Open AccessBoosting Nitrogen Reduction Reaction via Electronic Coupling of Atomically Dispersed Bismuth with Titanium Nitride Nanorods
Author(s) -
Xi Zichao,
Shi Ke,
Xu Xuan,
Jing Peng,
Liu Baocang,
Gao Rui,
Zhang Jun
Publication year - 2022
Publication title -
advanced science
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.388
H-Index - 100
ISSN - 2198-3844
DOI - 10.1002/advs.202104245
Subject(s) - nanorod , materials science , faraday efficiency , tin , reversible hydrogen electrode , chemical engineering , catalysis , redox , nitride , nitrogen , bismuth , yield (engineering) , carbon nitride , inorganic chemistry , nanotechnology , electrochemistry , electrode , chemistry , photocatalysis , layer (electronics) , composite material , metallurgy , organic chemistry , working electrode , engineering
Electrocatalytic nitrogen reduction reaction (NRR) is a promising alternative to the traditional Haber–Bosch process. However, the sluggish kinetics and competitive hydrogen evolution reaction result in poor NH 3 yield and low Faradaic efficiency (FE). Herein, single bismuth atoms incorporated hollow titanium nitride nanorods encapsulated in nitrogen‐doped carbon layer (NC) supported on carbon cloth (NC/Bi SAs/TiN/CC) is constructed for electrocatalytic NRR. Impressively, as an integrated electrode, it exhibits a superior ammonia yield rate of 76.15 µg mg cat −1 h −1 (9859 µg μmol Bi −1 h −1 ) at −0.8 V versus RHE and a high FE of 24.60% at −0.5 V versus RHE in 0.1 m Na 2 SO 4 solution, which can retain stable performance in 10 h continuous operation, surpassing the overwhelming majority of reported Bi‐based NRR catalysts. Coupling various characterizations with theory calculations, it is disclosed that the unique monolithic core‐shell configuration with porous structure endows abundant accessible active sites, outstanding charge‐transfer property, and good stability, while the cooperation effect of Bi SAs and TiN can simultaneously promote the hydrogenation of N 2 into NH 3 * on the TiN surface and the desorption of NH 3 * to release NH 3 on the Bi SA sites. These features result in the significant promotion of NRR performance.