Tuning the Water Reactivity of LaCoO3 Surfaces by Subsurface Engineering
(2026) In Langmuir 42(18). p.12498-12508- Abstract
Perovskite oxides are a versatile class of materials with tunable electronic structures, making them attractive for catalytic applications, including the oxygen evolution reaction (OER). The surface reactivity of these oxides is closely tied to the electronic structure of transition metal cations, particularly their 3d orbital occupation, which can be modulated by interfacial engineering. In this work, we investigate how subsurface engineering influences the interaction of ultrathin LaCoO3 films with water vapor. Using (near) ambient pressure core-level spectroscopy, we observe distinct differences in hydroxyl affinity and Co valence response depending on the electronic structure imposed by the underlying layer. Ultrathin... (More)
Perovskite oxides are a versatile class of materials with tunable electronic structures, making them attractive for catalytic applications, including the oxygen evolution reaction (OER). The surface reactivity of these oxides is closely tied to the electronic structure of transition metal cations, particularly their 3d orbital occupation, which can be modulated by interfacial engineering. In this work, we investigate how subsurface engineering influences the interaction of ultrathin LaCoO3 films with water vapor. Using (near) ambient pressure core-level spectroscopy, we observe distinct differences in hydroxyl affinity and Co valence response depending on the electronic structure imposed by the underlying layer. Ultrathin LaCoO3 films with a higher initial Co oxidation state show stronger hydroxyl affinity, while those with a lower Co valence show more significant electronic changes upon water exposure. Our findings demonstrate a form of “remote control” in surface chemistry, where subsurface electronic engineering dictates hydroxyl affinity and electronic response at the surface. This concept offers a new degree of freedom to optimize oxide–adsorbate interactions for (electro)catalysis.
(Less)
- author
- organization
- publishing date
- 2026-05
- type
- Contribution to journal
- publication status
- published
- subject
- in
- Langmuir
- volume
- 42
- issue
- 18
- pages
- 11 pages
- publisher
- The American Chemical Society (ACS)
- external identifiers
-
- pmid:42047255
- scopus:105038561083
- ISSN
- 0743-7463
- DOI
- 10.1021/acs.langmuir.5c06681
- language
- English
- LU publication?
- yes
- id
- df411651-6c64-4d63-9e8b-ec4ca240db1b
- date added to LUP
- 2026-08-17 15:32:18
- date last changed
- 2026-09-14 17:11:53
@article{df411651-6c64-4d63-9e8b-ec4ca240db1b,
abstract = {{<p>Perovskite oxides are a versatile class of materials with tunable electronic structures, making them attractive for catalytic applications, including the oxygen evolution reaction (OER). The surface reactivity of these oxides is closely tied to the electronic structure of transition metal cations, particularly their 3d orbital occupation, which can be modulated by interfacial engineering. In this work, we investigate how subsurface engineering influences the interaction of ultrathin LaCoO<sub>3</sub> films with water vapor. Using (near) ambient pressure core-level spectroscopy, we observe distinct differences in hydroxyl affinity and Co valence response depending on the electronic structure imposed by the underlying layer. Ultrathin LaCoO<sub>3</sub> films with a higher initial Co oxidation state show stronger hydroxyl affinity, while those with a lower Co valence show more significant electronic changes upon water exposure. Our findings demonstrate a form of “remote control” in surface chemistry, where subsurface electronic engineering dictates hydroxyl affinity and electronic response at the surface. This concept offers a new degree of freedom to optimize oxide–adsorbate interactions for (electro)catalysis.</p>}},
author = {{Kiens, Ellen M. and Pérez-Penco, Ester and van den Bosch, Iris C.G. and Mauri, Silvia and van der Minne, Emma and van Spronsen, Matthijs A. and de Groot, Frank and Mul, Guido and Koster, Gertjan and Torelli, Piero and Bliem, Roland and Mei, Bastian and Baeumer, Christoph}},
issn = {{0743-7463}},
language = {{eng}},
number = {{18}},
pages = {{12498--12508}},
publisher = {{The American Chemical Society (ACS)}},
series = {{Langmuir}},
title = {{Tuning the Water Reactivity of LaCoO<sub>3</sub> Surfaces by Subsurface Engineering}},
url = {{http://dx.doi.org/10.1021/acs.langmuir.5c06681}},
doi = {{10.1021/acs.langmuir.5c06681}},
volume = {{42}},
year = {{2026}},
}