Design of highly active catalytic reaction space utilizing crystalline surface of layered silicate

• Project/Area Number: 17K17906
• Research Category: Grant-in-Aid for Young Scientists (B)
• Allocation Type: Multi-year Fund
• Research Field: Inorganic industrial materials; Catalyst/Resource chemical process
• Research Institution: Hiroshima University
• Principal Investigator: Tsunoji Nao 広島大学, 工学研究科, 助教 (40758166)
• 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: ¥910,000 (Direct Cost: ¥700,000、Indirect Cost: ¥210,000); Fiscal Year 2018: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000); Fiscal Year 2017: ¥2,080,000 (Direct Cost: ¥1,600,000、Indirect Cost: ¥480,000)
• Keywords: 層状ケイ酸塩 / ゼオライト / 触媒 / 光触媒 / 層状化合物 / シクロヘキサン / 部分酸化 / バイオマス / 無機工業化学 / セラミックス

Outline of Final Research Achievements

Focusing on the crystalline surface structure and stacking order of layered silicate material, highly active and selective catalytic reaction space was designed on the novel layered silicates Hiroshima University Silicates (HUSs). Metal complex with uniform coordination state and high surface density was successfully immobilized via surface silanol group on the layered silicate. Incorporation of various compounds into the layered silicate material could control the stacking state of silicate layer and improve the mass-diffusion in the interlayer space. The obtained layered silicate based catalysts exhibited excellent catalytic performance for olefin epoxidation and photocatalytic partial oxidation of cyclohexane.

Academic Significance and Societal Importance of the Research Achievements

層状ケイ酸塩を用いた既存の設計手法は、導入されるユニットの機能、性質が根底に置かれ、層状ケイ酸塩の結晶性表面を利用する必然性がほとんど提示されてこなかった。本研究では、層状ケイ酸塩の結晶性表面に、その規則が反映された、金属酸化物活性種を設計し、高活性・高選択的な触媒反応場を構築する。母体の結晶構造によって定義可能な配位環境、空間分布を有する活性種のテーラーメイドが可能であるため、極めて精密な固体触媒の設計が可能となる。さらに、本材料の積層構造制御によって、層状ケイ酸塩を高活性触媒として利用していく上での大きな障害である層空間・層表面への物質の拡散の問題も解決できる。

