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

As a carbon‐neutral alternative technology to the Haber−Bosch process, electrochemical N2 reduction enables eco‐friendly NH3 synthesis under ambient conditions but requires electrocatalysts to drive the N2 reduction reaction (NRR). Here, P doping is proposed as a valid strategy to greatly increase the NRR activity of the V2O3/C shuttle‐like nanostructure. In 0.1 M Na2SO4, the NH3 yield of original V2O3/C is 12.6 μg h−1 mg−1cat. and a Faraday efficiency (FE) of 6.06% at −0.45 V and −0.25 V vs. reversible hydrogen electrode (RHE), respectively. P‐doped V2O3/C (P−V2O3/C), with a mass ratio of P of 6.05%, is capable of achieving a large NH3 yield of 22.4 μg h−1 mg−1cat. 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 NH3 formation. Combined with density functional theory calculations, the catalytic mechanism was further explored. P doping is an effective strategy to greatly enhance the NRR activity of V2O3/C shuttle‐like nanostructure. In 0.1 M Na2SO4, such P−V2O3/C attains a large NH3 yield of 22.4 μg h−1 mg−1cat. and a high Faradic efficiency of 13.78% at −0.35 V and −0.25 V vs. reversible hydrogen electrode, respectively.