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Title: A theoretical study on reaction mechanisms and kinetics of thiophene hydrodesulfurization over MoS2 catalysts

Abstract

In the present study, 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. The DDS route leading 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 barriersmore » in the DDS route.« less

Authors:
 [1];  [1];  [2];  [1];  [2];  [3]
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  1. Beijing Univ. of Chemical Technology, Beijing (China)
  2. Beijing Univ. of Chemical Technology, Beijing (China); Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  3. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1420437
Alternate Identifier(s):
OSTI ID: 1591660
Report Number(s):
PNNL-SA-130462
Journal ID: ISSN 0920-5861; PII: S0920586118300646; TRN: US1801495
Grant/Contract Number:  
91534201; 21476012; 21571012; 21407007; AC05-76RL01830
Resource Type:
Accepted Manuscript
Journal Name:
Catalysis Today
Additional Journal Information:
Journal Volume: 312; Journal ID: ISSN 0920-5861
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 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.
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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
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Jin, Qiu, Chen, Biaohua, Ren, Zhibo, Liang, Xin, Liu, Ning, and Mei, Donghai. Sat . "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. https://www.osti.gov/servlets/purl/1420437.
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@article{osti_1420437,
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 study, 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. The DDS route leading 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.},
doi = {10.1016/J.CATTOD.2018.02.013},
journal = {Catalysis Today},
number = ,
volume = 312,
place = {United States},
year = {Sat Feb 10 00:00:00 EST 2018},
month = {Sat Feb 10 00:00:00 EST 2018}
}
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Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1016/J.CATTOD.2018.02.013
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Cited by: 21 works
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Figures / Tables:

Fig. 1. Fig. 1. : (a) DFT optimized Mo-edge and S-edge of MoS2; (b) DFT optimized Mo-S connection edge. All edges with 50% sulfur coverage; The CUS sites were labelled on Mo-, Sand Mo-S connection edges.
All figures and tables (12 total)
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