DFT Insights into the Competitive Adsorption of Sulfur- and Nitrogen-Containing Compounds and Hydrocarbons on Co-Promoted Molybdenum Sulfide Catalysts
Abstract
The adsorption of 20 nitrogen-/sulfur-containing and hydrocarbon compounds on the sulfur edge of cobalt-promoted molybdenum sulfide (CoMoS) catalyst was studied using density functional theory, accounting for van der Waals interactions, to elicit comparative structure–property trends across different classes of molecules relevant to hydrotreating. Unhindered organosulfur compounds preferentially adsorb on a “CUS-like” site formed by the dimerization of two neighboring sulfur atoms on the edge to create a vacancy. Nitrogen-containing compounds and 4,6-dimethyldibenzothiophene, however, prefer the brim sites. Binding energy trends indicate that nitrogen-containing compounds will inhibit hydrodesulfurization on the brim sites and, relatively weakly, on the CUS-like sites. Edge vacancies are,thus, likely to be essential for hydrodesulfurization of unhindered organosulfur compounds. Furthermore, van der Waals forces contribute significantly to the binding energy of compounds (up to 1.0 eV for large compounds such as alkyl-substituted acridines) on CoMoS.
- Authors:
-
[1]
- Univ. of Wisconsin, Madison, WI (United States). Dept. of Chemical and Biological Engineering
- Publication Date:
- Research Org.:
- Univ. of Wisconsin, Madison, WI (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Biological and Environmental Research (BER); USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
- Contributing Org.:
- Pacific Northwest national lab (PNNL); Argonne national lab (ANL); National Energy Research Scientific Computing Center (NERSC); UW-Madison Center for High Throughput Computing (CHTC).
- OSTI Identifier:
- 1408882
- Grant/Contract Number:
- FG02-05ER15731; AC02-06CH11357; AC02-05CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ACS Catalysis
- Additional Journal Information:
- Journal Volume: 6; Journal Issue: 5; Journal ID: ISSN 2155-5435
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; CoMoS; density functional theory; hydrodesulfurization; organonitrogen inhibition; van der Waals interaction
Citation Formats
Rangarajan, Srinivas, and Mavrikakis, Manos. DFT Insights into the Competitive Adsorption of Sulfur- and Nitrogen-Containing Compounds and Hydrocarbons on Co-Promoted Molybdenum Sulfide Catalysts. United States: N. p., 2016.
Web. doi:10.1021/acscatal.6b00058.
Rangarajan, Srinivas, & Mavrikakis, Manos. DFT Insights into the Competitive Adsorption of Sulfur- and Nitrogen-Containing Compounds and Hydrocarbons on Co-Promoted Molybdenum Sulfide Catalysts. United States. https://doi.org/10.1021/acscatal.6b00058
Rangarajan, Srinivas, and Mavrikakis, Manos. Thu .
"DFT Insights into the Competitive Adsorption of Sulfur- and Nitrogen-Containing Compounds and Hydrocarbons on Co-Promoted Molybdenum Sulfide Catalysts". United States. https://doi.org/10.1021/acscatal.6b00058. https://www.osti.gov/servlets/purl/1408882.
@article{osti_1408882,
title = {DFT Insights into the Competitive Adsorption of Sulfur- and Nitrogen-Containing Compounds and Hydrocarbons on Co-Promoted Molybdenum Sulfide Catalysts},
author = {Rangarajan, Srinivas and Mavrikakis, Manos},
abstractNote = {The adsorption of 20 nitrogen-/sulfur-containing and hydrocarbon compounds on the sulfur edge of cobalt-promoted molybdenum sulfide (CoMoS) catalyst was studied using density functional theory, accounting for van der Waals interactions, to elicit comparative structure–property trends across different classes of molecules relevant to hydrotreating. Unhindered organosulfur compounds preferentially adsorb on a “CUS-like” site formed by the dimerization of two neighboring sulfur atoms on the edge to create a vacancy. Nitrogen-containing compounds and 4,6-dimethyldibenzothiophene, however, prefer the brim sites. Binding energy trends indicate that nitrogen-containing compounds will inhibit hydrodesulfurization on the brim sites and, relatively weakly, on the CUS-like sites. Edge vacancies are,thus, likely to be essential for hydrodesulfurization of unhindered organosulfur compounds. Furthermore, van der Waals forces contribute significantly to the binding energy of compounds (up to 1.0 eV for large compounds such as alkyl-substituted acridines) on CoMoS.},
doi = {10.1021/acscatal.6b00058},
journal = {ACS Catalysis},
number = 5,
volume = 6,
place = {United States},
year = {Thu Apr 07 00:00:00 EDT 2016},
month = {Thu Apr 07 00:00:00 EDT 2016}
}
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Works referenced in this record:
Deep HDS of diesel fuel: chemistry and catalysis
journal, November 2004
- Ho, Teh C.
