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Research Article

Asymmetrical π back-donation of hetero-dicationic Mo4+–Mo6+ pairs for enhanced electrochemical nitrogen reduction

Hao Tan1,§, Qianqian Ji1,§, Chao Wang1, Hengli Duan1, Yuan Kong2(), Yao Wang1, Sihua Feng1, Liyang Lv1, Fengchun Hu1, Wenhua Zhang1, Wangsheng Chu1(), Zhihu Sun1, Wensheng Yan1()
National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei 230029, China
Hefei National Laboratory for Physical Sciences at the Microscale and Department of Chemical, Physics and Synergetic Innovation Center of Quantum Information and Quantum Physics, University of Science and Technology of China, Hefei 230029, China

§ Hao Tan and Qianqian Ji contributed equally to this work.

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Hetero-dicationic Mo4+–Mo6+ pairs offer a unique active center to efficiently activate N≡N bond with a lying-down chemisorption configuration through an asymmetrical “π back-donation” process. 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  nitrogen reduction reaction (NRR) process tends to follow an associative mechanism.

Abstract

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.

Keywords

asymmetrical "π back-donation" processhetero-dicationic Mo4+–Mo6+ pairs nitrogen reduction reactionoperando experimental characterizations

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Nano Research
Volume 15 Issue 4,
April 2022
Pages 3010-3016
DOI: 10.1007/s12274-021-3934-6
Cite this article:
Tan H, Ji Q, Wang C, et al. Asymmetrical π back-donation of hetero-dicationic Mo4+–Mo6+ pairs for enhanced electrochemical nitrogen reduction. Nano Research, 2022, 15(4): 3010-3016. https://doi.org/10.1007/s12274-021-3934-6
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