Scalable Ir-Doped NiFe₂O₄/TiO₂ Heterojunction Anode for Decentralized Saline Wastewater Treatment and H₂ Production

Wastewater electrolysis cells (WECs) for decentralized wastewater treatment/reuse coupled with H₂ production can reduce the carbon footprint associated with transportation of water, waste, and energy carrier. This study reports Ir-doped NiFe₂O₄ (NFI, ~ 5 at% Ir) spinel layer with TiO₂ overlayer (NFI/TiO₂), as a scalable heterojunction anode for direct electrolysis of wastewater with circumneutral pH in a single-compartment cell. In dilute (0.1 M) NaCl solutions, the NFI/TiO₂ marks superior activity and selectivity for chlorine evolution reaction, outperforming the benchmark IrO₂. Robust operation in near-neutral pH was confirmed. Electroanalyses including operando X-ray absorption spectroscopy unveiled crucial roles of TiO₂ which serves both as the primary site for Cl^- chemisorption and a protective layer for NFI as an ohmic contact. Galvanostatic electrolysis of NH₄⁺-laden synthetic wastewater demonstrated that NFI/TiO₂ not only achieves quasi-stoichiometric NH₄⁺-to-N₂ conversion, but also enhances H₂ generation efficiency with minimal competing reactions such as reduction of dissolved oxygen and reactive chlorine. The scaled-up WEC with NFI/TiO₂ was demonstrated for electrolysis of toilet wastewater.