Controlled Synthesis of Unconventional Phase Alloy Nanobranches for Highly Selective Electrocatalytic Nitrite Reduction to Ammonia

Abstract The controlled synthesis of metal nanomaterials with unconventional phases is of significant importance to develop high‐performance catalysts for various applications. However, it remains challenging to modulate the atomic arrangements of metal nanomaterials, especially the alloy nanostructures that involve different metals with distinct redox potentials. Here we report the general one‐pot synthesis of IrNi, IrRhNi and IrFeNi alloy nanobranches with unconventional hexagonal close‐packed (hcp) phase. Notably, the as‐synthesized hcp IrNi nanobranches demonstrate excellent catalytic performance towards electrochemical nitrite reduction reaction (NO 2 RR), with superior NH 3 Faradaic efficiency and yield rate of 98.2 % and 34.6 mg h −1 mg cat −1 (75.5 mg h −1 mg Ir −1 ) at 0 and −0.1 V (vs reversible hydrogen electrode), respectively. Ex/in situ characterizations and theoretical calculations reveal that the Ir−Ni interactions within hcp IrNi alloy improve electron transfer to benefit both nitrite activation and active hydrogen generation, leading to a stronger reaction trend of NO 2 RR by greatly reducing energy barriers of rate‐determining step.