Simulated Temperature Programmed Desorption of Acetaldehyde on CeO2(111): Evidence for the Role of Oxygen Vacancy and Hydrogen Transfer

Zhao, Chuanlin; Xu, Ye

doi:10.1007/s11244-016-0703-y

Title: Simulated Temperature Programmed Desorption of Acetaldehyde on CeO₂(111): Evidence for the Role of Oxygen Vacancy and Hydrogen Transfer

Journal Article · Wed Sep 07 00:00:00 EDT 2016 · Topics in Catalysis

DOI:https://doi.org/10.1007/s11244-016-0703-y· OSTI ID:1461885

Zhao, Chuanlin ^[1]; Xu, Ye ^[1]

Louisiana State University, Baton Rouge, LA (United States). Department of Chemical Engineering

The temperature programmed desorption of acetaldehyde adsorbed on partially reduced CeO₂(111) has been studied in detail using microkinetic modeling based on self-consistent, periodic density functional theory calculations at the GGA-PW91+U level. Previous experimental studies (Chen et al. J. Phys. Chem. C 115: 3385, 2011; Calaza et al. J. Am. Chem. Soc. 134: 18034, 2012) have shown that, whereas on fully oxidized CeO₂(111) acetaldehyde desorbs molecularly with a peak temperature of 210 K, the polymerization and enolization of acetaldehyde dominate the surface reactivity on partially reduced CeO₂(111), resulting in acetaldehyde desorption at higher temperatures. Here we propose a comprehensive reaction mechanism that is consistent with the spectroscopic evidence of the identities of the surface intermediates and with the observed desorption activities, including the formation of ethylene and acetylene. Besides acetaldehyde (CH₃CHO) and its enolate (CH₂CHO), several other C₂H_xO species are proposed as key intermediates which are not seen spectroscopically, including ethoxy (CH₃CH₂O), ethyleneoxy (CH2CH2O), and formylmethylene (CHCHO). Our study suggests that oxygen vacancies play the critical role of activating the carbonyl bond and thereby facilitating b C–H bond scissions in acetaldehyde, leading to enolization, intermolecular hydrogen transfer, deoxygenation, and potentially C–C coupling reactions.

Cite

Export

Save

Research Organization:: Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)

Sponsoring Organization:: USDOE Office of Science (SC), Advanced Scientific Computing Research (ASCR)

DOE Contract Number:: AC02-05CH11231.

OSTI ID:: 1461885

Journal Information:: Topics in Catalysis, Vol. 60, Issue 6-7; ISSN 1022-5528

Publisher:: Springer

Country of Publication:: United States

Language:: English

References (60)

