Development of high density hydrogen storage materials using hydrogen boride

• Project Area: HYDROGENOMICS: Creation of Innovative Materials, Devices, and Reaction Processes using Higher-Order Hydrogen Functions
• Project/Area Number: 19H05046
• 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: University of Tsukuba
• Principal Investigator: 近藤 剛弘 筑波大学, 数理物質系, 准教授 (70373305)
• Project Period (FY): 2019-04-01 – 2021-03-31
• Project Status: Completed (Fiscal Year 2020)
• Budget Amount: ¥4,290,000 (Direct Cost: ¥3,300,000、Indirect Cost: ¥990,000); Fiscal Year 2020: ¥2,210,000 (Direct Cost: ¥1,700,000、Indirect Cost: ¥510,000); Fiscal Year 2019: ¥2,080,000 (Direct Cost: ¥1,600,000、Indirect Cost: ¥480,000)
• Keywords: ホウ化水素 / 水素貯蔵 / 炭素ドープ / 2次元物質 / 2次元シート / ボロン / ボロファン

Outline of Research at the Start

我々が世界で初めて単離生成を実現した二次元物質であるホウ化水素シートを基軸として新しい高密度水素貯蔵材料を開発します。炭素や窒素をホウ化水素シートに電子ドーパントとして導入し、水素とホウ素の反結合性軌道への電子注入を介して水素放出温度の低温・狭範化を実現させます。水素放出温度を縦軸、ドーパント電子量を横軸としてドーパント種の組み合わせ比ごとに定量的に温度制御範囲を明確化させ、電子状態解析と合わせて温度制御メカニズムも明確化させます。次に水素再貯蔵・放出温度狭範化・安定化を補助する材料を組み合わせ、特性・耐久性・繰り返し特性（再貯蔵）を明らかにします。以上により高密度水素貯蔵材料を開発します。

Outline of Annual Research Achievements

本研究の目的は、我々が世界で初めて単離生成を実現して2017年に論文発表した新規二次元物質であるホウ化水素シートを基軸として新しい高密度水素貯蔵材料を開発することです。本年度は、昨年度合成に成功した炭素ドープをしたホウ化水素シートの評価に注力しました。この結果、フーリエ変換赤外吸収分光で見られるB-H-Bの結合に由来する2500 cm-1付近に出現する吸収ピークが、炭素ドープ量の増加に伴い低波数側にシフトすることがわかりました。これは炭素ドープがホウ化水素シート全体のB-H-B結合に影響を及ぼしていることを示しており、昨年度見出された水素放出特性との良い相関関係があることを意味しています。現在定量的な解析により炭素ドープの効果についてまとめた内容を論文投稿する段階です。また、領域内の複数の研究者と共同研究を行い、重水素置換をしたホウ化水素の固体核磁気共鳴（NMR）解析や、有機分子との複合化をしたホウ化水素シートの合成を行い、後者では新しい特性を見出すことに成功しました（現在論文にまとめる前に知財申請を進めています）。さらに、領域内の研究者との共同研究によりホウ化水素シートと水との相互作用について調べた結果、ホウ化水素はホウ素同士の強固な結合ネットワークが存在しているため、ジボラン分子などとは異なりホウ素がマイナスの電荷を強固に維持できる性質があり、これがホウ化水素シートが加水分解をしない重要な要因であることがわかりました（論文投稿中）。また、ホウ化水素シートが還元剤として機能することやこの機能を利用して金属ナノ粒子とホウ化水素シートのナノコンポジット材料が自発的に形成することを見出した結果についてまとめた論文が、日本化学会のChemistry Letters誌でEditors Choice（優秀論文）に選出されました。

