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Title: Enhanced adsorption of CO 2 at steps of ultrathin ZnO: the importance of Zn–O geometry and coordination

In this paper, the interaction between CO 2 and ultrathin ZnO supported on Au(111) has been studied using temperature programmed desorption (TPD) and density functional theory (DFT) calculations. We find that CO 2 binds weakly on the planar ZnO bilayer and trilayer surfaces, desorbing at T = 130 K. CO 2 binds more strongly at the steps formed between ZnO bilayers and trilayers, desorbing at T = 285–320 K depending upon the CO 2 exposure. The adsorption energies determined from DFT calculations for CO 2 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 CO 2 exposures (7.7 and 19.5 kcal mol –1, respectively). The DFT calculations further identify that the most stable adsorption configuration of CO 2 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 CO 2 molecule to the tri-fold coordinated O anions at the trilayer edgemore » and to the neighboring Zn cations on the bilayer terrace, respectively, leading to CO 2 bending and formation of a carbonate-like species.« less
Authors:
ORCiD logo [1] ;  [2] ;  [1]
  1. National Energy Technology Lab. (NETL), Pittsburgh, PA, (United States); AECOM, South Park, PA (United States)
  2. National Energy Technology Lab. (NETL), Pittsburgh, PA, (United States)
Publication Date:
Grant/Contract Number:
FE0004000
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
Research Org:
National Energy Technology Lab. (NETL), Pittsburgh, PA, (United States)
Sponsoring Org:
USDOE Office of Fossil Energy (FE)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1478624

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., 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. doi:10.1039/c6cp08379j.
Deng, Xingyi, Sorescu, Dan C., and Lee, Junseok. 2017. "Enhanced adsorption of CO2 at steps of ultrathin ZnO: the importance of Zn–O geometry and coordination". United States. doi: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 = {2017},
month = {1}
}

Works referenced in this record:

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
  • DOI: 10.1103/PhysRevLett.77.3865

Projector augmented-wave method
journal, December 1994

Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996

Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996

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
  • DOI: 10.1103/PhysRevB.57.1505

A climbing image nudged elastic band method for finding saddle points and minimum energy paths
journal, December 2000
  • Henkelman, Graeme; Uberuaga, Blas P.; J�nsson, Hannes
  • The Journal of Chemical Physics, Vol. 113, Issue 22, p. 9901-9904
  • DOI: 10.1063/1.1329672