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タイトル: Molecule-Based Proton-Electron Mixed Conductor with the Highest Ambipolar Conductivity
著者: Wang, Peng-Hao
Yoshida, Yukihiro
Yasaka, Soichiro
Maesato, Mitsuhiko
Nakano, Yoshiaki  kyouindb  KAKEN_id  orcid https://orcid.org/0000-0003-3616-7286 (unconfirmed)
Kitagawa, Hiroshi
著者名の別形: 王, 鹏皓
吉田, 幸大
矢坂, 聡一朗
前里, 光彦
中野, 義明
北川, 宏
キーワード: Electrical conductivity
Molecules
Platinum
Proton conductivity
Salts
発行日: 29-Jan-2025
出版者: American Chemical Society (ACS)
誌名: Journal of the American Chemical Society
巻: 147
号: 4
開始ページ: 3804
終了ページ: 3812
抄録: Proton-electron mixed conductors (PEMCs) are an essential component for potential applications in hydrogen separation and energy conversion devices. However, the exploration of PEMCs with excellent mixed conduction, which is quantified by the ambipolar conductivity, σ[amb] = σ[e]σ[H]/(σ[e] + σ[H]) (σ[e]: electronic conductivity; σ[H]: proton conductivity), is still a great challenge, largely due to the lack of structural characterization of both conducting mechanisms. In this study, we prepared a molecule-based proton-electron mixed-conducting cation radical salt, (ET)₄[Pt₂(pop)₂(Hpop)₂]·PhCN (ET: bis(ethylenedithio)tetrathiafulvalene, pop²⁻: P₂H₂O₅²⁻), by electrocrystallization. The salt shows metallic electronic conduction, which arises from the (ET)₂[•+] layers, with a high σe value (1-2 S cm⁻¹ at room temperature). The metallic state was corroborated by magnetic susceptibility measurement and band structure calculation. The salt also shows superprotonic conduction (σH = 2.1 × 10⁻² S cm⁻¹ at room temperature under dried conditions), which relies on the one-dimensional (1D) hydrogen-bonding network of protonated paddlewheel-type Pt-dimer complex anions, [Pt₂(pop)₂(Hpop)₂]²⁻. Crystallographic and computational studies revealed the presence of infinite intra- and intermolecular O-H···O hydrogen bonds, which show a double-well-like potential energy curve with a negligible energy barrier in the 1D chain, facilitating Grotthuss-type proton hopping via Lewis basic sites. Among the structurally defined PEMCs, the present salt displays the highest room temperature σ[amb] value of 2.1 × 10⁻² S cm⁻¹ even under dried conditions. The σ[amb] value has the same order as those of reported perovskites-type metal oxides at high temperatures and achieves a level that is beneficial for the practical applications.
著作権等: This document is the Accepted Manuscript version of a Published Work that appeared in final form in [Journal of the American Chemical Society], Copyright © 2025 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/jacs.4c16779
The full-text file will be made open to the public on January 15, 2026 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/2433/294268
DOI(出版社版): 10.1021/jacs.4c16779
PubMed ID: 39814579
出現コレクション:学術雑誌掲載論文等

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