Hydrogen production from seawater electrolysis is highly promising for the capture and storage of intermittent renewable energy, but is hindered by the possibility of unwanted reactions at the anode. The oxidation reactions of chloride and (to a lesser extent) bromide, which can occur in parallel to the evolution of oxygen, lead to environmentally harmful by-products and thus represent undesirable side-reactions. We present some general considerations of solution chemistry and oxidation products that may be expected in a mixed acidic bromide/chloride electrolyte. We performed electrochemical model studies of the simultaneous oxidation of bromide and chloride and their mutual interaction on a Pt electrocatalyst, with the aim of deepening the general understanding of the anodic competition problem. Using simplified model systems, our findings suggest that the oxidation of bromide is hindered by competing chloride adsorption, in a way that can be quite satisfactorily modelled by a simple Langmuir isotherm describing the competing adsorption and reactivity of all species. The oxidation of chloride was however not properly captured by this same model, and may be substantially different. Furthermore, the formation of the interhalogen compound BrCl seems to occur in-between the oxidation of bromide and chloride.

During hydrogen production for (renewable) energy storage, direct seawater electrolysis offers several notable advantages over freshwater electrolysis. Unfortunately, it is also hindered by possible oxidation reactions of chloride and (to a lesser extent) bromide, which can occur in parallel to the evolution of oxygen and form harmful by-products at the anode. Although the respective oxidation reactions of Br^- and Cl^- have been researched quite well on Pt, not much is known concerning bromide oxidation and its effect on the evolution of chlorine and oxygen for metal oxides, which are the class of electrocatalysts overwhelmingly used in industry. Using glassy carbon-supported iridium oxide (IrO_x) as a model system, we investigated the oxidation behaviour of this well-known oxygen evolution catalyst in an acidic Br^-/Cl^- electrolyte. We first briefly discuss the solution chemistry and oxidation products that may be expected. Model studies were performed of the parallel evolution of Br₂, Cl₂ and O₂ to increase the understanding of the anodic competition problem, with a special focus on the selectivity towards oxygen. Using rotating ring-disk voltammetry and UV–Vis spectroscopy, our results suggest that bromide and chloride competitively absorb on IrO_x, but do not alter each other's oxidation reaction mechanisms, which both seem to adhere best to a Volmer-Heyrovský mechanism. We also find that bromide and chloride adsorption significantly slow down the oxygen evolution reaction, in an additive way. Even a relatively small amount of bromide highly affected the oxygen evolution selectivity. Formation of the interhalogen compound BrCl, which is possible in a mixed Br^-/Cl^- electrolyte, does not seem to occur.

The oxygen evolution reaction (OER) and chlorine evolution reaction (CER) are electrochemical processes with high relevance to water splitting for (solar) energy conversion and industrial production of commodity chemicals, respectively. Carrying out the two reactions separately is challenging, since the catalytic intermediates are linked by scaling relations. Optimizing the efficiency of OER over CER in acidic media has proven especially difficult. In this regard, we have investigated the OER versus CER selectivity of manganese oxide (MnO_x), a known OER catalyst. Thin films (∼5-20 nm) of MnO_x were electrodeposited on glassy carbon-supported hydrous iridium oxide (IrO_x/GC) in aqueous chloride solutions of pH ∼0.9. Using rotating ring-disk electrode voltammetry and online electrochemical mass spectrometry, it was found that deposition of MnO_x onto IrO_x decreases the CER selectivity of the system in the presence of 30 mM Cl^- from 86% to less than 7%, making it a highly OER-selective catalyst. Detailed studies of the CER mechanism and ex-situ structure studies using SEM, TEM, and XPS suggest that the MnO_x film is in fact not a catalytically active phase, but functions as a permeable overlayer that disfavors the transport of chloride ions.