In-situ generated metal/alloy nanoparticles within monolithic hydridosilica support applied to catalytic reactions

• Project/Area Number: 26288106
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Partial Multi-year Fund
• Section: 一般
• Research Field: Inorganic industrial materials
• Research Institution: Kyoto University
• Principal Investigator: Nakanishi Kazuki 京都大学, 理学(系)研究科(研究院), 准教授 (00188989)
• Co-Investigator(Kenkyū-buntansha): 嶋田 豊司 奈良工業高等専門学校, その他部局等, 教授 (20303802) ; 金森 主祥 京都大学, 理学(系)研究科(研究院), 助教 (60452265) ; 亀井 稔之 奈良工業高等専門学校, その他部局等, 准教授 (70534452)
• Project Period (FY): 2014-04-01 – 2017-03-31
• Project Status: Completed (Fiscal Year 2016)
• Budget Amount: ¥17,290,000 (Direct Cost: ¥13,300,000、Indirect Cost: ¥3,990,000); Fiscal Year 2016: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000); Fiscal Year 2015: ¥2,340,000 (Direct Cost: ¥1,800,000、Indirect Cost: ¥540,000); Fiscal Year 2014: ¥13,390,000 (Direct Cost: ¥10,300,000、Indirect Cost: ¥3,090,000)
• Keywords: ヒドリドシリカ / 多孔体 / ナノ粒子 / 還元反応 / モノリス担体 / 触媒反応 / 階層的多孔構造 / 触媒 / 粒径分布 / 流通反応 / モノリス / 合金ナノ粒子 / カップリング反応

Outline of Final Research Achievements

Hydrolysis/polycondensation of trialkoxysilanes was carefully conducted to preserve Si-H ligands followed by the sol-gel transition accompanied by phase separation, which lead to the formation of hierarchically macro/meso-porous hydridosilica monoliths. By introducing noble metals solutions with optimized solvent composition into the hydridosilica monoliths, metal/alloy nanoparticles were formed in a controlled manner. The catalytic performance was evaluated using the monolithic flow-through reactors with embedded metal/alloy nanoparticles as catalysts. Dehydrogenation catalyzed by borane catalyst was also explored to modify silica supports with well-defined pore structure with polymeric reagents bearing Si-H groups. The metal/alloy nanoparticles were produced on the surface of silica support of which catalytic performance was examined in detail.

Research Products

• [Int'l Joint Research] Rutgers University(米国)
• [Int'l Joint Research] University of Montpellier 2(France)
• [Int'l Joint Research] Rutgars University(米国)
• [Int'l Joint Research] University of Montpellier II(France)
• [Journal Article] Grafted Polymethylhydrosiloxane on Hierarchically Porous Silica Monoliths: A New Path to Monolith Supported Palladium Nanoparticles for Continuous Flow Catalysis Applications (2017)
  • Author(s): Carl-Hugo Pelisson, Takahiro Nakanishi, Yang Zhu, Kei Morisato, Toshiyuki Kamei, Ayaka Maeno, Hironori Kaji, Shunki Muroyama, Masamoto Tafu, Kazuyoshi Kanamori, Toyoshi Shimada, Kazuki Nakanishi
  • Journal Title: ACS Applied Materials and Interfaces Volume: 9 Pages: 406-412
  • DOI: 10.1021/acsami.6b12653
  • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
• [Journal Article] Amine/hydrido Bifunctional Nanoporous Silica with Small Metal Nanoparticles Made Onsite: Efficient Dehydrogentaion Catalyst (2017)
  • Author(s): Yang Zhu, Takahiro Nakanishi, Kazuyoshi Kanamori, Kazuki Nakanishi*, Shun Ichii, Kohji Iwaida, Yu Masui, Toshiyuki Kamei, Toyoshi Shimada, Akihito Kumamoto, Yumi H. Ikuhara, Mina Jeon, George Hasegawa, Masamoto Tafu, Chang W. Yoon, Tewodros Asefa
