{"created":"2023-05-15T08:44:47.176541+00:00","id":10075,"links":{},"metadata":{"_buckets":{"deposit":"f50e366f-ae17-4b0e-915f-53daafb4133f"},"_deposit":{"created_by":13,"id":"10075","owners":[13],"pid":{"revision_id":0,"type":"depid","value":"10075"},"status":"published"},"_oai":{"id":"oai:uec.repo.nii.ac.jp:00010075","sets":["6"]},"author_link":["26920","26921","26922","26923","26924","26925"],"control_number":"10075","item_10001_biblio_info_7":{"attribute_name":"書誌情報","attribute_value_mlt":[{"bibliographicIssueDates":{"bibliographicIssueDate":"2021-06-04","bibliographicIssueDateType":"Issued"},"bibliographicIssueNumber":"11","bibliographicPageEnd":"6708","bibliographicPageStart":"6698","bibliographicVolumeNumber":"11","bibliographic_titles":[{"bibliographic_title":"ACS Catalysis","bibliographic_titleLang":"en"}]}]},"item_10001_description_5":{"attribute_name":"抄録","attribute_value_mlt":[{"subitem_description":"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.","subitem_description_type":"Abstract"}]},"item_10001_publisher_8":{"attribute_name":"出版者","attribute_value_mlt":[{"subitem_publisher":"American Chemical Society"}]},"item_10001_relation_14":{"attribute_name":"DOI","attribute_value_mlt":[{"subitem_relation_type":"isVersionOf","subitem_relation_type_id":{"subitem_relation_type_id_text":"10.1021/acscatal.1c00946","subitem_relation_type_select":"DOI"}}]},"item_10001_relation_17":{"attribute_name":"関連サイト","attribute_value_mlt":[{"subitem_relation_type_id":{"subitem_relation_type_id_text":"https://doi.org/10.1021/acscatal.1c00946","subitem_relation_type_select":"DOI"}}]},"item_10001_rights_15":{"attribute_name":"権利","attribute_value_mlt":[{"subitem_rights":"(c) 2021 American Chemical Society"}]},"item_10001_source_id_9":{"attribute_name":"ISSN","attribute_value_mlt":[{"subitem_source_identifier":"21555435","subitem_source_identifier_type":"ISSN"}]},"item_10001_version_type_20":{"attribute_name":"著者版フラグ","attribute_value_mlt":[{"subitem_version_resource":"http://purl.org/coar/version/c_ab4af688f83e57aa","subitem_version_type":"AM"}]},"item_creator":{"attribute_name":"著者","attribute_type":"creator","attribute_value_mlt":[{"creatorNames":[{"creatorName":"Acharyya, Shankha S.","creatorNameLang":"en"}],"nameIdentifiers":[{}]},{"creatorNames":[{"creatorName":"Ghosh, Shilpi","creatorNameLang":"en"}],"nameIdentifiers":[{}]},{"creatorNames":[{"creatorName":"Yoshida, Yusuke","creatorNameLang":"en"}],"nameIdentifiers":[{}]},{"creatorNames":[{"creatorName":"Kaneko, Takuma","creatorNameLang":"en"}],"nameIdentifiers":[{}]},{"creatorNames":[{"creatorName":"Sasaki, Takehiko","creatorNameLang":"en"}],"nameIdentifiers":[{}]},{"creatorNames":[{"creatorName":"Iwasawa, Yasuhiro","creatorNameLang":"en"}],"nameIdentifiers":[{}]}]},"item_files":{"attribute_name":"ファイル情報","attribute_type":"file","attribute_value_mlt":[{"accessrole":"open_date","date":[{"dateType":"Available","dateValue":"2022-06-05"}],"displaytype":"detail","filename":"ACS Catal_article_rev_Y.Iwasawa.pdf","filesize":[{"value":"1.1 MB"}],"format":"application/pdf","licensetype":"license_note","mimetype":"application/pdf","url":{"label":"ACS Catal_article_rev_Y.Iwasawa.pdf","url":"https://uec.repo.nii.ac.jp/record/10075/files/ACS Catal_article_rev_Y.Iwasawa.pdf"},"version_id":"555e2af1-bbb7-4596-b877-82a043652b10"}]},"item_keyword":{"attribute_name":"キーワード","attribute_value_mlt":[{"subitem_subject":"catalytic Csp3−H activation","subitem_subject_language":"en","subitem_subject_scheme":"Other"},{"subitem_subject":"confined Cs+ single site in Y zeolite pore","subitem_subject_language":"en","subitem_subject_scheme":"Other"},{"subitem_subject":"ammoxidation of toluene and its derivatives","subitem_subject_language":"en","subitem_subject_scheme":"Other"},{"subitem_subject":"selective nitrile synthesis","subitem_subject_language":"en","subitem_subject_scheme":"Other"},{"subitem_subject":"catalysis mechanism","subitem_subject_language":"en","subitem_subject_scheme":"Other"}]},"item_language":{"attribute_name":"言語","attribute_value_mlt":[{"subitem_language":"eng"}]},"item_resource_type":{"attribute_name":"資源タイプ","attribute_value_mlt":[{"resourcetype":"journal article","resourceuri":"http://purl.org/coar/resource_type/c_6501"}]},"item_title":"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","item_titles":{"attribute_name":"タイトル","attribute_value_mlt":[{"subitem_title":"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","subitem_title_language":"en"}]},"item_type_id":"10001","owner":"13","path":["6"],"pubdate":{"attribute_name":"PubDate","attribute_value":"2022-06-05"},"publish_date":"2022-06-05","publish_status":"0","recid":"10075","relation_version_is_last":true,"title":["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"],"weko_creator_id":"13","weko_shared_id":-1},"updated":"2023-07-21T02:41:46.260965+00:00"}