Greatly Enhanced Electrocatalytic N₂ Reduction over V₂O₃/C by P Doping

As a carbon‐neutral alternative technology to the Haber−Bosch process, electrochemical N 2 reduction enables eco‐friendly NH 3 synthesis under ambient conditions but requires electrocatalysts to drive the N 2 reduction reaction (NRR). Here, P doping is proposed as a valid strategy to greatly increase the NRR activity of the V 2 O 3 /C shuttle‐like nanostructure. In 0.1 M Na 2 SO 4 , the NH 3 yield of original V 2 O 3 /C is 12.6 μg h −1 mg −1 cat. and a Faraday efficiency (FE) of 6.06% at −0.45 V and −0.25 V vs. reversible hydrogen electrode (RHE), respectively. P‐doped V 2 O 3 /C (P−V 2 O 3 /C), with a mass ratio of P of 6.05%, is capable of achieving a large NH 3 yield of 22.4 μg h −1 mg −1 cat. at −0.35 V vs. RHE, and a high FE of 13.78% at −0.25 V vs. RHE. It also shows high electrochemical durability and outstanding selectivity for NH 3 formation. Combined with density functional theory calculations, the catalytic mechanism was further explored.