Nitrate electroreduction: volcanoes à la carte.
- 1Nano-Bio Spectroscopy Group, European Theoretical Spectroscopy Facility (ETSF), Department of Advanced Materials and Polymers: Physics, Chemistry and Technology, University of the Basque Country EHU Av. Tolosa 72 20018 San Sebastián Spain [email protected] [email protected].
- 2Aristotle University of Thessaloniki, Faculty of Sciences, School of Chemistry 54124 Thessaloniki Greece [email protected].
- 3Ikerbasque, Basque Foundation for Science Plaza de Euskadi 5 48009 Bilbao Spain.
Abstract
The electrochemical nitrate reduction reaction (NO₃RR) is a promising strategy for sustainable ammonia production and nitrate remediation, but its complex reaction mechanism poses significant experimental and computational challenges. While simplified reaction pathways are frequently adopted in density functional theory studies for the sake of affordability, the impact of their approximations on the predicted catalytic trends remains largely unexplored. In this work, we investigate how different choices in the reaction coordinates, ranging from a complete pathway to progressively simplified pictures, affect the modelling of the NO₃RR to NO(g) on transition-metal electrodes through free-energy diagrams and volcano plots at different applied potentials. We illustrate how some mechanistic simplifications substantially alter the predicted critical reaction steps and their magnitude, and reshape volcano plots, while others closely reproduce the original trends. These observations provide practical guidelines to refine computational high-throughput electrocatalyst screening workflows for the NO₃RR and other electrocatalytic reactions.
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BibTeX
@article{salomone2026nitrate,
title = {{Nitrate electroreduction: volcanoes à la carte.}},
author = {Mattia Salomone and Ioannis Katsounaros and Federico Calle-Vallejo},
journal = {Chemical science},
year = {2026},
month = oct,
doi = {10.1039/d6sc05985f},
url = {https://europepmc.org/article/MED/42948063},
note = {CC BY-NC},
}
RIS
TY - JOUR
TI - Nitrate electroreduction: volcanoes à la carte.
AU - Mattia Salomone
AU - Ioannis Katsounaros
AU - Federico Calle-Vallejo
PY - 2026
DA - 2026/10/15
JO - Chemical science
DO - 10.1039/d6sc05985f
UR - https://europepmc.org/article/MED/42948063
AB - The electrochemical nitrate reduction reaction (NO₃RR) is a promising strategy for sustainable ammonia production and nitrate remediation, but its complex reaction mechanism poses significant experimental and computational challenges. While simplified reaction pathways are frequently adopted in density functional theory studies for the sake of affordability, the impact of their approximations on the predicted catalytic trends remains largely unexplored. In this work, we investigate how different choices in the reaction coordinates, ranging from a complete pathway to progressively simplified pictures, affect the modelling of the NO₃RR to NO(g) on transition-metal electrodes through free-energy diagrams and volcano plots at different applied potentials. We illustrate how some mechanistic simplifications substantially alter the predicted critical reaction steps and their magnitude, and reshape volcano plots, while others closely reproduce the original trends. These observations provide practical guidelines to refine computational high-throughput electrocatalyst screening workflows for the NO₃RR and other electrocatalytic reactions.
SN - 2041-6520
SN - 2041-6539
ER -