Temperature-Dependent Water Oxidation Kinetics: Implications and Insights.

As a vital process for solar fuel synthesis, water oxidation remains a challenging reaction to perform using durable and cost-effective systems. Despite decades of intense research, our understanding of the detailed processes involved is still limited, particularly under photochemical conditions. Recent research has shown that the overall kinetics of water oxidation by a molecular dyad depends on the coordination between photocharge generation and the subsequent chemical steps. This work explores similar effects of heterogeneous solar water oxidation systems. By varying a key variable, the reaction temperature, we discovered distinctly different behaviors on two model systems, TiO₂ and Fe₂O₃. TiO₂ exhibited a monotonically increasing water oxidation performance with rising temperature across the entire applied potential range, between 0.1 and 1.5 V vs the reversible hydrogen electrode (RHE). In contrast, Fe₂O₃ showed increased performance with increasing temperature at high applied potentials (>1.2 V vs RHE) but decreased performance at low applied potentials (<1.2 V vs RHE). This decrease in performance with temperature on Fe₂O₃ was attributed to an increased level of electron-hole recombination, as confirmed by intensity-modulated photocurrent spectroscopy (IMPS). The origin of the differing temperature dependences on TiO₂ and Fe₂O₃ was further ascribed to their different surface chemical kinetics. These results highlight the chemical nature of charge recombination in photoelectrochemical (PEC) systems, where surface electrons recombine with holes stored in surface chemical species. They also indicate that PEC kinetics are not constrained by a single rate-determining chemical step, highlighting the importance of an integrated approach to studying such systems. Moreover, the results suggest that for practical solar water splitting devices higher temperatures are not always beneficial for reaction rates, especially under low driving force conditions.