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Impact Of Ni Promotion On The Hydrogenation Pathways Of Phenanthrene On MoS2/γ-Al2O3

Eva Schachtl, Jong Suk Yoo, O. Gutiérrez, F. Studt, J. Lercher
Published 2017 · Chemistry

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Abstract The reaction network and elementary steps of the hydrogenation of phenanthrene are explored on parent and Ni-promoted MoS 2 /γ-Al 2 O 3 . Two pathways were identified, i.e., Path 1: Phenanthrene ⇌ 9,10-dihydrophenanthrene (DiHPhe) → 1,2,3,4,4a,9,10,10a-octahydro-phenanthrene ( asym OHPhe), and Path 2: Phenanthrene → 1,2,3,4-tetrahydrophenanthrene (TetHPhe) → 1,2,3,4,5,6,7,8-octahydrophenanthrene. The steps TetHPhe →  asym OHPhe (hydrogenation), and DiHPhe → TetHPhe (hydrogenation-isomerization) become notable at phenanthrene conversions above 20%. The reaction preferentially proceeds via Path 1 (90% selectivity) on MoS 2 /Al 2 O 3 . Ni promotion (Ni/(Ni + Mo) molar ratio of 0.3 at the edges on MoS 2 ) increases the hydrogenation activity per active edge twofold and leads to 50% selectivity to both pathways. The reaction orders in H 2 vary from ∼0.8 on MoS 2 /Al 2 O 3 to ∼1.2 on Ni-MoS 2 /Al 2 O 3 , whereas the reaction orders in phenanthrene (∼0.6) hardly depend on Ni promotion. The reaction orders in H 2 S are zero on MoS 2 /Al 2 O 3 and slightly negative on Ni-MoS 2 /Al 2 O 3 . DFT calculations indicate that phenanthrene is preferentially adsorbed parallel to the basal planes, while H is located at the edges perpendicular to the basal planes. Theory also suggests that Ni atoms, incorporated preferentially on the S-edges, increase the stability of hydrogenated intermediates. Hydrogenation of phenanthrene proceeds through quasi-equilibrated adsorption of the reactants followed by consecutive addition of hydrogen pairs to the adsorbed hydrocarbon. The rate determining steps for the formation of DiHPhe and TetHPhe are the addition of the first and second hydrogen pair, respectively. The concentration of SH groups (activated H at the edges) increases with Ni promotion linearly correlating the rates of Path 1 and Path 2, albeit with different functions. The enhancing effect of Ni on Path 2 is attributed to accelerated hydrogen addition to adsorbed hydrocarbons without important changes in their coverages.
This paper references
10.1016/J.JCAT.2011.04.001
Effect of the support on the high activity of the (Ni)Mo/ZrO2–SBA-15 catalyst in the simultaneous hydrodesulfurization of DBT and 4,6-DMDBT
O. Gutiérrez (2011)
10.1021/JP0536549
CO adsorption on CoMo and NiMo sulfide catalysts: a combined IR and DFT study.
A. Travert (2006)
10.1016/0021-9517(83)90010-6
Characterization of the structures and active sites in sulfided CoMoAl2O3 and NiMoAl2O3 catalysts by NO chemisorption
Nan-Yu Topsøe (1983)
10.1016/J.JCAT.2007.04.013
Location and coordination of promoter atoms in Co- and Ni-promoted MoS2-based hydrotreating catalysts
J. V. Lauritsen (2007)
10.1021/acs.jpclett.5b01217
Pathways for H2 Activation on (Ni)-MoS2 Catalysts.
Eva Schachtl (2015)
10.1021/ACSCATAL.6B02753
Carbon–Carbon Bond Scission Pathways in the Deoxygenation of Fatty Acids on Transition-Metal Sulfides
Manuel F. Wagenhofer (2017)
10.1063/1.3086040
Density functional study of the adsorption and van der Waals binding of aromatic and conjugated compounds on the basal plane of MoS(2).
P. G. Moses (2009)
10.1021/IE501397N
Kinetics of Phenanthrene Hydrogenation System over CoMo/Al2O3 Catalyst
Huibin Yang (2014)
10.1002/cctc.201300856
γ‐Al2O3‐Supported and Unsupported (Ni)MoS2 for the Hydrodenitrogenation of Quinoline in the Presence of Dibenzothiophene
J. Hein (2014)
10.1006/JCAT.1993.1056
FTIR Studies of Mo/Al2O3-Based Catalysts: II. Evidence for the Presence of SH Groups and Their Role in Acidity and Activity
N. Topsoe (1993)
10.1039/C4CY01162G
Rational design of MoS 2 catalysts: tuning the structure and activity via transition metal doping
C. Tsai (2015)
10.1039/c001069c
Compensation effect and volcano curve in toluene hydrogenation catalyzed by transition metal sulfides.
