Nanoporous Intermetallic Pd₃Bi for Efficient Electrochemical Nitrogen Reduction

Abstract Electrocatalytic nitrogen reduction at ambient temperature is a green technology for artificial nitrogen fixation but greatly challenging with low yield and poor selectivity. Here, a nanoporous ordered intermetallic Pd₃Bi prepared by converting chemically etched nanoporous PdBi₂ exhibits efficient electrocatalytic nitrogen reduction under ambient conditions. The resulting nanoporous intermetallic Pd₃Bi can achieve high activity and selectivity with an NH₃ yield rate of 59.05 ± 2.27 µg h⁻¹ mg_cat⁻¹ and a Faradaic efficiency of 21.52 ± 0.71% at −0.2 V versus the reversible hydrogen electrode in 0.05 m H₂SO₄ electrolyte, outperforming most of the reported catalysts in electrochemical nitrogen reduction reaction (NRR). Operando X‐ray absorption spectroscopy studies combined with density functional theory calculations reveal that strong coupling between the Pd–Bi sites bridges the electron‐transfer channel of intermetallic Pd₃Bi, in which the Bi sites can absorb N₂ molecules and lower the energy barrier of *N₂ for N₂ adsorption and activation. Meanwhile, the intermetallic Pd₃Bi with bicontinuous nanoporous structure can accelerate the electron transport during the NRR process, thus improving the NRR performance.