Research Progress Status

令和2年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

令和2年度が最終年度であるため、記入しない。

Research Products

• [Int'l Joint Research] CSIC(スペイン)
• [Journal Article] Ethanol-ethylene conversion mechanism on hydrogen boride sheets probed by in situ infrared absorption spectroscopy (2021)
  • Author(s): Fujino Asahi、Ito Shin-ichi、Goto Taiga、Ishibiki Ryota、Osuga Ryota、Kondo Junko N.、Fujitani Tadahiro、Nakamura Junji、Hosono Hideo、Kondo Takahiro
  • Journal Title: Physical Chemistry Chemical Physics Volume: 23 Issue: 13 Pages: 7724-7734
  • DOI: 10.1039/d0cp03079a
  • Peer Reviewed
• [Journal Article] Hydrogen Generation Induced by Ultraviolet Light Irradiation on Hydrogen Boride Sheets (2020)
  • Author(s): KONDO Takahiro、MIYAUCHI Masahiro
  • Journal Title: Vacuum and Surface Science Volume: 63 Issue: 7 Pages: 352-357
  • DOI: 10.1380/vss.63.352
  • NAID: 130007872354
  • ISSN: 2433-5835, 2433-5843
  • Year and Date: 2020-07-10
  • Peer Reviewed
• [Journal Article] Creation of new 2D materials using boron (2020)
  • Author(s): 近藤 剛弘
  • Journal Title: Oyo Buturi Volume: 89 Issue: 3 Pages: 152-156
  • DOI: 10.11470/oubutsu.89.3_152
  • NAID: 130007806957
  • ISSN: 0369-8009, 2188-2290
  • Year and Date: 2020-03-10
• [Journal Article] Diborane Concatenation Leads to New Planar Boron Chemistry (2020)
  • Author(s): Oliva‐Enrich Josep M.、Kondo Takahiro、Alkorta Ibon、Elguero Jos?、Klein Douglas J.
  • Journal Title: ChemPhysChem Volume: 21 Issue: 21 Pages: 2460-2467
  • DOI: 10.1002/cphc.202000554
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Acid Assisted Synthesis of HB Sheets through Exfoliation of MgB2 Bulk in Organic Media (2020)
  • Author(s): Kawamura Reiya、Yamaguchi Akira、Shimada Chika、Ishibiki Ryota、Fujita Takeshi、Kondo Takahiro、Miyauchi Masahiro
  • Journal Title: Chemistry Letters Volume: 49 Issue: 10 Pages: 1194-1196
  • DOI: 10.1246/cl.200203
  • NAID: 130007923163
  • Peer Reviewed
• [Journal Article] Hydrogen Boride Sheets as Reductants and the Formation of Nanocomposites with Metal Nanoparticles (2020)
  • Author(s): Ito Shin-ichi、Hirabayashi Toru、Ishibiki Ryota、Kawamura Reiya、Goto Taiga、Fujita Takeshi、Yamaguchi Akira、Hosono Hideo、Miyauchi Masahiro、Kondo Takahiro
  • Journal Title: Chemistry Letters Volume: 49 Issue: 7 Pages: 789-793
  • DOI: 10.1246/cl.200206
  • NAID: 130007872492
  • Peer Reviewed / Open Access
• [Journal Article] ホウ化水素シートの光機能─ 軽量・安全・光応答性の水素キャリア材料─ (2020)
  • Author(s): 宮内 雅浩, 近藤 剛弘
  • Journal Title: セラミックス Volume: 55 Pages: 591-594
  • Peer Reviewed
• [Journal Article] Chemically Modified Borophene (2020)
  • Author(s): Kondo Takahiro、Matsuda Iwao
  • Journal Title: 2D Boron: Boraphene, Borophene, Boronene Volume: 0 Pages: 89-119
  • DOI: 10.1007/978-3-030-49999-0_5
