Jahn–Teller Distortions Induced by in situ Li Migration in λ‐MnO2 for Boosting Electrocatalytic Nitrogen Fixation

Author:

Gao Zijian123,Zhao Zhi‐hao4,Wang Haifan23,Bai Yiling56,Zhang Xuehua37,Zhang Zeyu8,Mei Hui4,Yuan Menglei4,Zhang Guangjin239ORCID

Affiliation:

1. Chengdu Institute of Organic Chemistry Chinese Academy of Sciences Chengdu 610041 P. R. China

2. Center of Materials Science and Optoeletronics Engineering Chinese Academy of Sciences Beijing 100049 P. R. China

3. CAS Key Laboratory of Green Process and Engineering, Institute of Process Engineering Chinese Academy of Sciences Beijing 100190 P. R. China

4. State Key Laboratory of Solidification Processing and School of Materials Science and Engineering Northwestern Polytechnical University Xi'an 710072 P. R. China

5. State Key Laboratory of Coal Conversion, CAS Key Laboratory of Carbon Materials, Institute of Coal Chemistry Chinese Academy of Sciences Taiyuan 030001 P. R. China

6. National Energy Center for Coal to Liquids Synfuels China Technology Co. Ltd Beijing 101400 P. R. China

7. State Key Laboratory of Petroleum Molecular & Process Engineering(RIPP, SINOPEC) Beijing 101407 P. R. China

8. Queen Mary University of London Engineering School Northwestern Polytechnical University Xi'an 710129 P. R. China

9. Key Laboratory of Green and High-value Utilization of Salt Lake Resources Chinese Academy of Sciences Beijing 100190 P. R. China

Abstract

AbstractLithium‐mediated electrochemical nitrogen reduction reaction (Li‐NRR) completely eschews the competitive hydrogen evolution reaction (HER) occurred in aqueous system, whereas the continuous deposition of lithium readily blocks the active sites and further reduces the reaction kinetics. Herein, we propose an innovative in situ Li migration strategy to realize that Li substitutes Mn sites in λ‐MnO2 instead of evolving into the dead Li. Comprehensive characterizations corroborate that the intercalation of Li+ at high voltage breaks the structural integrity of MnO6 octahedron and further triggers unique Jahn–Teller distortions, which promotes the spin state regulation of Mn sites to generate the ameliorative eg orbital configuration and accelerates N≡N bond cleavage via eg‐σ and eg‐π* interaction. To this end, the resulted cationic disordered LiMnO4 delivers the recorded highest NH3 yield rate of 220 μg h−1 cm−2 and a Faradaic efficiency (FE) 83.80 % in organic electrolyte.

Funder

National Natural Science Foundation of China

China Postdoctoral Science Foundation

Publisher

Wiley

Subject

General Chemistry,Catalysis

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