Design and dynamic control of nano-space in the ionic crystals of nano-sized spherical polyoxometalates

• Project/Area Number: 26286001
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Partial Multi-year Fund
• Section: 一般
• Research Field: Nanostructural chemistry
• Research Institution: Nihon University
• Principal Investigator: OZEKI Tomoji 日本大学, 文理学部, 教授 (60214136)
• Project Period (FY): 2014-04-01 – 2019-03-31
• Project Status: Completed (Fiscal Year 2018)
• Budget Amount: ¥16,380,000 (Direct Cost: ¥12,600,000、Indirect Cost: ¥3,780,000); Fiscal Year 2018: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000); Fiscal Year 2017: ¥1,820,000 (Direct Cost: ¥1,400,000、Indirect Cost: ¥420,000); Fiscal Year 2016: ¥2,080,000 (Direct Cost: ¥1,600,000、Indirect Cost: ¥480,000); Fiscal Year 2015: ¥2,210,000 (Direct Cost: ¥1,700,000、Indirect Cost: ¥510,000); Fiscal Year 2014: ¥8,710,000 (Direct Cost: ¥6,700,000、Indirect Cost: ¥2,010,000)
• Keywords: ナノ構造 / ポリオキソメタレート / 結晶構造制御 / Ｘ線回折 / X線回折 / 質量分析

Outline of Final Research Achievements

Reversible water absorption and desorption was observed for the crystals of a spherical polyoxometalate composed mainly of 132 molybdenum and 504 oxygen atoms whose diameter approximates to 3 nm. Single crystal synchrotron X-ray diffraction revealed that this phenomenon is reversible and takes place repeatedly. The stability of the spherical polyoxometalate with 132 molybdenum atoms was examined in its aqueous solutions, revealing that it is metastable and decomposes into a smaller spherical polyoxometalates with 102 molybdenum atoms.

Academic Significance and Societal Importance of the Research Achievements

モリブデン１３２原子などからなるナノサイズ球状ポリ酸は、分子貯蔵材料や触媒として注目を集めている化合物である。その結晶の可逆的な水の吸収・放出現象を明らかにした本研究は、この化合物の分子貯蔵材料としての機能発現機構の解明に資するとともに、機能向上の方針を与えるものとなる。また、溶液中での安定性を解明した成果は、注目を集めていながら未だに性質が詳らかになっていないこの化合物が、本質的に不安定なものであることを明らかにしたという学術的意義がある上に、この化合物を触媒として用いる際の条件設定に対して重要な情報を与えるものである。

