Pathways for Ethanol Dehydrogenation and Dehydration Catalyzed by Ceria (111) and (100) Surfaces

Beste, Ariana

doi:10.1021/jp509686f

Title: Pathways for Ethanol Dehydrogenation and Dehydration Catalyzed by Ceria (111) and (100) Surfaces

Journal Article · Thu Jan 08 00:00:00 EST 2015 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/jp509686f· OSTI ID:1185705

Beste, Ariana ^[1]

Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

We have performed computations to better understand how surface structure affects selectivity in dehydrogenation and dehydration reactions of alcohols. Ethanol reactions on the (111) and (100) ceria surfaces were studied starting from the dominant surface species, ethoxy. We used DFT (PBE+U) to explore reaction pathways leading to ethylene and acetaldehyde and calculated estimates of rate constants employing transition state theory. To assess pathway contributions, we carried out kinetic analysis. Our results show that intermediate and transition state structures are stabilized on the (100) surface compared to the (111) surface. Formation of acetaldehyde over ethylene is kinetically and thermodynamically preferred on both surfaces. Our results are consistent with temperature programmed surface reaction and steady-state experiments, where acetaldehyde was found as the main product and evidence was presented that ethylene formation at higher temperature originates from changes in adsorbate and surface structure.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1185705

Journal Information:: Journal of Physical Chemistry. C, Vol. 119, Issue 5; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 41 works

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References (39)

