Competing Ring-Opening and Hofmann Elimination Pathways in Aqueous TEMPO Catholytes: A First-Principles Study
Abstract
Aqueous redox-flow batteries based on TEMPO derivatives are promising for large-scale energy storage, but their practical use is limited by the chemical instability of the oxidized N -oxoammonium state. In this work, we investigate the degradation of five TEMPO derivatives using ab initio molecular dynamics combined with enhanced sampling. Two proposed degradation mechanisms, ring opening and Hofmann elimination, are examined and their corresponding activation free energies are compared. For all derivatives considered, ring opening exhibits a lower activation free energy than Hofmann elimination, identifying it as the kinetically preferred degradation pathway. The magnitude of the ring-opening barrier, however, varies significantly between molecules, showing that different functionalizations strongly influence its stability toward degradation. The predicted preference for ring opening is consistent with available experimental studies, which have identified or inferred ring-opening degradation for several TEMPO-based catholytes. These results provide an atomistic picture of degradation pathways that are difficult to resolve experimentally and highlight the importance of molecular structure in controlling the kinetic stability of TEMPO derivatives in aqueous electrolytes.
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BibTeX
@misc{mouaffac2026competing,
title = {{Competing Ring-Opening and Hofmann Elimination Pathways in Aqueous TEMPO Catholytes: A First-Principles Study}},
author = {Line Mouaffac and Maiwenn Souetre and Guillaume Jeanmairet and Mathieu Salanne},
howpublished = {arXiv},
year = {2026},
month = sep,
doi = {10.48550/arxiv.2609.08721},
eprint = {2609.08721},
archivePrefix = {arXiv},
url = {https://arxiv.org/abs/2609.08721},
}
RIS
TY - UNPB
TI - Competing Ring-Opening and Hofmann Elimination Pathways in Aqueous TEMPO Catholytes: A First-Principles Study
AU - Line Mouaffac
AU - Maiwenn Souetre
AU - Guillaume Jeanmairet
AU - Mathieu Salanne
PY - 2026
DA - 2026/09/14
PB - arXiv
DO - 10.48550/arxiv.2609.08721
UR - https://arxiv.org/abs/2609.08721
AB - Aqueous redox-flow batteries based on TEMPO derivatives are promising for large-scale energy storage, but their practical use is limited by the chemical instability of the oxidized N -oxoammonium state. In this work, we investigate the degradation of five TEMPO derivatives using ab initio molecular dynamics combined with enhanced sampling. Two proposed degradation mechanisms, ring opening and Hofmann elimination, are examined and their corresponding activation free energies are compared. For all derivatives considered, ring opening exhibits a lower activation free energy than Hofmann elimination, identifying it as the kinetically preferred degradation pathway. The magnitude of the ring-opening barrier, however, varies significantly between molecules, showing that different functionalizations strongly influence its stability toward degradation. The predicted preference for ring opening is consistent with available experimental studies, which have identified or inferred ring-opening degradation for several TEMPO-based catholytes. These results provide an atomistic picture of degradation pathways that are difficult to resolve experimentally and highlight the importance of molecular structure in controlling the kinetic stability of TEMPO derivatives in aqueous electrolytes.
ER -