Catalytic Conversion of Biomass to Monofunctional Hydrocarbons and Targeted Liquid-Fuel Classes Kunkes, E. L.; Simonetti, D. A.; West, R. M. Science, Vol. 322, Issue 5900 https://doi.org/10.1126/science.1159210	journal	October 2008
Thermal desorption of gases Redhead, P. A. Vacuum, Vol. 12, Issue 4 https://doi.org/10.1016/0042-207X(62)90978-8	journal	July 1962
Role of CeO2 in Ni/CeO2–Al2O3 catalysts for carbon dioxide reforming of methane Wang, Shaobin; (Max) Lu, G. Q. Applied Catalysis B: Environmental, Vol. 19, Issue 3-4 https://doi.org/10.1016/S0926-3373(98)00081-2	journal	December 1998
Catalytic purification of waste gases containing VOC mixtures with Ce/Zr solid solutions Gutiérrez-Ortiz, José I.; de Rivas, Beatriz; López-Fonseca, Rubén Applied Catalysis B: Environmental, Vol. 65, Issue 3-4 https://doi.org/10.1016/j.apcatb.2006.02.001	journal	June 2006
Variations in Reactivity on Different Crystallographic Orientations of Cerium Oxide Mullins, David R.; Albrecht, Peter M.; Calaza, Florencia Topics in Catalysis, Vol. 56, Issue 15-17 https://doi.org/10.1007/s11244-013-0146-7	journal	July 2013
Reactivity of Hydroxyls and Water on a CeO ₂ (111) Thin Film Surface: The Role of Oxygen Vacancy Chen, Bohao; Ma, Yunsheng; Ding, Liangbing The Journal of Physical Chemistry C, Vol. 117, Issue 11 https://doi.org/10.1021/jp312406f	journal	March 2013
Structure sensitivity of the methanation reaction: H2-induced CO dissociation on nickel surfaces Andersson, M. P.; Abild-Pedersen, F.; Remediakis, I. N. Journal of Catalysis, Vol. 255, Issue 1 https://doi.org/10.1016/j.jcat.2007.12.016	journal	April 2008
Studies of the water-gas-shift reaction on ceria-supported Pt, Pd, and Rh: Implications for oxygen-storage properties Bunluesin, T.; Gorte, R. J.; Graham, G. W. Applied Catalysis B: Environmental, Vol. 15, Issue 1-2 https://doi.org/10.1016/S0926-3373(97)00040-4	journal	January 1998
Role of oxygen vacancies in the surface evolution of H at CeO ₂ (111): a charge modification effect Wu, Xin-Ping; Gong, Xue-Qing; Lu, Guanzhong Physical Chemistry Chemical Physics, Vol. 17, Issue 5 https://doi.org/10.1039/C4CP04766D	journal	January 2015
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
Activity of CeOx and TiOx Nanoparticles Grown on Au(111) in the Water-Gas Shift Reaction Rodriguez, J. A.; Ma, S.; Liu, P. Science, Vol. 318, Issue 5857 https://doi.org/10.1126/science.1150038	journal	December 2007
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
Effects of hydrogen and water on the activity and selectivity of acetic acid hydrogenation on ruthenium Olcay, Hakan; Xu, Ye; Huber, George W. Green Chem., Vol. 16, Issue 2 https://doi.org/10.1039/c4gc00011k	journal	January 2014
Molecular-Level Understanding of CeO ₂ as a Catalyst for Partial Alkyne Hydrogenation Carrasco, Javier; Vilé, Gianvito; Fernández-Torre, Delia The Journal of Physical Chemistry C, Vol. 118, Issue 10 https://doi.org/10.1021/jp410478c	journal	January 2014
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
Calibration of the DFT/GGA+U Method for Determination of Reduction Energies for Transition and Rare Earth Metal Oxides of Ti, V, Mo, and Ce Lutfalla, Suzanne; Shapovalov, Vladimir; Bell, Alexis T. Journal of Chemical Theory and Computation, Vol. 7, Issue 7 https://doi.org/10.1021/ct200202g	journal	June 2011
Integration of C–C coupling reactions of biomass-derived oxygenates to fuel-grade compounds Gürbüz, Elif I.; Kunkes, Edward L.; Dumesic, James A. Applied Catalysis B: Environmental, Vol. 94, Issue 1-2 https://doi.org/10.1016/j.apcatb.2009.11.001	journal	February 2010
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
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
Use of CeO2-based oxides in the three-way catalysis Kašpar, J.; Fornasiero, P.; Graziani, M. Catalysis Today, Vol. 50, Issue 2 https://doi.org/10.1016/S0920-5861(98)00510-0	journal	April 1999
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
Reactivity and reaction intermediates for acetic acid adsorbed on CeO2(1 1 1) Calaza, Florencia C.; Chen, Tsung-Liang; Mullins, David R. Catalysis Today, Vol. 253 https://doi.org/10.1016/j.cattod.2015.03.033	journal	September 2015
Rationalization of the Hubbard U parameter in CeO _x from first principles: Unveiling the role of local structure in screening Lu, Deyu; Liu, Ping The Journal of Chemical Physics, Vol. 140, Issue 8 https://doi.org/10.1063/1.4865831	journal	February 2014
Adsorption and Reaction of Acetaldehyde on Shape-Controlled CeO ₂ Nanocrystals: Elucidation of Structure–Function Relationships Mann, Amanda K. P.; Wu, Zili; Calaza, Florencia C. ACS Catalysis, Vol. 4, Issue 8 https://doi.org/10.1021/cs500611g	journal	June 2014
Hydrogen activation, diffusion, and clustering on CeO ₂ (111): A DFT+ U study Fernández-Torre, Delia; Carrasco, Javier; Ganduglia-Pirovano, M. Verónica The Journal of Chemical Physics, Vol. 141, Issue 1 https://doi.org/10.1063/1.4885546	journal	July 2014
DFT-driven multi-site microkinetic modeling of ethanol conversion to ethylene and diethyl ether on γ-Al2O3(1 1 1) Christiansen, Matthew A.; Mpourmpakis, Giannis; Vlachos, Dionisios G. Journal of Catalysis, Vol. 323 https://doi.org/10.1016/j.jcat.2014.12.024	journal	March 2015
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
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
Polymerization and decarbonylation reactions of aldehydes on the Pd(111) surface Davis, J. L.; Barteau, M. A. Journal of the American Chemical Society, Vol. 111, Issue 5 https://doi.org/10.1021/ja00187a035	journal	March 1989
Periodic Density Functional Theory Study of VO _n Species Supported on the CeO ₂ (111) Surface Popa, Cristina; Ganduglia-Pirovano, María Verónica; Sauer, Joachim The Journal of Physical Chemistry C, Vol. 115, Issue 15 https://doi.org/10.1021/jp108185y	journal	March 2011
