Altering Hydrogenation Pathways in Photocatalytic Nitrogen Fixation by Tuning Local Electronic Structure of Oxygen Vacancy with Dopant

To avoid the energy‐consuming step of direct N≡N bond cleavage, photocatalytic N2 fixation undergoing the associative pathways has been developed for mild‐condition operation. However, it is a fundamental yet challenging task to gain comprehensive understanding on how the associative pathways (i.e.,...

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Published in:Angewandte Chemie International Edition 2021-07, Vol.60 (29), p.16085-16092
Main Authors: Bo, Yanan, Wang, Haiyun, Lin, Yunxiang, Yang, Tian, Ye, Run, Li, Yu, Hu, Canyu, Du, Pengye, Hu, Yangguang, Liu, Zhi, Long, Ran, Gao, Chao, Ye, Bangjiao, Song, Li, Wu, Xiaojun, Xiong, Yujie
Format: Article
Language:English
Subjects:
active sites
Catalysts
Dopants
Electronic structure
Fine structure
Hydrogenation
hydrogenation pathway
local electronic structure
Nanofibers
Nitrogen
Nitrogen fixation
Nitrogenation
Oxygen
oxygen vacancy
Photocatalysis
photocatalytic nitrogen fixation
Titanium dioxide
Ultrastructure
Vacancies
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Summary:To avoid the energy‐consuming step of direct N≡N bond cleavage, photocatalytic N2 fixation undergoing the associative pathways has been developed for mild‐condition operation. However, it is a fundamental yet challenging task to gain comprehensive understanding on how the associative pathways (i.e., alternating vs. distal) are influenced and altered by the fine structure of catalysts, which eventually holds the key to significantly promote the practical implementation. Herein, we introduce Fe dopants into TiO2 nanofibers to stabilize oxygen vacancies and simultaneously tune their local electronic structure. The combination of in situ characterizations with first‐principles simulations reveals that the modulation of local electronic structure by Fe dopants turns the hydrogenation of N2 from associative alternating pathway to associative distal pathway. This work provides fresh hints for rationally controlling the reaction pathways toward efficient photocatalytic nitrogen fixation. Modulating the local electronic structure of nearby oxygen vacancy by doping enables the control of N2 hydrogenation from the associative alternating pathway to a more favorable associative distal pathway, thus contributing to improved performance for NH3 evolution in photocatalytic nitrogen fixation.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.202104001