RT Journal Article A1 Hao Tan,Qianqian Ji,Chao Wang,Hengli Duan,Yuan Kong,Yao Wang,Sihua Feng,Liyang Lv,Fengchun Hu,Wenhua Zhang,Wangsheng Chu,Zhihu Sun,Wensheng Yan; AD National Synchrotron Radiation Laboratory, 中国 ; National Synchrotron Radiation Laboratory, 中国 ; National Synchrotron Radiation Laboratory, 中国 ; National Synchrotron Radiation Laboratory, 中国 ; 合肥微尺度物理科学国家实验室和化学、物理与量子信息与量子物理协同创新中心, 中国 ; National Synchrotron Radiation Laboratory, 中国 ; National Synchrotron Radiation Laboratory, 中国 ; National Synchrotron Radiation Laboratory, 中国 ; National Synchrotron Radiation Laboratory, 中国 ; National Synchrotron Radiation Laboratory, 中国 ; National Synchrotron Radiation Laboratory, 中国 ; National Synchrotron Radiation Laboratory, 中国 ; National Synchrotron Radiation Laboratory, 中国 T1 Asymmetrical π back-donation of hetero-dicationic Mo4+–Mo6+ pairs for enhanced electrochemical nitrogen reduction YR 2022 IS 4 vo 15 OP 3010-OP 3016 K1 nitrogen reduction reaction;asymmetrical "π back-donation" process;hetero-dicationic Mo4+–Mo6+ pairs;operando experimental characterizations AB The breaking of nonpolar N≡N bond of dinitrogen is the biggest dilemma for electrocatalytic nitrogen reduction reaction (NRR) application, driving electron migration between catalysts and N≡N bond (termed “π back-donation” process) is crucial for attenuating interfacial energy barrier but still remains challenging. Herein, using density functional theory calculations, we revealed that constructing a unique hetero-dicationic Mo4+–Mo6+ pair could effectively activate N≡N bond with a lying-down chemisorption configuration by an asymmetrical “π back-donation” process. As a proof-of-concept demonstration, we synthesized MoO2@MoO3 heterostructure with double Mo sites (Mo4+–Mo6+), which are embedded in graphite, for electrochemical nitrogen reduction. Impressively, this hetero-dicationic Mo4+–Mo6+ pair catalysts display more excellent catalytic performance with a high NH3 yield (60.9 µg·h−1·mg−1) and Faradic efficiency (23.8%) as NRR catalysts under ambient conditions than pristine MoO2 and MoO3. Operando characterizations using synchrotron-based spectroscopic techniques identified the emergence of a key *N2Hy intermediate on Mo sites during NRR, which indicates that the Mo sites are active sites and the NRR process tends to follow an associative mechanism. This novel type of hetero-dicationic catalyst has tremendous potential as a new class of transition metal-based catalysts with promising applications in electrocatalysis and catalysts for energy conversion and storage. SN 1998-0124 LA EN