Sustainable Coproduction of Two Disinfectants via Hydroxide-Balanced Modular Electrochemical Synthesis Using a Redox...

Challenges posed by the sacrificial auxiliary reactions and expensive ion-exchange membranes in conventional electrosynthesis necessitate developing new electrochemical processes to enable efficient and sustainable distributed electrochemical manufacturing. Modular electrochemical synthesis (ModES) using a redox reservoir (RR) offers a promising membrane-free approach to improve energy efficiency and reduce waste through the pairing of multiple independent oxidative and reductive half-reactions; however, undesired ion-imbalance and induced pH changes in the existing ModES process limit sustained production. Here we present Ni(OH)₂ as a heterogeneous RR that can selectively store and transport the hydroxide ions involved in the target half-reactions by reversible conversion with NiOOH to enable an ion-balanced ModES of two common disinfectants, hydrogen peroxide (H₂O₂) and sodium hypochlorite (NaClO). This hydroxide-balanced ModES realizes stable operation without appreciable pH swing to accumulate practically useful concentrations of H₂O₂ and NaClO up to 251 and 481 ppm, respectively. These results illustrate additional design principles for electrosynthesis without sacrificial auxiliary reactions and the need for ion-selective RRs for modular electrochemical manufacturing.