Coordination Engineering of Pd nanoclusters for highly efficient electrocatalytic conversion of nitrate to ammonia

How to achieve high energy efficiency ammonia (NH₃) synthesis is an important subject in energy industry. The traditional Haber-Bosch process demands high energy consumption and high CO₂ emissions, so electrochemical reduction of nitrate selectivity for NH₃ under ambient conditions offers a promising solution. In this study, the average size of palladium nanoclusters was ∼ 0.5 nm, and in order to obtain high NH₃ activity and selectivity simultaneously, palladium nanoclusters with different ligands were designed. The experiments demonstrated that the Pd-P coordination endows the supported Pd nanoclusters highest ammonia Faraday efficiency of 92.8 % and ammonia yield 1329.4 mmol h⁻¹ g_cat^-1. To decipher the ligand coordination effect on the catalytic performance, advanced techniques and theoretical analyses were applied for clarifying the reaction pathways and illustrating the role of electronegative P in facilitating NH₃ production.