Research Products

• [Int'l Joint Research] J. H. Institute of Physical Chemistry/Charles University(チェコ)
• [Int'l Joint Research] J. H. Institute of Physical Chemistry(チェコ)
• [Journal Article] Merging periodic mesoporous organosilica (PMO) with mesoporous aluminosilica (Al/Si-PMO): A catalyst for green oxidation (2020)
  • Author(s): Doustkhah Esmail、Mohtasham Hamed、Hasani Morteza、Ide Yusuke、Rostamnia Sadegh、Tsunoji Nao、Hussein N. Assadi M.
  • Journal Title: Molecular Catalysis Volume: 482 Pages: 110676-110676
  • DOI: 10.1016/j.mcat.2019.110676
  • Peer Reviewed
• [Journal Article] Theoretical study on 31P NMR chemical shifts of phosphorus-modified CHA zeolites (2020)
  • Author(s): Zhao Pei、Boekfa Bundet、Nishitoba Toshiki、Tsunoji Nao、Sano Tsuneji、Yokoi Toshiyuki、Ogura Masaru、Ehara Masahiro
  • Journal Title: Microporous and Mesoporous Materials Volume: 294 Pages: 109908-109908
  • DOI: 10.1016/j.micromeso.2019.109908
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] In Situ Spectroscopic Studies on the Redox Cycle of NH3?SCR over Cu‐CHA Zeolites (2020)
  • Author(s): Liu Chong、Kubota Hiroe、Amada Takehiro、Kon Kenichi、Toyao Takashi、Maeno Zen、Ueda Kakuya、Ohyama Junya、Satsuma Atsushi、Tanigawa Takuya、Tsunoji Nao、Sano Tsuneji、Shimizu Ken-ichi
  • Journal Title: ChemCatChem Volume: 12 Issue: 11 Pages: 1-11
  • DOI: 10.1002/cctc.202000024
  • NAID: 120007044524
  • Peer Reviewed
• [Journal Article] Photocatalytic Activation of C-H Bonds by Spatially Controlled Chlorine and Titanium on the Silicate Layer (2019)
  • Author(s): Tsunoji Nao、Nishida Hidechika、Ide Yusuke、Komaguchi Kenji、Hayakawa Shinjiro、Yagenji Yuya、Sadakane Masahiro、Sano Tsuneji
  • Journal Title: ACS Catalysis Volume: 9 Issue: 6 Pages: 5742-5751
  • DOI: 10.1021/acscatal.9b01284
  • Peer Reviewed
• [Journal Article] Condensed ferric dimers for green photocatalytic synthesis of nylon precursors (2019)
  • Author(s): Ide Yusuke、Tominaka Satoshi、Yoneno Yumi、Komaguchi Kenji、Takei Toshiaki、Nishida Hidechika、Tsunoji Nao、Machida Akihiko、Sano Tsuneji
  • Journal Title: Chemical Science Volume: 10 Issue: 27 Pages: 6604-6611
  • DOI: 10.1039/c9sc01253b
  • Peer Reviewed / Open Access
• [Journal Article] Immobilization of Preyssler type heteropoly acids on siliceous mesoporous supports and their catalytic activities in the dehydration of ethanol (2019)
  • Author(s): Mahuya Bandyopadhyay, Divya Jadav, Nao Tsunoji, Tsuneji Sano, Masahiro Sadakane
  • Journal Title: Reaction Kinetics, Mechanisms and Catalysis Volume: 128 Issue: 1 Pages: 139-147
  • DOI: 10.1007/s11144-019-01646-1
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Formation Pathway of AEI Zeolites as a Basis for a Streamlined Synthesis (2019)
  • Author(s): Tsunoji Nao、Shimono Daigo、Tsuchiya Kazuyoshi、Sadakane Masahiro、Sano Tsuneji
  • Journal Title: Chemistry of Materials Volume: 32 Issue: 1 Pages: 60-74
  • DOI: 10.1021/acs.chemmater.9b02227
  • Peer Reviewed
• [Journal Article] Microporous materials formed via intercalation of ultrathin coordination polymers in a layered silicate (2019)
  • Author(s): Ide Yusuke、Tominaka Satoshi、Okuyama Taiki、Tsunoji Nao、Ohara Koji、Mitome Masanori、Sano Tsuneji、Bando Yoshio、Golberg Dmitri
  • Journal Title: Nano Energy Volume: 59 Pages: 162-168
  • DOI: 10.1016/j.nanoen.2019.02.016
  • Peer Reviewed
• [Journal Article] Zeolitic intralayer microchannels of magadiite, a natural layered silicate, to boost green organic synthesis (2018)
  • Author(s): Ide Yusuke、Tominaka Satoshi、Kono Hiroyuki、Ram Rahul、Machida Akihiko、Tsunoji Nao
  • Journal Title: Chemical Science Volume: 9 Issue: 46 Pages: 8637-8643
  • DOI: 10.1039/c8sc03712d
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Highly-Active Layered Titanosilicate Catalyst with High Surface Density of Isolated Titanium on the Accessible Interlayer Surface (2018)
  • Author(s): Tsunoji Nao、Opanasenko Maksym V.、Kubu Martin、Cejka Jiri、Nishida Hidechika、Hayakawa Shinjiro、Ide Yusuke、Sadakane Masahiro、Sano Tsuneji
  • Journal Title: ChemCatChem Volume: 印刷中 Issue: 12 Pages: 2536-2540
  • DOI: 10.1002/cctc.201800413
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Synthesis of phosphorus-modified AFX zeolite using a dual-template method with tetraethylphosphonium hydroxide as phosphorus modification agent (2018)
