Cu-MOF-Derived Nano-Dendritic Self-Supported Electrodes for Efficient Electrochemical Nitrate-to-Ammonia Conversion

Electrochemical nitrate reduction reaction (eNO₃RR) has emerged as a promising alternative to the energy-intensive and carbon-intensive Haber-Bosch process for green ammonia synthesis. However, the intrinsic complexity of the eight-electron transfer pathway and inevitable competing side reactions limit the activity and selectivity of eNO₃RR. Maximizing the utilization of active sites and ensuring structural stability in electrocatalysts are essential for promoting surface proton-coupled electron transfer and improving Faradaic efficiency. Herein, we present a copper metal-organic framework (Cu-MOF)-derived electrocatalyst synthesized via in situ electrosynthesis on copper foam, using cetyltrimethylammonium bromide (CTAB) as a structure-directing agent, followed by electroreduction to produce a self-supported, nano-dendritic structure. This three-dimensional architecture exposes abundant active sites and facilitates electron transport, enabling efficient nitrate-to-ammonia conversion. The optimized CTAB-assisted electrode achieves an ammonia yield of 14.33 ± 0.61 mg h^-1 cm^-2 with a Faradaic efficiency of 90.95 ± 2.28% at -1.7 V versus Ag/AgCl. This study introduces a versatile design strategy for copper-based electrocatalysts that integrates structural stability with high activity, offering a sustainable approach for both ammonia production and nitrate remediation.