- Catalysis Today, Vol. 98, Issue 1-2
Recent advances in the science and technology of ultra low sulfur diesel (ULSD) production
journal, July 2010
- Stanislaus, Antony; Marafi, Abdulazeem; Rana, Mohan S.
- Catalysis Today, Vol. 153, Issue 1-2
Mechanisms of hydrodesulfurization and hydrodenitrogenation
journal, January 2006
- Prins, R.; Egorova, M.; Röthlisberger, A.
- Catalysis Today, Vol. 111, Issue 1-2
Poisoning of thiophene hydrodesulfurization by nitrogen compounds
journal, April 1988
- Lavopa, V.
- Journal of Catalysis, Vol. 110, Issue 2
Reactivities, reaction networks, and kinetics in high-pressure catalytic hydroprocessing
journal, September 1991
- Girgis, Michael J.; Gates, Bruce C.
- Industrial & Engineering Chemistry Research, Vol. 30, Issue 9
Inhibition of the Hydrogenation and Hydrodesulfurization Reactions by Nitrogen Compounds over NiMo/Al2O3
journal, April 2008
- Beltramone, A. R.; Crossley, S.; Resasco, D. E.
- Catalysis Letters, Vol. 123, Issue 3-4
Inhibition of nitrogen compounds on the hydrodesulfurization of substituted dibenzothiophenes in light cycle oil
journal, August 2004
- Yang, Hong; Chen, Jinwen; Fairbridge, Craig
- Fuel Processing Technology, Vol. 85, Issue 12
Poisoning effect of nitrogen compounds on the performance of CoMoS/Al2O3 catalyst in the hydrodesulfurization of dibenzothiophene, 4-methyldibenzothiophene, and 4,6-dimethyldibenzothiophene
journal, December 2001
- Kwak, Chan; Lee, Jung Joon; Bae, Jun Sang
- Applied Catalysis B: Environmental, Vol. 35, Issue 1
Poisoning effect of nitrogen compounds on dibenzothiophene hydrodesulfurization on sulfided NiMo/Al2O3 catalysts and relation to gas-phase basicity
journal, January 1986
- Nagai, M.
- Journal of Catalysis, Vol. 97, Issue 1
Organic nitrogen compounds in gas oil blends, their hydrotreated products and the importance to hydrotreatment
journal, February 2001
- Zeuthen, Per; Knudsen, Kim G.; Whitehurst, D. D.
- Catalysis Today, Vol. 65, Issue 2-4
Competitive hydrodesulfurization of 4,6-dimethyldibenzothiophene, hydrodenitrogenation of 2-methylpyridine, and hydrogenation of naphthalene over sulfided NiMo/γ-Al2O3
journal, June 2004
- Egorova, Marina; Prins, Roel
- Journal of Catalysis, Vol. 224, Issue 2
Mutual influence of the HDS of dibenzothiophene and HDN of 2-methylpyridine
journal, January 2004
- Egorova, M.
- Journal of Catalysis, Vol. 221, Issue 1
Inhibition effects observed between dibenzothiophene and carbazole during the hydrotreating process
journal, July 2004
- Laredo, G.
- Applied Catalysis A: General, Vol. 265, Issue 2
Inhibition effects of nitrogen compounds on the hydrodesulfurization of dibenzothiophene: Part 2
journal, April 2003
- Laredo, Georgina C.; Altamirano, Efraı́n; De los Reyes, J. Antonio
- Applied Catalysis A: General, Vol. 243, Issue 2
Inhibition effects of nitrogen compounds on the hydrodesulfurization of dibenzothiophene
journal, February 2001
- Laredo S., Georgina C.; De los Reyes H., J. Antonio; Luis Cano D., J.
- Applied Catalysis A: General, Vol. 207, Issue 1-2
Correlating the electronic properties and HDN reactivities of organonitrogen compounds: an ab initio DFT study
journal, November 2004
- Sun, Mingyong; Nelson, Alan E.; Adjaye, John
- Journal of Molecular Catalysis A: Chemical, Vol. 222, Issue 1-2
Adsorption Thermodynamics of Sulfur- and Nitrogen-containing Molecules on NiMoS: A DFT Study
journal, July 2006
- Sun, Mingyong; Nelson, Alan E.; Adjaye, John
- Catalysis Letters, Vol. 109, Issue 3-4
Adsorption and hydrogenation of pyridine and pyrrole on NiMoS: an ab initio density-functional theory study
journal, April 2005
- Sun, M.; Nelson, A.; Adjaye, J.
