Elucidation of Reactivity and Reaction Mechanisms of Gas-phase Multi-elemental Clusters under Thermal Conditions

• Project/Area Number: 17K14433
• Research Category: Grant-in-Aid for Young Scientists (B)
• Allocation Type: Multi-year Fund
• Research Field: Physical chemistry
• Research Institution: Tohoku University
• Principal Investigator: Nagata Toshiaki 東北大学, 理学研究科, JSPS特別研究員(PD) (80783373)
• Project Period (FY): 2017-04-01 – 2020-03-31
• Project Status: Completed (Fiscal Year 2019)
• Budget Amount: ¥4,420,000 (Direct Cost: ¥3,400,000、Indirect Cost: ¥1,020,000); Fiscal Year 2019: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000); Fiscal Year 2018: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000); Fiscal Year 2017: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000)
• Keywords: 気相クラスター / 気相反応 / 反応機構 / 幾何構造 / 質量分析 / イオン移動度分析 / クラスター / 反応性 / 速度定数 / 衝突誘起解離 / 昇温脱離 / 赤外分光 / 物理化学 / 化学反応

Outline of Final Research Achievements

Chemical reactions of gas-phase metal and metal oxide clusters with gaseous molecules were studied experimentally and computationally. The clusters were generated by laser vaporization method in a vacuum chamber and then reacted with gaseous molecules using a reaction cell. The resulted species were analyzed by gas-phase temperature programmed desorption and ion mobility mass spectrometry, which provided information of binding energies and forms of the molecules adsorbed on the clusters. Geometrical structures of the clusters after the reactions were discussed by comparing the experimental results with quantum chemical calculations.

Academic Significance and Societal Importance of the Research Achievements

金属や金属酸化物の気相クラスターは触媒反応のモデル系として研究される。従来の実験研究はクラスターが真空中に孤立した断熱条件での反応研究が主であったが、これは実際の触媒反応の環境とは大きく異なる。本研究では、反応で生成したエネルギーが速やかに拡散して熱平衡に達するような熱的条件下での反応実験を展開することで、よりリアルなモデル系として気相クラスターを扱う研究を行った。また、気相クラスターの反応機構について、これまでは理論計算に頼る研究が多く為されてきたが、本研究では実験科学的に反応過程のエネルギーや構造の情報を取得する手法を進展させた。

