Understanding and predicting improved sulfide catalysts: Insights from first principles modeling
Understanding and predicting improved sulfide catalysts: Insights from first principles modeling
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DOI：
10.1016/j.apcata.2007.01.005
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发表时间：
2007-04
影响因子：
5.5
通讯作者：
P. Raybaud
中科院分区：
文献类型：
--
作者：
P. Raybaud
本文综述了近年来加氢处理硫化物催化剂的研究进展，介绍了基于密度泛函理论（DFT）结合热力学模型和微观动力学模型的理论方法。我们首先说明了许多概念的现代DFT模拟更好地了解工业Co（Ni）MoS活性相：本地化和促进剂的作用，电子性质和形态变化引起的反应条件或促进剂添加。然后，它示出了如何支持效果可以通过DFT建模提供新的见解的局部结构和能量稳定性的活性相支持接口，其中表征技术达到其极限。以γ-Al_2O_3和锐钛矿型TiO_2为例进行了比较。最后，DFT模拟和微观动力学模型有助于合理化加氢脱硫（HDS）或加氢（HYD）活动和计算的硫-金属键能描述符之间的“火山曲线”型关系。这种方法开辟了新的路线，使用系统的DFT模拟作为预测工具。DFT模拟的硫化物催化领域的前景提出了建议。
This paper is a review of recent advances accomplished in the field of hydrotreatment (HDT) sulfide catalysts and using theoretical approaches based on the density functional theory (DFT) combined with thermodynamic models and microkinetic models. We illustrate first numerous concepts of modern DFT simulation for a better understanding of the industrial Co(Ni)MoS active phases: localization and role of the promoter, electronic properties and morphological changes induced by the reaction conditions or by promoter addition. Then, it is shown how support effects can be modeled by DFT to provide new insights on the local structure and energy stability of the active phase-support interface, where characterization techniques reach their limits. The comparison between γ-alumina and anatase-TiO2supports is chosen as a relevant example. Finally, DFT simulations and microkinetic models help to rationalize “volcano-curve” type relationships between hydrodesulfurization (HDS) or hydrogenation (HYD) activities and the calculated sulfur–metal bond energy descriptor. This approach opens new routes to use systematic DFT simulations as a predictive tool. Perspectives for DFT simulations in the area of catalysis by sulfides are suggested.