Research Products

• [Journal Article] Fully protonated B-type hexamolybdoplatinate [H6PtMo6O24]2? and its adduct formation with [Pt(OH)6]2? (2017)
  • Author(s): Ozeki Tomoji、Yagasaki Atsushi
  • Journal Title: IUCrData Volume: 2 Issue: 12
  • DOI: 10.1107/s2414314617017527
  • Peer Reviewed / Open Access
• [Journal Article] Reaction of the Hydrogen-bonded Hexamolybdoplatinate Tetramer [H23(PtMo6O24)4]9- with Methanol: Formation of the Methylated Hydrogen-bonded Hexamolybdoplatinate Trimer [(H4Me2PtMo6O24)(H3Me3PtMo6O24)2]6- (2016)
  • Author(s): J. Imai, T. Ozeki, A. Yagasaki
  • Journal Title: Chemistry Letters Volume: 45 Issue: 1 Pages: 19-20
  • DOI: 10.1246/cl.150897
  • NAID: 130005118777
  • Peer Reviewed
• [Journal Article] Control over the preference for binding sites of polyoxometalates to silver ethynide clusters by surface charge modification (2015)
  • Author(s): S. Tamari, K. Ono, M. Hashimoto, T. Ozeki
  • Journal Title: Dalton Transactions Volume: 44 Issue: 44 Pages: 19056-19058
  • DOI: 10.1039/c5dt02972d
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Asymmetrically Fused Polyoxometalate–Silver Alkynide Composite Cluster (2015)
  • Author(s): M. Kurasawa, F. Arisaka, T. Ozeki
  • Journal Title: Inorganic Chemistry Volume: 54 Issue: 4 Pages: 1650-1654
  • DOI: 10.1021/ic502644v
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Synthesis, structure and valence-trapping vs. detrapping for new trinuclear iron pentafluoro benzoate complexes: possible recognition of organic molecules by 57Fe Mössbauer spectroscopy (2014)
  • Author(s): S. Onaka, Y. Sakai, T. Ozeki, T. Nakamoto, Y. Kobayashi, M. Takahashi, R. Ogiso, T. Takayama, M. Shiotsuka
  • Journal Title: Dalton Transactions Volume: 43 Issue: 18 Pages: 1477-9226
  • DOI: 10.1039/c3dt53623h
  • Peer Reviewed
• [Journal Article] Formation of a Kagome Lattice with Huge Channels by Very Large Spherical Anions (2014)
  • Author(s): M. Saito, T. Ozeki
  • Journal Title: Photon Factory Activity Report 2012 Part A, Highlights and Facility Report Volume: 2012 Pages: 36-37
  • Peer Reviewed
• [Journal Article] Synthesis and Structural Characterization of Isomers of Ru-Substituted Keggin-Type Germanotungstate with dmso Ligand (2014)
  • Author(s): N. Shimizu, T. Ozeki, H. Shikama, T. Sano, M. Sadakane
  • Journal Title: Journal of Cluster Science Volume: 25 Issue: 3 Pages: 755-770
  • DOI: 10.1007/s10876-013-0641-9
  • Peer Reviewed
• [Journal Article] ポリオキソメタレートイオンの対称性と結晶構造 (2014)
  • Author(s): 尾関智二
  • Journal Title: 触媒 Volume: 56 Pages: 330-335
  • Peer Reviewed
• [Presentation] ヘキサモリブドクロム酸塩の擬多形 (2019)
  • Author(s): 高柳真由; 森谷峻; 岡安志人; 大橋賢二; 尾関智二
  • Organizer: 日本化学会第99春季年会
• [Presentation] Keplerate型球状ポリ酸の分解生成物の解明 (2019)
  • Author(s): 塩川優一; 大橋賢二; 尾関智二
  • Organizer: 日本化学会第99春季年会
• [Presentation] タングステン原子導入に伴う132核Keplerate型球状ポリモリブデン酸のスペクトル変化 (2019)
  • Author(s): 堀明日佳; 大橋賢二; 尾関智二
  • Organizer: 日本化学会第99春季年会
• [Presentation] 4核マンガン錯体を含むサンドイッチ型ポリ酸と銀エチニド錯体からなる二種の新規ポリ酸-銀クラスター複合体の合成とその構造 (2019)
  • Author(s): 大橋賢二; 尾関智二
  • Organizer: 日本化学会第99春季年会
• [Presentation] 水溶液中におけるボール型ポリ酸の分解過程の解明 (2018)
