Enhanced adsorption of CO2 at steps of ultrathin ZnO: the importance of Zn–O geometry and coordination
Abstract
In this paper, the interaction between CO2 and ultrathin ZnO supported on Au(111) has been studied using temperature programmed desorption (TPD) and density functional theory (DFT) calculations. We find that CO2 binds weakly on the planar ZnO bilayer and trilayer surfaces, desorbing at T = 130 K. CO2 binds more strongly at the steps formed between ZnO bilayers and trilayers, desorbing at T = 285–320 K depending upon the CO2 exposure. The adsorption energies determined from DFT calculations for CO2 on the ZnO planar surfaces and at the steps are ~5.8 and 19.0 kcal mol–1, respectively, agreeing with the apparent activation energies of desorption (Ed) estimated based on the TPD peaks at the limit of low CO2 exposures (7.7 and 19.5 kcal mol–1, respectively). The DFT calculations further identify that the most stable adsorption configuration of CO2 at the steps of ultrathin ZnO is facilitated by the geometry and coordination of the Zn cations and O anions near the step region. Specifically, the enhanced adsorption takes place via bonding of both the C and O atoms of the CO2 molecule to the tri-fold coordinated O anions at the trilayer edge and to the neighboring Zn cations on the bilayer terrace,more »
- Authors:
-
- National Energy Technology Lab. (NETL), Pittsburgh, PA, (United States); AECOM, South Park, PA (United States)
- National Energy Technology Lab. (NETL), Pittsburgh, PA, (United States)
- Publication Date:
- Research Org.:
- National Energy Technology Lab. (NETL), Pittsburgh, PA, (United States)
- Sponsoring Org.:
- USDOE Office of Fossil Energy (FE)
- OSTI Identifier:
- 1478624
- Grant/Contract Number:
- FE0004000
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Physical Chemistry Chemical Physics. PCCP (Print)
- Additional Journal Information:
- Journal Name: Physical Chemistry Chemical Physics. PCCP (Print); Journal Volume: 19; Journal Issue: 7; Journal ID: ISSN 1463-9076
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Deng, Xingyi, Sorescu, Dan C., and Lee, Junseok. Enhanced adsorption of CO2 at steps of ultrathin ZnO: the importance of Zn–O geometry and coordination. United States: N. p., 2017.
Web. doi:10.1039/c6cp08379j.
Deng, Xingyi, Sorescu, Dan C., & Lee, Junseok. Enhanced adsorption of CO2 at steps of ultrathin ZnO: the importance of Zn–O geometry and coordination. United States. https://doi.org/10.1039/c6cp08379j
Deng, Xingyi, Sorescu, Dan C., and Lee, Junseok. Thu .
"Enhanced adsorption of CO2 at steps of ultrathin ZnO: the importance of Zn–O geometry and coordination". United States. https://doi.org/10.1039/c6cp08379j. https://www.osti.gov/servlets/purl/1478624.
@article{osti_1478624,
title = {Enhanced adsorption of CO2 at steps of ultrathin ZnO: the importance of Zn–O geometry and coordination},
author = {Deng, Xingyi and Sorescu, Dan C. and Lee, Junseok},
abstractNote = {In this paper, the interaction between CO2 and ultrathin ZnO supported on Au(111) has been studied using temperature programmed desorption (TPD) and density functional theory (DFT) calculations. We find that CO2 binds weakly on the planar ZnO bilayer and trilayer surfaces, desorbing at T = 130 K. CO2 binds more strongly at the steps formed between ZnO bilayers and trilayers, desorbing at T = 285–320 K depending upon the CO2 exposure. The adsorption energies determined from DFT calculations for CO2 on the ZnO planar surfaces and at the steps are ~5.8 and 19.0 kcal mol–1, respectively, agreeing with the apparent activation energies of desorption (Ed) estimated based on the TPD peaks at the limit of low CO2 exposures (7.7 and 19.5 kcal mol–1, respectively). The DFT calculations further identify that the most stable adsorption configuration of CO2 at the steps of ultrathin ZnO is facilitated by the geometry and coordination of the Zn cations and O anions near the step region. Specifically, the enhanced adsorption takes place via bonding of both the C and O atoms of the CO2 molecule to the tri-fold coordinated O anions at the trilayer edge and to the neighboring Zn cations on the bilayer terrace, respectively, leading to CO2 bending and formation of a carbonate-like species.},
doi = {10.1039/c6cp08379j},
journal = {Physical Chemistry Chemical Physics. PCCP (Print)},
number = 7,
volume = 19,
place = {United States},
year = {Thu Jan 26 00:00:00 EST 2017},
month = {Thu Jan 26 00:00:00 EST 2017}
}
Web of Science
Works referenced in this record:
Structural Transformations of Zinc Oxide Layers on Pt(111)
journal, November 2014
- Liu, Bo-Hong; McBriarty, Martin E.; Bedzyk, Michael J.
