Design of asymmetric nano-space in ionic crystals

• Project Area: Coordination Asymmetry: Design of Asymmetric Coordination Sphere and Anisotropic Assembly for the Creation of Functional Molecules
• Project/Area Number: 17H05356
• Research Category: Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)
• Allocation Type: Single-year Grants
• Review Section: Science and Engineering
• Research Institution: The University of Tokyo
• Principal Investigator: 内田 さやか 東京大学, 大学院総合文化研究科, 准教授 (10361510)
• Project Period (FY): 2017-04-01 – 2019-03-31
• Project Status: Completed (Fiscal Year 2018)
• Budget Amount: ¥5,460,000 (Direct Cost: ¥4,200,000、Indirect Cost: ¥1,260,000); Fiscal Year 2018: ¥2,730,000 (Direct Cost: ¥2,100,000、Indirect Cost: ¥630,000); Fiscal Year 2017: ¥2,730,000 (Direct Cost: ¥2,100,000、Indirect Cost: ¥630,000)
• Keywords: イオン結晶 / 複合材料・物性 / 分子性固体 / イオン伝導 / ポリマー / 吸着 / 触媒

Outline of Annual Research Achievements

近年、化石燃料に依存しない持続可能な社会の構築、深刻化する地球温暖化問題の解決手段の一つとして、水素をエネルギー源とする水素社会への移行が注目を浴びている。中でも燃料電池は、水素と空気中の酸素の化学反応を利用して電気を取り出すシステムであり、水素利用における最重要技術の一つである。しかし、反応により生成した水素イオンの伝導を担う電解質は、アモルファス材料が多いために組成-構造-性能の相関が不明瞭で性能向上の指針が得られにくく、さらに、フッ素や硫黄など環境に有害な元素を含むためにリサイクルや廃棄処理に問題があるなど、性能面、環境面で多くの課題がある。本研究は、新たな電解質材料の構成ブロックとして、金属酸化物クラスター（ポリオキソメタレート）とポリマー（ポリアリルアミン）に着目した。これらは、高い水素イオン伝導性を示す可能性があることが知られているものの、単独では、水蒸気や熱への耐性が低いという欠点がある。この欠点の解決に加え、組成-構造-性能の相関が明確な材料を合成することを目的とし、水中でポリオキソメタレートのカリウム塩とポリアリルアミンの塩酸塩を混合し、結晶化を試みた。得られた結晶の構造解析の結果、ポリオキソメタレートとカリウムイオンとの間に働く静電相互作用によりイオン結晶が構築され、結晶のナノ細孔には、水素イオンと結合したポリアリルアミンと水分子が含まれることがわかった。交流インピーダンス法と13C-CPMASNMR分光法により、得られた結晶が、実用化材料に匹敵する高い水素イオン伝導性を示し、その高い伝導性は、水素イオン、ポリアリルアミンと水分子が細孔中で密な水素結合ネットワークを形成し、さらに、ポリアリルアミンの側鎖が運動していることに由来することが明らかになった。

