Study of bromide complexation of group-4 elements for systematic discussion of halide complexation of Rf

• Project/Area Number: 20K15317
• Research Category: Grant-in-Aid for Early-Career Scientists
• Allocation Type: Multi-year Fund
• Review Section: Basic Section 34020:Analytical chemistry-related
• Research Institution: SALESIAN POLYTECHNIC (2021-2022); Institute of Physical and Chemical Research (2020)
• Principal Investigator: Yokokita Takuya サレジオ工業高等専門学校, その他部局等, 助教 (10802655)
• Project Period (FY): 2020-04-01 – 2023-03-31
• Project Status: Completed (Fiscal Year 2022)
• Budget Amount: ¥4,160,000 (Direct Cost: ¥3,200,000、Indirect Cost: ¥960,000); Fiscal Year 2022: ¥780,000 (Direct Cost: ¥600,000、Indirect Cost: ¥180,000); Fiscal Year 2021: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000); Fiscal Year 2020: ¥1,820,000 (Direct Cost: ¥1,400,000、Indirect Cost: ¥420,000)
• Keywords: ラザホージウム / 臭化水素酸 / 硫酸 / イオン交換 / 固液抽出 / ジルコニウム / ハフニウム / トリウム / 陽イオン交換 / 陰イオン交換 / 紫外可視吸光スペクトル / ラザホージウム (Rf) / 臭化物 / 超重元素 / 化学種同定

Outline of Research at the Start

本研究の目的は、超重元素ラザホージウム(Rf) を含む第4族元素ジルコニウム(Zr)、ハフニウム(Hf)、Rfの臭化物錯形成を調べることである。まず、HBr及びHBrとLiBr混合溶液(HBr/LiBr) 中のZrとHfの化学種を同定し、Br－濃度変化に伴うZrとHfの臭化物錯形成を調べるため、分光分析を行う。次に、Zr、Hf、RfのHBr及びHBr/LiBr溶液系のイオン交換挙動を取得し、ZrとHfのイオン交換挙動をこれらの錯形成を基に解釈する。そして、RfとZrとHfのイオン交換挙動を比較し、単一原子でしか存在できないRfの臭化物錯形成を考察する。

Outline of Final Research Achievements

To study the bromide complexation of Rf, the bromide complexation of Zr and Hf were studied by using ion-exchange and UV-vis spectroscopic measurements in the hydrobromic acid system. On the other hand, the ion exchange reaction between Zr and Hf was slow, and it was difficult to obtain results below the chemical equilibrium for short-lived Rf. Therefore, experimental conditions need to be re-examined for the study of bromide complexes of Rf.
As a related study, a sulfuric acid complex of Rf was also studied: solvent extraction and ESI-MS measurements were performed to examine the dissolved states of Zr and Hf in sulfuric acid. We believe that this method can be used in other chemical reaction systems such as hydrobromic acid systems.

Academic Significance and Societal Importance of the Research Achievements

原子番号104番以降の超重元素に関しては、実験の難しさからこれまで実験がほとんど行われていない。そのような中で、最初の超重元素である104番元素のRfについては、いくつかの定量的な実験データも報告されており、さらなる実験データを取得することで、系統的な考察も行うことができ、超重元素領域における化学的性質の相対論効果の影響を調べることが可能となる。
今回、関連研究として研究を行った硫酸錯体の研究では、Rfと同族元素の間でイオン交換挙動に差が見られており、この実験データを考察し、Rfの化学における相対論効果の影響を調べることにつなげていくことができると考える。

