V<sub>2</sub>O<sub>3</sub>/VN electrocatalysts with coherent heterogeneous interfaces for selecting low‐energy nitrogen reduction pathways
Tae‐Yong An, Chengkai Xia, Minyeong Je, Hyunjung Lee, Seulgi Ji, Min Cheol Kim, Subramani Surendran, Mi‐Kyung Han, Jaehyoung Lim, Dong‐Kyu Lee, Joon‐Young Kim, Joon‐Young Kim, Tae‐Hoon Kim, Heechae Choi, Jung Kyu Kim, Jung Kyu Kim, Uk Sim
Abstract
Abstract Electrochemical nitrogen reduction reaction (NRR) is a sustainable alternative to the Haber‒Bosch process for ammonia (NH 3 ) 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 (V 2 O 3 /VN) hybrid electrocatalyst in which V 2 O 3 and VN coexist coherently at the heterogeneous interface. Since single‐phase V 2 O 3 and VN exhibit different surface catalytic kinetics for NRR, the V 2 O 3 /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 V 2 O 3 /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, V 2 O 3 , and VN x O y 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.