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Title: Atomistic determination of the surface structure of Cu 2O(111): experiment and theory

Abstract

Cuprous oxide (Cu 2O) is a promising catalyst for several important reactions. However, the atomic structures of defective Cu 2O surfaces, which critically affect the catalytic properties both thermodynamically and kinetically, are not unambiguously characterized. High-resolution scanning tunneling microscopy (STM), combined with density functional theory (DFT) calculations and STM simulations, has been used to determine the atomic structure of the (111) surface of a Cu 2O bulk crystal. The single crystal surface, processed by ultrahigh vacuum cleaning and oxygen annealing, shows a (1 x 1) periodicity in the low-energy electron diffraction pattern. The pristine (defect-free) Cu 2O(111) surface exhibits a lattice of protrusions with hexagonal symmetry under STM, which is attributed to the dangling bonds of the coordinatively unsaturated copper (Cu-U) atoms on the surface. Two types of surface atomic defects are also identified, including the Cu-U vacancy and the oxygen-vacancy-induced local surface restructuring. The electronic structure of this surface measured by dI/dV spectroscopy shows an energy band gap of approximate to 1.6-2.1 eV. Consistent with dI/dV measurements, DFT calculations identified surface states within the electronic band gap arising from the Cu ions on the surface. Our results provide a clear picture of the pristine and defective Cu 2O(111) surfacemore » structure in addition to the formation mechanism of the reconstructed surface, paving the way toward studying the site-dependent reactivity of this surface.« less

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2];  [3]; ORCiD logo [4]; ORCiD logo [1]; ORCiD logo [1]
  1. Center for Nanoscale Materials; Argonne National Laboratory; Argonne; USA
  2. Centre of Excellence in Exciton Science; UNSW; Sydney; Australia; Monash University
  3. Department of Chemistry; Northwestern University; Evanston; USA
  4. Department of Chemistry; Northwestern University; Evanston; USA; Chemical Sciences and Engineering Division
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1484245
Alternate Identifier(s):
OSTI ID: 1479122
Grant/Contract Number:  
AC02-06CH11357; FG02-09ER16109; DE AC02-05CH11231
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: 20; Journal Issue: 43; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English

Citation Formats

Zhang, Rui, Li, Liang, Frazer, Laszlo, Chang, Kelvin B., Poeppelmeier, Kenneth R., Chan, Maria K. Y., and Guest, Jeffrey R. Atomistic determination of the surface structure of Cu2O(111): experiment and theory. United States: N. p., 2018. Web. doi:10.1039/c8cp06023a.
Zhang, Rui, Li, Liang, Frazer, Laszlo, Chang, Kelvin B., Poeppelmeier, Kenneth R., Chan, Maria K. Y., & Guest, Jeffrey R. Atomistic determination of the surface structure of Cu2O(111): experiment and theory. United States. doi:10.1039/c8cp06023a.
Zhang, Rui, Li, Liang, Frazer, Laszlo, Chang, Kelvin B., Poeppelmeier, Kenneth R., Chan, Maria K. Y., and Guest, Jeffrey R. Mon . "Atomistic determination of the surface structure of Cu2O(111): experiment and theory". United States. doi:10.1039/c8cp06023a. https://www.osti.gov/servlets/purl/1484245.
@article{osti_1484245,
title = {Atomistic determination of the surface structure of Cu2O(111): experiment and theory},
author = {Zhang, Rui and Li, Liang and Frazer, Laszlo and Chang, Kelvin B. and Poeppelmeier, Kenneth R. and Chan, Maria K. Y. and Guest, Jeffrey R.},
abstractNote = {Cuprous oxide (Cu2O) is a promising catalyst for several important reactions. However, the atomic structures of defective Cu2O surfaces, which critically affect the catalytic properties both thermodynamically and kinetically, are not unambiguously characterized. High-resolution scanning tunneling microscopy (STM), combined with density functional theory (DFT) calculations and STM simulations, has been used to determine the atomic structure of the (111) surface of a Cu2O bulk crystal. The single crystal surface, processed by ultrahigh vacuum cleaning and oxygen annealing, shows a (1 x 1) periodicity in the low-energy electron diffraction pattern. The pristine (defect-free) Cu2O(111) surface exhibits a lattice of protrusions with hexagonal symmetry under STM, which is attributed to the dangling bonds of the coordinatively unsaturated copper (Cu-U) atoms on the surface. Two types of surface atomic defects are also identified, including the Cu-U vacancy and the oxygen-vacancy-induced local surface restructuring. The electronic structure of this surface measured by dI/dV spectroscopy shows an energy band gap of approximate to 1.6-2.1 eV. Consistent with dI/dV measurements, DFT calculations identified surface states within the electronic band gap arising from the Cu ions on the surface. Our results provide a clear picture of the pristine and defective Cu2O(111) surface structure in addition to the formation mechanism of the reconstructed surface, paving the way toward studying the site-dependent reactivity of this surface.},
doi = {10.1039/c8cp06023a},
journal = {Physical Chemistry Chemical Physics. PCCP (Print)},
number = 43,
volume = 20,
place = {United States},
year = {2018},
month = {1}
}

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