Interaction of sulfur dioxide and near-ambient pressures of water vapor with cuprous oxide surfaces
(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)
- author
- Soldemo, Markus
; Stenlid, Joakim Halldin
; Besharat, Zahra
; Johansson, Niclas
LU
; Önsten, Anneli
; Knudsen, Jan
LU
; Schnadt, Joachim
LU
; Göthelid, Mats ; Brinck, Tore and Weissenrieder, Jonas LU
- organization
- publishing date
- 2017
- 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:85032623324
- wos:000414724300019
- scopus:85032831257
- 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
- 2025-01-06 23:53:50
@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}}, }