- Journal of Catalysis, Vol. 231, Issue 1
First principles study of heavy oil organonitrogen adsorption on NiMoS hydrotreating catalysts
journal, November 2005
- Sun, Mingyong; Nelson, Alan E.; Adjaye, John
- Catalysis Today, Vol. 109, Issue 1-4
A density functional study of inhibition of the HDS hydrogenation pathway by pyridine, benzene, and H2S on MoS2-based catalysts
journal, January 2006
- Logadóttir, Áshildur; Moses, Poul Georg; Hinnemann, Berit
- Catalysis Today, Vol. 111, Issue 1-2
Adsorption of nitrogen- and sulfur-containing compounds on NiMoS for hydrotreating reactions: A DFT and vdW-corrected study
journal, September 2015
- Rangarajan, Srinivas; Mavrikakis, Manos
- AIChE Journal, Vol. 61, Issue 12
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
Promoter Sensitive Shapes of Co(Ni)MoS Nanocatalysts in Sulfo-Reductive Conditions
journal, November 2002
- Schweiger, Hannes; Raybaud, Pascal; Toulhoat, Hervé
- Journal of Catalysis, Vol. 212, Issue 1
Mixed sites and promoter segregation: A DFT study of the manifestation of Le Chatelier's principle for the Co(Ni)MoS active phase in reaction conditions
journal, January 2008
- Krebs, E.; Silvi, B.; Raybaud, P.
- Catalysis Today, Vol. 130, Issue 1
Location and coordination of promoter atoms in Co- and Ni-promoted MoS2-based hydrotreating catalysts
journal, July 2007
- Lauritsen, J.; Kibsgaard, J.; Olesen, G.
- Journal of Catalysis, Vol. 249, Issue 2
The role of Co–Mo–S type structures in hydrotreating catalysts
journal, April 2007
- Topsøe, Henrik
- Applied Catalysis A: General, Vol. 322
Comparative atomic-scale analysis of promotional effects by late 3d-transition metals in MoS2 hydrotreating catalysts
journal, June 2010
- Kibsgaard, Jakob; Tuxen, Anders; Knudsen, Kim G.
- Journal of Catalysis, Vol. 272, Issue 2
On the structure and composition of the phosphosulfide overlayer on Ni2P at hydrotreating conditions
journal, July 2006
- Nelson, A.; Sun, M.; Junaid, A.
- Journal of Catalysis, Vol. 241, Issue 1
Characterization of the structures and active sites in sulfided Co$z.sbnd;Mo/Al2O3 and Ni$z.sbnd;Mo/Al2O3 catalysts by NO chemisorption
journal, December 1983
- Topsoe, N.
- Journal of Catalysis, Vol. 84, Issue 2
Optimal promoter edge decoration of CoMoS catalysts: A combined theoretical and experimental study
journal, January 2008
- Gandubert, A. D.; Krebs, E.; Legens, C.
- Catalysis Today, Vol. 130, Issue 1
Atomic and electronic structure of nanoparticles
journal, February 2003
- Bollinger, M. V.; Jacobsen, K. W.; Nørskov, J. K.
- Physical Review B, Vol. 67, Issue 8
A Density Functional Study of the Chemical Differences between Type I and Type II MoS 2 -Based Structures in Hydrotreating Catalysts †
journal, February 2005
- Hinnemann, Berit; Nørskov, Jens K.; Topsøe, Henrik
- The Journal of Physical Chemistry B, Vol. 109, Issue 6
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
Shape and Edge Sites Modifications of MoS2 Catalytic Nanoparticles Induced by Working Conditions: A Theoretical Study
journal, April 2002
- Schweiger, Hannes; Raybaud, Pascal; Kresse, Georg
- Journal of Catalysis, Vol. 207, Issue 1
Structure, Energetics, and Electronic Properties of the Surface of a Promoted MoS2 Catalyst: An ab Initio Local Density Functional Study
journal, February 2000
- Raybaud, P.; Hafner, J.; Kresse, G.
