Atomically Dispersed Zinc(I) Active Sites to Accelerate Nitrogen Reduction Kinetics for Ammonia Electrosynthesis
Yan Kong, Yan Li, Xiahan Sang, Bin Yang, Zhongjian Li, Sixing Zheng, Qinghua Zhang, Siyu Yao, Xiaoxuan Yang, Lecheng Lei, Shaodong Zhou, Gang Wu, Yang Hou
Abstract
Abstract Developing highly active and stable nitrogen reduction reaction (NRR) catalysts for NH 3 electrosynthesis remains challenging. Herein, an unusual NRR electrocatalyst is reported with a single Zn(I) site supported on hollow porous N‐doped carbon nanofibers (Zn 1 N–C). The Zn 1 N–C nanofibers exhibit an outstanding NRR activity with a high NH 3 yield rate of ≈16.1 µg NH 3 h −1 mg cat −1 at −0.3 V and Faradaic efficiency (FE) of 11.8% in alkaline media, surpassing other previously reported carbon‐based NRR electrocatalysts with transition metals atomically dispersed and nitrogen coordinated (TM‐N x ) sites. 15 N 2 isotope labeling experiments confirm that the feeding nitrogen gas is the only nitrogen source in the production of NH 3 . Structural characterization reveals that atomically dispersed Zn(I) sites with Zn–N 4 moieties are likely the active sites, and the nearby graphitic N site synergistically facilitates the NRR process. In situ attenuated total reflectance‐Fourier transform infrared measurement and theoretical calculation elucidate that the formation of initial *NNH intermediate is the rate‐limiting step during the NH 3 production. The graphitic N atoms adjacent to the tetracoordinate Zn–N 4 moieties could significantly lower the energy barrier for this step to accelerate hydrogenation kinetics duing the NRR.