Pathways for Ethanol Dehydrogenation and Dehydration Catalyzed by Ceria (111) and (100) Surfaces Beste, Ariana; Overbury, Steven H. The Journal of Physical Chemistry C, Vol. 119, Issue 5 https://doi.org/10.1021/jp509686f	journal	January 2015
Improved initial guess for minimum energy path calculations Smidstrup, Søren; Pedersen, Andreas; Stokbro, Kurt The Journal of Chemical Physics, Vol. 140, Issue 21 https://doi.org/10.1063/1.4878664	journal	June 2014
Heterogeneous Catalytic Transfer Hydrogenation as an Effective Pathway in Biomass Upgrading Gilkey, Matthew J.; Xu, Bingjun ACS Catalysis, Vol. 6, Issue 3 https://doi.org/10.1021/acscatal.5b02171	journal	January 2016
Catalytic conversion of biomass to biofuels Alonso, David Martin; Bond, Jesse Q.; Dumesic, James A. Green Chemistry, Vol. 12, Issue 9, p. 1493-1513 https://doi.org/10.1039/c004654j	journal	January 2010
Reactions of Acetaldehyde on CeO2 and CeO2-Supported Catalysts Idriss, H.; Diagne, C.; Hindermann, J. P. Journal of Catalysis, Vol. 155, Issue 2 https://doi.org/10.1006/jcat.1995.1205	journal	September 1995
Adsorption and surface reactions of acetaldehyde on TiO2, CeO2 and Al2O3 Raskó, J.; Kiss, J. Applied Catalysis A: General, Vol. 287, Issue 2 https://doi.org/10.1016/j.apcata.2005.04.003	journal	June 2005
Renewable Hydrogen from Ethanol by Autothermal Reforming Deluga, G. A. Science, Vol. 303, Issue 5660 https://doi.org/10.1126/science.1093045	journal	February 2004
Efficient methods for finding transition states in chemical reactions: Comparison of improved dimer method and partitioned rational function optimization method Heyden, Andreas; Bell, Alexis T.; Keil, Frerich J. The Journal of Chemical Physics, Vol. 123, Issue 22 https://doi.org/10.1063/1.2104507	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
Oxygen Vacancies versus Fluorine at ${CeO}_{2} (111)$ : A Case of Mistaken Identity? Kullgren, J.; Wolf, M. J.; Castleton, C. W. M. Physical Review Letters, Vol. 112, Issue 15 https://doi.org/10.1103/PhysRevLett.112.156102	journal	April 2014
What Should We Demand from the Catalysts Responsible for Upgrading Biomass Pyrolysis Oil? Resasco, Daniel E. The Journal of Physical Chemistry Letters, Vol. 2, Issue 18 https://doi.org/10.1021/jz201135x	journal	August 2011
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
Highly active copper-ceria and copper-ceria-titania catalysts for methanol synthesis from CO2 Graciani, J.; Mudiyanselage, K.; Xu, F. Science, Vol. 345, Issue 6196 https://doi.org/10.1126/science.1253057	journal	July 2014
Reactions of Carboxylic Acids on Oxides Pestman, R.; Koster, R. M.; van Duijne, A. Journal of Catalysis, Vol. 168, Issue 2 https://doi.org/10.1006/jcat.1997.1624	journal	June 1997
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
Adsorption and Reaction of Acetaldehyde over CeO _X (111) Thin Films Chen, T. -L.; Mullins, D. R. The Journal of Physical Chemistry C, Vol. 115, Issue 8 https://doi.org/10.1021/jp110429s	journal	February 2011
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
VESTA : a three-dimensional visualization system for electronic and structural analysis Momma, Koichi; Izumi, Fujio Journal of Applied Crystallography, Vol. 41, Issue 3 https://doi.org/10.1107/S0021889808012016	journal	May 2008
Homolytic Products from Heterolytic Paths in H ₂ Dissociation on Metal Oxides: The Example of CeO ₂ García-Melchor, Max; López, Núria The Journal of Physical Chemistry C, Vol. 118, Issue 20 https://doi.org/10.1021/jp502309r	journal	May 2014
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
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
Comment on “Taming multiple valency with density functionals: A case study of defective ceria” Kresse, Georg; Blaha, Peter; Da Silva, Juarez L. F. Physical Review B, Vol. 72, Issue 23 https://doi.org/10.1103/PhysRevB.72.237101	journal	December 2005
Electron Localization Determines Defect Formation on Ceria Substrates Esch, F. Science, Vol. 309, Issue 5735 https://doi.org/10.1126/science.1111568	journal	July 2005
Promotional effect of rare earths and transition metals in the combustion of diesel soot over CeO2 and CeO2–ZrO2 Aneggi, Eleonora; de Leitenburg, Carla; Dolcetti, Giuliano Catalysis Today, Vol. 114, Issue 1 https://doi.org/10.1016/j.cattod.2006.02.008	journal	April 2006
Growth and Characterization of Rh and Pd Nanoparticles on Oxidized and Reduced CeO _x (111) Thin Films by Scanning Tunneling Microscopy Zhou, Jing; Baddorf, A. P.; Mullins, D. R. The Journal of Physical Chemistry C, Vol. 112, Issue 25 https://doi.org/10.1021/jp711198c	journal	May 2008
Adsorbate-substrate and adsorbate-adsorbate interactions of Na and K adlayers on Al(111) Neugebauer, Jörg; Scheffler, Matthias Physical Review B, Vol. 46, Issue 24 https://doi.org/10.1103/PhysRevB.46.16067	journal	December 1992
Interaction of Hydrogen with Cerium Oxide Surfaces: a Quantum Mechanical Computational Study Vicario, Gianpaolo; Balducci, Gabriele; Fabris, Stefano The Journal of Physical Chemistry B, Vol. 110, Issue 39 https://doi.org/10.1021/jp061375v	journal	October 2006
Ketonization of Carboxylic Acids: Mechanisms, Catalysts, and Implications for Biomass Conversion Pham, Tu N.; Sooknoi, Tawan; Crossley, Steven P. ACS Catalysis, Vol. 3, Issue 11 https://doi.org/10.1021/cs400501h	journal	October 2013
Electronic and Atomistic Structures of Clean and Reduced Ceria Surfaces Fabris, Stefano; Vicario, Gianpaolo; Balducci, Gabriele The Journal of Physical Chemistry B, Vol. 109, Issue 48 https://doi.org/10.1021/jp0511698	journal	December 2005
Temperature evolution of structure and bonding of formic acid and formate on fully oxidized and highly reduced CeO2(111) Gordon, Wesley O.; Xu, Ye; Mullins, David R. Physical Chemistry Chemical Physics, Vol. 11, Issue 47 https://doi.org/10.1039/b913310k	journal	January 2009

