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Unprecedented Catalysis of Cs+ Single Sites Confined in Y Zeolite Pores for Selective Csp3–H Bond Ammoxidation: Transformation of Inactive Cs+ Ions with a Noble Gas Electronic Structure to Active Cs+ Single Sites
https://uec.repo.nii.ac.jp/records/10075
https://uec.repo.nii.ac.jp/records/1007535342362-7b67-48e9-a57c-eec64eadf1bd
名前 / ファイル | ライセンス | アクション |
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ACS Catal_article_rev_Y.Iwasawa.pdf (1.1 MB)
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Item type | 学術雑誌論文 / Journal Article(1) | |||||
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公開日 | 2022-06-05 | |||||
タイトル | ||||||
言語 | en | |||||
タイトル | Unprecedented Catalysis of Cs+ Single Sites Confined in Y Zeolite Pores for Selective Csp3–H Bond Ammoxidation: Transformation of Inactive Cs+ Ions with a Noble Gas Electronic Structure to Active Cs+ Single Sites | |||||
言語 | ||||||
言語 | eng | |||||
キーワード | ||||||
言語 | en | |||||
主題 | catalytic Csp3−H activation | |||||
キーワード | ||||||
言語 | en | |||||
主題 | confined Cs+ single site in Y zeolite pore | |||||
キーワード | ||||||
言語 | en | |||||
主題 | ammoxidation of toluene and its derivatives | |||||
キーワード | ||||||
言語 | en | |||||
主題 | selective nitrile synthesis | |||||
キーワード | ||||||
言語 | en | |||||
主題 | catalysis mechanism | |||||
資源タイプ | ||||||
資源タイプ識別子 | http://purl.org/coar/resource_type/c_6501 | |||||
資源タイプ | journal article | |||||
著者 |
Acharyya, Shankha S.
× Acharyya, Shankha S.× Ghosh, Shilpi× Yoshida, Yusuke× Kaneko, Takuma× Sasaki, Takehiko× Iwasawa, Yasuhiro |
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抄録 | ||||||
内容記述タイプ | Abstract | |||||
内容記述 | We report the transformation of Cs+ ions with an inactive noble gas electronic structure to active Cs+ single sites chemically confined in Y zeolite pores (Cs+/Y), which provides an unprecedented catalysis for oxidative cyanation (ammoxidation) of Csp3–H bonds with O2 and NH3, although in general, alkali and alkaline earth metal ions without a moderate redox property cannot activate Csp3–H bonds. The Cs+/Y catalyst was proved to be highly efficient in the synthesis of aromatic nitriles with yields >90% in the selective ammoxidation of toluene and its derivatives as test reactions. The mechanisms for the genesis of active Cs+ single sites and the ammoxidation pathway of Csp3–H bonds were rationalized by density functional theory (DFT) simulations. The chemical confinement of large-sized Cs+ ions with the pore architecture of a Y zeolite supercage rendered the highest occupied molecular orbital (HOMO)–lowest unoccupied molecular orbital (LUMO) gap reduction, HOMO component change, and preferable coordination arrangement for the selective reaction promotion, which provides a trimolecular assembly platform to enable the coordination-promoted concerted ammoxidation pathway working closely on each Cs+ single site. The new reaction pathway without involvement of O2-dissociated O atom and lattice oxygen differs from the traditional redox catalysis mechanisms for the selective ammoxidation. | |||||
書誌情報 |
en : ACS Catalysis 巻 11, 号 11, p. 6698-6708, 発行日 2021-06-04 |
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出版者 | ||||||
出版者 | American Chemical Society | |||||
ISSN | ||||||
収録物識別子タイプ | ISSN | |||||
収録物識別子 | 21555435 | |||||
DOI | ||||||
関連タイプ | isVersionOf | |||||
識別子タイプ | DOI | |||||
関連識別子 | 10.1021/acscatal.1c00946 | |||||
権利 | ||||||
権利情報 | (c) 2021 American Chemical Society | |||||
関連サイト | ||||||
識別子タイプ | DOI | |||||
関連識別子 | https://doi.org/10.1021/acscatal.1c00946 | |||||
著者版フラグ | ||||||
出版タイプ | AM | |||||
出版タイプResource | http://purl.org/coar/version/c_ab4af688f83e57aa |