Hydrogen production from simple alkanes and oxygenated hydrocarbons over ceria–zirconia supported catalysts: Review Nahar, Gaurav; Dupont, Valerie Renewable and Sustainable Energy Reviews, Vol. 32 https://doi.org/10.1016/j.rser.2013.12.040	journal	April 2014
Investigation of reactive cerium-based oxides for H2 production by thermochemical two-step water-splitting Abanades, Stéphane; Legal, Alex; Cordier, Anne Journal of Materials Science, Vol. 45, Issue 15 https://doi.org/10.1007/s10853-010-4506-4	journal	April 2010
Nanostructured ceria-based materials: synthesis, properties, and applications Sun, Chunwen; Li, Hong; Chen, Liquan Energy & Environmental Science, Vol. 5, Issue 9 https://doi.org/10.1039/c2ee22310d	journal	January 2012
Oxygen Defects and Surface Chemistry of Ceria: Quantum Chemical Studies Compared to Experiment Paier, Joachim; Penschke, Christopher; Sauer, Joachim Chemical Reviews, Vol. 113, Issue 6 https://doi.org/10.1021/cr3004949	journal	December 2012
Surface structure dependence of selective oxidation of ethanol on faceted CeO2 nanocrystals Li, Meijun; Wu, Zili; Overbury, S. H. Journal of Catalysis, Vol. 306 https://doi.org/10.1016/j.jcat.2013.06.019	journal	October 2013
Theoretical Calculation of the Dehydrogenation of Ethanol on a Rh/CeO ₂ (111) Surface Chen, Hui-Lung; Liu, Shih-Hung; Ho, Jia-Jen The Journal of Physical Chemistry B, Vol. 110, Issue 30 https://doi.org/10.1021/jp0610259	journal	August 2006
Oxygen Vacancy-Assisted Coupling and Enolization of Acetaldehyde on CeO ₂ (111) Calaza, Florencia C.; Xu, Ye; Mullins, David R. Journal of the American Chemical Society, Vol. 134, Issue 43 https://doi.org/10.1021/ja3074243	journal	October 2012
Methanol Adsorption on the Clean CeO ₂ (111) Surface: A Density Functional Theory Study Mei, Donghai; Deskins, N. Aaron; Dupuis, Michel The Journal of Physical Chemistry C, Vol. 111, Issue 28 https://doi.org/10.1021/jp072181y	journal	July 2007
Adsorption and dissociation of methanol on the fully oxidized and partially reduced (111) cerium oxide surface: Dependence on the configuration of the cerium 4f electrons Beste, Ariana; Mullins, David R.; Overbury, Steven H. Surface Science, Vol. 602, Issue 1 https://doi.org/10.1016/j.susc.2007.10.024	journal	January 2008
Density Functional Theory Study of Methanol Decomposition on the CeO ₂ (110) Surface Mei, Donghai; Deskins, N. Aaron; Dupuis, Michel The Journal of Physical Chemistry C, Vol. 112, Issue 11 https://doi.org/10.1021/jp710484b	journal	February 2008
A density functional theory study of formaldehyde adsorption on ceria Mei, Donghai; Aaron Deskins, N.; Dupuis, Michel Surface Science, Vol. 601, Issue 21 https://doi.org/10.1016/j.susc.2007.08.027	journal	November 2007
A density functional theory study of formaldehyde adsorption and oxidation on CeO2(111) surface Teng, Bo-Tao; Jiang, Shi-Yu; Yang, Zong-Xian Surface Science, Vol. 604, Issue 1 https://doi.org/10.1016/j.susc.2009.10.024	journal	January 2010
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
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 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
Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium Kresse, G.; Hafner, J. Physical Review B, Vol. 49, Issue 20, p. 14251-14269 https://doi.org/10.1103/PhysRevB.49.14251	journal	May 1994
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set Kresse, G.; Furthmüller, J. Computational Materials Science, Vol. 6, Issue 1, p. 15-50 https://doi.org/10.1016/0927-0256(96)00008-0	journal	July 1996
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
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study Dudarev, S. L.; Botton, G. A.; Savrasov, S. Y. Physical Review B, Vol. 57, Issue 3, p. 1505-1509 https://doi.org/10.1103/PhysRevB.57.1505	journal	January 1998
Hydrogen Cycle on CeO ₂ (111) Surfaces: Density Functional Theory Calculations Watkins, Matthew B.; Foster, Adam S.; Shluger, Alexander L. The Journal of Physical Chemistry C, Vol. 111, Issue 42 https://doi.org/10.1021/jp071715s	journal	October 2007
CO Adsorption and Oxidation on Ceria Surfaces from DFT+U Calculations Huang, Min; Fabris, Stefano The Journal of Physical Chemistry C, Vol. 112, Issue 23 https://doi.org/10.1021/jp709898r	journal	May 2008
First-principles $LDA + U$ and $GGA + U$ study of cerium oxides: Dependence on the effective U parameter Loschen, Christoph; Carrasco, Javier; Neyman, Konstantin M. Physical Review B, Vol. 75, Issue 3 https://doi.org/10.1103/PhysRevB.75.035115	journal	January 2007
Insight into the Adsorption of Water on the Clean CeO ₂ (111) Surface with van der Waals and Hybrid Density Functionals Fernández-Torre, Delia; Kośmider, Krzysztof; Carrasco, Javier The Journal of Physical Chemistry C, Vol. 116, Issue 25 https://doi.org/10.1021/jp212605g	journal	June 2012
Ordered cerium oxide thin films grown on Ru(0001) and Ni(111) Mullins, D.R.; Radulovic, P.V.; Overbury, S.H. Surface Science, Vol. 429, Issue 1-3, p. 186-198 https://doi.org/10.1016/S0039-6028(99)00369-6	journal	June 1999
Thiolate Ligands as a Double-Edged Sword for CO Oxidation on CeO ₂ Supported Au ₂₅ (SCH ₂ CH ₂ Ph) ₁₈ Nanoclusters Wu, Zili; Jiang, De-en; Mann, Amanda K. P. Journal of the American Chemical Society, Vol. 136, Issue 16 https://doi.org/10.1021/ja5018706	journal	April 2014
Water Adsorption and Its Effect on the Stability of Low Index Stoichiometric and Reduced Surfaces of Ceria Molinari, Marco; Parker, Stephen C.; Sayle, Dean C. The Journal of Physical Chemistry C, Vol. 116, Issue 12 https://doi.org/10.1021/jp300576b	journal	March 2012
Surface structure determination of ${CeO}_{2} (001)$ by angle-resolved mass spectroscopy of recoiled ions Herman, G. S. Physical Review B, Vol. 59, Issue 23 https://doi.org/10.1103/PhysRevB.59.14899	journal	June 1999
The surface structure of CeO2(001) single crystals studied by elevated temperature STM Nörenberg, H.; Harding, J. H. Surface Science, Vol. 477, Issue 1 https://doi.org/10.1016/S0039-6028(01)00700-2	journal	April 2001
Surface properties of ${CeO}_{2}$ from first principles Skorodumova, N. V.; Baudin, M.; Hermansson, K. Physical Review B, Vol. 69, Issue 7 https://doi.org/10.1103/PhysRevB.69.075401	journal	February 2004
The electronic structure of oxygen vacancy defects at the low index surfaces of ceria Nolan, Michael; Parker, Stephen C.; Watson, Graeme W. Surface Science, Vol. 595, Issue 1-3 https://doi.org/10.1016/j.susc.2005.08.015	journal	December 2005
Adsorption and Reaction of C ₁ −C ₃ Alcohols over CeO _X (111) Thin Films Mullins, D. R.; Senanayake, S. D.; Chen, T. -L. The Journal of Physical Chemistry C, Vol. 114, Issue 40 https://doi.org/10.1021/jp103905e	journal	July 2010
Nudged elastic band method for finding minimum energy paths of transitions JÓNsson, Hannes; Mills, Greg; Jacobsen, Karsten W. Proceedings of the International School of Physics, Classical and Quantum Dynamics in Condensed Phase Simulations https://doi.org/10.1142/9789812839664_0016	conference	November 2011
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
Concepts of Modern Catalysis and Kinetics Chorkendorff, I.; Niemantsverdriet, J. W. https://doi.org/10.1002/3527602658	book	October 2003
Improved grid-based algorithm for Bader charge allocation Sanville, Edward; Kenny, Steven D.; Smith, Roger Journal of Computational Chemistry, Vol. 28, Issue 5 https://doi.org/10.1002/jcc.20575	journal	January 2007
A fast and robust algorithm for Bader decomposition of charge density Henkelman, Graeme; Arnaldsson, Andri; Jónsson, Hannes Computational Materials Science, Vol. 36, Issue 3 https://doi.org/10.1016/j.commatsci.2005.04.010	journal	June 2006
The Surface Dependence of CO Adsorption on Ceria Nolan, Michael; Watson, Graeme W. The Journal of Physical Chemistry B, Vol. 110, Issue 33 https://doi.org/10.1021/jp062499a	journal	August 2006
Unraveling the Complexity of Catalytic Reactions via Kinetic Monte Carlo Simulation: Current Status and Frontiers Stamatakis, Michail; Vlachos, Dionisios G. ACS Catalysis, Vol. 2, Issue 12 https://doi.org/10.1021/cs3005709	journal	November 2012