Research Progress Status

平成30年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

平成30年度が最終年度であるため、記入しない。

Research Products

• [Int'l Joint Research] Oakridge National Laboratory(米国)
• [Int'l Joint Research] 華南理工大学/清華大学(中国)
• [Int'l Joint Research] 北京化工大学(中国)
• [Journal Article] Rapid Formation of Small Mixed-Valence Luminescent Silver Clusters via Cation-Coupled Electron-Transfer in Redox-Active Porous Ionic Crystal Based on Dodecamolybdophosphate (2019)
  • Author(s): S. Uchida, T. Okunaga, Y. Harada, S. Magira, Y. Noda, T. Mizuno, T. Tachikawa
  • Journal Title: Nanoscale Volume: 11 Issue: 12 Pages: 5460-5466
  • DOI: 10.1039/c9nr00103d
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Confinement of Poly(allylamine) in Preyssler-Type Polyoxometalate and Potassium Ion Framework for Enhanced Proton Conductivity (2019)
  • Author(s): T. Iwano, S. Miyazawa, R. Osuga, J. N. Kondo, K. Honjo, T. Kitao, T. Uemura, S. Uchida
  • Journal Title: Communications Chemistry Volume: - Issue: 1
  • DOI: 10.1038/s42004-019-0111-x
  • Peer Reviewed / Open Access
• [Journal Article] Conductive Inorganic-Organic Hybrid Layered Crystals Composed of Keggin-type Polyoxotungstates and Heterocyclic Surfactant (2019)
  • Author(s): S. Otobe, Y. Kiyota, S. Magira, T. Misawa, K. Fujio, H. Naruke, S. Uchida, T. Ito
  • Journal Title: Eur. J. Inorg. Chem. Volume: - Issue: 3-4 Pages: 442-447
  • DOI: 10.1002/ejic.201800535
  • Peer Reviewed
• [Journal Article] Solid State Umbrella-type Inversion of a VO5 Square Pyramidal Unit in a Bowl-type Dodecavanadate Induced by Insertion and Elimination of a Guest Molecule (2018)
  • Author(s): Yuji Kikukawa, Kensuke Seto, Sayaka Uchida, Sho Kuwajima, Yoshihito Hayashi
  • Journal Title: Angewandte Chemie, International Edition Volume: 57 Issue: 49 Pages: 16051-16055
  • DOI: 10.1002/anie.201809120
  • Peer Reviewed
• [Journal Article] Spatial-Temporal Characteristics of Confined Polymer Motion Determine Proton Conduction of Polyoxometalate-Poly(ethylene glycol) Hybrid Nanocomposites (2018)
  • Author(s): H. Wu, L. Li, M. Tsuboi, Y. Cheng, W. Wang, E. Mamontov, S. Uchida, Z. Wang, P. Yin
  • Journal Title: J. Phys. Chem. Lett. Volume: 9 Issue: 19 Pages: 5572-5577
  • DOI: 10.1021/acs.jpclett.8b02113
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Effect of Ammonium Ion toward Proton Conduction in Porous Ionic Crystals Based on Keggin-type Silicododecatugstate (2018)
  • Author(s): S. Miyazawa, R. Hosono, R. Osuga, J. N. Kondo, S. Uchida
  • Journal Title: Acta. Cryst. C Volume: 74 Issue: 11 Pages: 1289-1294
  • DOI: 10.1107/s2053229618008227
  • Peer Reviewed
• [Journal Article] Porous Cubic Cesium Salts of Silicododecatungstate(molybdate)/Borododecatungstate Blends: Synthesis and Molecular Adsorption Properties (2018)
  • Author(s): T. Kotabe, Y. Ogasawara, K. Suzuki, S. Uchida, N. Mizuno, K. Yamaguchi
  • Journal Title: Inorg. Chem. Volume: 57 Issue: 15 Pages: 8821-8830
  • DOI: 10.1021/acs.inorgchem.8b00657
  • Peer Reviewed
• [Journal Article] Conductive Hybrid Crystal Composed of Polyoxovanadate and Deprotonatable Ionic-Liquid Surfactant (2018)
  • Author(s): T. Misawa, S. Koguchi, K. Niwa, Y. Kinoshita, S. Uchida, T. Ito
  • Journal Title: Inorg. Chem. Commun. Volume: 96 Pages: 24-29
  • DOI: 10.1016/j.inoche.2018.07.040
  • Peer Reviewed
• [Journal Article] Rapid Uptake / Release of Cs+ in Isostructural Redox-Active Porous Ionic Crystals with Large Molecular Size and Easily Reducible Dawson-Type Polyoxometalates as Building Blocks (2018)
  • Author(s): S. Hitose, S. Uchida
