Dual‐Metal Sites Boosting Polarization of Nitrogen Molecules for Efficient Nitrogen Photofixation
Yida Zhang, Tingting Hou, Quan Xu, Qingyu Wang, Yu Bai, Shaokang Yang, Dewei Rao, Lihui Wu, Haibin Pan, Jia‐Fu Chen, Gongming Wang, Junfa Zhu, Tao Yao, Xusheng Zheng
Abstract
Abstract 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.