Nanoporous Intermetallic Pd 3 Bi 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 Pd 3 Bi prepared by converting chemically etched nanoporous PdBi 2 exhibits efficient electrocatalytic nitrogen reduction under ambient conditions. The resulting nanoporous intermetallic Pd 3 Bi can achieve high activity and selectivity with an NH 3 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 H 2 SO 4 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 Pd 3 Bi, in which the Bi sites can absorb N 2 molecules and lower the energy barrier of *N 2 for N 2 adsorption and activation. Meanwhile, the intermetallic Pd 3 Bi with bicontinuous nanoporous structure can accelerate the electron transport during the NRR process, thus improving the NRR performance.