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Title: Atomistic determination of the surface structure of Cu2O(111): experiment and theory

Abstract

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 × 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 (CuU) atoms on the surface. Two types of surface atomic defects are also identified, including the CuU 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 ~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 mechanismmore » 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 [3]; ORCiD logo [1]; ORCiD logo [1]
  1. Argonne National Lab. (ANL), Argonne, IL (United States). Center for Nanoscale Materials
  2. Monash Univ., Melbourne, VIC (Australia). Centre of Excellence in Exciton Science
  3. Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
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
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

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. Fri . "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 × 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 (CuU) atoms on the surface. Two types of surface atomic defects are also identified, including the CuU 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 ~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 = {10}
}

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Works referenced in this record:

Evaluation of defects in cuprous oxide through exciton luminescence imaging
journal, March 2015


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

CO 2 Adsorption on Cu 2 O(111): A DFT+U and DFT-D Study
journal, November 2013

  • Bendavid, Leah Isseroff; Carter, Emily A.
  • The Journal of Physical Chemistry C, Vol. 117, Issue 49
  • DOI: 10.1021/jp407468t

Surface oxides of the oxygen–copper system: Precursors to the bulk oxide phase?
journal, December 2007


Photocatalytic Conversion of Carbon Dioxide with Water into Methane: Platinum and Copper(I) Oxide Co-catalysts with a Core-Shell Structure
journal, April 2013

  • Zhai, Qingge; Xie, Shunji; Fan, Wenqing
  • Angewandte Chemie International Edition, Vol. 52, Issue 22
  • DOI: 10.1002/anie.201301473

Atomic structure of Cu2O(111)
journal, January 2009


Photovoltaic and Photoelectrochemical Solar Energy Conversion with Cu 2 O
journal, November 2015


Imaging Catalytic Activation of CO 2 on Cu 2 O (110): A First-Principles Study
journal, March 2018


Mechanism of C–C and C–H bond cleavage in ethanol oxidation reaction on Cu 2 O(111): a DFT-D and DFT+U study
journal, January 2017

  • Xu, Han; Miao, Bei; Zhang, Minhua
  • Physical Chemistry Chemical Physics, Vol. 19, Issue 38
  • DOI: 10.1039/C7CP04630H

From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999


Temperature dependence of luminescence lifetime in Cu2O
journal, May 2000


Growth and Surface Properties of Cuprous Oxide Films on Au(111)
journal, March 2015

  • Sträter, Hendrik; Fedderwitz, Hanna; Groß, Boris
  • The Journal of Physical Chemistry C, Vol. 119, Issue 11
  • DOI: 10.1021/jp511327h

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

Plane-wave pseudopotential density functional theory periodic slab calculations of CO adsorption on Cu2O(111) surface
journal, April 2005


Removal of Copper Vacancies in Cuprous Oxide Single Crystals Grown by the Floating Zone Method
journal, October 2013

  • Chang, Kelvin B.; Frazer, Laszlo; Schwartz, Johanna J.
  • Crystal Growth & Design, Vol. 13, Issue 11
  • DOI: 10.1021/cg401081m

Acceptor Levels in p -Type Cu 2 O : Rationalizing Theory and Experiment
journal, August 2009


Copper(I)-Based p -Type Oxides for Photoelectrochemical and Photovoltaic Solar Energy Conversion
journal, August 2016


Stable Aqueous Photoelectrochemical CO 2 Reduction by a Cu 2 O Dark Cathode with Improved Selectivity for Carbonaceous Products
journal, May 2016

  • Chang, Xiaoxia; Wang, Tuo; Zhang, Peng
  • Angewandte Chemie International Edition, Vol. 55, Issue 31
  • DOI: 10.1002/anie.201602973

Cu 2 O Nanowire Photocathodes for Efficient and Durable Solar Water Splitting
journal, February 2016


Reaction mechanism of CO oxidation on Cu2O(111): A density functional study
journal, October 2010

  • Sun, Bao-Zhen; Chen, Wen-Kai; Xu, Yi-Jun
  • The Journal of Chemical Physics, Vol. 133, Issue 15
  • DOI: 10.1063/1.3489663

All-oxide solar cells based on electrodeposited Cu2O absorber and atomic layer deposited ZnMgO on precious-metal-free electrode
journal, March 2017


Adsorption and dissociation of O2 on the Cu2O(111) surface: Thermochemistry, reaction barrier
journal, March 2011


High-pressure x-ray study of Cu 2 O and Ag 2 O
journal, May 1982


Undoped n -Type Cu 2 O: Fact or Fiction?
journal, August 2010

  • Scanlon, David O.; Watson, Graeme W.
  • The Journal of Physical Chemistry Letters, Vol. 1, Issue 17
  • DOI: 10.1021/jz100962n

Electronic structures of active sites on metal oxide surfaces: definition of the copper-zinc oxide methanol synthesis catalyst by photoelectron spectroscopy
journal, December 1993