Noëlle Bleuzen Guernalec (2010)
10.1002/cctc.201500706
Understanding Ni Promotion of MoS2/γ‐Al2O3 and its Implications for the Hydrogenation of Phenanthrene
Eva Schachtl (2015)
10.1016/J.JCAT.2011.02.002
Spectroscopy, microscopy and theoretical study of NO adsorption on MoS2 and Co–Mo–S hydrotreating catalysts
Nan-Yu Topsøe (2011)
10.1006/JCAT.1999.2598
DFT Calculations of Unpromoted and Promoted MoS2-Based Hydrodesulfurization Catalysts
L. Byskov (1999)
10.1021/JP0462052
Structure of the active sites of Co-Mo Hydrodesulfurization catalysts as studied by magnetic susceptibility measurement and NO adsorption.
Y. Okamoto (2005)
10.1016/J.JCAT.2014.12.034
Atom-resolved scanning tunneling microscopy investigations of molecular adsorption on MoS2 and CoMoS hydrodesulfurization catalysts
J. V. Lauritsen (2015)
10.1016/J.CATTOD.2009.03.023
On the dynamic model of promoted molybdenum sulfide catalysts
V. M. Kogan (2010)
10.1016/J.JCAT.2010.07.020
Temperature-programmed reduction of unpromoted MoS2-based hydrodesulfurization catalysts: First-principles kinetic Monte Carlo simulations and comparison with experiments
Nicolas Dinter (2010)
10.1016/J.JCAT.2005.05.009
Ab initio DFT study of hydrogen dissociation on MoS2, NiMoS, and CoMoS: mechanism, kinetics, and vibrational frequencies
M. Sun (2005)
10.1007/s10562-014-1279-4
Trends in Hydrodesulfurization Catalysis Based on Realistic Surface Models
P. G. Moses (2014)
10.1006/JCAT.1997.1558
Deuterium Tracer Studies on Hydrotreating Catalysts—Isotopic Exchange between Hydrogen and Hydrogen Sulfide on Sulfided NiMo/Al2O3
C. Thomas (1997)
10.1016/J.JCAT.2011.03.017
Free-energy profiles along reduction pathways of MoS2 M-edge and S-edge by dihydrogen: A first-principles study
P. Prodhomme (2011)
10.1006/JCAT.1999.2790
Alkyldibenzothiophenes Hydrodesulfurization-Promoter Effect, Reactivity, and Reaction Mechanism
F. Bataille (2000)
10.1016/J.JCAT.2016.05.004
Improved promoter effect in NiWS catalysts through a molecular approach and an optimized Ni edge decoration
T. Alphazan (2016)
10.1016/J.JCAT.2007.02.028
The hydrogenation and direct desulfurization reaction pathway in thiophene hydrodesulfurization over MoS2 catalysts at realistic conditions: A density functional study
P. G. Moses (2007)
10.1023/A:1019005312287
Deuterium tracer studies on hydrotreating catalysts. 3. Influence of nickel on the rates of H2–D3 and H2S–D2 isotopic exchange
C. Thomas (1999)
10.1016/J.JCAT.2012.08.004
Atomic-scale insight into adsorption of sterically hindered dibenzothiophenes on MoS2 and Co–Mo–S hydrotreating catalysts
A. Tuxen (2012)
10.1006/JCAT.1999.2587
Hydrogen–Deuterium Equilibration over Transition Metal Sulfide Catalysts: On the Synergetic Effect in CoMo Catalysts
Ejm Emiel Hensen (1999)
10.1021/IE8004258
Simultaneous Hydrogenation of Multiring Aromatic Compounds over NiMo Catalyst
A. Beltramone (2008)
10.1021/JA011634O
Hydrogen activation on Mo-based sulfide catalysts, a periodic DFT study.
A. Travert (2002)
10.1016/J.JCAT.2009.09.016
The effect of Co-promotion on MoS2 catalysts for hydrodesulfurization of thiophene: A density functional study
P. G. Moses (2009)
10.1021/IE00034A008
Catalytic hydroprocessing of simulated heavy coal liquids; 2: Reaction networks of aromatic hydrocarbons and sulfur and oxygen heterocyclic compounds
Michael J. Girgis (1994)
10.1038/1811428a0
‘Comprehensive’ Inorganic Chemistry
J. Bailar (1958)
10.1016/J.CATTOD.2008.09.041
Unsupported transition metal sulfide catalysts: 100 years of science and application
R. Chianelli (2009)
10.1016/S1381-1169(00)00404-0
Molecular aspects of the H2 activation on MoS2 based catalysts — the role of dynamic surface arrangements
L. Byskov (2000)
10.1016/J.CATTOD.2007.06.074
Naphthalene hydrogenation over a NiMo/γ-Al2O3 catalyst: Experimental study and kinetic modelling
C. C. Romero (2008)
10.1081/CR-120015483
HYDROGEN ACTIVATION BY TRANSITION METAL SULFIDES
M. Breysse (2002)
10.1016/J.JCAT.2014.01.014
Effects of composition and morphology of active phase of CoMo/Al2O3 catalysts prepared using Co2Mo10–heteropolyacid and chelating agents on their catalytic properties in HDS and HYD reactions
P. Nikulshin (2014)
10.1088/0953-8984/21/39/395502
QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials.
