Polarized Cu–Bi Site Pairs for Non‐Covalent to Covalent Interaction Tuning toward N<sub>2</sub> Photoreduction
Jun Di, Chao Chen, Yao Wu, Yunxuan Zhao, Chao Zhu, Yi Zhang, Changda Wang, Hailong Chen, Jun Xiong, Manzhang Xu, Jiexiang Xia, Jiadong Zhou, Yuxiang Weng, Li Song, Shuzhou Li, Wei Jiang, Zheng Liu
Abstract
Abstract A universal atomic layer confined doping strategy is developed to prepare Bi 24 O 31 Br 10 materials incorporating isolated Cu atoms. The local polarization can be created along the CuOBi atomic interface, which enables better electron delocalization for effective N 2 activation. The optimized Cu‐Bi 24 O 31 Br 10 atomic layers show 5.3× and 88.2× improved photocatalytic nitrogen fixation activity than Bi 24 O 31 Br 10 atomic layer and bulk Bi 24 O 31 Br 10 , respectively, with the NH 3 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 N 2 molecules, then further weaken the covalent bond order in NN. As a result, the hydrogenation pathways can be altered from the associative distal pathway for Bi 24 O 31 Br 10 to the alternating pathway for Cu‐Bi 24 O 31 Br 10 . This strategy provides an accessible pathway for designing polarized metal site pairs or tuning the non‐covalent interaction and covalent bond order.