Establishment of universal design and synthesis method of functional zeolite by interzeolite conversion using a dual-template method

• Project/Area Number: 16H04218
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Inorganic industrial materials
• Research Institution: Hiroshima University
• Principal Investigator: Sano Tsuneji 広島大学, 工学研究科, 教授 (80251974)
• Co-Investigator(Kenkyū-buntansha): 定金 正洋 広島大学, 工学研究科, 准教授 (10342792) ; 津野地 直 広島大学, 工学研究科, 助教 (40758166)
• Project Period (FY): 2016-04-01 – 2019-03-31
• Project Status: Completed (Fiscal Year 2018)
• Budget Amount: ¥16,770,000 (Direct Cost: ¥12,900,000、Indirect Cost: ¥3,870,000); Fiscal Year 2018: ¥2,080,000 (Direct Cost: ¥1,600,000、Indirect Cost: ¥480,000); Fiscal Year 2017: ¥3,380,000 (Direct Cost: ¥2,600,000、Indirect Cost: ¥780,000); Fiscal Year 2016: ¥11,310,000 (Direct Cost: ¥8,700,000、Indirect Cost: ¥2,610,000)
• Keywords: ゼオライト / 水熱転換 / 有機構造規定剤 / アンモニウムカチオン / ホスホニウムカチオン / NH3-SCR / 水熱合成 / 混合テンプレート / 多孔体

Outline of Final Research Achievements

We investigated syntheses of small-pore zeoliets such as CHA, AEI and AFX by a mixture of FAU zeolite with high Si/Al ratio and Al source as starting materials. It was found from ESI-MS analysis that a rapid decompsotion of high silica FAU zeolite occurred, giving locally ordered aluminosilicate speceoes (nanoparts) that assembel and evolve into another type of zeolite. Phosphorus-modified small-pore zeolites (CHA, AEI, and LEV) were also prepared by hydrothermal conversion of FAU zeolites with a mixture of an N-OSDA and P-OSDA. These P-modified zeolites exhibit a good catalytic activity and durability in the NH3-SCR process.

Academic Significance and Societal Importance of the Research Achievements

機能性材料ゼオライトを触媒として利用していく際の最大の課題は、構造・組成の安定性に影響する脱アルミニウムをいかに抑制できるかである。deNOx触媒として期待されている小細孔CHA及びAEIゼオライトにおいてホスホニウムカチオンをOSDA及びリン修飾剤とする合成法により、実用化の点からまだ十分と言えるレベルではないが、耐熱/耐水熱安定性を向上できることを明らかにした。ゼオライト合成に関する研究は世界で活発に行われ、筆者らのゼオライト水熱転換法を含む合成技術に関する新たな発見が続いており、高耐久性ゼオライトの設計・合成が近い将来可能になると期待している。

