Functionalized Metal-Organic Framework Thin Films for Stable and Efficient Electrochemical Water Oxidation under...

The development of molecularly modified metal-organic frameworks (MOFs) for electrochemical water oxidation has emerged as a promising strategy for efficient artificial photosynthesis. In this study, a ruthenium-based water oxidation catalyst (WOC) was incorporated into the UiO-67 framework, forming RuM-UiO-67 films grown directly on conductive FTO substrates. These modified films demonstrate efficient water oxidation activity at near-neutral pH (pH 6), operating at a low overpotential of ∼600 mV. The catalyst exhibits a turnover frequency (TOF) of (0.32 ± 0.02) s^-1 at 1.5 V versus the normal hydrogen electrode (NHE) in buffered solution (pH 6) for the oxygen evolution reaction. Notably, incorporation into the MOF results in a 12-fold increase in electroactive surface coverage compared to a monolayer of the same catalyst on bare FTO. Faradaic efficiency analysis revealed incomplete conversion to O₂, and follow-up iodometric analysis confirmed the formation of H₂O₂ as a competing two-electron oxidation product during electrocatalysis. These results highlight the utility of MOF-based architectures for maximizing the catalyst accessibility and stability under electrochemical water oxidation conditions.