Research Products

• [Int'l Joint Research] Begum Rokeya University(バングラデシュ)
• [Int'l Joint Research] Radboud Universiteit Nijmegen(オランダ)
• [Int'l Joint Research] Radboud Universiteit Nijmegen(オランダ)
• [Journal Article] Structure Assignment and Separation of Isomers of Palladium Oxide Cluster Anions Studied by Ion Mobility Mass Spectrometry (2020)
  • Author(s): M. Abdul Latif, Toshiaki Nagata, Motoyoshi Nakano, Keijiro Ohshimo, Fuminori Misaizu
  • Journal Title: The Journal of Physical Chemistry C Volume: - Issue: 17 Pages: 9604-9610
  • DOI: 10.1021/acs.jpcc.0c01847
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Structural Evolution of Iridium Oxide Cluster Anions IrnOm- (n = 5-8) with Sequential Oxidation: Binding Mode of O Atoms and Ir Framework (2019)
  • Author(s): R. Tomihara, K. Koyasu, T. Nagata, J. W. J. Wu, M. Nakano, K. Ohshimo, F. Misaizu, T. Tsukuda
  • Journal Title: J. Phys. Chem. C Volume: 123 Issue: 24 Pages: 15301-15306
  • DOI: 10.1021/acs.jpcc.9b02935
  • Peer Reviewed
• [Journal Article] Geometrical Structures of Gas Phase Cerium Oxide Cluster Cations Studied by Ion Mobility Mass Spectrometry (2019)
  • Author(s): T. Nagata, J. W. J. Wu, M. Nakano, K. Ohshimo, F. Misaizu
  • Journal Title: J. Phys. Chem. C Volume: 123 Issue: 27 Pages: 16641-16650
  • DOI: 10.1021/acs.jpcc.9b01378
  • Peer Reviewed
• [Journal Article] Compositions and Isomer Separation of Palladium Oxide Cluster Cations Studied by Ion Mobility Mass Spectrometry (2019)
  • Author(s): M. Abdul Latif, Jenna W. J. Wu, Toshiaki Nagata, Motoyoshi Nakano, Keijiro Ohshimo, Fuminori Misaizu
  • Journal Title: The Journal of Physical Chemistry C Volume: 123 Issue: 28 Pages: 17580-17587
  • DOI: 10.1021/acs.jpcc.9b03750
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Structures of Rhodium Oxide Cluster Cations Rh7Om+ (m = 4－7, 12, 14) Revealed by Infrared Multiple Photon Dissociation Spectroscopy (2019)
  • Author(s): Fumitaka Mafune, Kohei Koyama, Toshiaki Nagata, Satoshi Kudoh, Tomokazu Yasuike, Ken Miyajima, Douwe M. M. Huitema, Valeriy Chernyy, Joost M. Bakker
  • Journal Title: Journal of Physical Chemistry C Volume: 123 Issue: 10 Pages: 5964-5971
  • DOI: 10.1021/acs.jpcc.8b11068
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Structures of stoichiometric sodium oxide cluster cations studied by ion mobility mass spectrometry (2019)
  • Author(s): Motoyoshi Nakano, Yudai Ishimura, Riki Hotta, Daiki Hebiguchi, Toshiaki Nagata, Fuminori Misaizu
  • Journal Title: Chinese Journal of Chemical Physics Volume: 32 Issue: 2 Pages: 193-199
  • DOI: 10.1063/1674-0068/cjcp1812295
  • Peer Reviewed
• [Journal Article] Adsorption of Multiple NO Molecules on Rhn+ (n = 6, 7) Investigated by Infrared Multiple Photon Dissociation Spectroscopy (2018)
  • Author(s): Toshiaki Nagata, Satoshi Kudoh, Ken Miyajima, Joost M. Bakker, Fumitaka Mafune
  • Journal Title: The Journal of Physical Chemistry C Volume: 122 Issue: 40 Pages: 22884-22891
  • DOI: 10.1021/acs.jpcc.8b04729