Research Products

• [Journal Article] Co-precipitation behavior of single atoms of rutherfordium in basic solutions (2022)
  • Author(s): Y. Kasamatsu, K. Toyomura, H. Haba, T. Yokokita, Y. Shigekawa, A. Kino, Y. Yasuda, Y. Komori, J. Kanaya, M. Huang, M. Murakami, H. Kikunaga, E. Watanabe, T. Yoshimura, K. Morita, T. Mitsugashira, K. Takamiya, T. Ohtuski, A. Shinohara
  • Journal Title: RIKEN Accel. Prog. Rep. Volume: 55
  • Peer Reviewed / Open Access
• [Journal Article] Online anion-exchange experiment of 89mZr in the Adgen 464/HNO3 system for the chemical resarch of Rf (2022)
  • Author(s): E. Watanabe, T. Yokokita, Y. Kasamatsu, S. Hayami, K. Tonai, Y. Shigekawa, H. Haba, A. Shinohara
  • Journal Title: RIKEN Accel. Prog. Rep. Volume: 55 Pages: 120-121
  • Peer Reviewed / Open Access
• [Journal Article] Solvent extraction of Zr and Hf in trioctylamine/H2SO4 system (2022)
  • Author(s): T. Yokokita, H. Haba
  • Journal Title: RIKEN Accel. Prog. Rep. Volume: 55 Pages: 122-122
  • Peer Reviewed / Open Access
• [Journal Article] Anion- and cation-exchange studies of Zr, Hf, and Th using ion-exchange resin and fiber in H2SO4 media for chemical characterization of sulfate complex of Rf (2022)
  • Author(s): Yokokita Takuya、Yano Shinya、Komori Yukiko、Haba Hiromitsu
  • Journal Title: Journal of Radioanalytical and Nuclear Chemistry Volume: 331 Issue: 2 Pages: 1127-1134
  • DOI: 10.1007/s10967-021-08184-y
  • Peer Reviewed
• [Journal Article] Anion- and cation-exchange studies of Zr, Hf, and Th using ion-exchange resin and fiber in H2SO4 media for chemical characterization of sulfate complex of Rf (2021)
  • Author(s): E. Watanabe, Y. Kasamatsu, T. Yokokita, S. Hayami, K. Tonai, H. Ninomiya, N. Kondo, Y. Shigekawa, H. Haba, Y. Kitagawa, M. Nakano, and A. Shinohara
  • Journal Title: Solvent Extr. Ion Exch. Volume: 未定 Issue: 6 Pages: 1-16
  • DOI: 10.1080/07366299.2021.2020956
  • Peer Reviewed
• [Journal Article] Production of 266Bh in the 248Cm(23Na, 5n)266Bh reaction and its decay properties (2021)
  • Author(s): H. Haba et al.
  • Journal Title: RIKEN Accelerator Progress Report Volume: 54 Pages: 141-141
  • Peer Reviewed
• [Journal Article] Anion-exchange behavior of Db in HF/HNO3 solution (2021)
  • Author(s): M. Kato, S. Adachi, A. Toyoshima, K. Tsukada, M. Asai, T. Yokokita, Y. Komori, Y. Wang, Y. Shigekawa, D. Mori, H. Haba, A. Kashihara, A. Nakajima, K. Tokoi, Y. Suzuki, K. Nishizuka, K. Sueki
  • Journal Title: RIKEN Accelerator Progress Report Volume: 54 Pages: 147-147
  • Peer Reviewed
• [Journal Article] Anion exchange of Rf in H2SO4 using the batch-type solid-liquid extraction apparatus AMBER (2021)
  • Author(s): T. Yokokita, Y. Kasamatsu, E. Watanabe, Y. Komori, Y. Shigekawa, Y. Wang, D. Mori, H. Ninomiya, S. Hayami, K. Tonai, K. Ghosh, A. Shinohara, H. Haba
  • Journal Title: RIKEN Accelerator Progress Report Volume: 54 Pages: 148-148
  • Peer Reviewed
• [Journal Article] Online anion-exchange experiment of Zr in H2SO4 for the chemical study of Rf in H2SO4 (2021)
  • Author(s): T. Yokokita, Y. Shigekawa, Y. Wang, Y. Komori, Y. Kasamatsu, E. Watanabe, H. Haba
  • Journal Title: RIKEN Accelerator Progress Report Volume: 54 Pages: 149-149
  • Peer Reviewed
• [Journal Article] Solvent extraction of Zr and Hf from HCl by Aliquat 336 using a flow-type extraction apparatus toward online chemical studies of element 104, rutherfordium (2021)
  • Author(s): Y. Kasamatsu, N. Kondo, K. Nakamura, Y. Kuboki, H. Ninomiya, Y. Shigekawa, E. Watanabe, Y. Yasuda, K. Toyomura, M. Nagase, T. Yokokita, Y. Komori, H. Haba, T. Yoshimura, H. Itabashi, A. Shinohara
  • Journal Title: RIKEN Accelerator Progress Report Volume: 54 Pages: 150-150
  • Peer Reviewed
• [Journal Article] Cation- and anion-exchange behavior and UV-vis spectroscopy of Zr in HBr for chemical characterization of bromide complexes of Rf (2021)
  • Author(s): T. Yokokita and H. Haba
  • Journal Title: RIKEN Accelerator Progress Report Volume: 54 Pages: 151-151
  • Peer Reviewed
