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タイトル: | Mechanism of Reductive Fluorination by PTFE-Decomposition Fluorocarbon Gases for WO₃ |
著者: | Yamamoto, Hiroki Tada, Kohei Hwang, Jinkwang https://orcid.org/0000-0003-4800-3158 (unconfirmed) Hirai, Daigorou Hiroi, Zenji Matsumoto, Kazuhiko https://orcid.org/0000-0002-0770-9210 (unconfirmed) Hagiwara, Rika https://orcid.org/0000-0002-7234-3980 (unconfirmed) |
著者名の別形: | 山本, 大樹 黄, 珍光 松本, 一彦 萩原, 理加 |
キーワード: | Carbon Chemical reactions Gases Halogenation Organic reactions |
発行日: | 6-Feb-2023 |
出版者: | American Chemical Society (ACS) |
誌名: | Inorganic Chemistry |
巻: | 62 |
号: | 5 |
開始ページ: | 2116 |
終了ページ: | 2127 |
抄録: | Reductive fluorination, which entails the substitution of O²⁻ from oxide compounds with F⁻ from fluoropolymers, is considered a practical approach for preparing transition-metal oxyfluorides. However, the current understanding of the fundamental reaction paths remains limited due to the analytical complexities posed by high-temperature reactions in glassware. Therefore, to expand this knowledgebase, this study investigates the reaction mechanisms behind the reductive fluorination of WO₃ using polytetrafluoroethylene (PTFE) in an Ni reactor. Here, we explore varied reaction conditions (temperature, duration, and F/W ratio) to suppress the formation of carbon byproducts, minimize the dissipation of fluorine-containing tungsten (VI) compounds, and achieve a high fluorine content. The gas–solid reaction paths are analyzed using infrared spectroscopy, which revealed tetrafluoroethylene (C₂F₄), hexafluoropropene (C₃F₆), and iso-octafluoroisobutene (i-C₄F₈) to be the reactive components in the PTFE-decomposition gas during the reactions with WO₃ at 500 °C. CO₂ and CO are further identified as gaseous byproducts of the reaction evincing that the reaction is prompted by difluorocarbene (:CF₂) formed after the cleavage of C═C bonds in i-C₄F₈, C₃F₆, and C₂F₄ upon contact with the WO₃ surface. The solid–solid reaction path is established through a reaction between WO₃ and WO₃–xFx where solid-state diffusion of O²⁻ and F⁻ is discerned at 500 °C. |
著作権等: | This document is the Accepted Manuscript version of a Published Work that appeared in final form in Inorganic Chemistry, Copyright © 2023 American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.inorgchem.2c03761 The full-text file will be made open to the public on 23 January 2024 in accordance with publisher's 'Terms and Conditions for Self-Archiving'. This is not the published version. Please cite only the published version. この論文は出版社版でありません。引用の際には出版社版をご確認ご利用ください。 |
URI: | http://hdl.handle.net/2433/279295 |
DOI(出版社版): | 10.1021/acs.inorgchem.2c03761 |
PubMed ID: | 36690346 |
出現コレクション: | 学術雑誌掲載論文等 |
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