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Oxygen Release from Cationic Niobium-Vanadium Oxide Clusters, NbnVmOk+, Revealed by Gas Phase Thermal Desorption Spectrometry and Density Functional Theory Calculations (2017)
  • Author(s): Daigo Masuzaki, Toshiaki Nagata, Fumitaka Mafune
  • Journal Title: The Journal of Physical Chemistry A Volume: 121 Issue: 20 Pages: 3864-3870
  • DOI: 10.1021/acs.jpca.7b01961
  • Peer Reviewed
• [Journal Article] Thermal Analysis of Hydrated Gold Cluster Cations in the Gas Phase (2017)
  • Author(s): Toshiaki Nagata, Fumitaka Mafune
  • Journal Title: The Journal of Physical Chemistry C Volume: 121 Issue: 30 Pages: 16291-16299
  • DOI: 10.1021/acs.jpcc.7b04119
  • Peer Reviewed
• [Journal Article] Adsorption Forms of NO on Rhn+ (n = 6-16) Revealed by Infrared Multiple Photon Dissociation Spectroscopy (2017)
  • Author(s): Toshiaki Nagata, Kohei Koyama, Satoshi Kudoh, Ken Miyajima, Joost M. Bakker, Fumitaka Mafune
  • Journal Title: The Journal of Physical Chemistry C Volume: 121 Issue: 49 Pages: 27417-27426
  • DOI: 10.1021/acs.jpcc.7b08097
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Reduction Site in CenVmOk+ Revealed by Gas Phase Thermal Desorption Spectrometry (2017)
  • Author(s): Fumitaka Mafune, Daigo Masuzaki, Toshiaki Nagata
  • Journal Title: Topics in Catalysis Volume: 61 Issue: 1-2 Pages: 42-48
  • DOI: 10.1007/s11244-017-0862-5
  • Peer Reviewed
• [Presentation] イオン移動度質量分析法による酸化イットリウムクラスター正イオンの幾何構造の研究 (2020)
  • Author(s): 三竿 洋太朗, 堀田 力, 永田 利明, 中野 元善, 美齊津 文典
  • Organizer: 日本化学会第100春季年会
• [Presentation] イオン移動度質量分析法による酸化マンガンクラスターカチオンの構造研究 (2020)
  • Author(s): 永田 利明, 中野 元善, 美齊津 文典
  • Organizer: 日本化学会第100春季年会
• [Presentation] 食塩ナノ結晶への不純物臭化物イオン置換による安定性および構造の変化 (2020)
  • Author(s): 堀田 力, 永田 利明, 中野 元善, 大下 慶次郎, 美齊津 文典
  • Organizer: 日本化学会第100春季年会
• [Presentation] 酸化セリウムを基本とした多元素クラスターイオンの構造研究 (2019)
  • Author(s): 永田 利明
  • Organizer: 第8回イオン移動度研究会
  • Invited
• [Presentation] 塩化ナトリウムクラスターイオンの構造及び臭化物イオン取り込み現象の研究 (2019)
  • Author(s): 堀田 力, 永田 利明, 中野 元善, 美齊津 文典
  • Organizer: 第13回分子科学討論会
• [Presentation] Structure assignment and separation of isomers of palladium oxide cluster anions studied by ion mobility mass spectrometry (2019)
  • Author(s): Mohammad Abdul Latif, Toshiaki Nagata, Motoyoshi Nakano, Fuminori Misaizu
  • Organizer: 第13回分子科学討論会
• [Presentation] イオン移動度質量分析法の多元素クラスターイオンへの展開 (2019)
  • Author(s): 永田 利明, 中野 元善, 美齊津 文典
  • Organizer: 第13回分子科学討論会
• [Presentation] Irクラスター負イオンの成長および酸化の進行に伴う電子・幾何構造の変化 (2019)
  • Author(s): 小安 喜一郎, 冨原 良平, 永田 利明, Jenna W. J. Wu, 中野 元善, 大下 慶次郎, 美齊津 文典, 佃 達哉
  • Organizer: 第13回分子科学討論会
• [Presentation] Geometrical structures of ceria-based composite clusters studied by ion mobility mass spectrometry (2019)
  • Author(s): Toshiaki Nagata
  • Organizer: The 76th Fujihara Seminar: International Workshop on Designer Nanocluster Materials - From Gas Phase to Condensed Phase -
  • Int'l Joint Research / Invited
• [Presentation] イオン移動度質量分析法による金・セリア複合クラスター正イオンへのCO付加反応の研究 (2019)
  • Author(s): 永田 利明, 中野 元善, 美齊津 文典
  • Organizer: 日本化学会第99春季年会
• [Presentation] 塩化ナトリウムクラスターイオンにおける非岩塩型構造の形成 (2019)
  • Author(s): 堀田 力, 永田 利明, 中野 元善, 美齊津 文典
  • Organizer: 日本化学会第99春季年会