Research Products

• [Journal Article] Zeolite hydrothermal conversion in the presence of various cyclicalkylammonium cations and synthesis of nanosized BEA and MFI zeolites (2019)
  • Author(s): T. Tanigawa, N. Tsunoji, M. Sadakane, T. Sano
  • Journal Title: Microporous Mesoporous Mater. Volume: 277 Pages: 115-123
  • DOI: 10.1016/j.micromeso.2018.10.019
  • Peer Reviewed
• [Journal Article] Comparative study between high-silica faujasites (FAU) from organic-free system and the commercial zeolite Y (2019)
  • Author(s): S. Ferdov, K. Tsuchiya, N. Tsunoji, T. Sano
  • Journal Title: Microporous Mesoporous Mater. Volume: 276 Pages: 154-159
  • DOI: 10.1016/j.micromeso.2018.09.036
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Facile synthesis of highly crystalline EMT zeolite by hydrothermal conversion of FAU zeolite in the presence of 1,1'-(1,4-butanediyl)bis (1-azonia-4-azabicyclo[2,2,2]octane)dihydroxide (2019)
  • Author(s): K. Matsuda, K. Tsuchiya, N. Tsunoji, M. Sadakane, T. Sano
  • Journal Title: Microporous Mesoporous Mater. Volume: 274 Pages: 299-303
  • DOI: 10.1016/j.micromeso.2018.08.036
  • Peer Reviewed
• [Journal Article] Stepwise gel preparation for high-quality CHA zeolite synthesis: A common tool for synthesis diversification (2018)
  • Author(s): Y. Joich, D. Shimono, N. Tsunoji, Y. Takamitsu, M. Sadakane, T. Sano
  • Journal Title: Cryst. Growth Des. Volume: 18 Issue: 9 Pages: 5652-5662
  • DOI: 10.1021/acs.cgd.8b00963
  • Peer Reviewed
• [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] リン修飾小細孔ゼオライトの合成とNH3-SCR 触媒特性 (2018)
  • Author(s): 津野地直、佐野庸治
  • Journal Title: ゼオライト Volume: 35 Pages: 92-100
  • Peer Reviewed
• [Journal Article] 進化するゼオライト合成 (2018)
  • Author(s): 佐野庸治、津野地直
  • Journal Title: 触媒 Volume: 60 Pages: 240-246
  • Peer Reviewed
• [Journal Article] An isomorphously substituted Fe-BEA zeolite with high Fe content: facile synthesis and characterization (2018)
  • Author(s): Y. Naraki, K. Ariga, H. Oka, H. Kurashige, T. Sano
  • Journal Title: J. Nanosci. Nanotechnol. Volume: 18 Pages: 11-19
  • Peer Reviewed
• [Journal Article] A Collective Case Screening of the Zeolites made in Japan for High Performance NH3-SCR of NOx (2018)
  • Author(s): V. Subramaniam, T. Onishi, Y. Shimada, Y. Kubota, T. Masuda, Y. Nakasaka, M. Matsukata, K. Itabashi, T. Okubo, T. Sano, N. Tsunoji, T. Yokoi, M. Ogura
  • Journal Title: Bull. Chem. Soc. Jpn. Volume: 91 Issue: 3 Pages: 355-361
  • DOI: 10.1246/bcsj.20170352
  • NAID: 130006507116
  • Peer Reviewed
• [Journal Article] Incorporation of various heterometal atoms in CHA zeolites by hydrothermal conversion of FAU zeolite and their performance for selective catalytic reduction of NOx with ammonia (2017)
  • Author(s): Tomoka Takata, Nao Tsunoji, Yasuyuki Takamitsu, Masahiro Sadakane, and Tsuneji Sano
  • Journal Title: Microporous Mesoporous Mater. Volume: 246 Pages: 89-101
  • DOI: 10.1016/j.micromeso.2017.03.018
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Mesoporous MCM-48 immobilized with aminopropyltriethoxysilane: a potential catalyst for transesterification of triacetin (2017)
