In Situ Growth of Fe₂O₃ Nanorod Arrays on Carbon Cloth with Rapid Charge Transfer for Efficient Nitrate Electroreduction to Ammonia

Electrochemical reduction of nitrate to ammonia (NH3), a green NH3 production route upon combining with renewable energy sources, is an appealing and alternative method to the Haber–Bosch process. However, this process not only involves the complicated eight-electron reduction to transform nitrate into various nitrogen products but simultaneously suffers from the competitive hydrogen evolution reaction, challenged by a lack of efficient catalysts. Herein, the in situ growth of Fe2O3 nanorod arrays on carbon cloth (Fe2O3 NRs/CC) is reported to exhibit a high NH3 yield rate of 328.17 μmol h–1 cm–2 at −0.9 V versus RHE, outperforming most of the reported Fe catalysts. An in situ growth strategy provides massive exposed active sites and a fast electron-transport channel between the carbon cloth and Fe2O3, which accelerates the charge-transport rate and facilitates the conversion of nitrate to NH3. In situ Raman spectroscopy in conjunction with attenuated total reflection Fourier transform infrared spectroscopy reveals the catalytic mechanism of nitrate to NH3. Our study provides not only an efficient catalyst for NH3 production but also useful guidelines for the pathways and mechanism of nitrate electroreduction to NH3.