A mesoporous electrode strategy for probing ions at the electrode-electrolyte interface using in situ X-ray absorption spectroscopy.
7 affiliations
- 1Leiden Institute of Chemistry, Leiden University, Leiden, The Netherlands. [email protected].
- 2Department of Physics, Tamkang University, New Taipei City, Taiwan.
- 3Department of Atomic-Scale Dynamics in Light-Energy Conversion, Helmholtz-Zentrum Berlin für Materialien und Energie, Albert-Einstein-Straße 15, 12489 Berlin, Germany.
- 4Division of Synchrotron Radiation, Lund University, Lund, Sweden.
- 5Department of Chemistry, University of Bath, Bath, BA2 7AY, UK.
- 6Department of Inorganic Chemistry, Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, 14195, Berlin, Germany.
- 7Max Planck Institute for Chemical Energy Conversion, Stiftstrasse 34-36, 45470, Mülheim an der Ruhr, Germany.
Abstract
Electrolyte ions present at the electrode-electrolyte interface critically influence electrocatalytic reactions, yet direct, quantitative detection of interfacial ions under operating conditions remains challenging due to dominant bulk electrolyte signals. Here, we present an interface-sensitive soft X-ray absorption spectroscopy (XAS) approach that enables quantitative tracking of interfacial ion behavior at electrified platinum (Pt) surfaces. Mesoporous Pt films with high surface-area-to-volume ratios were fabricated via soft-templated electrodeposition onto SiNx windows, strongly enhancing the relative contribution of the interfacial electrolyte within nanoscale pores while effectively attenuating signals from the bulk. Using Na⁺ as a model cation, Na K-edge XAS measurements reveal pronounced dependencies of interfacial ion concentration on applied potential, electrolyte pH, and bulk concentration. The observed trends highlight the role of surface chemistry in interfacial ion behavior. In addition to concentration changes, potential-dependent modifications of the Na⁺ hydration shell are identified, indicating re-organization of the solvation of the ions at the interface. These results highlight the capability of our methodology to quantitatively probe ion-specific behavior in the electrical double layer under operando conditions. We foresee that the method can be extended to a wide range of ionic and molecular species relevant to electrocatalysis and energy conversion.
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BibTeX
@article{rodriguez2026mesoporous,
title = {{A mesoporous electrode strategy for probing ions at the electrode-electrolyte interface using in situ X-ray absorption spectroscopy.}},
author = {Jan Sebastian Dominic Rodriguez and Alfred Larsson and Nipon Deka and Rianne Jorritsma and Hassan Javed and Kees Kolmeijer and Ajsa Cuprija and Wanli Liu and Nicole Barber and Adam M Squires and Detre Teschner and Aliakbar Ghafari and Cheng-Hao Chuang and Rik V Mom},
journal = {Physical chemistry chemical physics : PCCP},
year = {2026},
month = oct,
doi = {10.1039/d6cp01946c},
url = {https://europepmc.org/article/MED/42969468},
note = {CC BY},
}
RIS
TY - JOUR
TI - A mesoporous electrode strategy for probing ions at the electrode-electrolyte interface using in situ X-ray absorption spectroscopy.
AU - Jan Sebastian Dominic Rodriguez
AU - Alfred Larsson
AU - Nipon Deka
AU - Rianne Jorritsma
AU - Hassan Javed
AU - Kees Kolmeijer
AU - Ajsa Cuprija
AU - Wanli Liu
AU - Nicole Barber
AU - Adam M Squires
AU - Detre Teschner
AU - Aliakbar Ghafari
AU - Cheng-Hao Chuang
AU - Rik V Mom
PY - 2026
DA - 2026/10/27
JO - Physical chemistry chemical physics : PCCP
DO - 10.1039/d6cp01946c
UR - https://europepmc.org/article/MED/42969468
AB - Electrolyte ions present at the electrode-electrolyte interface critically influence electrocatalytic reactions, yet direct, quantitative detection of interfacial ions under operating conditions remains challenging due to dominant bulk electrolyte signals. Here, we present an interface-sensitive soft X-ray absorption spectroscopy (XAS) approach that enables quantitative tracking of interfacial ion behavior at electrified platinum (Pt) surfaces. Mesoporous Pt films with high surface-area-to-volume ratios were fabricated via soft-templated electrodeposition onto SiNx windows, strongly enhancing the relative contribution of the interfacial electrolyte within nanoscale pores while effectively attenuating signals from the bulk. Using Na⁺ as a model cation, Na K-edge XAS measurements reveal pronounced dependencies of interfacial ion concentration on applied potential, electrolyte pH, and bulk concentration. The observed trends highlight the role of surface chemistry in interfacial ion behavior. In addition to concentration changes, potential-dependent modifications of the Na⁺ hydration shell are identified, indicating re-organization of the solvation of the ions at the interface. These results highlight the capability of our methodology to quantitatively probe ion-specific behavior in the electrical double layer under operando conditions. We foresee that the method can be extended to a wide range of ionic and molecular species relevant to electrocatalysis and energy conversion.
SN - 1463-9076
SN - 1463-9084
ER -