物理化学学报Issue(11)：2063-2070,8.DOI:10.3866/PKU.WHXB201409221
噻吩在γ-Mo2N（100）表面上加氢脱硫反应的密度泛函理论研究
Density Functional Theory Study of Thiophene Hydrodesulfurization onγ-Mo2N(100) Surface
摘要
Abstract
The hydrodesulfurization (HDS) of thiophene on anγ-Mo2N(100) surface was investigated by density functional theory (DFT) and different configurations of thiophene onγ-Mo2N(100) surface were considered. After geometric optimization, it was confirmed that theη5-Mo2N configuration was the most stable adsorption model with an adsorption energy of-0.56 eV, where thiophene absorbed on 4-fold hcp vacant sites paral el to the surface with the S atom bonded to a Mo2 atom. The stable coadsorption of H atoms and thiophene on hcp sites showed that the hcp site is the active site for thiophene HDS onγ-Mo2N(100). A direct desulfurization reaction pathway in HDS of thiophene dominated the process on theγ-Mo2N(100) surface, which could be divided into the removal of the S atom and the hydrogenation saturation of C4 species. To identify the intermediate products and the most probable reaction mechanism of thiophene HDS, a transition state search was carried out. The results indicated that the reaction of the first H atom required an activation energy of 1.69 eV, which was the rate-determining step in the HDS of thiophene. The thiol group (―SH) and butadiene were preferential y formed after hydrogenation of thiophene, and―SH detached from mercaptan was the intermediate of H2S. 2-Butene and butane were the products of the hydrogenation saturation of butadiene. H2S, 2-butene, and butane were easily desorbed fromγ-Mo2N(100) to give the products because of weak adsorption.关键词
噻吩/氮化钼/加氢脱硫/反应机理/密度泛函理论Key words
Thiophene/Molybdenum nitride/Hydrodesulfurization/Reaction mechanism/Density functional theory分类
化学化工引用本文复制引用
徐坤,冯杰,褚绮,张丽丽,李文英..噻吩在γ-Mo2N（100）表面上加氢脱硫反应的密度泛函理论研究[J].物理化学学报,2014,(11):2063-2070,8.基金项目
The project was supported by the National High Technology Research and Development Program of China (863)(2011AA05A204).国家高技术研究发展计划项目(863)(2011AA05A204)资助 （863）
