Publication date: 15th December 2025
The electrochemical nitrate reduction reaction (eNO3RR) has emerged as a sustainable alternative to the energy-intensive Haber–Bosch process, offering dual benefits of decentralized ammonia production and the remediation of nitrate-rich wastewater. However, achieving high selectivity and activity toward ammonia remains challenging due to sluggish hydrogenation steps and competing hydrogen evolution. In the present work, we explore CuO/CeO2 heterostructures as efficient catalysts for eNO₃RR, leveraging the oxygen-vacancy-rich nature of ceria to enhance copper–intermediate interactions and promote hydrogenation pathways. CuO/CeO₂ catalysts were synthesized via co-precipitation (CP) and deposition-precipitation (DP) routes.The DP-CuO/CeO2 catalyst exhibited superior structural features, including higher crystallinity and smaller particle size with significantly enhanced electrochemical performance. Product analysis revealed 46% NO2⁻ and 28% NH3 formation while suppressing the competing HER. In parallel, we investigated the small molecule oxidation reaction (SMOR) as the anodic counterpart to create an energy-efficient paired electrolysis system. In case of methanol oxidation, DP-CuO/CeO₂ again outperformed the CP catalyst, showing a 280 mV earlier onset and a fivefold higher current density at 1.8 V. Such bifunctional behaviour highlights the potential of a single catalyst system to simultaneously upgrade nitrate at the cathode and alcohol at the anode. By integrating eNO3RR with alcohol oxidation, this paired electrolysis strategy aims to lower overall cell potential while generating value-added products on both sides: ammonia at the cathode and formate at the anode. The results showcase DP-CuO/CeO2 as a promising bifunctional catalyst and lay the groundwork for future demonstration of a fully optimized paired NO3RR–SMOR electrolyzer.
1. IIT Gandhinagar
2. Dr. Biswajit Mondal
3. Prime Minister's Research Fellowship
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