Effect of External Electric Field on Nitrogen Activation on a Trimetal Cluster
Abstract Efficient nitrogen (N 2 ) fixation and activation under mild conditions are crucial for modern society. External electric fields ( F electric ) can significantly affect N 2 activation. In this work, the effect of F electric on N 2 activation by Nb 3 clusters supported in a sumanene bowl was...
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Published in | Chemphyschem p. e202300961 |
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Main Authors | , , |
Format | Journal Article |
Language | English |
Published |
23.07.2024
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Online Access | Get full text |
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Summary: | Abstract Efficient nitrogen (N 2 ) fixation and activation under mild conditions are crucial for modern society. External electric fields ( F electric ) can significantly affect N 2 activation. In this work, the effect of F electric on N 2 activation by Nb 3 clusters supported in a sumanene bowl was studied by density functional theory calculations. Four typical systems at different stages of N−N activation were studied, including two intermediates and two transition states. The impact of F electric on various properties related to N 2 activation was investigated, including the N−N bond length, overlap population density of states (OPDOS), total energy of the system, adsorption energy of N 2 , decomposition of energy changes, and electron transfer. The sumanene not only functions as a support and protective substrate, but also serves as a donor or acceptor under different F electric conditions. Negative F electric is beneficial to N−N bond activation because it promotes electron transfer to the N−N region and improves the d–π* orbital hybridization between metals and N 2 in the activation process. Positive F electric improves d–π* orbital hybridization only when the N−N is nearly dissociated. The microscopic mechanism of F electric ′s effects provides insight into N 2 activation and theoretical guidance for the design of catalytic reaction conditions for nitrogen reduction reactions (NRR). |
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Bibliography: | ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23 |
ISSN: | 1439-4235 1439-7641 1439-7641 |
DOI: | 10.1002/cphc.202300961 |