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

Abstract

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.

Nanocarbon for Energy Material Applications: N2 Reduction Reaction

“…Note that other oxide/nanocarbon materials have been reported for this reaction. For example, -V 2 O 3 /C P-doped, [134] showing a NH 3 formation rate of 22.4 µg h −1 mg cat −1 at −0.35 V versus RHE, and an FE of 13.8% at −0.25 V versus RHE -oxygen vacancy-rich NiCo 2 O 4 on hollow N-carbon polyhedra [135] showing a NH 3 formation rate of 17.8 µg h −1 mg −1 with Faradaic efficiency of 5.3% -vanadium carbide nanoparticles/carbon sphere [136] showing a NH 3 formation rate of 34.6 µg h −1 mg cat −1 and Faradaic efficiency of 12.2% at −0.40 V versus RHE -copper supported on activated carbon functionalized with sulfonate groups (Cu/AC-S), [137] showing a NH 3 formation rate of 9.7 µg h −1 mg −1 and a Faradaic efficiency of 15.9% at −0.3 V versus RHE.…”

WO3 Rich in Oxygen Vacancies Through Ion‐Exchange Reaction for Enhanced Electrocatalytic N2 Reduction to NH3

“…Some studies have shown that defect engineering can regulate and modify the local coordination environment of electrocatalysts and promote intrinsic activity. Recent advances in defect engineering of nanostructured electrocatalysts, including vacancy, heteroatom doping, [16] facet engineering and surface modification, are summarized. Lai et al.…”

Composites of Vanadium (III) Oxide (V2O3) Incorporating with Amorphous C as Pt-Free Counter Electrodes for Low-Cost and High-Performance Dye-Sensitized Solar Cells

“…is because of their unmatched structural types, multiphase states, and easy modification. 35 , 36 As shown in our previous work, 37 V 2 O 3 -based CEs had been successfully prepared using VOCl 3 as metal precursors with the urea–metal route. The DSSCs using V 2 O 3 CEs showed a decent PCE value of 5.40%.…”