Similar Records

Coupling of Acetaldehyde to Crotonaldehyde on CeO _2–x (111): Bifunctional Mechanism and Role of Oxygen Vacancies

Journal Article · Wed Oct 24 00:00:00 EDT 2018 · Journal of Physical Chemistry. C · OSTI ID:1461885

Zhao, Chuanlin; Watt, Charles L.; Kent, Paul R.; +5 more

Elucidating the Mechanism of Ambient-Temperature Aldol Condensation of Acetaldehyde on Ceria

Journal Article · Wed Jun 30 00:00:00 EDT 2021 · ACS Catalysis · OSTI ID:1461885

Bhasker-Ranganath, Suman; Rahman, Md. Saeedur; Zhao, Chuanlin; +3 more

Ethylene Glycol Adsorption and Reaction over CeOX(111) Thin Films

Journal Article · Sat Dec 31 00:00:00 EST 2011 · Journal of Physical Chemistry C · OSTI ID:1461885

Chen, T; Mullins, D

Title: Simulated Temperature Programmed Desorption of Acetaldehyde on CeO2(111): Evidence for the Role of Oxygen Vacancy and Hydrogen Transfer

Citation Formats

References (60)

Similar Records

Related Subjects

Title: Simulated Temperature Programmed Desorption of Acetaldehyde on CeO₂(111): Evidence for the Role of Oxygen Vacancy and Hydrogen Transfer