  • Journal Title: ACS Applied Materials and Interfaces Volume: 9 Pages: 36-41
  • DOI: 10.1021/acsami.6b12972
  • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
• [Journal Article] Monolithic Acidic Catalysts for the Dehydration of Xylose into Furfural (2016)
  • Author(s): Yang Zhu, Kazuyoshi Kanamori, Brun Nicolas, Pelisson Carl-Hugo, Moitra Nirmalya, Fajula Francois, Hulea Vasile, Galarneau Anne, Kazuyuki Takeda, Kazuki Nakanishi
  • Journal Title: Catalysis Communications Volume: 87 Pages: 112-115
  • DOI: 10.1016/j.catcom.2016.09.014
  • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
• [Journal Article] Metal Zirconium Phosphate Macroporous Monoliths: Versatile Synthesis, Thermal Expansion and Mechanical Properties (2016)
  • Author(s): Yang Zhu, Kazuyoshi Kanamori, Nirmalya Moitra, Kohei Kadono, Shugo Ohi, Norimasa Shimobayashi, Kazuki Nakanishi
  • Journal Title: Microporous and Mesoporous Materials Volume: 225 Pages: 122-127
  • DOI: 10.1016/j.micromeso.2015.12.002
  • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
• [Journal Article] Hierarchically Porous Titanium Phosphate Monoliths and Their Crystallization Behavior in Ethylene Glycol (2016)
  • Author(s): Yang Zhu, Koji Yoneda, Kazuyoshi Kanamori, Kazuyuki Takeda, Tsutomu Kiyomura, Hiroki Kurata, Kazuki Nakanishi
  • Journal Title: New Journal of Chemistry Volume: - Pages: 4153-4159
  • DOI: 10.1039/c5nj02820e
  • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
• [Journal Article] HPLC separation of unsaturated organic compounds by Ag nanoparticles embedded monolithic silica column (2015)
  • Author(s): Yang ZHU, Kei MORISATO, George HASEGAWA, Nirmalya MOITRA, Tsutomu KIYOMURA, Hiroki KURATA, Kazuyoshi KANAMORI, Kazuki NAKANISHI
  • Journal Title: Journal of Separation Science Volume: 38 Pages: 2841-2847
  • DOI: 10.1002/jssc.201500444
  • Peer Reviewed
• [Journal Article] Direct preparation and conversion of copper hydroxide-based monolithic xerogels with hierarchical pores (2015)
  • Author(s): Shotaro FUKUMOTO, Kazuki NAKANISHI*, Kazuyoshi KANAMORI
  • Journal Title: New Journal of Chemistry Volume: 39 Pages: 6771-6777
  • DOI: 10.1039/c5nj00479a
  • NAID: 120005676687
  • Peer Reviewed
• [Journal Article] Mechanically stable, hierarchically porous Cu3(btc)2 (HKUST-1) monoliths via direct conversion of copper(II) hydroxide-based monoliths. (2015)
  • Author(s): Moitra, N.; Fukumoto, S.; Reboul, J.; Sumida, K.; Zhu, Y.; Nakanishi, K.; Furukawa, S.; Kitagawa, S.; Kanamori, K.
  • Journal Title: Chemical Communications Volume: 51 Pages: 3511-3514
  • DOI: 10.1039/c4cc09694k
  • NAID: 120005555506
  • Peer Reviewed / Open Access
• [Journal Article] Synthesis of robust hierarchically porous zirconium phosphate monolith for efficient ion adsorption. (2015)
  • Author(s): Zhu, Y.; Shimizu, T.; Kitashima, T.; Morisato, K.; Moitra, N.; Brun, N.; Kanamori, K.; Takeda, K.; Tafu, M.; Nakanishi, K.
  • Journal Title: New Journal of Chemistry Volume: 39 Pages: 2444-2450
  • DOI: 10.1039/c4nj01749h
  • Peer Reviewed
• [Journal Article] Reduction on reactive pore surfaces as a practical approach to supported metal alloy nanoparticles. (2014)
  • Author(s): Moitra, N.; Kanamori, K.; Ikuhara, Y. H., Gao, X.; Hasegawa, G.; Takeda, K.; Zhu, Y.; Shimada, T.; Nakanishi, K.
