LAUSR

Existing chlor-alkali processes generally use asbestos, mercury or fluorine-containing ion-exchange membranes to separate the simultaneous chlorine production on the anode and hydrogen production on the cathode, and form sodium hydroxide in the electrolyte. Here, using the Na+ de-intercalation/intercalation of a Na0.44MnO2 electrode as a redox mediator, we decouple the chlor-alkali process into two independent steps: a H2 production step with the NaOH formation in the electrolyte and a Cl2 production step. The first step involves a cathodic H2 evolution reaction (H2O → H2) and an anodic Na+ de-intercalation reaction (Na0.44MnO2 → Na0.44−xMnO2), during which NaOH is produced in the electrolyte solution. The second step depends on a cathodic Na+ intercalation reaction (Na0.44−xMnO2 → Na0.44MnO2) and an anodic Cl2 production (Cl → Cl2). The cycle of the two steps provides a membrane-free process, which is potentially a promising direction for developing clean chlor-alkali technology.The chlor-alkali process is an important industrial process to make commodity chemicals; however, it usually requires the use of dangerous chemicals as membrane material. Here, the authors demonstrate clean, membrane-free chlor-alkali electrolysis, where chlorine evolution and hydrogen/sodium hydroxide production are completely decoupled.