COH formations are 0.09 eV and 0.35 eV larger than that for direct CO dissociation on Mn/Fe(100), respectively. An empty site is created with a CO hydrogenation (CO* + H* → COH* + *, CO* + H* → CHO* + *), while an active site is consumed with a CO direct dissociation (CO* + * → C* + O*). The number of unoccupied active sites can affect the way of CO dissociation. On surfaces with considerable unoccupied active sites, direct CO dissociation mechanism is the preferred route. Under conditions favoring a very low number of unoccupied active sites and a mass of adsorbed H on surfaces, H-assisted CO dissociation via COH will take place. Graphic Abstract

中文翻译：

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Mn 掺杂 Fe(100) 表面的 CO 解离机制：计算研究

摘要 采用周期密度函数理论(DFT)和动力学蒙特卡罗(kMC)方法研究了Mn掺杂Fe(100)表面的CO解离过程。通过 DFT 计算获得相关原子过程的能量学信息和相关物种的吸附特征。随后，使用 DFT 结果作为数据库执行 kMC 模拟。模拟表明，CHO 和 COH 形成的能垒分别比在 Mn/Fe(100) 上直接解离 CO 的能垒大 0.09 eV 和 0.35 eV。通过 CO 加氢 (CO* + H* → COH* + *, CO* + H* → CHO* + *) 创建一个空位点，而通过 CO 直接解离 (CO* + * → C* + O*)。未占据的活性位点的数量会影响 CO 解离的方式。在具有大量未占据活性位点的表面上，直接的 CO 解离机制是首选途径。在有利于极少量未占据活性位点和大量吸附在表面上的 H 的条件下，H 将通过 COH 辅助 CO 解离。图形摘要