噻吩在<em>γ</em>-Mo<sub>2</sub>N(100)表面上加氢脱硫反应的密度泛函理论研究

引用本文: 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, 30(11): 2063-2070. doi: 10.3866/PKU.WHXB201409221 shu

Citation: XU Kun, FENG Jie, CHU Qi, ZHANG Li-Li, LI Wen-Ying. Density Functional Theory Study of Thiophene Hydrodesulfurization on γ-Mo₂N(100) Surface[J]. Acta Physico-Chimica Sinica, 2014, 30(11): 2063-2070. doi: 10.3866/PKU.WHXB201409221 shu

噻吩在γ-Mo₂N(100)表面上加氢脱硫反应的密度泛函理论研究

基金项目:
国家高技术研究发展计划项目(863) (2011AA05A204)资助 (863) (2011AA05A204)

摘要:

利用密度泛函理论研究了γ-Mo₂N(100)表面上的噻吩加氢脱硫(HDS)过程. 噻吩在γ-Mo₂N(100)表面上不同作用形式的结构优化结果显示, η5-Mo₂N吸附构型最稳定, 具有最大的吸附能(-0.56 eV), 此时噻吩通过S原子与Mo2原子相连平行表面吸附在四重空位(hcp 位). H原子和噻吩在hcp位发生稳定共吸附, hcp位是噻吩HDS的活性位点. 噻吩在γ-Mo₂N(100)表面进行直接脱硫反应, HDS过程分为S原子脱除和C₄产物加氢饱和两部分. 过渡态搜索确定了HDS最可能的反应机理及中间产物, 首个H原子的反应需要最大的活化能(1.69 eV),是噻吩加氢脱硫的控速步骤. 伴随H原子的不断加入, 噻吩在γ-Mo₂N(100)表面上优先生成―SH和丁二烯, 随后―SH加氢生成H₂S, 丁二烯加氢饱和生成2-丁烯和丁烷. 由于较弱的吸附, H₂S、2-丁烯和丁烷很容易在γ-Mo₂N(100)表面脱附成为产物.

关键词:

English

Density Functional Theory Study of Thiophene Hydrodesulfurization on γ-Mo₂N(100) Surface

1.
Training Base of State Key Laboratory of Coal Science and Technology Jointly Constructed by Shanxi Province and Ministry of Science and Technology, Taiyuan University of Technology, Taiyuan 030024, P. R. China
Received Date: 20 June 2014
Available Online: 30 October 2014
Fund Project:
国家高技术研究发展计划项目(863) (2011AA05A204)资助

Abstract:

The hydrodesulfurization (HDS) of thiophene on an γ-Mo₂N(100) surface was investigated by density functional theory (DFT) and different configurations of thiophene on γ-Mo₂N(100) surface were considered. After geometric optimization, it was confirmed that the η5-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 parallel 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 on γ-Mo₂N(100). A direct desulfurization reaction pathway in HDS of thiophene dominated the process on the γ-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 preferentially 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 from γ-Mo₂N(100) to give the products because of weak adsorption.

Key words:

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沈阳化工大学材料科学与工程学院沈阳 110142

噻吩在γ-Mo₂N(100)表面上加氢脱硫反应的密度泛函理论研究

English

Density Functional Theory Study of Thiophene Hydrodesulfurization on γ-Mo₂N(100) Surface

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中国化学会秘书处

噻吩在γ-Mo2N(100)表面上加氢脱硫反应的密度泛函理论研究

English

Density Functional Theory Study of Thiophene Hydrodesulfurization on γ-Mo2N(100) Surface

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

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CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

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 on γ-Mo₂N(100) Surface

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