  • Author(s): Mahuya Bandyopadhyay, Nao Tsunoji, Tsuneji Sano
  • Journal Title: Catal. Lett. Volume: 147 Issue: 4 Pages: 1040-1050
  • DOI: 10.1007/s10562-017-1997-5
  • Peer Reviewed / Open Access / Int'l Joint Research / Acknowledgement Compliant
• [Journal Article] ZTS-1 and ZTS-2: Novel intergrowth zeolites with AFX/CHA structure (2017)
  • Author(s): Y. Naraki, K. Ariga, K. Nakamura, K. Okushita, T. Sano
  • Journal Title: Microporous Mesoporous Mater. Volume: 254 Pages: 160-169
  • DOI: 10.1016/j.micromeso.2017.04.004
  • Peer Reviewed
• [Journal Article] Synthesis of phosphorus-modified small-pore zeolites utilizing tetraalkyl phosphonium cations as both structure-directing and phosphorous modification agents (2016)
  • Author(s): Y. Yamasaki, N. Tsunoji, Y. Takamitsu, M. Sadakane, T. Sano
  • Journal Title: Microporous Mesoporous Mater. Volume: 223 Pages: 129-139
  • DOI: 10.1016/j.micromeso.2015.10.038
  • Peer Reviewed
• [Journal Article] One-pot Synthesis of Phosphorus-modified AEI Zeolites Derived by the Dual-template Method as a Durable Catalyst with Enhanced Thermal/Hydrothermal Stability for Selective Catalytic Reduction of NO<i>_x</i> by NH₃ (2016)
  • Author(s): Y. Kakiuchi, Y. Yamasaki, N. Tsunoji, Y. Takamitsu, M. Sadakane, T. Sano
  • Journal Title: Chemistry Letters Volume: 45 Issue: 2 Pages: 122-124
  • DOI: 10.1246/cl.150997
  • NAID: 130005124756
  • ISSN: 0366-7022, 1348-0715
  • Peer Reviewed
• [Journal Article] Nanosized CHA zeolites with high thermal and hydrothermal stability derived from the hydrothermal conversion of FAU zeolite (2016)
  • Author(s): T.Takata, N.Tsunoji, Y.Takamitsu, M.Sadakane, T.Sano
  • Journal Title: Microporous Mesoporous Mater. Volume: 225 Pages: 524-533
  • DOI: 10.1016/j.micromeso.2016.01.045
  • Peer Reviewed
• [Journal Article] Hydrothermal conversion of titanated FAU to AEI zeolite and its enhanced catalytic performance for NOx reduction (2016)
  • Author(s): N.Funase, T.Takata, N.Tsunoji,, Y.Takamitsu, M.Sadakane, T.Sano
  • Journal Title: Adv. Porous Mater. Volume: 4 Issue: 1 Pages: 62-72
  • DOI: 10.1166/apm.2016.1101
  • Peer Reviewed
• [Presentation] テトラエチルホスホニウム存在下でのFAU-GMEゼオライト水熱転換 (2018)
  • Author(s): 三谷絵美・津野地直・定金正洋・佐野庸治
  • Organizer: 第34回ゼオライト研究発表会
• [Presentation] [Dab-4]2+カチオン存在下におけるFAU-EMTゼオライト水熱転換 (2018)
  • Author(s): 大西美冴・松田啓吾・土谷和愛・津野地直・定金正洋・佐野庸治
  • Organizer: 第34回ゼオライト研究発表会
• [Presentation] ゼオライト合成の多様化を目的とした多段階の合成ゲル調製法の開発とCHAゼオライト合成への応用 (2018)
  • Author(s): 津野地直・城一洋子・下野大悟・高光泰之・定金正洋・佐野庸治
  • Organizer: 第34回ゼオライト研究発表会
• [Presentation] 種々なシリカアルミナ源からのAEI型ゼオライトの合成過程の調査とその物性評価 (2018)
  • Author(s): 下野大悟・城一洋子・高光泰之・津野地直・定金正洋・佐野庸治
  • Organizer: 第34回ゼオライト研究発表会
• [Presentation] 混合テンプレート法によるAFX/CHA連晶体の合成と高機能化 (2018)
  • Author(s): 土谷和愛・津野地直・定金正洋・佐野庸治
  • Organizer: 第34回ゼオライト研究発表会
• [Presentation] アモルファス原料とSi/Al比の異なる出発FAUゼオライトを様々に組み合わせたCHAゼオライト合成 (2018)
  • Author(s): 谷川卓也・山崎義貴・津野地直・定金正洋・佐野庸治
  • Organizer: 第34回ゼオライト研究発表会
• [Presentation] 耐久性ゼオライトの合成―脱アルミニウムとの戦いー (2018)
  • Author(s): 佐野庸治
  • Organizer: 第34回ゼオライト研究発表会
  • Invited
