Multi modal time-resolved infrared and X-ray spectroscopic operando studies of the CO oxidation and NO reduction reactions on Rh(111)
Rämisch, Lisa LU ; Temperton, Robert LU ; Gericke, Sabrina M. LU ; Pfaff, Sebastian LU ; Shavorskiy, Andrey LU ; Lundgren, Edvin LU ; Zetterberg, Johan LU
and García-Martínez, Fernando
(2025)
In Applied Surface Science
687.
- Abstract
We present an operando study where Ambient-Pressure X-ray Photoelectron Spectroscopy (AP-XPS), Polarization Modulation-InfraRed Reflection Absorption Spectroscopy (PM-IRRAS) and Mass Spectrometry (MS) were employed simultaneously with sub-minute time resolution to monitor the CO oxidation and NO reduction reactions on Rh(111). AP-XPS is a powerful tool to follow reactions at the surface-gas interface at near-ambient pressures, yet with challenges at sub-minute time resolutions. PM-IRRAS allows to identify molecular adsorbate sites with sub-minute resolution. Therefore, PM-IRRAS can serve as complementary tool alongside dynamic AP-XPS measurements, when the interpretation of photoemission spectra is limited by overlapping contributions... (More)
We present an operando study where Ambient-Pressure X-ray Photoelectron Spectroscopy (AP-XPS), Polarization Modulation-InfraRed Reflection Absorption Spectroscopy (PM-IRRAS) and Mass Spectrometry (MS) were employed simultaneously with sub-minute time resolution to monitor the CO oxidation and NO reduction reactions on Rh(111). AP-XPS is a powerful tool to follow reactions at the surface-gas interface at near-ambient pressures, yet with challenges at sub-minute time resolutions. PM-IRRAS allows to identify molecular adsorbate sites with sub-minute resolution. Therefore, PM-IRRAS can serve as complementary tool alongside dynamic AP-XPS measurements, when the interpretation of photoemission spectra is limited by overlapping contributions and low statistics. This multi-modal setup simultaneously monitors individual adsorption sites of molecular adsorbates, the build-up of surface atomic species and oxides, and the effect of the surface chemical species on the catalyst reactivity. To demonstrate the combined setup, model reactions (CO oxidation, NO reduction) were studied on Rh(111) in the mbar range of pressures. For CO oxidation, a decrease of the surface activity towards CO2 production is observed as the Rh surface oxide develops. For NO reduction, a steady N2/CO2 production and an O-free active stage of the reaction are shown. The presented setup provides valuable insights into surface chemical reactions with sub-minute time resolution.
(Less)
- author
- Rämisch, Lisa
LU
; Temperton, Robert
LU
; Gericke, Sabrina M.
LU
; Pfaff, Sebastian
LU
; Shavorskiy, Andrey
LU
; Lundgren, Edvin
LU
; Zetterberg, Johan
LU
and García-Martínez, Fernando
- organization
- publishing date
- 2025-04-01
- type
- Contribution to journal
- publication status
- published
- subject
- keywords
- Mass spectrometry, NAP-XPS, Operando catalysis, PM-IRRAS, Reactor development, Reflectance microscopy, Surface spectroscopy
- in
- Applied Surface Science
- volume
- 687
- article number
- 161989
- publisher
- Elsevier
- external identifiers
-
- scopus:85214231329
- ISSN
- 0169-4332
- DOI
- 10.1016/j.apsusc.2024.161989
- language
- English
- LU publication?
- yes
- additional info
- Publisher Copyright: © 2024
- id
- 88bfbe7a-703a-4948-b15a-df107a38290f
- date added to LUP
- 2025-03-21 10:31:57
- date last changed
- 2025-04-04 14:53:54
@article{88bfbe7a-703a-4948-b15a-df107a38290f,
abstract = {{<p>We present an operando study where Ambient-Pressure X-ray Photoelectron Spectroscopy (AP-XPS), Polarization Modulation-InfraRed Reflection Absorption Spectroscopy (PM-IRRAS) and Mass Spectrometry (MS) were employed simultaneously with sub-minute time resolution to monitor the CO oxidation and NO reduction reactions on Rh(111). AP-XPS is a powerful tool to follow reactions at the surface-gas interface at near-ambient pressures, yet with challenges at sub-minute time resolutions. PM-IRRAS allows to identify molecular adsorbate sites with sub-minute resolution. Therefore, PM-IRRAS can serve as complementary tool alongside dynamic AP-XPS measurements, when the interpretation of photoemission spectra is limited by overlapping contributions and low statistics. This multi-modal setup simultaneously monitors individual adsorption sites of molecular adsorbates, the build-up of surface atomic species and oxides, and the effect of the surface chemical species on the catalyst reactivity. To demonstrate the combined setup, model reactions (CO oxidation, NO reduction) were studied on Rh(111) in the mbar range of pressures. For CO oxidation, a decrease of the surface activity towards CO2 production is observed as the Rh surface oxide develops. For NO reduction, a steady N<sub>2</sub>/CO<sub>2</sub> production and an O-free active stage of the reaction are shown. The presented setup provides valuable insights into surface chemical reactions with sub-minute time resolution.</p>}},
author = {{Rämisch, Lisa and Temperton, Robert and Gericke, Sabrina M. and Pfaff, Sebastian and Shavorskiy, Andrey and Lundgren, Edvin and Zetterberg, Johan and García-Martínez, Fernando}},
issn = {{0169-4332}},
keywords = {{Mass spectrometry; NAP-XPS; Operando catalysis; PM-IRRAS; Reactor development; Reflectance microscopy; Surface spectroscopy}},
language = {{eng}},
month = {{04}},
publisher = {{Elsevier}},
series = {{Applied Surface Science}},
title = {{Multi modal time-resolved infrared and X-ray spectroscopic operando studies of the CO oxidation and NO reduction reactions on Rh(111)}},
url = {{http://dx.doi.org/10.1016/j.apsusc.2024.161989}},
doi = {{10.1016/j.apsusc.2024.161989}},
volume = {{687}},
year = {{2025}},
}