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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
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)
CO adsorption on CoMo and NiMo sulfide catalysts: a combined IR and DFT study.
A. Travert (2006)
Characterization of the structures and active sites in sulfided CoMoAl2O3 and NiMoAl2O3 catalysts by NO chemisorption
Nan-Yu Topsøe (1983)
Location and coordination of promoter atoms in Co- and Ni-promoted MoS2-based hydrotreating catalysts
J. V. Lauritsen (2007)
Pathways for H2 Activation on (Ni)-MoS2 Catalysts.
Eva Schachtl (2015)
Carbon–Carbon Bond Scission Pathways in the Deoxygenation of Fatty Acids on Transition-Metal Sulfides
Manuel F. Wagenhofer (2017)
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)
Kinetics of Phenanthrene Hydrogenation System over CoMo/Al2O3 Catalyst
Huibin Yang (2014)
γ‐Al2O3‐Supported and Unsupported (Ni)MoS2 for the Hydrodenitrogenation of Quinoline in the Presence of Dibenzothiophene
J. Hein (2014)
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)
Rational design of MoS 2 catalysts: tuning the structure and activity via transition metal doping
C. Tsai (2015)
Compensation effect and volcano curve in toluene hydrogenation catalyzed by transition metal sulfides.
Noëlle Bleuzen Guernalec (2010)
Understanding Ni Promotion of MoS2/γ‐Al2O3 and its Implications for the Hydrogenation of Phenanthrene
Eva Schachtl (2015)
Spectroscopy, microscopy and theoretical study of NO adsorption on MoS2 and Co–Mo–S hydrotreating catalysts
Nan-Yu Topsøe (2011)
DFT Calculations of Unpromoted and Promoted MoS2-Based Hydrodesulfurization Catalysts
L. Byskov (1999)
Structure of the active sites of Co-Mo Hydrodesulfurization catalysts as studied by magnetic susceptibility measurement and NO adsorption.
Y. Okamoto (2005)
Atom-resolved scanning tunneling microscopy investigations of molecular adsorption on MoS2 and CoMoS hydrodesulfurization catalysts
J. V. Lauritsen (2015)
On the dynamic model of promoted molybdenum sulfide catalysts
V. M. Kogan (2010)
Temperature-programmed reduction of unpromoted MoS2-based hydrodesulfurization catalysts: First-principles kinetic Monte Carlo simulations and comparison with experiments
Nicolas Dinter (2010)
Ab initio DFT study of hydrogen dissociation on MoS2, NiMoS, and CoMoS: mechanism, kinetics, and vibrational frequencies
M. Sun (2005)
Trends in Hydrodesulfurization Catalysis Based on Realistic Surface Models
P. G. Moses (2014)
Deuterium Tracer Studies on Hydrotreating Catalysts—Isotopic Exchange between Hydrogen and Hydrogen Sulfide on Sulfided NiMo/Al2O3
C. Thomas (1997)
Free-energy profiles along reduction pathways of MoS2 M-edge and S-edge by dihydrogen: A first-principles study
P. Prodhomme (2011)
Alkyldibenzothiophenes Hydrodesulfurization-Promoter Effect, Reactivity, and Reaction Mechanism
F. Bataille (2000)
Improved promoter effect in NiWS catalysts through a molecular approach and an optimized Ni edge decoration
T. Alphazan (2016)
The hydrogenation and direct desulfurization reaction pathway in thiophene hydrodesulfurization over MoS2 catalysts at realistic conditions: A density functional study
P. G. Moses (2007)
Deuterium tracer studies on hydrotreating catalysts. 3. Influence of nickel on the rates of H2–D3 and H2S–D2 isotopic exchange
C. Thomas (1999)
Atomic-scale insight into adsorption of sterically hindered dibenzothiophenes on MoS2 and Co–Mo–S hydrotreating catalysts
A. Tuxen (2012)
Hydrogen–Deuterium Equilibration over Transition Metal Sulfide Catalysts: On the Synergetic Effect in CoMo Catalysts
Ejm Emiel Hensen (1999)
Simultaneous Hydrogenation of Multiring Aromatic Compounds over NiMo Catalyst
A. Beltramone (2008)
Hydrogen activation on Mo-based sulfide catalysts, a periodic DFT study.
A. Travert (2002)
The effect of Co-promotion on MoS2 catalysts for hydrodesulfurization of thiophene: A density functional study
P. G. Moses (2009)
Catalytic hydroprocessing of simulated heavy coal liquids; 2: Reaction networks of aromatic hydrocarbons and sulfur and oxygen heterocyclic compounds
Michael J. Girgis (1994)
‘Comprehensive’ Inorganic Chemistry
J. Bailar (1958)
Unsupported transition metal sulfide catalysts: 100 years of science and application
R. Chianelli (2009)
Molecular aspects of the H2 activation on MoS2 based catalysts — the role of dynamic surface arrangements
L. Byskov (2000)
Naphthalene hydrogenation over a NiMo/γ-Al2O3 catalyst: Experimental study and kinetic modelling
C. C. Romero (2008)
M. Breysse (2002)
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)
QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials.
P. Giannozzi (2009)
Active edge sites in MoSe2 and WSe2 catalysts for the hydrogen evolution reaction: a density functional study.
C. Tsai (2014)
An object-oriented scripting interface to a legacy electronic structure code
S. R. Bahn (2002)
The delplot technique: a new method for reaction pathway analysis
N. Bhore (1990)
Aromatic Hydrogenation Catalysis: A Review
A. Stanislaus (1994)
Reactivities, reaction networks, and kinetics in high-pressure catalytic hydroprocessing
M. Girgis (1991)
Selective poisoning of the direct denitrogenation route in o-propylaniline HDN by DBT on Mo and NiMo/γ-Al2O3 sulfide catalysts
A. Hrabar (2011)
Effects of the Support on the Performance and Promotion of (Ni)MoS2 Catalysts for Simultaneous Hydrodenitrogenation and Hydrodesulfurization
O. Gutiérrez (2014)
Periodic Trends Transition Metal Sulfide Catalysis: Intuition and Theory
R. Chianelli (2006)
Hydrogenation of polynuclear aromatic hydrocarbons. 2. quantitative structure/reactivity correlations
S. C. Korre (1994)
Elucidation of Retarding Effects of Sulfur and Nitrogen Compounds on Aromatic Compounds Hydrogenation
A. Ishihara (2003)
Polynuclear Aromatic Hydrocarbons Hydrogenation. 1. Experimental Reaction Pathways and Kinetics
S. C. Korre (1995)

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On the enhanced catalytic activity of acid-treated, trimetallic Ni-Mo-W sulfides for quinoline hydrodenitrogenation
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