Elucidating the electrochemical behavior and reaction pathway of 1,4-Dioxane: An integrated experimental and simulation approach

1,4-Dioxane, a potential human carcinogen, poses significant environmental challenges as a contaminant in water resources, and the efficient degradation of this compound is crucial for successfully optimizing its electrochemical removal. For the prediction and enhancement of degradation efficiency, a precise identification of kinetic parameters, reaction conditions, and degradation products, along with an understanding of the mechanisms involved, is required. But, most of these parameters are often not provided in the current literature. This study investigates the electrochemical behavior and reaction mechanism of 1,4-Dioxane using palladium‑ruthenium bimetallic nanocatalysts on glassy carbon electrodes by both experimental and simulation analyses. The characterization of fabricated nanocatalyst was carried out using STEM-EDX and UV–visible spectroscopy. The electrochemical features and redox reaction mechanism of 1,4-dioxane were systematically explained through the quantification of the half-wave potential (E 1/2 ), diffusion coefficient (D), rate constant (k), transfer coefficient (α), and charge transfer resistance (R ct ), utilizing cyclic voltammetry (CV), chronoamperometry (CA), rotating disk electrode - hydrodynamic voltammetry (RDE-HDV), and electrochemical impedance spectroscopy (EIS). Simulations conducted with the KISSA1D software yielded convincing findings that align with the experimental results, confirming the accuracy of the modeling and underlining the reliability of the experimental methodology. In addition, the final reduction of 1,4-dioxane to carbon dioxide and water was revealed by LC-MS analysis. This research improves our understanding of the kinetic behaviors and underlying mechanisms in redox reactions and fills the gap between theoretical concepts and practical applications in electrochemistry, and environmental chemistry. • PdRu bimetallic nanocatalysts exhibit strong electrocatalytic performance toward 1,4-dioxane oxidation in water • The redox mechanism of 1,4-dioxane is primarily diffusion-controlled and exhibits quasi-reversibility. • High diffusion coefficient and electron transfer rate confirm effective charge transport at the nanocatalyst-electrolyte interface. • Low charge transfer resistance observed in electrochemical impedance analysis indicates rapid reaction kinetics in the presence of nanocatalyst. • Simulation results align closely with experimental data, validating the proposed electrochemical model.