Self‐Supported Pd Nanorod Arrays for High‐Efficient Nitrate Electroreduction to Ammonia

Electrochemical nitrate (NO₃ ^- ) reduction to ammonia (NH₃ ) offers a promising pathway to recover NO₃ ^- pollutants from industrial wastewater that can balance the nitrogen cycle and sustainable green NH₃ production. However, the efficiency of electrocatalytic NO₃ ^- reduction to NH₃ synthesis remains low for most of electrocatalysts due to complex reaction processes and severe hydrogen precipitation reaction. Herein, high performance of nitrate reduction reaction (NO₃ ^- RR) is demonstrated on self-supported Pd nanorod arrays in porous nickel framework foam (Pd/NF). It provides a lot of active sites for H* adsorption and NO₃ ^- activation leading to a remarkable NH₃ yield rate of 1.52 mmol cm^-2 h^-1 and a Faradaic efficiency of 78% at -1.4 V versus RHE. Notably, it maintains a high NH₃ yield rate over 50 cycles in 25 h showing good stability. Remarkably, large-area Pd/NF electrode (25 cm² ) shows a NH₃ yield of 174.25 mg h^-1 , be promising candidate for large-area device for industrial application. In situ FTIR spectroscopy and density functional theory calculations analysis confirm that the enrichment effect of Pd nanorods encourages the adsorption of H species for ammonia synthesis following a hydrogenation mechanism. This work brings a useful strategy for designing NO₃ ^- RR catalysts of nanorod arrays with customizable compositions.