Long distance bimetallic site in crystal with relay metal-N-N-metal mechanism and new descriptors for electrocatalytic nitrogen reduction reaction

There are great challenges in achieving high activity and selectivity in nitrogen fixation. Developing bimetal catalyst is effective approach to enhance NRR performance due to involvement of both metal sites. Herein, we propose long distance bimetal site separated by vacancy in crystal for NRR catal...

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Bibliographic Details
Published in:Applied catalysis. A, General General, 2023-02, Vol.652, p.119030, Article 119030
Main Authors: Gao, Yongqi, Zhang, Dewei, Yuan, Hao, Min, Yuxiang, Chen, Siyu, Xu, Lai
Format: Article
Language:English
Subjects:
Descriptor
Electrocatalysis
Long Distance Bimetallic Site
Nitrogen Reduction Reaction
Relay Metal-N-N-Metal Mechanism
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Summary:There are great challenges in achieving high activity and selectivity in nitrogen fixation. Developing bimetal catalyst is effective approach to enhance NRR performance due to involvement of both metal sites. Herein, we propose long distance bimetal site separated by vacancy in crystal for NRR catalysis with experimental support and locate the best catalyst through extensive screening. The halogen vacancies capture N2 and N2 locates between the two metal atoms. From orbital and electronic structure analysis, we propose the relay Metal-N-N-Metal mechanism, we also find new descriptors to predict NRR activity, which is the sum of d-band center gap of bimetal, and the sum of spin moment of bimetal. Thus, the spin polarization of bimetals can promote the activity of NRR. Based on multi-step screening, we have located systems with sound NRR performance, with limiting potential of −0.17 V, and better than most of the proposed catalysts. Our work provides a new strategy for exploring new catalyst and paves the way of designing and understanding the mechanism of long-distance bimetallic crystals for high performance NRR catalyst. [Display omitted] •Through high-throughput screening, we found an efficient NRR electrocatalyst, Cs2MnCrCl5.75, its UL is only − 0.17 V.•The “Metal-N-N-Metal” Relay mechanism was proposed, which provides new insights for the study of NRR.•We proposed new descriptor, d-band center gap and spin moment, that can predict the catalytic performance.
ISSN:0926-860X
1873-3875
DOI:10.1016/j.apcata.2023.119030