Polarized Cu–Bi Site Pairs for Non‐Covalent to Covalent Interaction Tuning toward N2 Photoreduction. Issue 37 (11th August 2022)

• Record Type: Journal Article
• Authors: Di, Jun; Chen, Chao; Wu, Yao; Zhao, Yunxuan; Zhu, Chao; Zhang, Yi; Wang, Changda; Chen, Hailong; Xiong, Jun; Xu, Manzhang; Xia, Jiexiang; Zhou, Jiadong; Weng, Yuxiang; Song, Li; Li, Shuzhou; Jiang, Wei; Liu, Zheng
• Is Part Of: Advanced materials. Volume 34:Issue 37(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-08-11
• Subjects: altered hydrogenation pathways -- atomic layers -- non‐covalent interactions -- polarized metal sites; Materials -- Periodicals; Chemical vapor deposition -- Periodicals; 620.11
• DOI: 10.1002/adma.202204959
• Languages: English
• ISSNs: 0935-9648

Abstract

Abstract: A universal atomic layer confined doping strategy is developed to prepare Bi24 O31 Br10 materials incorporating isolated Cu atoms. The local polarization can be created along the CuOBi atomic interface, which enables better electron delocalization for effective N2 activation. The optimized Cu‐Bi24 O31 Br10 atomic layers show 5.3× and 88.2× improved photocatalytic nitrogen fixation activity than Bi24 O31 Br10 atomic layer and bulk Bi24 O31 Br10, respectively, with the NH3 generation rate reaching 291.1 µmol g −1 h −1 in pure water. The polarized Cu–Bi site pairs can increase the non‐covalent interaction between the catalyst's surface and N2 molecules, then further weaken the covalent bond order in NN. As a result, the hydrogenation pathways can be altered from the associative distal pathway for Bi24 O31 Br10 to the alternating pathway for Cu‐Bi24 O31 Br10 . This strategy provides an accessible pathway for designing polarized metal site pairs or tuning the non‐covalent interaction and covalent bond order. Abstract : A universal atomic‐layer‐confined doping strategy is developed to prepare Bi24 O31 Br10 materials incorporating isolated Cu (Fe, Co, Ni) atoms. The polarized Cu–Bi site pairs favor better electron delocalization for effective N2 activation, and can work as reactive sites to tune the non‐covalent interactions of the intermediates, optimize the covalent bond order in NN, and alter the hydrogenation pathways.