Direct Seawater Electrolysis via Synergistic Acidification by Inorganic Precipitation and Proton Flux from Bipolar Membrane

This report describes direct seawater electrolysis (DSE) wherein natural seawater is used as a catholyte without filtration or pretreatment; seawater is acidified to a pH of 2 while hydroxide ions are produced at the cathode by the hydrogen evolution reaction (HER). It results from the cooperative effect of hydroxide ions trapped through inorganic precipitation at the cathode and proton flux from water dissociation in a bipolar membrane (BPM; used as a separator). The acidification of the catholyte in the proposed BPM-DSE substantially mitigates cathode passivation, eliminates the requirement of additional processes for treatment of inorganic precipitates dispersed in the catholyte, and reduces the cathode potential (𝐸𝑐) required for the HER to enable long-term DSE. The BPM in this system plays a critical role in maintaining the electrolyte concentration, suppressing the chlorine evolution reaction (ClER), and maximizing the oxygen evolution reaction. These findings are expected to suggest a breakthrough toward large-scale operation of DSE that successfully overcomes challenges such as energy consumption, inorganic precipitation, ClER, and corrosion.