Abstract Higher alcohols synthesis (HAS) directly from syngas, as environment-friendly liquid fuel or fuel additives, is regarded as a “green” route. It is essential for catalyst design to study reaction mechanism of HAS. To obtain carbon chain growth mechanism, the reaction network of HAS from syngas on CoCu(100) surface was systematically studied by density functional theory (DFT) calculation and kinetic Monte Carlo (kMC) simulation. Firstly, the energetics of the key elementary reactions of HAS on CoCu(100) were obtained by DFT calculation. And then the reaction processes of carbon chain growth were simulated with kMC method. Finally, the reaction mechanism of carbon chain growth on CoCu(100) was analyzed. The results show that CH is not easy to generate and easy to transform into CH2 on CoCu(100). CH2 and CH3 are easy to form and they are the key intermediates to achieve carbon chain growth. The addition of Co can promote the C O bond of CH2O scission to form CH2, inhibit the formation of CH3O, change the reaction pathway on CoCu(100), and thus improve the selectivity of C2+ alcohols.

中文翻译：

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CoCu(100)上合成气合成高级醇的碳链增长机制：DFT和kMC联合研究

摘要 由合成气直接合成高级醇（HAS），作为环保的液体燃料或燃料添加剂，被认为是一条“绿色”路线。研究HAS的反应机理对于催化剂设计至关重要。为了获得碳链生长机制，通过密度泛函理论（DFT）计算和动力学蒙特卡罗（kMC）模拟系统地研究了合成气在CoCu（100）表面上的反应网络。首先，通过DFT计算获得了HAS在CoCu(100)上的关键元素反应的能量学。然后用kMC方法模拟了碳链增长的反应过程。最后分析了CoCu(100)上碳链生长的反应机理。结果表明，在CoCu(100)上CH不易生成且容易转化为CH2。CH2和CH3容易形成，是实现碳链增长的关键中间体。Co的加入可以促进CH2O断裂的CO键形成CH2，抑制CH3O的形成，改变CoCu(100)上的反应途径，从而提高C2+醇的选择性。