  • Solomon, Edward I.; Jones, Paul M.; May, Jennifer A.
  • Chemical Reviews, Vol. 93, Issue 8
  • DOI: 10.1021/cr00024a003

Thermodynamic stability and structure of copper oxide surfaces: A first-principles investigation
journal, March 2007


CO 2 conversion to methanol on Cu( i ) oxide nanolayers and clusters: an electronic structure insight into the reaction mechanism
journal, January 2015

  • Uzunova, Ellie L.; Seriani, Nicola; Mikosch, Hans
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 16
  • DOI: 10.1039/C5CP01267H

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


Theory and Application for the Scanning Tunneling Microscope
journal, June 1983


Incorrect DFT-GGA predictions of the stability of non-stoichiometric/polar dielectric surfaces: the case of Cu 2 O(111)
journal, January 2016

  • Nilius, Niklas; Fedderwitz, Hanna; Groß, Boris
  • Physical Chemistry Chemical Physics, Vol. 18, Issue 9
  • DOI: 10.1039/C5CP06933E

First-Principles Predictions of the Structure, Stability, and Photocatalytic Potential of Cu 2 O Surfaces
journal, September 2013

  • Bendavid, Leah Isseroff; Carter, Emily A.
  • The Journal of Physical Chemistry B, Vol. 117, Issue 49
  • DOI: 10.1021/jp406454c

Special points for Brillouin-zone integrations
journal, June 1976

  • Monkhorst, Hendrik J.; Pack, James D.
  • Physical Review B, Vol. 13, Issue 12, p. 5188-5192
  • DOI: 10.1103/PhysRevB.13.5188

Bulk and surface properties of Cu2O: A first-principles investigation
journal, June 2009

  • Islam, Mazharul M.; Diawara, Boubakar; Maurice, Vincent
  • Journal of Molecular Structure: THEOCHEM, Vol. 903, Issue 1-3
  • DOI: 10.1016/j.theochem.2009.02.037

Importance of reference Hamiltonians containing exact exchange for accurate one-shot G W calculations of Cu 2 O
journal, June 2012


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


Temperature-dependent phase evolution of copper-oxide thin-films on Au(111)
journal, January 2018

  • Möller, Christoph; Fedderwitz, Hanna; Noguera, Claudine
  • Physical Chemistry Chemical Physics, Vol. 20, Issue 8
  • DOI: 10.1039/C7CP08387D

Band-structure calculations for the 3 d transition metal oxides in G W
journal, February 2013


TiO2-based Photocatalysis: Surface Defects, Oxygen and Charge Transfer
journal, July 2005


Dehydrogenation of methanol on Cu 2 O(100) and (111)
journal, June 2017

  • Besharat, Zahra; Halldin Stenlid, Joakim; Soldemo, Markus
  • The Journal of Chemical Physics, Vol. 146, Issue 24
  • DOI: 10.1063/1.4989472

Interaction of Sulfur Dioxide and Near-Ambient Pressures of Water Vapor with Cuprous Oxide Surfaces
journal, October 2017

  • Soldemo, Markus; Stenlid, Joakim Halldin; Besharat, Zahra
  • The Journal of Physical Chemistry C, Vol. 121, Issue 43
  • DOI: 10.1021/acs.jpcc.7b06486

Giant Rydberg excitons in the copper oxide Cu2O
journal, October 2014

  • Kazimierczuk, T.; Fröhlich, D.; Scheel, S.
  • Nature, Vol. 514, Issue 7522
  • DOI: 10.1038/nature13832

Cupric oxide inclusions in cuprous oxide crystals grown by the floating zone method
journal, June 2015

  • Frazer, Laszlo; Chang, Kelvin B.; Poeppelmeier, Kenneth R.
  • Science and Technology of Advanced Materials, Vol. 16, Issue 3
  • DOI: 10.1088/1468-6996/16/3/034901

Oxidation energies of transition metal oxides within the GGA + U framework
journal, May 2006


Density functional theory study on the mechanism of CO sensing on Cu2O (111) surface: Influence of the pre-adsorbed oxygen atom
journal, January 2014


Binary copper oxide semiconductors: From materials towards devices
journal, June 2012

  • Meyer, B. K.; Polity, A.; Reppin, D.
  • physica status solidi (b), Vol. 249, Issue 8
  • DOI: 10.1002/pssb.201248128

Role of Defects in Surface Chemistry on Cu 2 O(111)
journal, September 2013

  • Önsten, Anneli; Weissenrieder, Jonas; Stoltz, Dunja
  • The Journal of Physical Chemistry C, Vol. 117, Issue 38
  • DOI: 10.1021/jp3112217

Defects in Cu2O, CuAlO2 and SrCu2O2 transparent conducting oxides
journal, September 2008


Photoemission and low-energy-electron-diffraction study of clean and oxygen-dosed Cu 2 O (111) and (100) surfaces
journal, January 1991


Stable Aqueous Photoelectrochemical CO 2 Reduction by a Cu 2 O Dark Cathode with Improved Selectivity for Carbonaceous Products
journal, May 2016