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The authors investigated the chemical degradation mechanisms of five TEMPO catholyte derivatives in their oxidized *N*-oxoammonium state by modeling competing ring-opening and Hofmann elimination pathways. Using ab initio molecular dynamics with enhanced sampling, they discovered that ring-opening consistently exhibits lower activation free energy barriers across all derivatives, establishing it as the kinetically dominant degradation route. Resolving this atomistic mechanism resolves ambiguous experimental observations and provides actionable kinetic parameters for designing chemically stable organic catholytes.
Ring opening—not Hofmann elimination—is the universal kinetic bottleneck driving the degradation of oxidized TEMPO flow-battery catholytes, though functional group tailoring can significantly widen the protective energy barrier.
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.