Phenol Deoxygenation Mechanisms on Fe(110) and Pd(111)

Hensley, Alyssa J. R.; Wang, Yong; McEwen, Jean-Sabin

doi:10.1021/cs501403w

Phenol Deoxygenation Mechanisms on Fe(110) and Pd(111)

Journal Article · Tue Dec 02 00:00:00 EST 2014 · ACS Catalysis

DOI:https://doi.org/10.1021/cs501403w· OSTI ID:1772899

Hensley, Alyssa J. R. ^[1]; Wang, Yong ^[2]; McEwen, Jean-Sabin ^[3]

Washington State Univ., Pullman, WA (United States); Washington State University
Washington State Univ., Pullman, WA (United States); Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Washington State Univ., Pullman, WA (United States)

The catalytic deoxygenation of phenolic compounds has become a major area of interest in recent years as they are produced during the pyrolysis of lignin and are present in biofuels. Our previous work showed that a PdFe bimetallic catalyst was catalytically active for the deoxygenation of phenolics. In order to better understand and control the catalytic deoxygenation reaction of phenolics, the detailed surface reaction mechanisms are needed for phenol, a key intermediate in phenolic deoxygeantion. Here, we have examined five distinct reaction mechanisms for the deoxygenation of phenol on the Fe (110) and Pd (111) surfaces so as to identify the most likely deoxygenation mechanism on these surfaces. Here, our results show that the elementary phenol deoxygenation reaction step for each mechanism was highly endothermic on Pd (111) while the same mechanisms are exothermic on Fe (110). Based on the reaction energy studies, detailed mechanistic studies were performed on the Fe (110) surface and it was found that the most energetically and kinetically favorable reaction mechanism occurs via the direct cleavage of the C-O bond.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1772899

Journal Information:: ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 2 Vol. 5; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (58)

