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Title: D 2O Interaction with Planar ZnO(0001) Bilayer Supported on Au(111): Structures, Energetics and Influence of Hydroxyls

Here, we investigate the interaction between D 2O and the planar ZnO(0001) bilayer grown on Au(111) with temperature programmed desorption (TPD), low energy electron diffraction (LEED), X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT) calculations. We show that D 2O molecules adsorbed on this planar surface form two ordered overlayers, a (3 × 3) and a (√3 × √3) R30°, not seen before on any of the bulk ZnO single crystal surfaces. The apparent activation energies of desorption (Ed) estimated from TPD peaks are 15.2 and 16.7–17.3 kcal/mol for (3 × 3) and (√3 × √3) R30°, respectively, which agree well with the adsorption energy values calculated from DFT (14.9–15.6 kcal/mol and 16.8–16.9 kcal/mol, respectively). The DFT calculations reveal that the formation of the overlayers takes place at different packing densities and is mediated by extensive hydrogen bonding among the molecules. The hydroxyl groups, which accumulate very slowly on the ZnO(0001) bilayer surface under the standard ultrahigh vacuum (UHV) environment, strongly suppress the formation of the (√3 × √3) R30° overlayer but have less impact on the (3 × 3) overlayer. These findings are explained based on the difference in packing densities of the overlayers such that only themore » (3 × 3) overlayer with a more open structure can accommodate small amounts of the adsorbed hydroxyl groups.« less
Authors:
 [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:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 120; Journal Issue: 15; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
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:
1478191

Deng, Xingyi, Sorescu, Dan C., and Lee, Junseok. D2O Interaction with Planar ZnO(0001) Bilayer Supported on Au(111): Structures, Energetics and Influence of Hydroxyls. United States: N. p., Web. doi:10.1021/acs.jpcc.6b00862.
Deng, Xingyi, Sorescu, Dan C., & Lee, Junseok. D2O Interaction with Planar ZnO(0001) Bilayer Supported on Au(111): Structures, Energetics and Influence of Hydroxyls. United States. doi:10.1021/acs.jpcc.6b00862.
Deng, Xingyi, Sorescu, Dan C., and Lee, Junseok. 2016. "D2O Interaction with Planar ZnO(0001) Bilayer Supported on Au(111): Structures, Energetics and Influence of Hydroxyls". United States. doi:10.1021/acs.jpcc.6b00862. https://www.osti.gov/servlets/purl/1478191.
@article{osti_1478191,
title = {D2O Interaction with Planar ZnO(0001) Bilayer Supported on Au(111): Structures, Energetics and Influence of Hydroxyls},
author = {Deng, Xingyi and Sorescu, Dan C. and Lee, Junseok},
abstractNote = {Here, we investigate the interaction between D2O and the planar ZnO(0001) bilayer grown on Au(111) with temperature programmed desorption (TPD), low energy electron diffraction (LEED), X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT) calculations. We show that D2O molecules adsorbed on this planar surface form two ordered overlayers, a (3 × 3) and a (√3 × √3)R30°, not seen before on any of the bulk ZnO single crystal surfaces. The apparent activation energies of desorption (Ed) estimated from TPD peaks are 15.2 and 16.7–17.3 kcal/mol for (3 × 3) and (√3 × √3)R30°, respectively, which agree well with the adsorption energy values calculated from DFT (14.9–15.6 kcal/mol and 16.8–16.9 kcal/mol, respectively). The DFT calculations reveal that the formation of the overlayers takes place at different packing densities and is mediated by extensive hydrogen bonding among the molecules. The hydroxyl groups, which accumulate very slowly on the ZnO(0001) bilayer surface under the standard ultrahigh vacuum (UHV) environment, strongly suppress the formation of the (√3 × √3)R30° overlayer but have less impact on the (3 × 3) overlayer. These findings are explained based on the difference in packing densities of the overlayers such that only the (3 × 3) overlayer with a more open structure can accommodate small amounts of the adsorbed hydroxyl groups.},
doi = {10.1021/acs.jpcc.6b00862},
journal = {Journal of Physical Chemistry. C},
number = 15,
volume = 120,
place = {United States},
year = {2016},
month = {3}
}