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Title: A Theoretical Study on Reaction Mechanisms and Kinetics of Thiophene Hydrodesulfurization over MoS2 Catalysts

Abstract

In the present work, thiophene hydrodesulphurization (HDS) over the Mo-edge, the S-edge, and the Mo-S connection edge of MoS2 catalyst with 50% sulfur coverage was studied using first-principles based microkinetic modeling. Two parallel HDS routes, i.e., direct desulfurization (DDS) and hydrogenation (HYD) were taken into account. It has been found that the major reaction route of thiophene HDS on the Mo- and the Mo-S edges is temperature dependent. In the low temperature range of 500~600 K, the HYD route is dominant, leading to the C4H8 formation. As the temperature increases, the DDS route becomes competitive with the HYD route. At the temperature above 650 K, the DDS route will be the dominant HDS reaction route on the Mo- and the Mo-S edges. While the DDS route that leads to the formation of C4H6 is the major thiophene HDS reaction route on the S-edge in the entire temperature range of 500~750 K. The microkinetic modeling results show the overall HDS activity on the S-edge is lower than it on the Mo- and the Mo-S edges. The Mo-S edge also provides a preferential reaction pathway, which facilitates 2-hydrothiophene migration from the Mo-edge to the S-edge, followed by remaining elementary steps with lowermore » activation barriers in the DDS route. The work was financially supported by the National Natural Science Foundation of China (No. 21476012, 21571012, 21407007 and 91534201). The computing time was granted by a scientific theme user proposal in the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL), which is a U.S. Department of Energy national scientific user facility located at Pacific Northwest National Laboratory (PNNL) in Richland, Washington. Part of computing time was provided the National Energy Research Scientific Computing Center (NERSC). D. Mei is supported by the US Department of Energy, Office of Sciences, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences.« less

Authors:
; ; ; ; ;
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1490215
Report Number(s):
PNNL-SA-130462
Journal ID: ISSN 0920-5861
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Catalysis Today
Additional Journal Information:
Journal Volume: 312; Journal Issue: C; Journal ID: ISSN 0920-5861
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
Thiophene, hydrodesulphurization, MoS2, DFT, microkinetic modeling

Citation Formats

Jin, Qiu, Chen, Biaohua, Ren, Zhibo, Liang, Xin, Liu, Ning, and Mei, Donghai. A Theoretical Study on Reaction Mechanisms and Kinetics of Thiophene Hydrodesulfurization over MoS2 Catalysts. United States: N. p., 2018. Web. doi:10.1016/j.cattod.2018.02.013.
Jin, Qiu, Chen, Biaohua, Ren, Zhibo, Liang, Xin, Liu, Ning, & Mei, Donghai. A Theoretical Study on Reaction Mechanisms and Kinetics of Thiophene Hydrodesulfurization over MoS2 Catalysts. United States. https://doi.org/10.1016/j.cattod.2018.02.013
Jin, Qiu, Chen, Biaohua, Ren, Zhibo, Liang, Xin, Liu, Ning, and Mei, Donghai. 2018. "A Theoretical Study on Reaction Mechanisms and Kinetics of Thiophene Hydrodesulfurization over MoS2 Catalysts". United States. https://doi.org/10.1016/j.cattod.2018.02.013.
@article{osti_1490215,
title = {A Theoretical Study on Reaction Mechanisms and Kinetics of Thiophene Hydrodesulfurization over MoS2 Catalysts},
author = {Jin, Qiu and Chen, Biaohua and Ren, Zhibo and Liang, Xin and Liu, Ning and Mei, Donghai},
abstractNote = {In the present work, thiophene hydrodesulphurization (HDS) over the Mo-edge, the S-edge, and the Mo-S connection edge of MoS2 catalyst with 50% sulfur coverage was studied using first-principles based microkinetic modeling. Two parallel HDS routes, i.e., direct desulfurization (DDS) and hydrogenation (HYD) were taken into account. It has been found that the major reaction route of thiophene HDS on the Mo- and the Mo-S edges is temperature dependent. In the low temperature range of 500~600 K, the HYD route is dominant, leading to the C4H8 formation. As the temperature increases, the DDS route becomes competitive with the HYD route. At the temperature above 650 K, the DDS route will be the dominant HDS reaction route on the Mo- and the Mo-S edges. While the DDS route that leads to the formation of C4H6 is the major thiophene HDS reaction route on the S-edge in the entire temperature range of 500~750 K. The microkinetic modeling results show the overall HDS activity on the S-edge is lower than it on the Mo- and the Mo-S edges. The Mo-S edge also provides a preferential reaction pathway, which facilitates 2-hydrothiophene migration from the Mo-edge to the S-edge, followed by remaining elementary steps with lower activation barriers in the DDS route. The work was financially supported by the National Natural Science Foundation of China (No. 21476012, 21571012, 21407007 and 91534201). The computing time was granted by a scientific theme user proposal in the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL), which is a U.S. Department of Energy national scientific user facility located at Pacific Northwest National Laboratory (PNNL) in Richland, Washington. Part of computing time was provided the National Energy Research Scientific Computing Center (NERSC). D. Mei is supported by the US Department of Energy, Office of Sciences, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences.},
doi = {10.1016/j.cattod.2018.02.013},
url = {https://www.osti.gov/biblio/1490215}, journal = {Catalysis Today},
issn = {0920-5861},
number = C,
volume = 312,
place = {United States},
year = {2018},
month = {8}
}

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Works referencing / citing this record: