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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]
  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. https://doi.org/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. 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.
@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 = {2018},
month = {2}
}

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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.

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Works referenced in this record:

A DFT study of the electronic structure of cobalt and nickel mono-substituted MoS2 triangular nanosized clusters
journal, November 2009

  • Zuriaga-Monroy, Carolina; Martínez-Magadán, José-Manuel; Ramos, Estrella
  • Journal of Molecular Catalysis A: Chemical, Vol. 313, Issue 1-2
  • DOI: 10.1016/j.molcata.2009.08.001

Location and coordination of promoter atoms in Co- and Ni-promoted MoS2-based hydrotreating catalysts
journal, July 2007


Recent advances in the science and technology of ultra low sulfur diesel (ULSD) production
journal, July 2010


A density functional theory comparison of anatase (TiO2)- and γ-Al2O3-supported MoS2 catalysts
journal, May 2005


DFT study of thiophene adsorption on molybdenum sulfide
journal, April 2006


DBT derivatives adsorption over molybdenum sulfide catalysts: a theoretical study
journal, May 2004


Free-energy profiles along reduction pathways of MoS2 M-edge and S-edge by dihydrogen: A first-principles study
journal, June 2011

  • Prodhomme, Pierre-Yves; Raybaud, Pascal; Toulhoat, Hervé
  • Journal of Catalysis, Vol. 280, Issue 2
  • DOI: 10.1016/j.jcat.2011.03.017

The effect of Co-promotion on MoS2 catalysts for hydrodesulfurization of thiophene: A density functional study
journal, December 2009


The active site for isoprene hydrogenation on MoS2/$gamma;-Al2O3 catalysts*1
journal, February 1988


Ab Initio Study of the H2–H2S/MoS2 Gas–Solid Interface: The Nature of the Catalytically Active Sites
journal, January 2000


A density functional study of inhibition of the HDS hydrogenation pathway by pyridine, benzene, and H2S on MoS2-based catalysts
journal, January 2006


DFT Calculations of Unpromoted and Promoted MoS2-Based Hydrodesulfurization Catalysts
journal, October 1999

  • Byskov, Line S.; Nørskov, Jens K.; Clausen, Bjerne S.
  • Journal of Catalysis, Vol. 187, Issue 1
  • DOI: 10.1006/jcat.1999.2598

Deep desulfurization: reactions, catalysts and technological challenges
journal, September 2003


Influence of sulfur vacancy on thiophene hydrodesulfurization mechanism at different MoS 2 edges: A DFT study
journal, June 2017


Computational studies of (mixed) sulfide hydrotreating catalysts
journal, January 2008


Computational Chemistry Analysis of Hydrodesulfurization Reactions Catalyzed by Molybdenum Disulfide Nanoparticles
journal, December 2015

  • Kumar, Narendra; Seminario, Jorge M.
  • The Journal of Physical Chemistry C, Vol. 119, Issue 52
  • DOI: 10.1021/acs.jpcc.5b09712

Ab initiomolecular dynamics for liquid metals
journal, January 1993


Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996


Accurate and simple analytic representation of the electron-gas correlation energy
journal, June 1992


Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999


Special points for Brillouin-zone integrations
journal, June 1976

  • Monkhorst, Hendrik J.; Pack, James D.
  • Physical Review B, Vol. 13, Issue 12, p. 5188-5192
  • DOI: 10.1103/PhysRevB.13.5188

Surface Structure and Stability of MoS x Model Clusters
journal, October 2005

  • Wen, Xiao-Dong; Zeng, Tao; Li, Yong-Wang
  • The Journal of Physical Chemistry B, Vol. 109, Issue 39
  • DOI: 10.1021/jp051540r

Theoretical Study of the MoS 2 (100) Surface:  A Chemical Potential Analysis of Sulfur and Hydrogen Coverage
journal, November 2000

  • Cristol, S.; Paul, J. F.; Payen, E.
  • The Journal of Physical Chemistry B, Vol. 104, Issue 47
  • DOI: 10.1021/jp0023819

Theoretical Study of the MoS 2 (100) Surface:  A Chemical Potential Analysis of Sulfur and Hydrogen Coverage. 2. Effect of the Total Pressure on Surface Stability
journal, June 2002

  • Cristol, S.; Paul, J. F.; Payen, E.
  • The Journal of Physical Chemistry B, Vol. 106, Issue 22
  • DOI: 10.1021/jp0134603

Adaptive kinetic Monte Carlo simulation of methanol decomposition on Cu(100)
journal, December 2009

  • Xu, Lijun; Mei, Donghai; Henkelman, Graeme
  • The Journal of Chemical Physics, Vol. 131, Issue 24
  • DOI: 10.1063/1.3281688

Mechanistic insights into the structure-dependent selectivity of catalytic furfural conversion on platinum catalysts
journal, June 2015

  • Cai, Qiu-Xia; Wang, Jian-Guo; Wang, Yang-Gang
  • AIChE Journal, Vol. 61, Issue 11
  • DOI: 10.1002/aic.14902

Thiophene hydrodesulfurization over nickel phosphide catalysts: effect of the precursor composition and support
journal, April 2005


Density Functional Theory Investigation on Thiophene Hydrodesulfurization Mechanism Catalyzed by ReS 2 (001) Surface
journal, May 2016

  • Huang, Yucheng; Liu, Hai; Chen, Xi
  • The Journal of Physical Chemistry C, Vol. 120, Issue 22
  • DOI: 10.1021/acs.jpcc.6b02769

    Works referencing / citing this record: