The fundamental understanding of the electrode/electrolyte interface is of pivotal importance for the efficient electrochemical conversion and storage of electrical energy. However, the reasons for the low rate of electrocatalytic oxygen evolution and issues of long-term material stability, which are central constraints for attaining desirable efficiency for sustainable technologies like water electrolysis or electrochemical CO 2 reduction, are still not completely resolved. While a lot of attention has been directed towards the search for new materials with unique (electro)catalytic properties, experimental results accumulated during the last four decades and prediction from models suggest that RuO 2 possesses superior activity for oxygen evolution under acidic conditions. Considering that RuO 2 is a material of choice, we show that tailoring the surface morphology on the meso-and macroscale has great potential for the improvement of the efficiency of this gas evolving reaction. Advanced analytical tools have been utilized for the combined investigation of both activity and stability. Namely, the potential dependent frequencies of gas-bubble evolution, an indicator for the activity of the electrode, were acquired by scanning electrochemical microscopy (SECM), while the dissolution of RuO 2 was monitored using a micro electrochemical scanning flow cell combined with an inductively coupled plasma mass spectrometer (SFC-ICP-MS). The obtained fundamental insights will aid improving the design and thus performance of electrode materials for water oxidation.

We present a zinc|ferricyanide hybrid flow battery that achieves extensive first-pass desalination while simultaneously supplying electrical energy (10 Wh/L). We demonstrate 85% salt removal from simulated seawater (35 g/L NaCl) and 86% from hypersaline brine (100 g/L NaCl), together with reversible battery operation over 100 h with high round-trip efficiency (84.8%). The system has a high operating voltage (E 0 = +1.25 V), low specific energy consumption (2.11 Wh/L for 85% salt removal), and a desalination flux (4.7 mol/m 2 •h) on par with that of reverse osmosis membranes. Salt removal was similarly effective at higher feed salinities, for which reverse osmosis becomes physically impossible because of the pressure required. The results have positive implications for regions that rely on desalination for their freshwater needs, especially where sea salinity is high. Alternatively, the battery may also be useful in minimal liquid discharge wastewater treatment if operated as a brine concentrator.

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Oxidation of iron surfaces and oxide growth mechanisms have been studied using reactive molecular dynamics. Oxide growth kinetics on Fe(100), (110), and (111) surface orientations has been investigated at various temperatures and/or an external electric field. The oxide growth kinetics decreases in the order of (110), (111), and (100) surfaces at 300 K over 1 ns timescale while higher temperature increases the oxidation rate. The oxidation rate shows a transition after an initial high rate, implying that the oxide formation mechanism evolves, with iron cation re-ordering. In early stages of surface oxide growth, oxygen transport through iron interstitial sites is dominant, yielding non-stoichiometric wüstite characteristics. The dominant oxygen inward transport decreases as the oxide thickens, evolving into more stoichiometric oxide phases such as wüstite or hematite. This also suggests that cation outward transport increases correspondingly. In addition to oxidation kinetics simulations, formed oxide layers have been relaxed in the range of 600-1500 K to investigate diffusion characteristics, fitting these results into an Arrhenius relation. The activation energy of oxygen diffusion in oxide layers formed on Fe(100), (110), and (111) surfaces was estimated to be 0.32, 0.26, and 0.28 eV, respectively. Comparison between our modeling results and literature data is then discussed. An external electric field (10 MV cm(-1)) facilitates initial oxidation kinetics by promoting oxygen transport through iron lattice interstitial sites, but reaches self-limiting thickness, showing that similar oxide formation stages are maintained when cation transport increases. The effect of the external electric field on iron oxide structure, composition, and oxide activation energy is found to be minimal, whereas cation outward migration is slightly promoted.