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Intrinsic Electron Localization of Metastable MoS 2 Boosts Electrocatalytic Nitrogen Reduction to Ammonia
Author(s) -
Lin Gaoxin,
Ju Qiangjian,
Guo Xiaowei,
Zhao Wei,
Adimi Samira,
Ye Jinyu,
Bi Qingyuan,
Wang Jiacheng,
Yang Minghui,
Huang Fuqiang
Publication year - 2021
Publication title -
advanced materials
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 10.707
H-Index - 527
eISSN - 1521-4095
pISSN - 0935-9648
DOI - 10.1002/adma.202007509
Subject(s) - materials science , metastability , faraday efficiency , electron transfer , metal , electrochemistry , nitrogen , adsorption , ammonia , chemical physics , photochemistry , inorganic chemistry , electrode , chemistry , organic chemistry , metallurgy
The advancement of efficient electrocatalysts toward the nitrogen reduction reaction (NRR) is critical in sustainable ammonia synthesis under ambient pressure and temperature. Manipulating the electronic configuration of electrocatalysts is particularly vital to form metal–nitrogen (MN) bonds during the NRR through regulating the active electronic states of sites. Here, in sharp contrast to stable 2H MoS 2 without metal chains, MoMo bonding in metastable polymorphs of MoS 2 bulk (zigzag chain in the 1T′ phase and diamond chain in the 1T″′ phase) is discovered to significantly increase intrinsic electron localization around the metal chains. This can enhance the charge transfer from the adsorbed nitrogen molecule to the metal chains, allowing for boosted NRR kinetics. The electrochemical experiments show that the NH 3 yield rate and the faradaic efficiency of the metastable 1T″′ MoS 2 rich with abundant Mo–Mo bonds are about 9 and 12 times above average than those of 2H MoS 2 , correspondingly. Theoretical simulations reveal the high local electron density surrounding the MoMo chains and sites can promote π back‐donation, which is beneficial for increasing nitrogen adsorption, strengthening the MN bonds, and reducing the cleavage barrier of the triple NN bond.