A two-layer ONIOM study of thiophene cracking catalyzed by proton- and cation-exchanged FAU zeolite

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• 作者：Yingxin Sun ; Xinfeng Mao ; Supeng Pei
• 关键词：Thiophene ; Hydrodesulfurization mechanism ; Cation ; exchanged FAU zeolite ; C ; S bond cracking ; Bimolecular desulfurization step
• 刊名：Journal of Molecular Modeling
• 出版年：2016
• 出版时间：February 2016
• 年：2016
• 卷：22
• 期：2
• 全文大小：1,842 KB
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• 作者单位：Yingxin Sun (1)
  Xinfeng Mao (1)
  Supeng Pei (1)
  
  1. School of Chemical and Environmental Engineering, Shanghai Institute of Technology, Shanghai, China
  
• 刊物类别：Chemistry and Materials Science
• 刊物主题：Chemistry
  Computer Applications in Chemistry
  Biomedicine
  Molecular Medicine
  Health Informatics and Administration
  Life Sciences
  Computer Application in Life Sciences
  
• 出版者：Springer Berlin / Heidelberg
• ISSN：0948-5023

文摘

A two-layer ONIOM study on the hydrodesulfurization mechanism of thiophene in H-FAU and M-FAU (M = Li+, Na+, and K+) has been carried out. The calculated results reveal that in H-FAU, for a unimolecular mechanism, the rate-determining step is hydrogenation of alkoxide intermediate. The assistance of H₂O and H₂S molecules does not reduce the difficulty of the C-S bond cracking step more effectively. A bimolecular hydrodesulfurization mechanism is more favorable due to the lower activation barriers. The rate-determining step is the formation of 2-methylthiophene, not the C-S bond cracking of thiophene. Moreover, the ring opening of thiophene is much easier to occur than the desulfurization step. A careful analysis of energetics indicates that H₂S, propene, and methyl thiophene are the major products for the hydrodesulfurization process of thiophene over H-FAU zeolite, in good agreement with experimental findings. In M-FAU zeolites, both unimolecular and bimolecular cracking processes are difficult to occur because of the high energy barriers. Compared to the case on H-FAU, the metal cations on M-FAU increase the difficulty of occurrence of bimolecular polymerization and subsequent C-S bond cracking steps.