  • Journal Title: Journal of Materials Chemistry A Volume: 2 Pages: 12535-12544
  • DOI: 10.1039/c4ta01767f
  • Peer Reviewed
• [Journal Article] Surface functionalization of silica by Si-H activation of hydrosilanes. (2014)
  • Author(s): Moitra, N.; Ichii, S.; Kamei, T.; Kanamori, K.; Zhu, Y.; Takeda, K.; Nakanishi, K.; Shimada, T.
  • Journal Title: Journal of American Chemical Society Volume: 136 Pages: 11570-11573
  • DOI: 10.1021/ja504115d
  • Peer Reviewed
• [Journal Article] A new hierarchically porous Pd@HSQ monolithic catalyst for Mizoroki–Heck cross-coupling reactions (2014)
  • Author(s): N. Moitra, A. Matsushima, T. Kamei, K. Kanamori, Y. H. Ikuhara, X. Gao, K. Takeda, Y.Zhu, K. Nakanishi and T. Shimada
  • Journal Title: New Journal of Chemistry Volume: 38 Pages: 1144-1149
  • DOI: 10.1039/c3nj01433a
  • NAID: 120005595823
  • Peer Reviewed
• [Presentation] Preparation of hierarchically porous vanadium phosphate monolith (2016)
  • Author(s): Ayumu TANAKA*, Yang ZHU, Kazuyoshi KANAMORI, Kazuki NAKANISHI
  • Organizer: 6th International Congress on Ceramics
  • Place of Presentation: Dresden, Germany
  • Year and Date: 2016-08-21
  • Int'l Joint Research
• [Presentation] Preparation of macroporous manganese oxide monolith from manganese salt via epoxide-mediated sol-gel route (2016)
  • Author(s): Keisuke MATSUURA*, Yang ZHU, Kazuyoshi KANAMORI, Kazuki NAKANISHI
  • Organizer: 6th International Congress on Ceramics
  • Place of Presentation: Dresden, Germany
  • Year and Date: 2016-08-21
  • Int'l Joint Research
• [Presentation] Monolithic porous media for separations - and beyond (2016)
  • Author(s): Kazuki NAKANISHI
  • Organizer: 44th International Symposium on High Performance Liquid Phase Separations and Related Techniques
  • Place of Presentation: San Francisco, California, USA
  • Year and Date: 2016-06-20
  • Int'l Joint Research / Invited
• [Presentation] Metal zirconium phosphate macroporous monoliths: versatile synthesis, thermal expansion and mechanical properties (2016)
  • Author(s): Yang ZHU*, Kazuyoshi KANAMORI, Kazuki NAKANISHI
  • Organizer: 13th International Conference on Ceramic Processing Science
  • Place of Presentation: Nara, Japan
  • Year and Date: 2016-05-08
  • Int'l Joint Research
• [Presentation] Surface-functionalized hierarchically porous oxide monoliths for separation media, catalyst supports and flow-through reactors (2016)
  • Author(s): Kazuki NAKANISHI*, Carl-Hugo PELISSON, Takahiro NAKANISHI, Yang ZHU, Nirmalya MOITRA, Kazuyoshi KANAMORI, Toyoshi SHIMADA
  • Organizer: 13th International Conference on Ceramic Processing Science
  • Place of Presentation: Nara, Japan
  • Year and Date: 2016-05-08
  • Int'l Joint Research / Invited
• [Presentation] Sol-gel synthesis of porous monolithic phosphate materials (2015)
  • Author(s): Yang ZHU*, Koji YONEDA, Ayumu TANAKA, Kazuyoshi KANAMORI, Kazuki NAKANISHI
  • Organizer: XVIII International Sol-Gel Conference
  • Place of Presentation: 京都府京都市
  • Year and Date: 2015-09-06
  • Int'l Joint Research
• [Presentation] Preparation and pore structure control of macroporous SnO2 gel (2015)
  • Author(s): Yoshinao SUZUKI*, Nirmalya MOITRA, Yang ZHU, Kazuyoshi KANAMORI, Kazuki NAKANISHI
  • Organizer: XVIII International Sol-Gel Conference
  • Place of Presentation: 京都府京都市
  • Year and Date: 2015-09-06
