Cargando…
Nb(12)(+)—niobespherene: a full-metal hollow-cage cluster with superatomic stability and resistance to CO attack
Why one chemical is more stable than another is not always easy to understand. A unified answer for metal clusters has led to the establishment of the superatom concept, which rationalizes the delocalization of electrons; however, cluster stability based on superatom theory has not been confirmed un...
Autores principales: | , , , , , |
---|---|
Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
Oxford University Press
2022
|
Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10081918/ https://www.ncbi.nlm.nih.gov/pubmed/37035019 http://dx.doi.org/10.1093/nsr/nwac197 |
_version_ | 1785021216298369024 |
---|---|
author | Huang, Benben Zhang, Hanyu Gan, Wen Yang, Mengzhou Luo, Zhixun Yao, Jiannian |
author_facet | Huang, Benben Zhang, Hanyu Gan, Wen Yang, Mengzhou Luo, Zhixun Yao, Jiannian |
author_sort | Huang, Benben |
collection | PubMed |
description | Why one chemical is more stable than another is not always easy to understand. A unified answer for metal clusters has led to the establishment of the superatom concept, which rationalizes the delocalization of electrons; however, cluster stability based on superatom theory has not been confirmed unambiguously for any metal other than the s- and p-blocks of the periodic table of elements. Here, we have prepared pure niobium clusters and observed their reactions with CO under sufficient gas collision conditions. We find prominent inertness of Nb(12)(+), which survives CO attack. Comprehensive theoretical calculation results reveal that the inertness of Nb(12)(+) is associated with its cage structure and well-organized superatomic orbitals, giving rise to energetic superiority among the studied clusters. It is revealed that not only the 5s but also the 4d electrons of Nb delocalize in the cluster and significantly contribute to the superatomic state, resulting in reasonable cage aromaticity. This hollow-cage cluster, which we have called a ‘niobespherene’, provides a clue with regard to designing new materials of all-metal aromaticity and Nb-involved catalysts free of CO poisoning. |
format | Online Article Text |
id | pubmed-10081918 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2022 |
publisher | Oxford University Press |
record_format | MEDLINE/PubMed |
spelling | pubmed-100819182023-04-08 Nb(12)(+)—niobespherene: a full-metal hollow-cage cluster with superatomic stability and resistance to CO attack Huang, Benben Zhang, Hanyu Gan, Wen Yang, Mengzhou Luo, Zhixun Yao, Jiannian Natl Sci Rev Research Article Why one chemical is more stable than another is not always easy to understand. A unified answer for metal clusters has led to the establishment of the superatom concept, which rationalizes the delocalization of electrons; however, cluster stability based on superatom theory has not been confirmed unambiguously for any metal other than the s- and p-blocks of the periodic table of elements. Here, we have prepared pure niobium clusters and observed their reactions with CO under sufficient gas collision conditions. We find prominent inertness of Nb(12)(+), which survives CO attack. Comprehensive theoretical calculation results reveal that the inertness of Nb(12)(+) is associated with its cage structure and well-organized superatomic orbitals, giving rise to energetic superiority among the studied clusters. It is revealed that not only the 5s but also the 4d electrons of Nb delocalize in the cluster and significantly contribute to the superatomic state, resulting in reasonable cage aromaticity. This hollow-cage cluster, which we have called a ‘niobespherene’, provides a clue with regard to designing new materials of all-metal aromaticity and Nb-involved catalysts free of CO poisoning. Oxford University Press 2022-09-22 /pmc/articles/PMC10081918/ /pubmed/37035019 http://dx.doi.org/10.1093/nsr/nwac197 Text en © The Author(s) 2022. Published by Oxford University Press on behalf of China Science Publishing & Media Ltd. https://creativecommons.org/licenses/by/4.0/This is an Open Access article distributed under the terms of the Creative Commons Attribution License (https://creativecommons.org/licenses/by/4.0/), which permits unrestricted reuse, distribution, and reproduction in any medium, provided the original work is properly cited. |
spellingShingle | Research Article Huang, Benben Zhang, Hanyu Gan, Wen Yang, Mengzhou Luo, Zhixun Yao, Jiannian Nb(12)(+)—niobespherene: a full-metal hollow-cage cluster with superatomic stability and resistance to CO attack |
title | Nb(12)(+)—niobespherene: a full-metal hollow-cage cluster with superatomic stability and resistance to CO attack |
title_full | Nb(12)(+)—niobespherene: a full-metal hollow-cage cluster with superatomic stability and resistance to CO attack |
title_fullStr | Nb(12)(+)—niobespherene: a full-metal hollow-cage cluster with superatomic stability and resistance to CO attack |
title_full_unstemmed | Nb(12)(+)—niobespherene: a full-metal hollow-cage cluster with superatomic stability and resistance to CO attack |
title_short | Nb(12)(+)—niobespherene: a full-metal hollow-cage cluster with superatomic stability and resistance to CO attack |
title_sort | nb(12)(+)—niobespherene: a full-metal hollow-cage cluster with superatomic stability and resistance to co attack |
topic | Research Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10081918/ https://www.ncbi.nlm.nih.gov/pubmed/37035019 http://dx.doi.org/10.1093/nsr/nwac197 |
work_keys_str_mv | AT huangbenben nb12niobesphereneafullmetalhollowcageclusterwithsuperatomicstabilityandresistancetocoattack AT zhanghanyu nb12niobesphereneafullmetalhollowcageclusterwithsuperatomicstabilityandresistancetocoattack AT ganwen nb12niobesphereneafullmetalhollowcageclusterwithsuperatomicstabilityandresistancetocoattack AT yangmengzhou nb12niobesphereneafullmetalhollowcageclusterwithsuperatomicstabilityandresistancetocoattack AT luozhixun nb12niobesphereneafullmetalhollowcageclusterwithsuperatomicstabilityandresistancetocoattack AT yaojiannian nb12niobesphereneafullmetalhollowcageclusterwithsuperatomicstabilityandresistancetocoattack |