Nanoporous Palladium Hydride for Electrocatalytic N2 Reduction under Ambient Conditions

Abstract The electrocatalytic nitrogen reduction reaction (NRR) is an alternative eco‐friendly strategy for sustainable N 2 fixation with renewable energy. However, NRR suffers from sluggish kinetics owing to difficult N 2 adsorption and N≡N cleavage. Now, nanoporous palladium hydride is reported as electrocatalyst for electrochemical N 2 reduction under ambient conditions, achieving a high ammonia yield rate of 20.4 μg h −1 mg −1 with a Faradaic efficiency of 43.6 % at low overpotential of 150 mV. Isotopic hydrogen labeling studies suggest the involvement of lattice hydrogen atoms in the hydride as active hydrogen source. In situ Raman analysis and density functional theory (DFT) calculations further reveal the reduction of energy barrier for the rate‐limiting *N 2 H formation step. The unique protonation mode of palladium hydride would provide a new insight on designing efficient and robust electrocatalysts for nitrogen fixation.