- Journal of Catalysis, Vol. 190, Issue 1
Ab-initio energy profiles for thiophene HDS on the MoS2 (1010) edge-surface
book, January 1999
- Raybaud, P.; Hafner, J.; Kresse, G.
- Studies in Surface Science and Catalysis
Vacancy Formation on MoS 2 Hydrodesulfurization Catalyst: DFT Study of the Mechanism
journal, April 2003
- Paul, Jean-François; Payen, Edmond
- The Journal of Physical Chemistry B, Vol. 107, Issue 17
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
Hydrogen Activation on Mo-Based Sulfide Catalysts, a Periodic DFT Study
journal, June 2002
- Travert, Arnaud; Nakamura, Hiroyuki; van Santen, Rutger A.
- Journal of the American Chemical Society, Vol. 124, Issue 24
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
The single-layered morphology of supported MoS2-based catalysts—The role of the cobalt promoter and its effects in the hydrodesulfurization of dibenzothiophene
journal, July 2008
- Berhault, Gilles; Perez De la Rosa, Myriam; Mehta, Apurva
- Applied Catalysis A: General, Vol. 345, Issue 1
Active sites and support effects in hydrodesulfurization catalysts
journal, August 1986
- Topsøe, Henrik; Clausen, Bjerne S.
- Applied Catalysis, Vol. 25, Issue 1-2
Atomic-scale insight into structure and morphology changes of MoS2 nanoclusters in hydrotreating catalysts
journal, January 2004
- Lauritsen, J. V.; Bollinger, M. V.; Lægsgaard, E.
- Journal of Catalysis, Vol. 221, Issue 2, p. 510-522
Recent STM, DFT and HAADF-STEM studies of sulfide-based hydrotreating catalysts: Insight into mechanistic, structural and particle size effects
journal, January 2008
- Besenbacher, F.; Brorson, M.; Clausen, B. S.
- Catalysis Today, Vol. 130, Issue 1
A geometrical model of the active phase of hydrotreating catalysts
journal, December 1984
- Kasztelan, S.; Toulhoat, H.; Grimblot, J.
- Applied Catalysis, Vol. 13, Issue 1
Structure-Function Relations in Molybdenum Sulfide Catalysts: The "Rim-Edge" Model
journal, October 1994
- Daage, M.; Chianelli, R. R.
- Journal of Catalysis, Vol. 149, Issue 2
Recent density functional studies of hydrodesulfurization catalysts: insight into structure and mechanism
journal, January 2008
- Hinnemann, Berit; Moses, Poul Georg; Nørskov, Jens K.
- Journal of Physics: Condensed Matter, Vol. 20, Issue 6
Corrigendum to “The hydrogenation and direct desulfurization reaction pathway in thiophene hydrodesulfurization over MoS2 catalysts at realistic conditions: A density functional study” [J. Catal. 248 (2007) 188]
journal, November 2008
- Moses, Poul Georg; Hinnemann, Berit; Topsøe, Henrik
- Journal of Catalysis, Vol. 260, Issue 1
Atomic-scale insight into the origin of pyridine inhibition of MoS2-based hydrotreating catalysts
journal, May 2010
- Temel, Burcin; Tuxen, Anders K.; Kibsgaard, Jakob
- Journal of Catalysis, Vol. 271, Issue 2
The effect of Co-promotion on MoS2 catalysts for hydrodesulfurization of thiophene: A density functional study
journal, December 2009
- Moses, Poul Georg; Hinnemann, Berit; Topsøe, Henrik
- Journal of Catalysis, Vol. 268, Issue 2
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996
- Kresse, G.; Furthmüller, J.
- Computational Materials Science, Vol. 6, Issue 1, p. 15-50
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
Erratum: Atoms, molecules, solids, and surfaces: Applications of the generalized gradient approximation for exchange and correlation
journal, August 1993
- Perdew, John P.; Chevary, J. A.; Vosko, S. H.
- Physical Review B, Vol. 48, Issue 7
Adsorbate-substrate and adsorbate-adsorbate interactions of Na and K adlayers on Al(111)
journal, December 1992
- Neugebauer, Jörg; Scheffler, Matthias
- Physical Review B, Vol. 46, Issue 24
Ab initio density functional studies of transition-metal sulphides: I. Crystal structure and cohesive properties
journal, December 1997
- Raybaud, P.; Kresse, G.; Hafner, J.
- Journal of Physics: Condensed Matter, Vol. 9, Issue 50
Ab initio density functional studies of transition-metal sulphides: II. Electronic structure
journal, December 1997
- Raybaud, P.; Hafner, J.; Kresse, G.
