Unveiling the Cerium(III)/(IV) Structures and Charge-Transfer Mechanism in Sulfuric Acid

[Image: see text] The Ce(3+)/Ce(4+) redox couple has a charge transfer (CT) with extreme asymmetry and a large shift in redox potential depending on electrolyte composition. The redox potential shift and CT behavior are difficult to understand because neither the cerium structures nor the CT mechanism are well understood, limiting efforts to improve the Ce(3+)/Ce(4+) redox kinetics in applications such as energy storage. Herein, we identify the Ce(3+) and Ce(4+) structures and CT mechanism in sulfuric acid via extended X-ray absorption fine structure spectroscopy (EXAFS), kinetic measurements, and density functional theory (DFT) calculations. We show EXAFS evidence that confirms that Ce(3+) is coordinated by nine water molecules and suggests that Ce(4+) is complexed by water and three bisulfates in sulfuric acid. Despite the change in complexation within the first coordination shell between Ce(3+) and Ce(4+), we show that the kinetics are independent of the electrode, suggesting outer-sphere electron-transfer behavior. We identify a two-step mechanism where Ce(4+) exchanges the bisulfate anions with water in a chemical step followed by a rate-determining electron transfer step that follows Marcus theory (MT). This mechanism is consistent with all experimentally observed structural and kinetic data. The asymmetry of the Ce(3+)/Ce(4+) CT and the observed shift in the redox potential with acid is explained by the addition of the chemical step in the CT mechanism. The fitted parameters from this rate law qualitatively agree with DFT-predicted free energies and the reorganization energy. The combination of a two-step mechanism with MT should be considered for other metal ion CT reactions whose kinetics have not been appropriately described.