  • Author(s): 塩川優一; 大橋賢二; 尾関智二
  • Organizer: 錯体化学会第68回討論会
• [Presentation] Weakley型ポリ酸[M4(L)2(PW9O34)2]10-を用いた新規-銀クラスター複合体の合成 (2018)
  • Author(s): 山村拓; 大橋賢二; 尾関智二
  • Organizer: 錯体化学会第68回討論会
• [Presentation] Photocatalytic hydrogen evolution reaction using the polyoxometalatesilver ethynide composite cluste (2018)
  • Author(s): Ohashi, Kenji; Ozeki, Tomoji
  • Organizer: 43rd International Conference on Coordination Chemistry
  • Int'l Joint Research
• [Presentation] Surface electron densities of polyoxometalates probed by composite cluster formation with silver ethynides (2018)
  • Author(s): Ozeki, Tomoji; Ohashi, Kenji; Kurasawa, Mariko; Tamari, Sho; Umemoto, Yuta; Kitamura, Kazuki; Onuma, Yoshiaki; Yamamura, Taku; Kurita, Kengo; Morikawa, Shinya
  • Organizer: 43rd International Conference on Coordination Chemistry
  • Int'l Joint Research
• [Presentation] Development of the hydrogen production catalyst using the polyoxometalate-silver ethynide composite cluster (2018)
  • Author(s): Ohashi, Kenji; Ozeki, Tomoji
  • Organizer: International symposium on Metal-Oxo Cluster Sciences: Exploring Novel Possibilities
  • Int'l Joint Research
• [Presentation] Crystals of polyoxometalate and related compounds exhibiting twinning by merohedry (2018)
  • Author(s): Ozeki, Tomoji; Ohashi, Kenji; Shikama, Hideyasu
  • Organizer: International symposium on Metal-Oxo Cluster Sciences: Exploring Novel Possibilities
  • Int'l Joint Research
• [Presentation] Crystal and solution structures of polyoxometalates and related clusters (2018)
  • Author(s): Ozeki, Tomoji
  • Organizer: AsCA 2018/CRYSTAL 32, a combined conference of the Asian Crystallographic Association (AsCA) and the Society of Crystallographers in Australia and New Zealand (SCANZ)
  • Int'l Joint Research
• [Presentation] Decomposition products of the spherical Keplerate type polyoxometalate (2018)
  • Author(s): Shiokawa, Yuichi; Ohashi, Kenji; Ozeki, Tomoji
  • Organizer: AsCA 2018/CRYSTAL 32, a combined conference of the Asian Crystallographic Association (AsCA) and the Society of Crystallographers in Australia and New Zealand (SCANZ)
  • Int'l Joint Research
• [Presentation] SAXSによるポリオキソメタレート溶存状態の研究 (2018)
  • Author(s): 尾関智二
  • Organizer: PF研究会「多様な物質・生命科学研究に広がる小角散乱～多（他）分野の小角散乱を学ぼう！」
• [Presentation] ポリ酸-銀エチニド複合クラスターによる水素生成光触媒反応機構の解明 (2018)
  • Author(s): 大橋賢二; 尾関智二
  • Organizer: 日本化学会第98春季年会
• [Presentation] Weakley型ポリ酸を用いた新規ポリ酸-銀クラスター複合体の合成 (2018)
  • Author(s): 山村拓; 大橋賢二; 尾関智二
  • Organizer: 日本化学会第98春季年会
• [Presentation] ボール型ポリ酸の分解過程の解明 (2018)
  • Author(s): 塩川優一; 大橋賢二; 尾関智二
  • Organizer: 日本化学会第98春季年会
• [Presentation] Polyoxometalate-Silver Ethynide Composite Clusters (2017)
  • Author(s): Tomoji Ozeki
  • Organizer: International Symposium on Frontiers in Metal Oxide Cluster Science: From Fundamentals to Environmental Applications
  • Int'l Joint Research / Invited
• [Presentation] Analyses of the dimensions of nano-scale polyoxometalates in their solutions (2017)
  • Author(s): Tomoji Ozeki
  • Organizer: Frontiers in Metal Oxide Cluster Science
  • Int'l Joint Research
