Oxide Encapsulated Ruthenium Oxide Catalysts for Selective Oxygen Evolution in Unbuffered pH Neutral Seawater

Direct seawater electrolysis is a promising approach to producing green hydrogen in water-scarce environments using renewable energy. However, the undesirable chlorine evolution reaction (CER) and hypochlorite evolution reaction (HCER) compete with the desired oxygen evolution reaction (OER) at the anode electrocatalyst. This issue is most pronounced in unbuffered pH neutral solutions due to local acidification resulting from the OER. To overcome this challenge, this study explores the use of silicon oxide (SiOx) and titanium oxide (TiOx) nanoscale overlayers coated on metallic ruthenium (Ru) and ruthenium oxide (RuOx) thin film electrodes to block chloride ions from reaching active sites during operation in unbuffered 0.6 M NaCl electrolyte. Using a combination of (electro)analytical techniques, encapsulated RuOx anodes are shown to effectively suppress Cl- transport to buried catalyst active sites while allowing for the desired OER to occur, leading to increases in OER faradaic efficiency at moderate overpotentials. Evidence for the ability of SiOx overlayers to block Cl- ions from reaching the active buried interface was obtained by monitoring the OH stretching mode of OH adsorbates using in situ Raman spectroscopy. This study also reports trade-offs between the activity, selectivity, and stability of bare and encapsulated Ru and RuOx electrocatalysts, finding that the magnitude of these trade-offs strongly depends on the nature of both the catalyst and overlayer material. The most promising anode electrocatalyst is RuOx encapsulated by 4 nm of SiOx, which gives the largest improvement in OER faradaic efficiency while demonstrating a relatively stable operating current and minimal increases in overpotential.