• [Journal Article] Co-precipitation behaviour of single atoms of rutherfordium in basic solutions (2021)
  • Author(s): Y. Kasamatsu, K. Toyomura, H. Haba, T. Yokokita, A. Kino, Y. Yasuda, Y. Komori, J. Kanaya, M.H. Huang, M. Murakami, H. Kikunaga, E. Watanabe, T. Yoshimura, K. Morita, T. Mitsugashira, K. Takamiya, T. Ohtsuki, A. Shinohara
  • Journal Title: NATURE CHEMISTRY Volume: 13 Issue: 3 Pages: 226-230
  • DOI: 10.1038/s41557-020-00634-6
  • Peer Reviewed
• [Journal Article] Production of Bh266 in the Cm248(Na23,5n)Bh266 reaction and its decay properties (2020)
  • Author(s): Haba H.他（Shigekawa Y. 19番目）
  • Journal Title: Physical Review C Volume: 102 Issue: 2 Pages: 024625-024625
  • DOI: 10.1103/physrevc.102.024625
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Solvent Extraction of Zr and Hf from HCl by Aliquat 336 using a Flow-Type Extraction Apparatus Toward Online Chemical Studies of Element 104, Rutherfordium (2020)
  • Author(s): Kasamatsu Yoshitaka、Kondo Narumi、Nakamura Kouhei、Kuboki Yuki、Ninomiya Hidemi、Shigekawa Yudai、Watanabe Eisuke、Yasuda Yuki、Toyomura Keigo、Nagase Masahiro、Yokokita Takuya、Komori Yukiko、Haba Hiromitsu、Yoshimura Takashi、Itabashi Hideyuki、Shinohara Atsushi
  • Journal Title: Solvent Extraction and Ion Exchange Volume: 38 Issue: 3 Pages: 318-327
  • DOI: 10.1080/07366299.2020.1726075
  • Peer Reviewed
• [Journal Article] On-line anion-exchange experiment of Nb and Ta in HF/HNO3 mixture solution for Db chemistry (2020)
  • Author(s): S. Adachi, A. Toyoshima, K. Tsukada, H. Haba, Y. Komori, T. Yokokita, Y. Shigekawa, Y. Wang, A. Kashihara, M. Kato, A. Nakajima, K. Sueki
  • Journal Title: RIKEN Accelerator Progress Report 2019 Volume: 53 Pages: 162-162
• [Journal Article] Anion-exchange behavior of Nb, Ta and Pa in H2SO4 (2020)
  • Author(s): M. Kato, K. Tsukada, H. Haba, Y. Komori, T. Yokokita, D. Mori, S. Adachi, A. Kashihara, K. Sueki
  • Journal Title: RIKEN Accelerator Progress Report 2019 Volume: 53 Pages: 163-163
• [Journal Article] Anion exchange of Nb and Ta in HF/HCl mixture solution for Db chemistry (2020)
  • Author(s): T. Yokokita, H. Haba
  • Journal Title: RIKEN Accelerator Progress Report 2019 Volume: 53 Pages: 164-164
• [Journal Article] Anion exchange of element 104, Rf, at 0.11 M H2SO4 by using batch-type solid-liquid extraction apparatus, AMBER (2020)
  • Author(s): T. Yokokita, Y. Kasamatsu, E. Watanabe, Y. Komori, Y. Shigekawa, Y. Wang, D. Mori, H. Ninomiya, S. Hayami, K. Tonai, K. Ghosh, A. Shinohara, H. Haba
  • Journal Title: RIKEN Accelerator Progress Report 2019 Volume: 53 Pages: 165-165
• [Journal Article] Anion exchange of Zr, Hf, and Th by the automated extraction apparatus: toward the chemical study of 104Rf in HNO3 (2020)
  • Author(s): E. Watanabe, T. Yokokita, Y. Kasamatsu, S. Hayami, K. Tonai, Y. Shigekawa, H. Haba, A. Shinohara
  • Journal Title: RIKEN Accelerator Progress Report 2019 Volume: 53 Pages: 166-166
• [Journal Article] An attempt to modify the membrane degasser (MDG) (2020)
  • Author(s): Y. Komori, K. Ooe, T. Yokokita. Y. Shigekawa, H. Haba
  • Journal Title: RIKEN Accelerator Progress Report 2019 Volume: 53 Pages: 169-169
• [Presentation] クラウンエーテルを用いた102番元素ノーベリウムの硝酸系固液抽出実験 (2022)
  • Author(s): 渡邉瑛介, 笠松良崇, 横北卓也, 中西諒平 大髙咲希 板倉悠大 , 益田遼太郎, 王瑞麟, 重河優大, 南部明弘, 殷小杰, 羽場宏光, 高宮幸一, 篠原厚
  • Organizer: 日本放射化学会第66回討論会 (2022)
• [Presentation] Zr及びHfのスルファト錯体推定に向けたTOA/H2SO4系の溶媒抽出 (2022)
  • Author(s): 横北卓也, 羽場宏光
  • Organizer: 日本化学会第102春季年会 (2022)
• [Presentation] HF/HNO3系における Db の陰イオン交 換挙動 (2020)
  • Author(s): 加藤 瑞 穂, 安達 サディア, 豊嶋 厚史, 塚田 和明, 浅井 雅人, 羽場 宏光, 横北 卓 也, 小森 有希子, 重河 優大, Yang Wang, 森 大輝, 柏原 歩那, 床井 健運, 中島 朗久, 鈴木 雄介, 西塚 魁人, 末木 啓介
  • Organizer: 日本放射化学会第 64 回討論会（2020）
• [Presentation] 硫酸系における Rf の陰イオン交換: 分配係数の硫酸濃度依存性 (2020)
  • Author(s): 横北 卓也, 笠松 良崇, 渡邉 瑛介, 小森 有 希子, 重河 優大, 森 大輝, 王 洋, 二 宮 秀美, 速水 翔, 東内 克馬, ゴーシ ュ コースタブ, 篠原 厚, 羽場 宏光
  • Organizer: 日本放射化学会第 64 回討論会（2020）
• [Presentation] Rf の化学研究に向けた 89mZr の硝酸系でのオンライン陰イオン交換実験 (2020)
  • Author(s): 渡邉 瑛介, 笠松 良崇, 横北 卓也, 速水 翔, 東内 克馬, 重河 優大, 羽場 宏光, 篠原 厚
  • Organizer: 日本放射化学会第 64 回討論会（2020）