V₂O₃/VN electrocatalysts with coherent heterogeneous interfaces for selecting low-energy nitrogen reduction pathways

Abstract

Electrochemical nitrogen reduction reaction (NRR) is a sustainable alternative to the Haber–Bosch process for ammonia (NH₃) production. However, the significant uphill energy in the multistep NRR pathway is a bottleneck for favorable serial reactions. To overcome this challenge, we designed a vanadium oxide/nitride (V₂O₃/VN) hybrid electrocatalyst in which V₂O₃ and VN coexist coherently at the heterogeneous interface. Since single-phase V₂O₃ and VN exhibit different surface catalytic kinetics for NRR, the V₂O₃/VN hybrid electrocatalyst can provide alternating reaction pathways, selecting a lower energy pathway for each material in the serial NRR pathway. As a result, the ammonia yield of the V₂O₃/VN hybrid electrocatalyst was 219.6 µg h^–1 cm^–2, and the Faradaic efficiency was 18.9%, which is much higher than that of single-phase VN, V₂O₃, and VNxOy solid solution catalysts without heterointerfaces. Density functional theory calculations confirmed that the composition of these hybrid electrocatalysts allows NRR to proceed from a multistep reduction reaction to a low-energy reaction pathway through the migration and adsorption of intermediate species. Therefore, the design of metal oxide/nitride hybrids with coherent heterointerfaces provides a novel strategy for synthesizing highly efficient electrochemical catalysts that induce steps favorable for the efficient low-energy progression of NRR.

Keywords

coherent heterogeneous interfaces / green ammonia synthesis / hybrid electrocatalyst / lowenergy progression / nitrogen reduction reaction (NRR) / vanadium oxide/nitride (V2O3/VN)

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