Mediated Electrochemical Reduction of Iron (Oxyhydr-)Oxides under Defined Thermodynamic Boundary Conditions

Iron (oxyhydr-)oxide reduction has been extensively studied because of its importance in pollutant redox dynamics and biogeochemical processes. Yet, experimental studies linking oxide reduction kinetics to thermodynamics remain scarce. Here, we used mediated electrochemical reduction (MER) to directly quantify the extents and rates of ferrihydrite, goethite, and hematite reduction over a range of negative reaction free energies, Δ_rG, that were obtained by systematically varying pH (5.0 to 8.0), applied reduction potentials (-0.53 to -0.17 V vs SHE), and Fe²⁺ concentrations (up to 40 μM). Ferrihydrite reduction was complete and fast at all tested Δ_rG values, consistent with its comparatively low thermodynamic stability. Reduction of the thermodynamically more stable goethite and hematite changed from complete and fast to incomplete and slow as Δ_rG values became less negative. Reductions at intermediate Δ_rG values showed negative linear correlations between the natural logarithm of the reduction rate constants and Δ_rG. These correlations imply that thermodynamics controlled goethite and hematite reduction rates. Beyond allowing to study iron oxide reduction under defined thermodynamic conditions, MER can also be used to capture changes in iron oxide reducibility during phase transformations, as shown for Fe²⁺-facilitated transformation of ferrihydrite to goethite.