• [Presentation] Synthesis of phosphorus-modified AFX zeolite by the dual-template method with tetraethylphosphonium hydroxide as phosphorus modification agent (2018)
  • Author(s): E. Mitani, Y. Yamasaki, N. Tsunoji, M. Sadakane, T. Sano
  • Organizer: ZMPC2018
  • Int'l Joint Research
• [Presentation] Control of Si/Al ratio and crystal size of CHA zeolite by combining dealuminated FAU with different Si/Al ratio and additional Si or Al source (2018)
  • Author(s): T. Tanigawa, Y. Yamasaki, N. Tsunoji, M. Sadakane, T. Sano
  • Organizer: ZMPC2018
  • Int'l Joint Research
• [Presentation] Facile synthesis of highly crystalline EMT zeolite by hydrothermal conversion of FAU zeolite in the presence of 1,1-(1,4-butanediyl) bis(1-azonia-4-azabicyclo[2,2,2]octane) dihydroxide (2018)
  • Author(s): K. Matsuda, K. Tsuchiya, N. Funase, N. Tsunoji, M. Sadakane, T. Sano
  • Organizer: ZMPC2018
  • Int'l Joint Research
• [Presentation] Rational synthesis of small-pore zeolite through multi-step hydrogel preparation; A common technical tool for high-quality zeolite synthesis (2018)
  • Author(s): D. Shimono, Y. Jyoichi, N. Tsunoji, M. Sadakane, T. Sano
  • Organizer: ZMPC2018
  • Int'l Joint Research
• [Presentation] Facile ssynthesis of phosphorus-modified small pore zeolites with tetraalkylphosphonium cations and thei NH3-SCR catalytic performance (2017)
  • Author(s): Y.Kakiuchi, Y.Yamasaki, N.Tsunoji, Y.Takamitsu, M.Sadakane, T.Sano
  • Organizer: 7th International FEZA Conference, Sofia, Bulgaria
  • Int'l Joint Research
• [Presentation] Synthesis and characterization of titanated AEI zeolite by hydrothermal conversion of titanated FAU zeolite (2017)
  • Author(s): N.Funase, N.Tsunoji, Y.Takamitsu, M.Sadakane, T.Sano
  • Organizer: 7th International FEZA Conference, Sofia, Bulgaria
  • Int'l Joint Research
• [Presentation] Nanosized CHA zeolite with high thermal/hydrothermal stability derived from hydrothermal conversion of FAU zeolite (2016)
  • Author(s): T.Takata N.Tsunoji, Y.Takamitsu, M.Sadakane, T.Sano
  • Organizer: 18th International Zeolite Conference
  • Place of Presentation: Rio de Janeiro, Brazil
  • Year and Date: 2016-06-19
  • Int'l Joint Research
• [Presentation] Highly active and selective Ti-incorporated porous silica catalysts derived from grafting of titanium(IV) acetylacetone (2016)
  • Author(s): N.Tsunoji, M.Fukuda, Y.Yagenji, M.Sadakane, T.Sano
  • Organizer: 18th International Zeolite Conference
  • Place of Presentation: Rio de Janeiro, Brazil
  • Year and Date: 2016-06-19
  • Int'l Joint Research
• [Presentation] Synthesis of phosphorus-modified small-pore zeolites utilizing tetraalkyl phosphonium cations as both structure-directing and phosphorous modification agents (2016)
  • Author(s): Y.Yamasaki, N.Tsunoji, Y.Takamitsu, M.Sadakane,T.Sano
  • Organizer: 18th International Zeolite Conference
  • Place of Presentation: Rio de Janeiro, Brazil
  • Year and Date: 2016-06-14
  • Int'l Joint Research
• [Book] ナノ空間材料 (2016)
  • Author(s): 津野地直、佐野庸治
  • Total Pages: 999
  • Publisher: エヌ・ティー・エス
• [Book] Encyclopedia of Membranes (2016)
  • Author(s): T.Sano
  • Total Pages: 999
  • Publisher: Springer-Verlag Berlin Heidelberg