Direct versus Hydrogen-Assisted CO Dissociation on the Fe (100) Surface: a DFT Study Elahifard, Mohammad Reza; Jigato, Manuel Pérez; Niemantsverdriet, J. W. Hans ChemPhysChem, Vol. 13, Issue 1 https://doi.org/10.1002/cphc.201100759	journal	December 2011
Universality in Heterogeneous Catalysis Nørskov, J. K.; Bligaard, T.; Logadottir, A. Journal of Catalysis, Vol. 209, Issue 2 https://doi.org/10.1006/jcat.2002.3615	journal	July 2002
The Synergy of the Support Acid Function and the Metal Function in the Catalytic Hydrodeoxygenation of m-Cresol Foster, Andrew J.; Do, Phuong T. M.; Lobo, Raul F. Topics in Catalysis, Vol. 55, Issue 3-4 https://doi.org/10.1007/s11244-012-9781-7	journal	March 2012
Catalytic hydrodeoxygenation I. Conversions of o-, p-, and m-cresols Odebunmi, E. Journal of Catalysis, Vol. 80, Issue 1 https://doi.org/10.1016/0021-9517(83)90229-4	journal	March 1983
Characterization and upgrading of bio-oils produced by rapid thermal processing Maggi, Rosanna; Delmon, Bernard Biomass and Bioenergy, Vol. 7, Issue 1-6 https://doi.org/10.1016/0961-9534(94)00062-X	journal	January 1994
Catalytic hydrodeoxygenation Furimsky, Edward Applied Catalysis A: General, Vol. 199, Issue 2, p. 147-190 https://doi.org/10.1016/S0926-860X(99)00555-4	journal	June 2000
Vanadium catalyzed guaiacol deoxygenation Filley, J. Journal of Molecular Catalysis A: Chemical, Vol. 139, Issue 2-3 https://doi.org/10.1016/S1381-1169(98)00202-7	journal	March 1999
Simulation of phenol formation from benzene with a Pd membrane reactor: ab initio periodic density functional study Orita, Hideo; Itoh, Naotsugu Applied Catalysis A: General, Vol. 258, Issue 1 https://doi.org/10.1016/j.apcata.2003.08.001	journal	February 2004
Study of the “Fast SCR”-like mechanism of H2-assisted SCR of NOx with ammonia over Ag/Al2O3 Doronkin, Dmitry E.; Fogel, Sebastian; Tamm, Stefanie Applied Catalysis B: Environmental, Vol. 113-114 https://doi.org/10.1016/j.apcatb.2011.11.042	journal	February 2012
Guaiacol derivatives and inhibiting species adsorption over MoS2 and CoMoS catalysts under HDO conditions: A DFT study Badawi, Michael; Paul, Jean-François; Cristol, Sylvain Catalysis Communications, Vol. 12, Issue 10 https://doi.org/10.1016/j.catcom.2011.02.010	journal	May 2011
Bio-oil catalytic reforming without steam addition: Application to hydrogen production and studies on its mechanism Wang, Shurong; Li, Xinbao; Zhang, Fan International Journal of Hydrogen Energy, Vol. 38, Issue 36 https://doi.org/10.1016/j.ijhydene.2013.10.032	journal	December 2013
Aqueous-phase hydrodeoxygenation of bio-derived phenols to cycloalkanes Zhao, Chen; He, Jiayue; Lemonidou, Angeliki A. Journal of Catalysis, Vol. 280, Issue 1 https://doi.org/10.1016/j.jcat.2011.02.001	journal	May 2011
Selective catalytic hydroalkylation and deoxygenation of substituted phenols to bicycloalkanes Zhao, Chen; Camaioni, Donald M.; Lercher, Johannes A. Journal of Catalysis, Vol. 288 https://doi.org/10.1016/j.jcat.2012.01.005	journal	April 2012
Carbon-supported bimetallic Pd–Fe catalysts for vapor-phase hydrodeoxygenation of guaiacol Sun, Junming; Karim, Ayman M.; Zhang, He Journal of Catalysis, Vol. 306 https://doi.org/10.1016/j.jcat.2013.05.020	journal	October 2013
Impact of solvent for individual steps of phenol hydrodeoxygenation with Pd/C and HZSM-5 as catalysts He, Jiayue; Zhao, Chen; Lercher, Johannes A. Journal of Catalysis, Vol. 309 https://doi.org/10.1016/j.jcat.2013.09.009	journal	January 2014
Kinetics and mechanism of m-cresol hydrodeoxygenation on a Pt/SiO2 catalyst Nie, Lei; Resasco, Daniel E. Journal of Catalysis, Vol. 317 https://doi.org/10.1016/j.jcat.2014.05.024	journal	August 2014
Selective conversion of m-cresol to toluene over bimetallic Ni–Fe catalysts Nie, Lei; de Souza, Priscilla M.; Noronha, Fabio B. Journal of Molecular Catalysis A: Chemical, Vol. 388-389 https://doi.org/10.1016/j.molcata.2013.09.029	journal	July 2014
Atomic and molecular adsorption on Pd(111) Herron, Jeffrey A.; Tonelli, Scott; Mavrikakis, Manos Surface Science, Vol. 606, Issue 21-22 https://doi.org/10.1016/j.susc.2012.07.003	journal	November 2012
Adsorption of phenol on Fe (110) and Pd (111) from first principles Hensley, Alyssa J. R.; Wang, Yong; McEwen, Jean-Sabin Surface Science, Vol. 630 https://doi.org/10.1016/j.susc.2014.08.003	journal	December 2014
