Quantitative Determination of C–C Coupling Mechanisms and Detailed Analyses on the Activity and Selectivity for Fischer–Tropsch Synthesis on Co(0001): Microkinetic Modeling with Coverage Effects
Quantitative Determination of C–C Coupling Mechanisms and Detailed Analyses on the Activity and Selectivity for Fischer–Tropsch Synthesis on Co(0001): Microkinetic Modeling with Coverage Effects
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DOI：
10.1021/acscatal.9b01150
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发表时间：
2019-05
期刊：
影响因子：
12.9
通讯作者：
Zihao Yao;Chenxi Guo;Yu Mao;P. Hu
中科院分区：
文献类型：
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作者：
Zihao Yao;Chenxi Guo;Yu Mao;P. Hu
费托合成在重整自然资源以满足全球对商品的需求方面发挥着重要作用，而目前石油正在枯竭，人口正在增长。机制已经研究了很长时间，但它们仍然是一个激烈辩论的问题。在这项工作中，所有可能的基元反应步骤在一个平坦的钴表面上使用密度泛函理论（DFT）与货车德瓦尔斯相互作用计算。动力学模拟使用标准的DFT数据（自由能和障碍，在低覆盖率），所谓的非覆盖率依赖的动力学模型中常用的文献中，进行了比较，从覆盖率依赖的动力学模型的系统。我们表明，覆盖依赖的动力学模型产生的TOF这是大约6个数量级大于使用非覆盖依赖的动力学模型计算的TOF。此外，发现Co（0001）对烯烃的生成具有很高的选择性，很可能生成长链烯烃。
The Fischer–Tropsch synthesis plays a significant role in re-forming natural resources to meet global demand for commodities, while there is ongoing oil depletion and population growth. Mechanisms have long been investigated, but they are still a heavily debated issue. In this work, all of the possible elementary reaction steps on a flat cobalt surface were calculated using density functional theory (DFT) with van der Waals interactions. Kinetic simulations using standard DFT data (free energies and barriers at low coverages), the so-called non-coverage-dependent kinetic model commonly used in the literature, are compared to those from a coverage-dependent kinetic model for the system. We show that the coverage-dependent kinetic model gives rise to a TOF which is approximately 6 orders of magnitude larger than the TOF calculated using the non-coverage-dependent kinetic model. Furthermore, it is found that Co(0001) is highly selective to olefin production, and it is very likely to produce long-chain hydroc...