- Journal of Physics: Condensed Matter, Vol. 9, Issue 50
Van der Waals density functionals applied to solids
journal, May 2011
- Klimeš, Jiří; Bowler, David R.; Michaelides, Angelos
- Physical Review B, Vol. 83, Issue 19
Chemical accuracy for the van der Waals density functional
journal, December 2009
- Klimeš, Jiří; Bowler, David R.; Michaelides, Angelos
- Journal of Physics: Condensed Matter, Vol. 22, Issue 2
Atomic-scale insight into adsorption of sterically hindered dibenzothiophenes on MoS2 and Co–Mo–S hydrotreating catalysts
journal, November 2012
- Tuxen, Anders K.; Füchtbauer, Henrik G.; Temel, Burcin
- Journal of Catalysis, Vol. 295
Reactivities in deep catalytic hydrodesulfurization: challenges, opportunities, and the importance of 4-methyldibenzothiophene and 4,6-dimethyldibenzothiophene
journal, January 1997
- Gates, B. C.; Topsøe, Henrik
- Polyhedron, Vol. 16, Issue 18
Hydrodesulfurization of dibenzothiophene and 4,6-dimethyldibenzothiophene over sulfided NiMo/?-Al2O3, CoMo/?-Al2O3, and Mo/?-Al2O3 catalysts
journal, July 2004
- Egorova, M.
- Journal of Catalysis, Vol. 225, Issue 2
Proton Affinity and Protonation Sites of Aniline. Energetic Behavior and Density Functional Reactivity Indices
journal, April 2000
- Russo, Nino; Toscano, Marirosa; Grand, André
- The Journal of Physical Chemistry A, Vol. 104, Issue 17
The Protonation Site of Aniline Revisited: A 'Torture Test' for Electron Correlation Methods
book, March 2007
- Boese, A. Daniel; Martin, Jan M. L.; De Proft, Frank
- ACS Symposium Series
Theoretical Model Calculations of the Proton Affinities of Aminoalkanes, Aniline, and Pyridine
journal, January 1996
- Hillebrand, C.; Klessinger, M.; Eckert-Maksić, M.
- The Journal of Physical Chemistry, Vol. 100, Issue 23
Advances in Determining the Absolute Proton Affinities of Neutral Organic Molecules in the Gas Phase and Their Interpretation: A Theoretical Account
journal, June 2012
- Maksić, Zvonimir B.; Kovačević, Borislav; Vianello, Robert
- Chemical Reviews, Vol. 112, Issue 10
The role of Ni and Co promoters in the simultaneous HDS of dibenzothiophene and HDN of amines over Mo/γ-Al2O3 catalysts
journal, July 2006
- Egorova, M.; Prins, R.
- Journal of Catalysis, Vol. 241, Issue 1
Reactivity of olefins and inhibition effect on the hydrodesulfurization of a model FCC naphtha
journal, August 2015
- Morales-Valencia, Edgar M.; Baldovino-Medrano, Víctor G.; Giraldo, Sonia A.
- Fuel, Vol. 153
Hydrodesulfurization of Catalytic Cracked Gasoline. 2. The Difference between HDS Active Site and Olefin Hydrogenation Active Site
journal, December 1997
- Hatanaka, S.; Yamada, M.; Sadakane, O.
- Industrial & Engineering Chemistry Research, Vol. 36, Issue 12
Evidence of Br�nsted acidity on sulfided promoted and unpromoted Mo/Al2O3 catalysts
journal, September 1989
- Topsoe, N.
- Journal of Catalysis, Vol. 119, Issue 1
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journal, June 2018
- Grønborg, Signe S.; Salazar, Norberto; Bruix, Albert
- Nature Communications, Vol. 9, Issue 1
Co-Processing of Jatropha-Derived Bio-Oil with Petroleum Distillates over Mesoporous CoMo and NiMo Sulfide Catalysts
journal, February 2018
- Chen, Shih-Yuan; Nishi, Masayasu; Mochizuki, Takehisa
- Catalysts, Vol. 8, Issue 2
Insight into ethylene interactions with molybdenum suboxide cluster anions from photoelectron spectra of chemifragments
journal, February 2018
- Schaugaard, Richard N.; Topolski, Josey E.; Ray, Manisha
- The Journal of Chemical Physics, Vol. 148, Issue 5
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journal, August 2020
- Salazar, Norberto; Rangarajan, Srinivas; Rodríguez-Fernández, Jonathan
- Nature Communications, Vol. 11, Issue 1