• [Presentation] Geometrical structures of rhodium oxide cluster cations studied by ion mobility mass spectrometry (2019)
  • Author(s): Chang Su, Toshiaki Nagata, Motoyoshi Nakano, Fuminori Misaizu
  • Organizer: 日本化学会第99春季年会
• [Presentation] Structural transition in the sequential oxidation of iridium cluster anions revealed by ion mobility measurements (2019)
  • Author(s): Ryohei Tomihara, Toshiaki Nagata, Jenna W. J. Wu, Kiichirou Koyasu, Motoyoshi Nakano, Keijiro Ohshimo, Fuminori Misaizu, Tatsuya Tsukuda
  • Organizer: 日本化学会第99春季年会
• [Presentation] NO分子が付加した酸化セリウムクラスターカチオンの構造研究 (2018)
  • Author(s): 永田 利明, Jenna W. J. Wu, 中野 元善, 美齊津 文典
  • Organizer: 第7回イオン移動度研究会
• [Presentation] Adsorption reaction kinetics of water molecules on sodium fluoride cluster cations (2018)
  • Author(s): Riki Hotta, Jenna W. J. Wu, Toshiaki Nagata, Motoyoshi Nakano, Fuminori Misaizu
  • Organizer: 第34回化学反応討論会
• [Presentation] Adsorption Forms of NO on Rhn+ and RhnTa+ Revealed by Infrared Multiple Photon Dissociation (2018)
  • Author(s): Fumitaka Mafune, Toshiaki Nagata, Kohei Koyama, Satoshi Kudoh, Ken Miyajima, Joost M. Bakker
  • Organizer: International Bunsen Discussion Meeting: Gas Phase Model Systems on Catalysis (GPMC 2018)
  • Int'l Joint Research / Invited
• [Presentation] Geometrical structures and reactions of cerium oxide cluster cations studied by ion mobility mass spectrometry (2018)
  • Author(s): Toshiaki Nagata, Jenna W. J. Wu, Motoyoshi Nakano, Keijiro Ohshimo, Fuminori Misaizu
  • Organizer: International Bunsen Discussion Meeting: Gas Phase Model Systems on Catalysis (GPMC 2018)
  • Int'l Joint Research
• [Presentation] Active site structures of cationic cerium oxide clusters studied by ion mobility mass spectrometry and density functional theory calculations (2018)
  • Author(s): Toshiaki Nagata, Jenna W. J. Wu, Motoyoshi Nakano, Keijiro Ohshimo, Fuminori Misaizu
  • Organizer: 19th International Symposium on Small Particles and Inorganic Clusters (ISSPIC XIX)
  • Int'l Joint Research
• [Presentation] Ir酸化物クラスター負イオンのイオン移動度測定：酸化の進行に伴う構造モチーフの転換 (2018)
  • Author(s): 冨原 良平, 永田 利明, Jenna W. J. Wu, 小安 喜一郎, 中野 元善, 大下 慶次郎, 美齊津 文典, 佃 達哉
  • Organizer: 第12回分子科学討論会
• [Presentation] イオン移動度質量分析法による金・セリア複合クラスター正イオンの構造研究 (2018)
  • Author(s): 永田 利明, 中野 元善, 美齊津 文典
  • Organizer: 第12回分子科学討論会
• [Presentation] Structures of sodium oxide cluster ions studied by ion mobility mass spectrometry (2018)
  • Author(s): Yudai Ishimura, Riki Hotta, Daiki Hebiguchi, Toshiaki Nagata, Motoyoshi Nakano, Fuminori Misaizu
  • Organizer: 化学系学協会東北大会
• [Presentation] イオン移動度質量分析法を用いた酸化カルシウムクラスターカチオンの幾何構造の研究 (2018)
  • Author(s): 齋藤 周, 蛇口 大揮, 永田 利明, 中野 元善, 美齊津 文典
  • Organizer: 日本化学会第98春季年会
• [Presentation] イオン移動度質量分析法による酸化セリウムクラスターカチオンのNO分子との化学反応の研究 (2018)
  • Author(s): 永田 利明, Jenna Wu, 中野 元善, 美齊津 文典
  • Organizer: 日本化学会第98春季年会
• [Presentation] イオン移動度質量分析法によるセリウム酸化物クラスターカチオンの幾何構造の研究 (2017)
  • Author(s): 永田 利明, Jenna W. J. Wu, 中野 元善, 大下 慶次郎, 美齊津 文典
  • Organizer: 第11回分子科学討論会
• [Remarks] 触媒反応の中心をナノレベルで解き明かす
  • URL: http://www.chem.tohoku.ac.jp/research/research_outcome/p019.html