Proceedings of MATSUS Spring 2024 Conference (MATSUS24)
DOI: https://doi.org/10.29363/nanoge.matsus.2024.299
Publication date: 18th December 2023
The influence of the reaction environment on the rate and selectivity of electrocatalytic reactions has received increasing attention in the last years. With that, many insights were gained on how to optimize electrolyte compositions. In practice, however, ideal conditions cannot always directly be applied due to solubility or conductivity limitations. This is the case for, e.g., multivalent cations which significantly improve the reactivity of H2O – a key reactant in various electrocatalytic reduction and oxidation reactions. Such species are only soluble in acidic media (at pH below the ion´s pKa of hydrolysis), which limits their applicability under reducing conditions, which are often associated with an increase in local alkalinity. Therefore, new strategies are desired to ensure the presence of these reaction-boosting multivalent cations in the double layer under (local) alkaline conditions. Here, I discuss the modification of different electrocatalysts with porous amphoteric hydroxide layers. This strategy is depicted in Fig. 1, using as example the hydrogen (HER, 2H2O + 2e– à H2 + 2OH–) and oxygen (OER, 2OH− → ½O2 + H2O + 2e−) evolution reactions taking place in alkaline media (0.1 M KOH), and Al(OH)3. The Al(OH)3 is initially insoluble, but once either HER or OER start taking place, strong alkalinization or acidification of the interface, respectively, lead to the partial dissolution of the hydroxide locally forming Al(OH)–4 or M3+ ions. Here, I present new insights on the synthesis and characterization of various of these layers and the impact they have on the rate of different reactions in which H2O participates as a H+ or OH– donor.
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