Redox-mediated decoupled seawater direct splitting for H<sub>2</sub> production.

Liu, Tao; Lan, Cheng; Tang, Min; Li, Mengxin; Xu, Yitao; Yang, Hangrui; Deng, Qingyue; Jiang, Wenchuan et al. · Nat Commun · 2024

basic_science · Level V

Where this comes from

Abstract

Seawater direct electrolysis (SDE) using renewable energy provides a sustainable pathway to harness abundant oceanic hydrogen resources. However, the side-reaction of the chlorine electro-oxidation reaction (ClOR) severely decreased direct electrolysis efficiency of seawater and gradually corrodes the anode. In this study, a redox-mediated strategy is introduced to suppress the ClOR, and a decoupled seawater direct electrolysis (DSDE) system incorporating a separate O<sub>2</sub> evolution reactor is established. Ferricyanide/ferrocyanide ([Fe(CN)<sub>6</sub>]<sup>3-/4-</sup>) serves as an electron-mediator between the cell and the reactor, thereby enabling a more dynamically favorable half-reaction to supplant the traditional oxygen evolution reaction (OER). This alteration involves a straightforward, single-electron-transfer anodic reaction without gas precipitation and effectively eliminates the generation of chlorine-containing byproducts. By operating at low voltages (~1.37 V at 10 mA cm<sup>-2</sup> and ~1.57 V at 100 mA cm<sup>-2</sup>) and maintaining stability even in a Cl<sup>-</sup>-saturated seawater electrolyte, this system has the potential of undergoing decoupled seawater electrolysis with zero chlorine emissions. Further improvements in the high-performance redox-mediators and catalysts can provide enhanced cost-effectiveness and sustainability of the DSDE system.