  • Journal Title: Inorg. Chem. Volume: 57 Issue: 9 Pages: 4833-4836
  • DOI: 10.1021/acs.inorgchem.8b00801
  • Peer Reviewed
• [Journal Article] Cu Species Incorporated into Amorphous ZrO2 with High Activity and Selectivity in CO2-to-methanol Hydrogenation (2018)
  • Author(s): A. Katagiri, K. Kiyota, T. Honma, H. Kamei, A. Nariyuki, S. Uchida, S. Satokawa
  • Journal Title: J. Phys. Chem. C Volume: 122 Issue: 10 Pages: 5430-5442
  • DOI: 10.1021/acs.jpcc.7b11284
  • Peer Reviewed
• [Journal Article] Highly pH-Dependent Facile-Preparation of Amorphous High Surface Area Aluminum Hydroxide-Bicarbonates with [e-Al13O4(OH)24(H2O)12]7+ (2018)
  • Author(s): Y. Kinoshita, R. Osuga, J. N. Kondo, Y. Ogasawara, S. Uchida
  • Journal Title: Chem. Lett. Volume: 47 Issue: 5 Pages: 668-670
  • DOI: 10.1246/cl.180103
  • NAID: 130006732228
  • Peer Reviewed
• [Journal Article] High Proton Conduction in Crystalline Composites Based on Preyssler-type Polyoxometalates and Polymers under Non-humidified or Humidified Conditions (2017)
  • Author(s): K. Niinomi, S. Miyazawa, M. Hibino, N. Mizuno, S. Uchida
  • Journal Title: Inorg. Chem. Volume: 56 Issue: 24 Pages: 15187-15193
  • DOI: 10.1021/acs.inorgchem.7b02524
  • Peer Reviewed
• [Journal Article] Proton Conduction in Alkali Metal Ion-Exchanged Porous Ionic Crystals (2017)
  • Author(s): S. Uchida, R. Hosono, R. Eguchi, R. Kawahara, R. Osuga, J. N. Kondo, M. Hibino, N. Mizuno
  • Journal Title: Phys.Chem.Chem.Phys. Volume: 19 Issue: 43 Pages: 29077-29083
  • DOI: 10.1039/c7cp04619g
  • Peer Reviewed
• [Presentation] ポリオキソメタレートとポリアリルアミンからなる結晶性高プロトン伝導体の創製 (2019)
  • Author(s): 岩野 司・宮沢 哲・内田 さやか
  • Organizer: 日本化学会第99春季年会
• [Presentation] Dawson型ポリオキソメタレートとポリマーからなる結晶性複合体とプロトン伝導 (2019)
  • Author(s): 友田 雅大・内田 さやか
  • Organizer: 日本化学会第99春季年会
• [Presentation] レドックス型多孔性イオン結晶を用いた還元的銀導入とその反応ダイナミクス (2019)
  • Author(s): 奥永 友貴・野田 泰斗・立川 貴士・内田 さやか
  • Organizer: 日本化学会第99春季年会
• [Presentation] Cation Uptake and Conduction in Porous Ionic Crystals Based on Polyoxometalates (2017)
  • Author(s): Sayaka Uchida
  • Organizer: The 1st International Symposium on Coordination Ionic Compounds
  • Int'l Joint Research / Invited
• [Presentation] Selective and Rapid Cation Uptake and Conduction in Porous Ionic Crystals Based on Polyoxometalates (2017)
  • Author(s): Sayaka Uchida
  • Organizer: 4th Japan-Canada Joint Symposium on Coordination Chemistry
  • Int'l Joint Research / Invited
• [Presentation] Selective and Fast Ion Uptake / Conduction in Porous Ionic Crystals Based on Polyoxometalates (2017)
  • Author(s): Sayaka Uchida
  • Organizer: 11th Japan-China Joint Symposium on Metal Cluster Compounds
  • Int'l Joint Research / Invited
• [Presentation] Porous Ionic Crystals based on Polyoxometlates (2017)
  • Author(s): Sayaka Uchida
  • Organizer: Post-symposium of Frontiers in Metal Oxide Cluster Science-V
  • Int'l Joint Research / Invited
• [Presentation] Cation Uptake and Conduction in Redox-Active Porous Ionic Crystals Based on Polyoxometalates (2017)
  • Author(s): Sayaka Uchida
  • Organizer: Frontiers in Metal Oxide Cluster Science-V (FMOCS V)
  • Int'l Joint Research / Invited
• [Presentation] Cation Uptake and Conduction in Redox-Active Porous Ionic Crystals Based on Polyoxometalates (2017)
  • Author(s): Sayaka Uchida
  • Organizer: Pre-symposium of Frontiers in Metal Oxide Cluster Science-V
  • Int'l Joint Research / Invited
• [Book] Polyoxometalate-Based Assemblies and Functional Materials (2018)
  • Author(s): Sayaka Uchida (Yufei Song, Ed.)
  • Total Pages: 167
  • Publisher: Springer
  • ISBN: 9783319759043