- The Journal of Physical Chemistry C, Vol. 118, Issue 49
Tunable Lattice Constant and Band Gap of Single- and Few-Layer ZnO
journal, March 2016
- Lee, Junseok; Sorescu, Dan C.; Deng, Xingyi
- The Journal of Physical Chemistry Letters, Vol. 7, Issue 7
Steps on anatase TiO2(101)
journal, July 2006
- Gong, Xue-Qing; Selloni, Annabella; Batzill, Matthias
- Nature Materials, Vol. 5, Issue 8
Generalized Gradient Approximation Made Simple
journal, October 1996
- Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
- Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
Evidence for bicarbonate formation on vacuum annealed TiO2(110) resulting from a precursor-mediated interaction between CO2 and H2O
journal, March 1998
- Henderson, Michael A.
- Surface Science, Vol. 400, Issue 1-3
Projector augmented-wave method
journal, December 1994
- Blöchl, P. E.
- Physical Review B, Vol. 50, Issue 24, p. 17953-17979
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996
- Kresse, G.; Furthmüller, J.
- Computational Materials Science, Vol. 6, Issue 1, p. 15-50
Impact of Defects on the Surface Chemistry of ZnO(0001̄)−O
journal, June 2002
- Lindsay, Robert; Michelangeli, Ela; Daniels, Benjamin G.
- Journal of the American Chemical Society, Vol. 124, Issue 24
Growth and Surface Structure of Zinc Oxide Layers on a Pd(111) Surface
journal, August 2010
- Weirum, G.; Barcaro, G.; Fortunelli, A.
- The Journal of Physical Chemistry C, Vol. 114, Issue 36
D 2 O Interaction with Planar ZnO(0001) Bilayer Supported on Au(111): Structures, Energetics and Influence of Hydroxyls
journal, April 2016
- Deng, Xingyi; Sorescu, Dan C.; Lee, Junseok
- The Journal of Physical Chemistry C, Vol. 120, Issue 15
Observation of Depolarized ZnO(0001) Monolayers: Formation of Unreconstructed Planar Sheets
journal, July 2007
- Tusche, C.; Meyerheim, H. L.; Kirschner, J.
- Physical Review Letters, Vol. 99, Issue 2
Energetics of CO 2 and H 2 O Adsorption on Zinc Oxide
journal, July 2014
- Gouvêa, Douglas; Ushakov, Sergey V.; Navrotsky, Alexandra
- Langmuir, Vol. 30, Issue 30
Adsorption of carbon monoxide and carbon dioxide on annealed and defect zinc oxide (000) surfaces studied by photoelectron spectroscopy (XPS and UPS)
journal, January 1988
- Au, C. T.; Hirsch, W.; Hirschwald, W.
- Surface Science, Vol. 197, Issue 3
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996
- Kresse, G.; Furthmüller, J.
- Physical Review B, Vol. 54, Issue 16, p. 11169-11186
Role of Steps in the Dissociative Adsorption of Water on Rutile
journal, April 2013
- Kristoffersen, H. H.; Hansen, J. Ø.; Martinez, U.
- Physical Review Letters, Vol. 110, Issue 14
Vicinal Rutile TiO 2 Surfaces and Their Interactions with O 2
journal, February 2014
- Rieboldt, Felix; Bechstein, Ralf; Besenbacher, Flemming
- The Journal of Physical Chemistry C, Vol. 118, Issue 7
Electron-Induced Dissociation of CO 2 on TiO 2 (110)
journal, July 2011
- Lee, Junseok; Sorescu, Dan C.; Deng, Xingyi
- Journal of the American Chemical Society, Vol. 133, Issue 26
The orientation of formate and carbonate on ZnO(101̄0)
journal, December 1993
- Davis, R.; Walsh, J. F.; Muryn, C. A.
- Surface Science, Vol. 298, Issue 1
Bridging the structure gap: Chemistry of nanostructured surfaces at well-defined defects
journal, March 2008
- Vattuone, L.; Savio, L.; Rocca, M.
- Surface Science Reports, Vol. 63, Issue 3
Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study
journal, January 1998
- Dudarev, S. L.; Botton, G. A.; Savrasov, S. Y.
- Physical Review B, Vol. 57, Issue 3, p. 1505-1509
Adsorption dynamics of CO2 on Zn-ZnO(0001): A molecular beam study
journal, January 2005
- Wang, J.; Burghaus, U.
- The Journal of Chemical Physics, Vol. 122, Issue 4
CO2 Activation by ZnO through the Formation of an Unusual Tridentate Surface Carbonate
journal, July 2007
- Wang, Yuemin; Kováčik, Roman; Meyer, Bernd
- Angewandte Chemie International Edition, Vol. 46, Issue 29
Validation of density-functional versus density-functional+U approaches for oxide ultrathin films
journal, March 2010
- Barcaro, Giovanni; Thomas, Iorwerth Owain; Fortunelli, Alessandro
- The Journal of Chemical Physics, Vol. 132, Issue 12
The bending machine: CO 2 activation and hydrogenation on δ-MoC(001) and β-Mo 2 C(001) surfaces
journal, January 2014
- Posada-Pérez, Sergio; Viñes, Francesc; Ramirez, Pedro J.