• [Presentation] The pH driven nuclearity growths of nano-scale polyoxomolybdates and their structure directed crystallization (2017)
  • Author(s): Tomoji Ozeki
  • Organizer: International Forum in Metal Oxide Cluster Science
  • Int'l Joint Research / Invited
• [Presentation] ポリ酸の結晶構造と溶液構造 (2017)
  • Author(s): 尾関智二
  • Organizer: 平成29年度日本結晶学会年会
  • Invited
• [Presentation] Evaluation of Results (2016)
  • Author(s): Tomoji Ozeki
  • Organizer: 14th Conference of the Asian Crystallographic Association, Satellite Meeting II, School of Single Crystal Structure Determination
  • Place of Presentation: Hanoi University of Science and Technology, Hanoi, Vietnam
  • Year and Date: 2016-12-03
  • Int'l Joint Research / Invited
• [Presentation] 小角散乱を用いたポリオキソメタレートの溶液内会合状態の研究 (2016)
  • Author(s): 尾関智二
  • Organizer: PF研究会「徹底討論！小角散乱の魅力～基礎・応用・産業利用」
  • Place of Presentation: 高エネルギー加速器研究機構物質構造化学研究所、茨城県つくば市
  • Year and Date: 2016-03-30
• [Presentation] The stability difference of MO42- (M = Mo, W) encapsulating silver(I) ethynide clusters (2016)
  • Author(s): K. Ohashi, T. Kojima, M. Sadakane, M. Hashimoto, T. Ozeki
  • Organizer: 日本化学会第96春季年会
  • Place of Presentation: 同志社大学京田辺キャンパス、京都府京田辺市
  • Year and Date: 2016-03-24
• [Presentation] Designer polyoxometalate - silver alkynide chimera cluster (2015)
  • Author(s): T. Ozeki, M. Kurasawa, F. Arisaka
  • Organizer: The International Chemical Congress of Pacific Basin Societies 2015 (Pacifichem 2015)
  • Place of Presentation: Honolulu, Hawaii, USA
  • Year and Date: 2015-12-15
  • Int'l Joint Research
• [Presentation] MO42- (M = Mo, W) encapsulating silver(I) ethynide clusters formed by template exchange reactions abstracting MO42- groups from the Keggin-type polyoxometalates (2015)
  • Author(s): K. Ohashi, T. Kojima, M. Sadakane, M. Hashimoto, T. Ozeki
  • Organizer: The International Chemical Congress of Pacific Basin Societies 2015 (Pacifichem 2015)
  • Place of Presentation: Honolulu, Hawaii, USA
  • Year and Date: 2015-12-15
  • Int'l Joint Research
• [Presentation] Hydrogen-bonded trimer of methylated molybdoplatinate (2015)
  • Author(s): J. Imai, T. Ozeki, A. Yagasaki
  • Organizer: The International Chemical Congress of Pacific Basin Societies 2015 (Pacifichem 2015)
  • Place of Presentation: Honolulu, Hawaii, USA
  • Year and Date: 2015-12-15
  • Int'l Joint Research / Invited
• [Presentation] Template effects on the formation and stabilities of silver tetracosa clusters (2015)
  • Author(s): K. Ohashi, T. Kojima, M. Sadakane, M. Hashimoto, T. Ozeki
  • Organizer: 錯体化学会 第65回討論会
  • Place of Presentation: 奈良女子大学、奈良県奈良市
  • Year and Date: 2015-09-21
• [Book] 理科年表 2019（机上版） (2018)
  • Author(s): 国立天文台、気象庁、久我隆弘、西原寛、須貝俊彦、小澤一仁、藤井敏嗣、纐纈一起、田口聡、石井守、浅島誠、肱岡靖明、菅原正雄、尾関智二ほか
  • Total Pages: 1160
  • Publisher: 丸善出版
  • ISBN: 9784621303320
• [Book] 理科年表 平成30年 第91冊 (2017)
  • Author(s): 国立天文台、気象庁、久我隆弘、西原寛、須貝俊彦、小澤一仁、藤井敏嗣、纐纈一起、家森俊彦、石井守、浅島誠、肱岡靖明、大谷義近、菅原正雄、尾関智二ほか
  • Publisher: 丸善出版
  • ISBN: 9784621302170
• [Remarks]
  • URL: http://dep.chs.nihon-u.ac.jp/chemistry/ozeki1.html
• [Funded Workshop] International symposium on Metal-Oxo Cluster Sciences: Exploring Novel Possibilities (2018)