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

Zhang, Rui; Li, Liang; Frazer, Laszlo; Chang, Kelvin B.; Poeppelmeier, Kenneth R.; Chan, Maria K.  Y.; Guest, Jeffrey R.

doi:10.1039/c8cp06023a

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

Journal Article · 11 October 2018 · Physical Chemistry Chemical Physics. PCCP

DOI: https://doi.org/10.1039/c8cp06023a · OSTI ID:1484245

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Argonne National Lab. (ANL), Argonne, IL (United States). Center for Nanoscale Materials
Monash Univ., Melbourne, VIC (Australia). Centre of Excellence in Exciton Science
Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry

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 (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 ~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.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC02-05CH11231; AC02-06CH11357; SC0001785

OSTI ID:: 1484245

Journal Information:: Physical Chemistry Chemical Physics. PCCP, Journal Name: Physical Chemistry Chemical Physics. PCCP Journal Issue: 43 Vol. 20; ISSN 1463-9076; ISSN PPCPFQ

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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