- Phys. Chem. Chem. Phys., Vol. 16, Issue 28
Adsorption sites and microstructures of on Fe(111) derived from specular and off-specular HREELS
journal, April 2001
- Heß, G.; Baumgartner, Ch.; Froitzheim, H.
- Physical Review B, Vol. 63, Issue 16
Surface chemistry of carbon dioxide
journal, January 1996
- Freund, H. -J.; Roberts, M. W.
- Surface Science Reports, Vol. 25, Issue 8
The Surface Science of Catalysis and More, Using Ultrathin Oxide Films as Templates: A Perspective
journal, July 2016
- Freund, Hans-Joachim
- Journal of the American Chemical Society, Vol. 138, Issue 29
Accurate Molecular Van Der Waals Interactions from Ground-State Electron Density and Free-Atom Reference Data
journal, February 2009
- Tkatchenko, Alexandre; Scheffler, Matthias
- Physical Review Letters, Vol. 102, Issue 7
A fast and robust algorithm for Bader decomposition of charge density
journal, June 2006
- Henkelman, Graeme; Arnaldsson, Andri; Jónsson, Hannes
- Computational Materials Science, Vol. 36, Issue 3
Graphitic Nanofilms as Precursors to Wurtzite Films: Theory
journal, February 2006
- Freeman, Colin L.; Claeyssens, Frederik; Allan, Neil L.
- Physical Review Letters, Vol. 96, Issue 6
Adsorption and interaction of carbon dioxide, formic acid and hydrogen/carbon dioxide mixtures on () zinc oxide surfaces studied by photoelectron spectroscopy (XPS and UPS)
journal, January 1988
- Au, C. T.; Hirsch, W.; Hirschwald, W.
- Surface Science, Vol. 199, Issue 3
Interplay between Steps and Oxygen Vacancies on Curved TiO 2 (110)
journal, February 2016
- Miccio, Luis A.; Setvin, Martin; Müller, Moritz
- Nano Letters, Vol. 16, Issue 3
Improved grid-based algorithm for Bader charge allocation
journal, January 2007
- Sanville, Edward; Kenny, Steven D.; Smith, Roger
- Journal of Computational Chemistry, Vol. 28, Issue 5
A climbing image nudged elastic band method for finding saddle points and minimum energy paths
journal, December 2000
- Henkelman, Graeme; Uberuaga, Blas P.; Jónsson, Hannes
- The Journal of Chemical Physics, Vol. 113, Issue 22, p. 9901-9904
Reduced Step Edges on Rutile as Competing Defects to Oxygen Vacancies on the Terraces and Reactive Sites for Ethanol Dissociation
journal, October 2012
- Martinez, U.; Hansen, J. Ø.; Lira, E.
- Physical Review Letters, Vol. 109, Issue 15
Activation of Carbon Dioxide on ZnO Nanoparticles Studied by Vibrational Spectroscopy
journal, May 2010
- Noei, Heshmat; Wöll, Christof; Muhler, Martin
- The Journal of Physical Chemistry C, Vol. 115, Issue 4
Growth of ZnO thin films—experiment and theory
journal, January 2005
- Claeyssens, Frederik; Freeman, Colin L.; Allan, Neil L.
- J. Mater. Chem., Vol. 15, Issue 1
Kinetic Implications of Dynamical Changes in Catalyst Morphology during Methanol Synthesis over Cu/ZnO Catalysts
journal, June 1997
- Ovesen, C. V.; Clausen, B. S.; Schiøtz, J.
- Journal of Catalysis, Vol. 168, Issue 2
In Situ Observations of Free-Standing Graphene-like Mono- and Bilayer ZnO Membranes
journal, October 2015
- Quang, Huy T.; Bachmatiuk, Alicja; Dianat, Arezoo
- ACS Nano, Vol. 9, Issue 11
The interaction of CO2 with sodium-promoted W(011)
journal, January 2005
- Viñes, F.; Borodin, A.; Höfft, O.
- Physical Chemistry Chemical Physics, Vol. 7, Issue 22
Adsorption of CO2 on pristine Zn–ZnO(0001) and defected Zn–ZnO(0001): A thermal desorption spectroscopy study
journal, March 2005
- Wang, J.; Hokkanen, B.; Burghaus, U.
- Surface Science, Vol. 577, Issue 2-3
Growth of Single- and Bilayer ZnO on Au(111) and Interaction with Copper
journal, May 2013
- Deng, Xingyi; Yao, Kun; Sun, Keju
- The Journal of Physical Chemistry C, Vol. 117, Issue 21
CO oxidation over ZnO films on Pt(111) at near-atmospheric pressures
journal, May 2013
- Martynova, Y.; Liu, B. -H.; McBriarty, M. E.
- Journal of Catalysis, Vol. 301