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Operando Stability Studies of Ultrathin Single-Crystalline IrO2(110) Films under Acidic Oxygen Evolution Reaction Conditions

Weber, Tim ; Vonk, Vedran ; Escalera-López, Daniel ; Abbondanza, Giuseppe LU ; Larsson, Alfred LU ; Koller, Volkmar ; Abb, Marcel J.S. ; Hegedüs, Zoltan ; Bäcker, Thomas and Lienert, Ulrich , et al. (2021) In ACS Catalysis 11(20). p.12651-12660
Abstract

The anodic corrosion behavior of 50 Å thick single-crystalline IrO2(110) films supported on slightly bulk-reduced TiO2(110) single crystals is studied during acidic water splitting by a unique combination of operando techniques, namely, synchrotron-based high-energy X-ray reflectivity (XRR) and surface X-ray diffraction (SXRD) together with highly sensitive inductively coupled plasma mass spectrometry (ICP-MS). Corrosion-induced structural and morphological changes of the IrO2(110) model electrode can be followed on the atomic scale by operando XRR and SXRD that are supplemented with ex situ scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS), whereas with ICP-MS, the corrosion rate can be quantified down to 1... (More)

The anodic corrosion behavior of 50 Å thick single-crystalline IrO2(110) films supported on slightly bulk-reduced TiO2(110) single crystals is studied during acidic water splitting by a unique combination of operando techniques, namely, synchrotron-based high-energy X-ray reflectivity (XRR) and surface X-ray diffraction (SXRD) together with highly sensitive inductively coupled plasma mass spectrometry (ICP-MS). Corrosion-induced structural and morphological changes of the IrO2(110) model electrode can be followed on the atomic scale by operando XRR and SXRD that are supplemented with ex situ scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS), whereas with ICP-MS, the corrosion rate can be quantified down to 1 pg·cm-2·s-1 with a time resolution on the second scale. The operando synchrotron-based X-ray scattering techniques are surprisingly sensitive to Ir corrosion of about 0.10 monolayer of IrO2(110) in ∼26 h, i.e., 0.4 pg·cm-2·s-1. The present study demonstrates that single-crystalline IrO2(110) films are much more stable than hitherto expected. Although the dissolution rate is very small, ICP-MS experiments reveal a significantly higher dissolution rate than the operando high-energy XRR/SXRD experiments. These differences in dissolution rate are suggested to be due to the different modi operandi encountered in ICP-MS (dynamic) and operando XRR/SXRD experiments (steady state), a fact that may need to be considered when hydrogen production is coupled to intermittent energy sources such as renewables.

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organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
electrocatalyst stability, HESXRD, IrO, operando studies, oxygen evolution reaction (OER), SFC-ICP-MS, single-crystalline model electrodes, XRR
in
ACS Catalysis
volume
11
issue
20
pages
10 pages
publisher
The American Chemical Society (ACS)
external identifiers
  • scopus:85117227250
ISSN
2155-5435
DOI
10.1021/acscatal.1c03599
language
English
LU publication?
yes
additional info
Publisher Copyright: © 2021 American Chemical Society.
id
96f8aeaa-7d54-459f-b200-660b4c46a75e
date added to LUP
2021-10-26 15:12:15
date last changed
2023-11-23 10:50:42
@article{96f8aeaa-7d54-459f-b200-660b4c46a75e,
  abstract     = {{<p>The anodic corrosion behavior of 50 Å thick single-crystalline IrO2(110) films supported on slightly bulk-reduced TiO2(110) single crystals is studied during acidic water splitting by a unique combination of operando techniques, namely, synchrotron-based high-energy X-ray reflectivity (XRR) and surface X-ray diffraction (SXRD) together with highly sensitive inductively coupled plasma mass spectrometry (ICP-MS). Corrosion-induced structural and morphological changes of the IrO2(110) model electrode can be followed on the atomic scale by operando XRR and SXRD that are supplemented with ex situ scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS), whereas with ICP-MS, the corrosion rate can be quantified down to 1 pg·cm-2·s-1 with a time resolution on the second scale. The operando synchrotron-based X-ray scattering techniques are surprisingly sensitive to Ir corrosion of about 0.10 monolayer of IrO2(110) in ∼26 h, i.e., 0.4 pg·cm-2·s-1. The present study demonstrates that single-crystalline IrO2(110) films are much more stable than hitherto expected. Although the dissolution rate is very small, ICP-MS experiments reveal a significantly higher dissolution rate than the operando high-energy XRR/SXRD experiments. These differences in dissolution rate are suggested to be due to the different modi operandi encountered in ICP-MS (dynamic) and operando XRR/SXRD experiments (steady state), a fact that may need to be considered when hydrogen production is coupled to intermittent energy sources such as renewables.</p>}},
  author       = {{Weber, Tim and Vonk, Vedran and Escalera-López, Daniel and Abbondanza, Giuseppe and Larsson, Alfred and Koller, Volkmar and Abb, Marcel J.S. and Hegedüs, Zoltan and Bäcker, Thomas and Lienert, Ulrich and Harlow, Gary S. and Stierle, Andreas and Cherevko, Serhiy and Lundgren, Edvin and Over, Herbert}},
  issn         = {{2155-5435}},
  keywords     = {{electrocatalyst stability; HESXRD; IrO; operando studies; oxygen evolution reaction (OER); SFC-ICP-MS; single-crystalline model electrodes; XRR}},
  language     = {{eng}},
  month        = {{10}},
  number       = {{20}},
  pages        = {{12651--12660}},
  publisher    = {{The American Chemical Society (ACS)}},
  series       = {{ACS Catalysis}},
  title        = {{Operando Stability Studies of Ultrathin Single-Crystalline IrO<sub>2</sub>(110) Films under Acidic Oxygen Evolution Reaction Conditions}},
  url          = {{http://dx.doi.org/10.1021/acscatal.1c03599}},
  doi          = {{10.1021/acscatal.1c03599}},
  volume       = {{11}},
  year         = {{2021}},
}