  • Author(s): Mitani Emi、Yamasaki Yoshitaka、Tsunoji Nao、Sadakane Masahiro、Sano Tsuneji
  • Journal Title: Microporous and Mesoporous Materials Volume: 267 Pages: 192-197
  • DOI: 10.1016/j.micromeso.2018.03.033
  • Peer Reviewed
• [Journal Article] Templated synthesis of atomically thin platy hematite nanoparticles within a layered silicate exhibiting efficient photocatalytic activity (2018)
  • Author(s): Mani Durai、Tsunoji Nao、Yumauchi Yusuke、Arivanandhan Mukannan、Jayavel Ramasamy、Ide Yusuke
  • Journal Title: Journal of Materials Chemistry A Volume: 6 Issue: 12 Pages: 5166-5171
  • DOI: 10.1039/c7ta10427h
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Thermally stable nanosized LEV zeolites synthesized by hydrothermal conversion of FAU zeolites in the presence of N,N-dimethylpiperidinium cations (2017)
  • Author(s): Funase Natsumi、Tanigawa Takuya、Yamasaki Yoshitaka、Tsunoji Nao、Sadakane Masahiro、Sano Tsuneji
  • Journal Title: Journal of Materials Chemistry A Volume: 5 Issue: 36 Pages: 19245-19254
  • DOI: 10.1039/c7ta04988a
  • Peer Reviewed
• [Journal Article] Design of a highly active base catalyst through utilizing organic-solvent-treated layered silicate Hiroshima University Silicates (2017)
  • Author(s): Tsunoji Nao、Bandyopadhyay Mahuya、Yagenji Yuya、Nishida Hidechika、Sadakane Masahiro、Sano Tsuneji
  • Journal Title: Dalton Transactions Volume: 46 Issue: 23 Pages: 7441-7450
  • DOI: 10.1039/c7dt00698e
  • Peer Reviewed / Int'l Joint Research
• [Presentation] Efficient Photocatalytic Activation of C－H Bonds by Control of Atom Spatial Distribution on the Layered Silicate (2020)
  • Author(s): 津野地直、定金正洋
  • Organizer: 日本化学会 第100春季年会 (2020)
• [Presentation] Stepwise Gel Preparation for High-Quality Small-Pore Zeolite Synthesis (2019)
  • Author(s): Nao Tsunoji, Masahiro Sadakane, Tsuneji Sano
  • Organizer: 19th International Zeolite Conference (19th IZC)
  • Int'l Joint Research
• [Presentation] Zeolite hydrothermal conversion in the presence of various cyclicalkylammonium cations and synthesis of nanosized BEA and MFI zeolites (2019)
  • Author(s): Nao Tsunoji, Takuya Tanigawa, Masahiro Sadakane, Tsuneji Sano
  • Organizer: 19th International Zeolite Conference (19th IZC)
  • Int'l Joint Research
• [Presentation] EFFICIENT PHOTOCATALYTIC ACTIVATION OF C-H BONDS BY SPATIALLY CONTROLLED CHLORINE AND TITANIUM ON THE SILICATE LAYER (2019)
  • Author(s): Nao Tsunoji, Hidechika Nishida, Masahiro Sadakane, Tsuneji Sano
  • Organizer: WORKSHOP on LAYERED MATERIALS
  • Int'l Joint Research
• [Presentation] SYNTHESIS AND CRYSTALLINE ALUMINOSILICATE NANOSHEETS WITH VERY THIN BUILDING UNIT (2019)
  • Author(s): Toshiaki Oguchi, Kazuki Enokawa, Nao Tsunoji, Masahiro Sadakane, Tsuneji Sano
  • Organizer: WORKSHOP on LAYERED MATERIALS
  • Int'l Joint Research
• [Presentation] Hydrothermal conversion of FAU zeolite by using cyclicalkylammonium cations (2019)
  • Author(s): Takuya Tanigawa, Nao Tsunoji, Masahiro Sadakane, Tsuneji Sano
  • Organizer: International Symposium on Porous Materials 2019
  • Int'l Joint Research
• [Presentation] Phosphorus modified small-pore zeolites and their catalytic performances in ethanol conversion and NH3-SCR reactions (2019)
  • Author(s): Yutaro Kakiuchi, T. Tanigawa, Nao Tsunoji, Masahiro Sadakane, Tsuneji Sano
  • Organizer: International Symposium on Porous Materials 2019
  • Int'l Joint Research
• [Presentation] ゼオライトとその層状類縁体の局所的・巨視的構造制御 (2019)
  • Author(s): 津野地 直
  • Organizer: JPIJS(石油学会ジュニア・ソサイアティ) 講演会
  • Invited
• [Presentation] 極めて薄いビルディングユニットを有する結晶性アルミノケイ酸塩ナノシートの合成 (2019)
  • Author(s): 小口稔明、可愛川和希、津野地直、定金正洋、佐野庸治
  • Organizer: 第 124 回触媒討論会
• [Presentation] 空間的に位置制御された Cl-Ti原子を介した光触媒的 C-H結合活性化 (2019)
  • Author(s): 津野地直、西田英央、井出裕介、定金正洋、佐野庸治
  • Organizer: 第 124 回触媒討論会
• [Presentation] FERゼオライトナノシートの効果的なプロトン交換と触媒特性 (2019)
  • Author(s): 可愛川和希、津野地直、定金正洋、佐野庸治
  • Organizer: 124 回触媒討論会
• [Presentation] 層状ケイ酸塩の 規則構造を活用したチタノシリ ケート光触媒への塩素の導入と シクロヘキサンの部分酸化反応 における大幅な活性向上 (2018)
  • Author(s): 西田英央、津野地直、井出裕介、薬研地 祐也、定金正洋、佐野庸治
  • Organizer: 第122回触媒討論会
• [Presentation] 新規層状ケイ酸塩HUSを用いた高活性触媒の設計 (2017)
  • Author(s): 津野地直、定金正洋、佐野庸治
  • Organizer: 第33回ゼオライト研究発表会
• [Presentation] シクロヘキサンの酸化におけるCl導入チタノシリケート光触媒の活性向上とその物性評価 (2017)
  • Author(s): 西田英央、津野地直、井出裕介、薬研地祐也、定金正洋、佐野庸治
  • Organizer: 第120回触媒討論会
• [Remarks]
  • URL: https://home.hiroshima-u.ac.jp/catalche/