  • Int'l Joint Research
• [Presentation] Synthesis of hierarchically macro/mesoporous titanium phosphate monolithic gels (2015)
  • Author(s): Koji YONEDA*, Yang ZHU, Kazuyoshi KANAMORI, Kazuki NAKANISHI
  • Organizer: XVIII International Sol-Gel Conference
  • Place of Presentation: 京都府京都市
  • Year and Date: 2015-09-06
  • Int'l Joint Research
• [Presentation] Surface modification of mesoporous silica with bifunctional hydrosilanes and formation of metal nanoparticles (2015)
  • Author(s): Takahiro NAKANISHI*, Nirmalya MOITRA, Kazuyoshi KANAMORI, Kazuki NAKANISHI, Tewodros ASEFA, Shun ICHII, Toyoshi SHIMADA
  • Organizer: XVIII International Sol-Gel Conference
  • Place of Presentation: 京都府京都市
  • Year and Date: 2015-09-06
  • Int'l Joint Research
• [Presentation] Preparation of hierarchically porous vanadium phosphate monolith with controlled pore parameters (2015)
  • Author(s): Ayumu TANAKA*, Yang ZHU, Kazuyoshi KANAMORI, Kazuki NAKANISHI
  • Organizer: XVIII International Sol-Gel Conference
  • Place of Presentation: 京都府京都市
  • Year and Date: 2015-09-06
  • Int'l Joint Research
• [Presentation] Preparation of macroporous manganese oxide monolith from manganese salt via epoxide-mediated sol-gel route (2015)
  • Author(s): Keisuke MATSUURA*, Yang ZHU, Kazuyoshi KANAMORI, Kazuki NAKANISHI
  • Organizer: XVIII International Sol-Gel Conference
  • Place of Presentation: 京都府京都市
  • Year and Date: 2015-09-06
  • Int'l Joint Research
• [Presentation] 柔軟性を示す多孔体：無機化学からのアプローチ (2015)
  • Author(s): 金森主祥
  • Organizer: 高分子加工技術研究会第83回例会
  • Place of Presentation: 京都府京都市
  • Year and Date: 2015-06-23
  • Invited
• [Presentation] Silicon-based hybrid microporous monoliths for heat-insulation, separation media and supported metal/alloy nanoparticles (2015)
  • Author(s): Kazuki NAKANISHI*, Kazuyoshi KANAMORI, Gen HAYASE, Nirmalya MOITRA
  • Organizer: 2015 MRS Spring Meeting & Exhibit
  • Place of Presentation: San Francisco, CA, USA
  • Year and Date: 2015-04-06
  • Int'l Joint Research / Invited
• [Presentation] Reduction on Reactive Pore Surface as a Versatile Approach to Monolith-Supported Metal Alloy Nanoparticles (2014)
  • Author(s): Kazuki NAKANISHI
  • Organizer: IUMRS-ICA 2014
  • Place of Presentation: 福岡大学（福岡県）
  • Year and Date: 2014-08-24 – 2014-08-30
• [Presentation] Functional porous silsesquioxane monolithic materials from organotrialkoxysilane-derived sol-gel systems (2014)
  • Author(s): Kazuyoshi KANAMORI, Nirmalya MOITRA, Gen HAYASE, Taiyo SHIMIZU, Kazuki NAKANISHI
  • Organizer: Nanoporous Materials - 7 (NANO-7, )
  • Place of Presentation: Niagara Falls, （カナダ）
  • Year and Date: 2014-06-22 – 2014-06-25
• [Presentation] Silicon-based hybrid macroporous monolith for heat insulation, separation media and supported metal nanoparticles (2014)
  • Author(s): Kazuki Nakanishi
  • Organizer: 6th Monolith Summer School & Symposium (MSS2014)
  • Place of Presentation: ポルトロージュ（スロベニア）
  • Year and Date: 2014-05-30 – 2014-06-04
  • Invited
• [Presentation] Porous silsesquioxane materials from organotrialkoxysilanes (2014)
  • Author(s): Kazuyoshi KANAMORI
  • Organizer: 2014 MRS Spring Meeting & Exhibit
  • Place of Presentation: サンフランシスコ（米国）
  • Year and Date: 2014-04-22 – 2014-04-25
  • Invited
• [Book] ナノ材料解析の実際 (2016)
  • Author(s): 中西和樹・金森主祥
  • Total Pages: 338
  • Publisher: 講談社