Probing the Effects of Electrode Composition and Morphology on the Effectiveness of Silicon Oxide Overlayers to Enhance Selective Oxygen Evolution in the Presence of Chloride Ions

[Image: see text] Seawater electrolysis offers significant logistical advantages over freshwater electrolysis but suffers from a fundamental selectivity problem at the anode. To prevent the evolution of toxic chlorine alongside the evolution of oxygen, a promising approach is the use of electrochemically inert overlayers. Such thin films can exert a perm-selective effect, allowing the transport of water and oxygen between the bulk electrolyte and the electrocatalytic buried interface while suppressing the transport of chloride ions. In this work, we investigate thin (5–20 nm) overlayer films composed of amorphous silicon oxide (SiO(x)) and their application to suppressing the chlorine evolution reaction (CER) in favor of the oxygen evolution reaction (OER) during acidic saltwater electrolysis on three different types of electrodes. While SiO(x) overlayers are seen to be an effective barrier against the CER on well-defined, smooth Pt thin films, decreasing the CER activity roughly 20-fold, this ability has not been previously explored on Ir-based catalysts with a higher surface area relevant to industrial applications. On amorphous iridium oxide electrodes, the selectivity toward the CER versus the OER was marginally reduced from ∼98 to ∼94%, which was attributed to the higher abundance of defects in overlayers deposited on the rougher electrode. On the other hand, Ir-based anodes consisting of thick mixed metal oxide films supported on Ti showed a significant decrease in CER selectivity, from ∼100 to ∼50%, although this came at the cost of reduced activity toward the OER. These results show that the morphology and composition of the underlying electrode play important roles in the effectiveness of the selective overlayers and provide guidance for further development of high-surface-area OER-selective anodes.