Methodological Optimization of ATR-IR Spectroelectrochemistry for Powdered and Poorly Conductive Electrocatalysts
6 affiliations
- 1Escuela de Doctorado UAM, Centro de Estudios de Posgrado, Universidad Autonoma de Madrid, C/Francisco Tomás y Valiente, nº 2. Ciudad Universitaria de Cantoblanco, Madrid, Spain, 28049
- 2Instituto de Ceramica y Vidrio (ICV
- 3CSIC
- 4Department of Chemistry, NIS Centre, INSTM Research Unit, Università di Torino, Via G. Quarello 15/A and Via P. Giuria 7, Turin, Italy, 10135
- 5Faculty of Engineering
- 6Hokkaido University
Abstract
In-situ infrared spectroscopy combined with electrochemistry has become a key tool for studying the processes that govern the activity of electrocatalysts under operating conditions. However, its application has been limited almost exclusively to model electrodes, which are either electronically conductive or specifically designed to maximise the ATR optical signal, thereby limiting its use for a family of emerging heterogenous catalysts typically available in powder form and exhibiting poor electrical conductivity. Extending ATR-IR spectroelectrochemistry to this type of catalyst requires simultaneously reconciling optical, adhesion and electrochemical requirements which, until now, have rarely been addressed systematically. Rather than focusing on the elucidation of electrocatalyst mechanisms, this paper presents a structured and transferable methodology for optimising ATR-IR spectroelectrochemical measurements on emerging classes of electrocatalyst. Three groups of interrelated parameters that mostly affect the feasibility of the technique, namely spectroscopic, interfacial and electrochemical parameters, are discussed proposing a step-by-step workflow that enables their methodological standardization and balance. The proposed workflow is validated by applying this methodology to three different materials (Ni(OH) 2 , ZnO and Zn-Al LDH) showing distinct spectroscopic, electrochemical and interfacial properties. The results demonstrate that, following appropriate optimisation, ATR spectroelectrochemistry can be extended to more challenging powdered catalyst layers, providing a practical and generalisable guide for future robust mechanistic investigations of this broad family of materials and contributing to the rational understanding and development of new electrocatalysts for reactions of energy and chemical interest.
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BibTeX
@misc{eliasrodriguezjara2026methodological,
title = {{Methodological Optimization of ATR-IR Spectroelectrochemistry for Powdered and Poorly Conductive Electrocatalysts}},
author = {Elías Rodríguez-Jara,† and Stefano Magliocco,† and Nevilia Iuliano and Mario Aparicio and Kiyoharu Tadanaga and Natale Gabriele Porcaro and Alessandro Piovano and Gloria Berlier and Silvia Bordiga and Nataly Carolina Rosero-Navarro* and Margherita Cavallo* and Francesca Bonino},
howpublished = {ChemRxiv},
year = {2026},
month = oct,
doi = {10.26434/chemrxiv.15011018/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15011018/v1},
note = {CC BY},
}
RIS
TY - UNPB
TI - Methodological Optimization of ATR-IR Spectroelectrochemistry for Powdered and Poorly Conductive Electrocatalysts
AU - Elías Rodríguez-Jara,†
AU - Stefano Magliocco,†
AU - Nevilia Iuliano
AU - Mario Aparicio
AU - Kiyoharu Tadanaga
AU - Natale Gabriele Porcaro
AU - Alessandro Piovano
AU - Gloria Berlier
AU - Silvia Bordiga
AU - Nataly Carolina Rosero-Navarro*
AU - Margherita Cavallo*
AU - Francesca Bonino
PY - 2026
DA - 2026/10/25
PB - ChemRxiv
DO - 10.26434/chemrxiv.15011018/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15011018/v1
AB - In-situ infrared spectroscopy combined with electrochemistry has become a key tool for studying the processes that govern the activity of electrocatalysts under operating conditions. However, its application has been limited almost exclusively to model electrodes, which are either electronically conductive or specifically designed to maximise the ATR optical signal, thereby limiting its use for a family of emerging heterogenous catalysts typically available in powder form and exhibiting poor electrical conductivity. Extending ATR-IR spectroelectrochemistry to this type of catalyst requires simultaneously reconciling optical, adhesion and electrochemical requirements which, until now, have rarely been addressed systematically. Rather than focusing on the elucidation of electrocatalyst mechanisms, this paper presents a structured and transferable methodology for optimising ATR-IR spectroelectrochemical measurements on emerging classes of electrocatalyst. Three groups of interrelated parameters that mostly affect the feasibility of the technique, namely spectroscopic, interfacial and electrochemical parameters, are discussed proposing a step-by-step workflow that enables their methodological standardization and balance. The proposed workflow is validated by applying this methodology to three different materials (Ni(OH) 2 , ZnO and Zn-Al LDH) showing distinct spectroscopic, electrochemical and interfacial properties. The results demonstrate that, following appropriate optimisation, ATR spectroelectrochemistry can be extended to more challenging powdered catalyst layers, providing a practical and generalisable guide for future robust mechanistic investigations of this broad family of materials and contributing to the rational understanding and development of new electrocatalysts for reactions of energy and chemical interest.
ER -