Adsorption and Desulfurization Mechanism of Thiophene on Layered FeS(001), (011), and (111) Surfaces: A Dispersion-Corrected Density Functional Theory Study.
Adsorption and Desulfurization Mechanism of Thiophene on Layered FeS(001), (011), and (111) Surfaces: A Dispersion-Corrected Density Functional Theory Study.
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DOI：
10.1021/acs.jpcc.7b08711
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发表时间：
2018-01-11
期刊：
影响因子：
--
通讯作者：
de Leeuw NH
中科院分区：
文献类型：
--
作者：
Dzade NY;de Leeuw NH
层状过渡金属硫族化合物已成为一类引人注目的新型催化材料。在这里，我们提出了周期性密度泛函理论（DFT）计算噻吩的吸附和直接脱硫反应途径上的（001），（011），（111）表面的层状硫化亚铁。噻吩吸附的基本方面，包括初始吸附几何形状，吸附能，结构参数，和电子性质，提出。从计算的吸附能来看，噻吩分子与FeS表面形成多个π键的平面吸附构型比直立吸附构型在能量上更有利，吸附强度按FeS（111）> FeS（011）> FeS（001）的顺序降低.噻吩在（011）和（111）表面上的吸附是通过电荷从相互作用的Fe d带转移到噻吩分子的π体系，引起分子内结构的变化，包括芳香性的丧失和C-S键的伸长.噻吩在反应性FeS表面上直接脱硫的基本步骤的热力学和动力学分析也被提出。噻吩的直接脱硫优先发生在（111）表面上，如通过该过程计算的总放热反应能量（ER =-0.15 eV）所反映的，活化能为1.58 eV。
Layered transition-metal chalcogenides have emerged as a fascinating new class of materials for catalysis. Here, we present periodic density functional theory (DFT) calculations of the adsorption of thiophene and the direct desulfurization reaction pathways on the (001), (011), and (111) surfaces of layered FeS. The fundamental aspects of the thiophene adsorption, including the initial adsorption geometries, adsorption energies, structural parameters, and electronic properties, are presented. From the calculated adsorption energies, we show that the flat adsorption geometries, wherein the thiophene molecule forms multiple π-bonds with the FeS surfaces, are energetically more favorable than the upright adsorption geometries, with the strength of adsorption decreasing in the order FeS(111) > FeS(011) > FeS(001). The adsorption of the thiophene onto the reactive (011) and (111) surfaces is shown to be characterized by charge transfer from the interacting Fe d-band to the π-system of the thiophene molecule, which causes changes of the intramolecular structure including loss of aromaticity and elongation of the C–S bonds. The thermodynamic and kinetic analysis of the elementary steps involved in the direct desulfurization of thiophene on the reactive FeS surfaces is also presented. Direct desulfurization of thiophene occurs preferentially on the (111) surface, as reflected by the overall exothermic reaction energy calculated for the process (ER = −0.15 eV), with an activation energy of 1.58 eV.
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