Facet-controlled palladium nanocrystalline for enhanced nitrate reduction towards ammonia

Electrochemical nitrate reduction reaction (NO₃^-RR) is considered an appealing way for producing ammonia (NH₃) under ambient conditions and solving environmental problems caused by nitrate, whereas the lack of adequate catalysts hampers the development of NO₃^-RR. Here, we firstly demonstrate that the Pd nanocrystalline with a well-desired facet can act as a highly efficient NO₃^-RR electrocatalyst for ambient ammonia synthesis. Pd (1 1 1) exhibits excellent activity and selectivity in reducing NO₃^- to NH₄⁺ with a Faradaic efficiency of 79.91% and an NH₄⁺ production of 0.5485 mmol h^-1 cm^-2 (2.74 mmol h^-1 mg^-1) in 0.1 M Na₂SO₄ (containing 0.1 M NO₃^-), which is 1.4 times higher than Pd (1 0 0) and 1.9 times higher than Pd (1 1 0), respectively. Density functional theory (DFT) calculation reveals that the superior NO₃^-RR activity of Pd (1 1 1) originates from its optimized activity of NO₃^- adsorption, smaller free energy change of the rate-limiting step (*NH₃ to NH₃), and poorer hydrogen evolution reaction activity (HER, competitive reaction). This work not only highlights the potentials of Pd-based nanocatalysts for NO₃^-RR but also provides new insight for the applications in NO₃^-RR of other facet-orientation nanomaterials.