  • ISBN: 9783030499983, 9783030499990
  • Peer Reviewed
• [Journal Article] Geometrical Frustration of B-H Bonds in Layered Hydrogen Borides Accessible by Soft Chemistry (2020)
  • Author(s): Satoshi Tominaka, Ryota Ishibiki, Asahi Fujino, Kohsaku Kawakami, Koji Ohara, Takuya Masuda, Iwao Matsuda, Hideo Hosono, Takahiro Kondo
  • Journal Title: Chem Volume: 6 Issue: 2 Pages: 406-418
  • DOI: 10.1016/j.chempr.2019.11.006
  • Peer Reviewed
• [Journal Article] Photoinduced hydrogen release from hydrogen boride sheets (2019)
  • Author(s): Reiya Kawamura, Nguyen Thanh Cuong, Takeshi Fujita, Ryota Ishibiki, Toru Hirabayashi, Akira Yamaguchi, Iwao Matsuda, Susumu Okada, Takahiro Kondo, Masahiro Miyauchi
  • Journal Title: Nature Communications Volume: 10 Issue: 1 Pages: 4880-4880
  • DOI: 10.1038/s41467-019-12903-1
  • NAID: 120007127794
  • Peer Reviewed / Open Access
• [Journal Article] Hydrogenated Borophene Shows Catalytic Activity as Solid Acid (2019)
  • Author(s): Asahi Fujino, Shin-ichi Ito, Taiga Goto, Ryota Ishibiki, Junko Kondo, Tadahiro Fujitani, Junji Nakamura, Hideo Hosono, Takahiro Kondo
  • Journal Title: ACS Omega Volume: 4 Issue: 9 Pages: 14100-14104
  • DOI: 10.1021/acsomega.9b02020
  • NAID: 120007133100
  • Peer Reviewed / Open Access
• [Presentation] Boron-based new two-dimensional materials: synthesis, characterization, and application (2021)
  • Author(s): Takahiro Kondo
  • Organizer: 第60回 フラーレン・ナノチューブ・グラフェン総合シンポジウム
  • Invited
• [Presentation] 炭素をドープしたホウ化水素シートの合成と評価 (2021)
  • Author(s): 川村陸，藤本義隆，石引涼太，後藤大河，伊藤伸一，藤田武志，徳永智春，宮内雅浩，飯村壮史，山本明保, 斎藤晋，細野秀雄，近藤剛弘
  • Organizer: 第14回物性科学領域横断研究会
• [Presentation] ホウ化水素シート上へのCO2の吸着と水素化反応 (2021)
  • Author(s): 後藤大河，伊藤伸一，近藤剛弘
  • Organizer: 2020年日本表面真空学会学術講演会
• [Presentation] 炭素をドープしたホウ化水素シートの合成と評価 (2021)
  • Author(s): 川村陸，藤本義隆，石引涼太，後藤大河，伊藤伸一，藤田武志，徳永智春，宮内雅浩，飯村壮史，山本明保，斎藤晋，細野秀雄，近藤剛弘
  • Organizer: 2020年日本表面真空学会学術講演会
• [Presentation] Adsorption and Hydrogenation of CO2 on Heat-Treated Hydrogen Boride Sheets (2021)
  • Author(s): T. Goto, S. Ito, T. Kondo
  • Organizer: 33rd International Microprocesses and Nanotechnology Conference (MNC2020)
• [Presentation] ドープ量を制御した炭素ドープホウ化水素シートの合成と評価 (2021)
  • Author(s): 川村陸，藤本義隆，石引涼太，後藤大河，伊藤伸一，藤田武志，徳永智春，宮内雅弘，飯村壮史，山本明保，斎藤晋，細野秀雄，近藤剛弘
  • Organizer: 第81回応用物理学会秋季学術講演会
• [Presentation] 新物質ホウ化水素シートの生成と機能 (2021)
  • Author(s): 近藤剛弘
  • Organizer: 東京大学物性研究所ワークショップ「ナノスケール物性科学の最先端と新展開」
  • Invited
• [Presentation] Carbon dopong of hydrogen boride sheet reduces H2 release temperature (2020)
  • Author(s): T. Kondo, Y. Fujimoto, R. Ishibiki, T. Goto, S. Ito, T. Fujita, A. Yamamoto, S. Saito, and H. Hosono
  • Organizer: 1st International Symposium Hydrogenomics combined with 14th International Symposium Hydrogen & Energy