Synthesis of Transportation Fuels from Biomass: Chemistry, Catalysts, and Engineering Huber, George W.; Iborra, Sara; Corma, Avelino Chemical Reviews, Vol. 106, Issue 9, p. 4044-4098 https://doi.org/10.1021/cr068360d	journal	September 2006
Acid and Basic Catalysis. Bronsted, J. N. Chemical Reviews, Vol. 5, Issue 3 https://doi.org/10.1021/cr60019a001	journal	October 1928
Recent Advances in Hydrotreating of Pyrolysis Bio-Oil and Its Oxygen-Containing Model Compounds Wang, Huamin; Male, Jonathan; Wang, Yong ACS Catalysis, Vol. 3, Issue 5 https://doi.org/10.1021/cs400069z	journal	April 2013
Enhanced Fe ₂ O ₃ Reducibility via Surface Modification with Pd: Characterizing the Synergy within Pd/Fe Catalysts for Hydrodeoxygenation Reactions Hensley, Alyssa J. R.; Hong, Yongchun; Zhang, Renqin ACS Catalysis, Vol. 4, Issue 10 https://doi.org/10.1021/cs500565e	journal	September 2014
Synergistic Catalysis between Pd and Fe in Gas Phase Hydrodeoxygenation of m -Cresol Hong, Yongchun; Zhang, He; Sun, Junming ACS Catalysis, Vol. 4, Issue 10 https://doi.org/10.1021/cs500578g	journal	August 2014
Pyrolysis of Wood/Biomass for Bio-oil: A Critical Review Mohan, Dinesh; Pittman,, Charles U.; Steele, Philip H. Energy & Fuels, Vol. 20, Issue 3, p. 848-889 https://doi.org/10.1021/ef0502397	journal	May 2006
Fuel Oil Quality of Biomass Pyrolysis OilsState of the Art for the End Users Oasmaa, Anja; Czernik, Stefan Energy & Fuels, Vol. 13, Issue 4 https://doi.org/10.1021/ef980272b	journal	July 1999
Catalytic Hydroprocessing of Chloropyridinols Kim, Dae I.; Allen, David T. Industrial & Engineering Chemistry Research, Vol. 33, Issue 12 https://doi.org/10.1021/ie00036a008	journal	December 1994
A Correlation of Reaction Rates Hammond, George S. Journal of the American Chemical Society, Vol. 77, Issue 2 https://doi.org/10.1021/ja01607a027	journal	January 1955
First-Principles Study of Phenol Hydrogenation on Pt and Ni Catalysts in Aqueous Phase Yoon, Yeohoon; Rousseau, Roger; Weber, Robert S. Journal of the American Chemical Society, Vol. 136, Issue 29 https://doi.org/10.1021/ja501592y	journal	July 2014
Chemisorption of Benzene on Pt(111), Pd(111), and Rh(111) Metal Surfaces: A Structural and Vibrational Comparison from First Principles Morin, C.; Simon, D.; Sautet, P. The Journal of Physical Chemistry B, Vol. 108, Issue 18 https://doi.org/10.1021/jp0373503	journal	May 2004
Ethanol and Water Adsorption on Close-Packed 3d, 4d, and 5d Transition-Metal Surfaces: A Density Functional Theory Investigation with van der Waals Correction Tereshchuk, Polina; Da Silva, Juarez L. F. The Journal of Physical Chemistry C, Vol. 116, Issue 46 https://doi.org/10.1021/jp308870d	journal	November 2012
Tailoring the Adsorption of Benzene on PdFe Surfaces: A Density Functional Theory Study Hensley, Alyssa J. R.; Zhang, Renqin; Wang, Yong The Journal of Physical Chemistry C, Vol. 117, Issue 46 https://doi.org/10.1021/jp406425q	journal	November 2013
Hydrogen-Assisted Transformation of CO ₂ on Nickel: The Role of Formate and Carbon Monoxide Vesselli, Erik; Rizzi, Michele; De Rogatis, Loredana The Journal of Physical Chemistry Letters, Vol. 1, Issue 1 https://doi.org/10.1021/jz900221c	journal	November 2009
Universal transition state scaling relations for (de)hydrogenation over transition metals Wang, S.; Petzold, V.; Tripkovic, V. Physical Chemistry Chemical Physics, Vol. 13, Issue 46 https://doi.org/10.1039/c1cp20547a	journal	January 2011
Computational study of the adsorption and dissociation of phenol on Pt and Rh surfaces Honkela, Maija L.; Björk, Jonas; Persson, Mats Physical Chemistry Chemical Physics, Vol. 14, Issue 16 https://doi.org/10.1039/c2cp24064e	journal	January 2012
Solvent effects on the hydrodeoxygenation of propanoic acid over Pd(111) model surfaces Behtash, Sina; Lu, Jianmin; Faheem, Muhammad Green Chem., Vol. 16, Issue 2 https://doi.org/10.1039/c3gc41368c	journal	January 2014
Inertia and driving force of chemical reactions Evans, M. G.; Polanyi, M. Transactions of the Faraday Society, Vol. 34 https://doi.org/10.1039/tf9383400011	journal	January 1938
A climbing image nudged elastic band method for finding saddle points and minimum energy paths Henkelman, Graeme; Uberuaga, Blas P.; Jónsson, Hannes The Journal of Chemical Physics, Vol. 113, Issue 22, p. 9901-9904 https://doi.org/10.1063/1.1329672	journal	December 2000
