Altering Hydrogenation Pathways in Photocatalytic Nitrogen Fixation by Tuning Local Electronic Structure of Oxygen Vacancy with Dopant. (14th June 2021)

• Record Type: Journal Article
• 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
• Is Part Of: Angewandte Chemie. Volume 133:Number 29(2021)
• Page Start: 16221
• Page End: 16228
• Publication Date: 2021-06-14
• Subjects: active sites -- hydrogenation pathway -- local electronic structure -- oxygen vacancy -- photocatalytic nitrogen fixation; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.202104001
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: 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. Abstract : 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.