  • Int'l Joint Research
• [Presentation] 炭素ドープホウ化水素シートの合成と評価 (2020)
  • Author(s): 川村陸，藤本義隆，石引涼太，後藤大河，伊藤伸一，藤田武志，徳永智春，宮内雅浩，飯村荘史，山本明保, 斎藤晋，細野秀雄，近藤剛弘
  • Organizer: 第67回応用物理学会春季学術講演会
• [Presentation] ホウ素と水素で構成される二次元物質ホウ化水素シートの特性 (2019)
  • Author(s): 近藤剛弘
  • Organizer: 第4回固体化学フォーラム研究会
  • Invited
• [Presentation] Hydrogen boride sheet shows catalytic activity as solid acid (2019)
  • Author(s): T. Kondo, A. Fujino, R. Ishibiki, S. Ito, J. N. Kondo, T. Fujitani, J. Nakamura, H. Hosono
  • Organizer: 8th European Conference on Boron chemistry, Montpellier
  • Int'l Joint Research
• [Presentation] Thermal and chemical stabilities of hydrogen boride sheet (2019)
  • Author(s): R. Ishibiki, I. Matsuda, A. Fujino, S. Ito, M. Miyauchi, J. Nakamura, H. Hosono, T. Kondo
  • Organizer: 8th European Conference on Boron chemistry, Montpellier
  • Int'l Joint Research
• [Presentation] Adsorption Property of CO2 on Hydrogen Boride Sheets with H-vacancy Defects (2019)
  • Author(s): Taiga Goto, Ryota Ishibiki, Shinichi Ito, Hideo Hosono, Takahiro Kondo
  • Organizer: The 11th International Conference on the Science and Technology for Advanced Ceramics
  • Int'l Joint Research
• [Presentation] A new solid acid catalyst of hydrogen boride sheets (2019)
  • Author(s): A. Fujino, R. Ishibiki, S. Ito, J. N. Kondo, T. Fujitani, J. Nakamura, H. Hosono, T. Kondo
  • Organizer: The 11th International Conference on the Science and Technology for Advanced Ceramics
  • Int'l Joint Research
• [Presentation] Thermal Stability of Two-dimensional Hydrogen Boride Sheets (2019)
  • Author(s): Ryota Ishibiki, Iwao Matsuda, Shin-ichi Ito, Junji Nakamura, Hideo Hosono, Takahiro Kondo
  • Organizer: The 11th International Conference on the Science and Technology for Advanced Ceramics
  • Int'l Joint Research
• [Presentation] New two-dimensional material: Borophane, synthesis, characterization, and application (2019)
  • Author(s): Takahiro Kondo
  • Organizer: ICAT/ETH Symposium
  • Int'l Joint Research / Invited
• [Presentation] Hydrogen Boride Sheets: Synthesis, Characterization, and Application (2019)
  • Author(s): Takahiro Kondo
  • Organizer: 20th International Symposium on Boron, Borides and Related Materials (ISBB 2019)
  • Int'l Joint Research / Invited
• [Presentation] CO2 Adsorption on Hydrogen Boride Sheets with H-vacancy Defects (2019)
  • Author(s): T. Goto, R. Ishibiki, S. Ito, H. Hosono, and T. Kondo
  • Organizer: 20th International Symposium on Boron, Borides and Related Materials (ISBB 2019)
  • Int'l Joint Research
• [Presentation] Structure and Electronic States Variations of Hydrogen Boride Nanosheets with Heating (2019)
  • Author(s): R. Ishibiki, I. Matsuda, S. Ito, J. Nakamura, H. Hosono, and T. Kondo