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Dehydrogenation of methanol to formaldehyde catalyzed by pristine and defective ceria surfaces Beste, Ariana; Overbury, Steven H. Physical Chemistry Chemical Physics, Vol. 18, Issue 15 https://doi.org/10.1039/c6cp00151c	journal	January 2016
Catalytic Enhancement of Aldol Condensation by Oxygen Vacancy on CeO ₂ Catalysts Liang, Zhe; Jiang, Dahao; Fang, Geqian ChemistrySelect, Vol. 4, Issue 14 https://doi.org/10.1002/slct.201900712	journal	April 2019
Microkinetic simulation and fitting of the temperature programmed reaction of methanol on CeO2(111): H2 and H2O + V production Savara, Aditya Reaction Kinetics, Mechanisms and Catalysis, Vol. 129, Issue 1 https://doi.org/10.1007/s11144-019-01710-w	journal	January 2020
A computational-experimental investigation on high ethylene selectivity in ethanol dehydration reaction found on WOx/ZrO2-activated carbon bi-support systems Rittiruam, Meena; Jongsomjit, Bunjerd; Praserthdam, Supareak Scientific Reports, Vol. 9, Issue 1 https://doi.org/10.1038/s41598-019-56373-3	journal	December 2019
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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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Title: Pathways for Ethanol Dehydrogenation and Dehydration Catalyzed by Ceria (111) and (100) Surfaces

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