Skip to main content

Lund University Publications

LUND UNIVERSITY LIBRARIES

Interaction of sulfur dioxide and near-ambient pressures of water vapor with cuprous oxide surfaces

Soldemo, Markus ; Stenlid, Joakim Halldin ; Besharat, Zahra ; Johansson, Niclas LU ; Önsten, Anneli ; Knudsen, Jan LU ; Schnadt, Joachim LU orcid ; Göthelid, Mats ; Brinck, Tore and Weissenrieder, Jonas LU (2017) In Journal of Physical Chemistry C 121(43). p.24011-24024
Abstract

The interaction of water vapor and sulfur dioxide (SO2) with single crystal cuprous oxide (Cu2O) surfaces of (100) and (111) termination was studied by photoelectron spectroscopy (PES) and density functional theory (DFT). Exposure to near-ambient pressures of water vapor, at 5 × 10-3 %RH and 293 K, hydroxylates both Cu2O surfaces with OH coverage up to 0.38 copper monolayers (ML) for (100) and 0.25 ML for (111). O 1s surface core level shifts indicate that the hydroxylation lifts the (3,0;1,1) reconstruction of the clean (100) surface. On both clean Cu2O terminations, SO2 adsorbs to unsaturated surface oxygen atoms to form SO3 species with coverage, after a saturating... (More)

The interaction of water vapor and sulfur dioxide (SO2) with single crystal cuprous oxide (Cu2O) surfaces of (100) and (111) termination was studied by photoelectron spectroscopy (PES) and density functional theory (DFT). Exposure to near-ambient pressures of water vapor, at 5 × 10-3 %RH and 293 K, hydroxylates both Cu2O surfaces with OH coverage up to 0.38 copper monolayers (ML) for (100) and 0.25 ML for (111). O 1s surface core level shifts indicate that the hydroxylation lifts the (3,0;1,1) reconstruction of the clean (100) surface. On both clean Cu2O terminations, SO2 adsorbs to unsaturated surface oxygen atoms to form SO3 species with coverage, after a saturating SO2 dose, corresponding to 0.20 ML on the Cu2O(100) surface and 0.09 ML for the Cu2O(111) surface. Our combined DFT and PES results suggest that the SO2 to SO3 transformation is largely facilitated by unsaturated copper atoms at the Cu2O(111) surface. SO3-terminated surfaces exposed to low doses of water vapor (=100 langmuirs) in ultrahigh vacuum show no adsorption or reaction. However, during exposure to near-ambient pressures of water vapor, the SO3 species dissociate, and sulfur replaces a Cu2O lattice oxygen in a reaction that forms Cu2S. The hydroxylation of the Cu2O surfaces is believed to play a central role in the reaction.

(Less)
Please use this url to cite or link to this publication:
author
; ; ; ; ; ; ; ; and
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Journal of Physical Chemistry C
volume
121
issue
43
pages
24011 - 24024
publisher
The American Chemical Society (ACS)
external identifiers
  • scopus:85032831257
  • scopus:85032623324
  • wos:000414724300019
ISSN
1932-7447
DOI
10.1021/acs.jpcc.7b06486
language
English
LU publication?
yes
id
47ec8ab7-d337-4488-91df-87d07a212378
date added to LUP
2017-11-10 11:49:47
date last changed
2024-03-18 00:23:53
@article{47ec8ab7-d337-4488-91df-87d07a212378,
  abstract     = {{<p>The interaction of water vapor and sulfur dioxide (SO<sub>2</sub>) with single crystal cuprous oxide (Cu<sub>2</sub>O) surfaces of (100) and (111) termination was studied by photoelectron spectroscopy (PES) and density functional theory (DFT). Exposure to near-ambient pressures of water vapor, at 5 × 10-3 %RH and 293 K, hydroxylates both Cu<sub>2</sub>O surfaces with OH coverage up to 0.38 copper monolayers (ML) for (100) and 0.25 ML for (111). O 1s surface core level shifts indicate that the hydroxylation lifts the (3,0;1,1) reconstruction of the clean (100) surface. On both clean Cu<sub>2</sub>O terminations, SO<sub>2</sub> adsorbs to unsaturated surface oxygen atoms to form SO<sub>3</sub> species with coverage, after a saturating SO<sub>2</sub> dose, corresponding to 0.20 ML on the Cu<sub>2</sub>O(100) surface and 0.09 ML for the Cu<sub>2</sub>O(111) surface. Our combined DFT and PES results suggest that the SO<sub>2</sub> to SO<sub>3</sub> transformation is largely facilitated by unsaturated copper atoms at the Cu<sub>2</sub>O(111) surface. SO<sub>3</sub>-terminated surfaces exposed to low doses of water vapor (=100 langmuirs) in ultrahigh vacuum show no adsorption or reaction. However, during exposure to near-ambient pressures of water vapor, the SO<sub>3</sub> species dissociate, and sulfur replaces a Cu<sub>2</sub>O lattice oxygen in a reaction that forms Cu<sub>2</sub>S. The hydroxylation of the Cu<sub>2</sub>O surfaces is believed to play a central role in the reaction.</p>}},
  author       = {{Soldemo, Markus and Stenlid, Joakim Halldin and Besharat, Zahra and Johansson, Niclas and Önsten, Anneli and Knudsen, Jan and Schnadt, Joachim and Göthelid, Mats and Brinck, Tore and Weissenrieder, Jonas}},
  issn         = {{1932-7447}},
  language     = {{eng}},
  number       = {{43}},
  pages        = {{24011--24024}},
  publisher    = {{The American Chemical Society (ACS)}},
  series       = {{Journal of Physical Chemistry C}},
  title        = {{Interaction of sulfur dioxide and near-ambient pressures of water vapor with cuprous oxide surfaces}},
  url          = {{http://dx.doi.org/10.1021/acs.jpcc.7b06486}},
  doi          = {{10.1021/acs.jpcc.7b06486}},
  volume       = {{121}},
  year         = {{2017}},
}