Insights from heterogeneous kinetic model: A framework for predicting electrochemical oxidizability from molecular...

The structure and properties of emerging contaminants (ECs) critically influence their electrochemical behavior. However, quantitative structure-activity relationships governing ECs degradation during electrochemical oxidation remains poorly elucidated. This study develops an interpretable predictive framework (X_deg) for systems with strong direct electron transfer (e.g., boron-doped diamond (BDD) anode system) under mass-transfer-controlled conditions, by integrating a heterogeneous kinetic model with global sensitivity analysis to evaluate the electrochemical degradation rates of ECs. Our framework identifies the adsorption/desorption equilibrium constant (b) and the second-order reaction rate constant of ECs with holes ( [Formula: see text] ) as the two key parameters, with weighting coefficients of 0.422 and 0.423 respectively, indicating that adsorption processes and direct electron transfer equally regulate ECs degradation efficiency. We further established straightforward parameter estimation methods whereby b is derived from hydrophobicity (logK_ow) and charge characteristics, while [Formula: see text] is predicted using Hammett constants (σ⁺) or electrophilic reactivity descriptors. Validated across 20 structurally diverse ECs, the framework demonstrates robust predictive capability (R² = 0.746) and strong generalizability. This approach enables rapid evaluation of electrochemical treatability directly from molecular features or functional groups, significantly reducing reliance on intensive experimental screening. Our work provides a mechanistic foundation for structure-based prediction of pollutant degradation and advances the fundamental understanding of reaction mechanisms in electrochemical advanced oxidation processes.