  • Organizer: 20th International Symposium on Boron, Borides and Related Materials (ISBB 2019)
  • Int'l Joint Research
• [Presentation] 二次元物質ホウ化水素シートの生成、特性、機能 (2019)
  • Author(s): 近藤剛弘
  • Organizer: 2019年日本表面真空学会学術講演会
  • Invited
• [Presentation] Hydrogenated borophene Sheets: Synthesis, Characterization, and Application (2019)
  • Author(s): Takahiro Kondo
  • Organizer: Joint Symposium on Nanomaterials for Energy Applications
  • Int'l Joint Research / Invited
• [Presentation] 水素とホウ素のみで構成される二次元物質ホウ化水素 (2019)
  • Author(s): 近藤剛弘
  • Organizer: 第2回ハイドロジェノミクス研究会
  • Invited
• [Presentation] Carbon Doping of Hydrogen Boride Sheet Reduces H2 Release Temperature (2019)
  • Author(s): Takahiro KONDO, Yoshitaka FUJIMOTO, Ryota ISHIBIKI, Taiga GOTO, Shin-ichi ITO, Takeshi FUJITA, Akiyasu YAMAMOTO, Susumu SAITO, Hideo HOSONO
  • Organizer: MATERIALS RESEARCH MEETING 2019 Materials Innovation for Sustainable Development Goals
  • Int'l Joint Research
• [Presentation] Hydrogenated Borophene Shows Catalytic Activity as Solid Acid (2019)
  • Author(s): Takahiro KONDO, Asahi FUJINO, Shin-ich ITO, Taiga GOTO, Ryota ISHIBIKI, Junko N KONDO, Tadahiro FUJITANI, Junji NAKAMURA, Hideo HOSONO
  • Organizer: MATERIALS RESEARCH MEETING 2019 Materials Innovation for Sustainable Development Goals
  • Int'l Joint Research
• [Presentation] Adsorption of CO2 on Hydrogen Boride Sheets with H-vacancy Defects (2019)
  • Author(s): Taiga GOTO, Ryota ISHIBIKI, Shin-ichi ITO, Hideo HOSONO, Takahiro KONDO
  • Organizer: MATERIALS RESEARCH MEETING 2019 Materials Innovation for Sustainable Development Goals
  • Int'l Joint Research
• [Presentation] Structure and Electronic States Changes of Hydrogen Boride Sheets with Heating (2019)
  • Author(s): Ryota ISHIBIKI, Iwao MATSUDA, Shin-ichi ITO, Hideo HOSONO, Takahiro KONDO
  • Organizer: MATERIALS RESEARCH MEETING 2019 Materials Innovation for Sustainable Development Goals
  • Int'l Joint Research
• [Patent(Industrial Property Rights)] 水素貯蔵放出材料およびその製造方法 (2019)
  • Inventor(s): 近藤剛弘, 石引涼太, 後藤大河, 伊藤伸一, 木下喜裕
  • Industrial Property Rights Holder: 近藤剛弘, 石引涼太, 後藤大河, 伊藤伸一, 木下喜裕
  • Industrial Property Rights Type: 特許
  • Industrial Property Number: 2019-207861
  • Filing Date: 2019
• [Patent(Industrial Property Rights)] 二次元ホウ化水素含有シートの製造方法、二次元ホウ化水素含有シート組成物およびその製造方法 (2019)
  • Inventor(s): 宮内雅浩, 河村玲哉, 近藤剛弘, 石引涼太
  • Industrial Property Rights Holder: 宮内雅浩, 河村玲哉, 近藤剛弘, 石引涼太
  • Industrial Property Rights Type: 特許
  • Industrial Property Number: 2019-207081
  • Filing Date: 2019
• [Patent(Industrial Property Rights)] 層状ホウ化水素 (2019)
  • Inventor(s): 近藤剛弘, 冨中悟史
  • Industrial Property Rights Holder: 近藤剛弘, 冨中悟史
  • Industrial Property Rights Type: 特許
  • Industrial Property Number: 2019-148099
  • Filing Date: 2019