Open AccessDual‐Metal Sites Boosting Polarization of Nitrogen Molecules for Efficient Nitrogen Photofixation
Author(s) -
Zhang Yida,
Hou Tingting,
Xu Quan,
Wang Qingyu,
Bai Yu,
Yang Shaokang,
Rao Dewei,
Wu Lihui,
Pan Haibin,
Chen Jiafu,
Wang Gongming,
Zhu Junfa,
Yao Tao,
Zheng Xusheng
Publication year - 2021
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.202100302
Subject(s) - catalysis , nitrogen fixation , antibonding molecular orbital , nitrogen , materials science , photochemistry , ammonia production , chemistry , inorganic chemistry , atomic orbital , electron , physics , biochemistry , organic chemistry , quantum mechanics
Constructing nitrogen (N 2 ) adsorption and activation sites on semiconductors is the key to achieving efficient N 2 photofixation. Herein, Mn–W dual‐metal sites on WO 3 are designed toward efficient N 2 photoreduction via controlled Mn doping. Impressively, the optimal 2.3% Mn‐doped WO 3 (Mn‐WO 3 ) exhibits a remarkable ammonia (NH 3 ) production rate of 425 µmol g cat. −1 h −1 , representing the best catalytic performance among the ever‐reported tungsten oxide‐based photocatalysts for N 2 fixation. Quasi in situ synchrotron radiation X‐ray spectroscopy directly identifies that the Mn–W dual‐metal sites can enhance the polarization of the adsorbed N 2 , which is beneficial to the N 2 activation. Further theoretical calculations reveal that the increased polarization is originated from the electron back‐donation into the antibonding orbitals of the adsorbed N 2 , hence lowering the reaction energy barrier toward the N 2 photofixation. The concept of dual sites construction for inert molecule activation offers a powerful platform toward rational design of highly efficient catalysts for nitrogen fixation and beyond.