A doubly nudged elastic band method for finding transition states Trygubenko, Semen A.; Wales, David J. The Journal of Chemical Physics, Vol. 120, Issue 5 https://doi.org/10.1063/1.1636455	journal	February 2004
Theoretical calculations of CH4 and H2 associative desorption from Ni(111): Could subsurface hydrogen play an important role? Henkelman, Graeme; Arnaldsson, Andri; Jónsson, Hannes The Journal of Chemical Physics, Vol. 124, Issue 4 https://doi.org/10.1063/1.2161193	journal	January 2006
A dimer method for finding saddle points on high dimensional potential surfaces using only first derivatives Henkelman, Graeme; Jónsson, Hannes The Journal of Chemical Physics, Vol. 111, Issue 15 https://doi.org/10.1063/1.480097	journal	October 1999
Chemical accuracy for the van der Waals density functional Klimeš, Jiří; Bowler, David R.; Michaelides, Angelos Journal of Physics: Condensed Matter, Vol. 22, Issue 2 https://doi.org/10.1088/0953-8984/22/2/022201	journal	December 2009
Structure and energetics of benzene adsorbed on transition-metal surfaces: density-functional theory with van der Waals interactions including collective substrate response Liu, Wei; Ruiz, Victor G.; Zhang, Guo-Xu New Journal of Physics, Vol. 15, Issue 5 https://doi.org/10.1088/1367-2630/15/5/053046	journal	May 2013
Special points for Brillouin-zone integrations Monkhorst, Hendrik J.; Pack, James D. Physical Review B, Vol. 13, Issue 12, p. 5188-5192 https://doi.org/10.1103/PhysRevB.13.5188	journal	June 1976
High-precision sampling for Brillouin-zone integration in metals Methfessel, M.; Paxton, A. T. Physical Review B, Vol. 40, Issue 6 https://doi.org/10.1103/PhysRevB.40.3616	journal	August 1989
Accurate and simple analytic representation of the electron-gas correlation energy Perdew, John P.; Wang, Yue Physical Review B, Vol. 45, Issue 23, p. 13244-13249 https://doi.org/10.1103/PhysRevB.45.13244	journal	June 1992
Atoms, molecules, solids, and surfaces: Applications of the generalized gradient approximation for exchange and correlation Perdew, John P.; Chevary, J. A.; Vosko, S. H. Physical Review B, Vol. 46, Issue 11 https://doi.org/10.1103/PhysRevB.46.6671	journal	September 1992
Ab initiomolecular dynamics for liquid metals Kresse, G.; Hafner, J. Physical Review B, Vol. 47, Issue 1, p. 558-561 https://doi.org/10.1103/PhysRevB.47.558	journal	January 1993
Structural properties of Fe crystals Zhong, W.; Overney, G.; Toma´nek, D. Physical Review B, Vol. 47, Issue 1 https://doi.org/10.1103/PhysRevB.47.95	journal	January 1993
Projector augmented-wave method Blöchl, P. E. Physical Review B, Vol. 50, Issue 24, p. 17953-17979 https://doi.org/10.1103/PhysRevB.50.17953	journal	December 1994
Periodic boundary conditions in ab initio calculations Makov, G.; Payne, M. C. Physical Review B, Vol. 51, Issue 7 https://doi.org/10.1103/PhysRevB.51.4014	journal	February 1995
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
From ultrasoft pseudopotentials to the projector augmented-wave method Kresse, G.; Joubert, D. Physical Review B, Vol. 59, Issue 3, p. 1758-1775 https://doi.org/10.1103/PhysRevB.59.1758	journal	January 1999
Ab initio studies of stepped Pd surfaces with and without S Makkonen, Ilja; Salo, Petri; Alatalo, Matti Physical Review B, Vol. 67, Issue 16 https://doi.org/10.1103/PhysRevB.67.165415	journal	April 2003
Phenol near Ni(111), Ni(110), and Ni(221) surfaces in a vertical ring geometry: A density functional study of the oxygen-surface bonding and O-H cleavage Ghiringhelli, Luca M.; Caputo, Riccarda; Site, Luigi Delle Physical Review B, Vol. 75, Issue 11 https://doi.org/10.1103/PhysRevB.75.113403	journal	March 2007
Van der Waals density functionals applied to solids Klimeš, Jiří; Bowler, David R.; Michaelides, Angelos Physical Review B, Vol. 83, Issue 19 https://doi.org/10.1103/PhysRevB.83.195131	journal	May 2011
The Path Forward for Biofuels and Biomaterials Ragauskas, Arthur J.; Williams, Charlotte K.; Davison, Brian H. Science, Vol. 311, Issue 5760, p. 484-489 https://doi.org/10.1126/science.1114736	journal	January 2006
Hydrodeoxygenation of Phenolic Compounds by Sulfided (Co)Mo/Al ₂ O ₃ Catalysts, a Combined Experimental and Theoretical Study Badawi, M.; Paul, J. -F.; Payen, E. Oil & Gas Science and Technology – Revue d’IFP Energies nouvelles, Vol. 68, Issue 5 https://doi.org/10.2516/ogst/2012041	journal	April 2013

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