P. Giannozzi (2009)
10.1039/c4cp01237b
Active edge sites in MoSe2 and WSe2 catalysts for the hydrogen evolution reaction: a density functional study.
C. Tsai (2014)
10.1109/5992.998641
An object-oriented scripting interface to a legacy electronic structure code
S. R. Bahn (2002)
10.1021/IE00098A025
The delplot technique: a new method for reaction pathway analysis
N. Bhore (1990)
10.1080/01614949408013921
Aromatic Hydrogenation Catalysis: A Review
A. Stanislaus (1994)
10.1021/IE00057A001
Reactivities, reaction networks, and kinetics in high-pressure catalytic hydroprocessing
M. Girgis (1991)
10.1016/J.JCAT.2011.05.017
Selective poisoning of the direct denitrogenation route in o-propylaniline HDN by DBT on Mo and NiMo/γ-Al2O3 sulfide catalysts
A. Hrabar (2011)
10.1021/CS500034D
Effects of the Support on the Performance and Promotion of (Ni)MoS2 Catalysts for Simultaneous Hydrodenitrogenation and Hydrodesulfurization
O. Gutiérrez (2014)
10.2516/OGST:2006022A
Periodic Trends Transition Metal Sulfide Catalysis: Intuition and Theory
R. Chianelli (2006)
10.1016/S0009-2509(05)80015-6
Hydrogenation of polynuclear aromatic hydrocarbons. 2. quantitative structure/reactivity correlations
S. C. Korre (1994)
10.1021/EF020283B
Elucidation of Retarding Effects of Sulfur and Nitrogen Compounds on Aromatic Compounds Hydrogenation
A. Ishihara (2003)
10.1021/IE00040A008
Polynuclear Aromatic Hydrocarbons Hydrogenation. 1. Experimental Reaction Pathways and Kinetics
S. C. Korre (1995)



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Hydrogen assisted catalytic biomass pyrolysis for green fuels
Magnus Zingler Stummann (2017)
10.1007/s11244-019-01169-y
The Influence of Active Phase Loading on the Hydrodeoxygenation (HDO) of Ethylene Glycol over Promoted MoS2/MgAl2O4 Catalysts
T. H. Dabros (2019)
Hydrodeoxygenation (HDO) of aliphatic oxygenates
T. H. Dabros (2020)
10.3390/CATAL9060521
Hydrodeoxygenation (HDO) of Aliphatic Oxygenates and Phenol over NiMo/MgAl2O4: Reactivity, Inhibition, and Catalyst Reactivation
T. H. Dabros (2019)
Hydrogen Assisted Catalytic Biomass Pyrolysis for Green Fuels-DTU Orbit (07/11/2019)
Stummann (2018)
10.1016/J.FUEL.2018.10.154
Designing supported NiMoS2 catalysts for hydrocracking of vacuum residue
Han-Beyol Park (2019)
10.1016/j.fuel.2019.116807
Catalytic hydropyrolysis of biomass using supported CoMo catalysts – Effect of metal loading and support acidity
Magnus Zingler Stummann (2020)
10.1021/acs.inorgchem.7b01420
Heterolytic H-H and H-B Bond Cleavage Reactions of {(IPr)Ni(μ-S)}2.
Frank Olechnowicz (2017)
10.1016/J.JPCS.2019.109123
A promising and new single-atom catalyst for CO oxidation: Si-embedded MoS2 monolayer
M. Esrafili (2019)
10.1016/j.fuel.2020.118270
Chemical insight into nano-catalytic in-situ upgrading and recovery of heavy oil
Seyed Moein Elahi (2020)
10.1002/anie.201808428
Active Sites on Nickel-Promoted Transition-Metal Sulfides That Catalyze Hydrogenation of Aromatic Compounds.
Wanqiu Luo (2018)
10.1016/J.FUPROC.2019.05.037
New insights into the effect of pressure on catalytic hydropyrolysis of biomass
Magnus Zingler Stummann (2019)
10.1016/J.PECS.2018.05.002
Transportation fuels from biomass fast pyrolysis, catalytic hydrodeoxygenation, and catalytic fast hydropyrolysis
T. H. Dabros (2018)
10.1016/j.jcat.2019.09.034
On the enhanced catalytic activity of acid-treated, trimetallic Ni-Mo-W sulfides for quinoline hydrodenitrogenation
Sylvia Albersberger (2019)
10.1016/J.CES.2020.116191
Insight into the Basic Strength-dependent Catalytic Performance in Aqueous Phase Oxidation of Glycerol to Glyceric acid
Hao Yan (2020)
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