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大学・研究所にある論文を検索できる 「Framework Compounds grown on Copper Hydroxides Nano-assemblies: Controlled Orientation and Multi-layered Structure toward Enhanced functionality」の論文概要。リケラボ論文検索は、全国の大学リポジトリにある学位論文・教授論文を一括検索できる論文検索サービスです。

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Framework Compounds grown on Copper Hydroxides Nano-assemblies: Controlled Orientation and Multi-layered Structure toward Enhanced functionality

生垣 賢 大阪府立大学 DOI:info:doi/10.24729/00017360

2021.04.21

概要

Metal-organic frameworks (MOFs), also called porous coordination polymers (PCPs),
are one of the most attractive microporous materials due to their ultra-high-specific
surface area, tunable nano-architectures, and chemical functionalities. These properties
make them promising materials for the applications, such as gas separation and storage1315
. MOFs are also expected for potential applications as sensors, microelectronics, and
transistors by a chemical functionalization of the micropores16-18. Positioning MOF
crystals and controlling an orientation of micropores allow to utilize unique
functionalities of the crystals for realistic device applications. For example, improved
electrical and optical properties are expected by accommodating electroconductive or
luminescent molecules in the pores of oriented MOFs19. Several approaches for
controlling the location and the orientation of MOF crystals on substrates have been
reported so far20-21. However, further improvements in the precise control of the location
of MOF crystals and alignment of pores along out-of-plane and in-plane directions on the
substrate are strongly required for achieving highly functional MOF-based devices. The
present contribution reviews our recent progress on the fabrication of MOF crystals
positioned at designated locations (MOF patterns) and with preferred crystallographic
orientation (oriented MOF) on various substrates. Assemblies of copper hydroxide were
employed as scaffolds and Cu(II) source for the MOF synthesis, which enable us to
prepare MOF patterns and oriented MOF thin films (Figure 1.1). ...

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参考文献

1. P. Falcalo, K. Okada, T. Hara, K. Ikigaki, Y. Tokudome, A. Thornton, A. J. Hill, T.

Williams, C. Doonan and M. Takahashi, “Centimetre-scale micropore alignment in

oriented polycrystalline metal–organic framework films via heteroepitaxial growth”,

Nature Mater., 16, 342–348 (2017). (Cover page paper, Focus paper of the issue)

DOI: 10.1038/nmat4815

(Not including in this thesis)

2. K. Okada, S. Sawai, K. Ikigaki, Y. Tokudome, P. Falcaro and M. Takahashi,

“Electrochemical sensor and catalyst on Cu3(BTC)2 coating electrode from Cu(OH)2

films”, CrystEngComm, 19, 4194–4200 (2017).

DOI: 10.1039/C7CE00416H.

(Not including in this thesis)

3. (Debate Review) K. Ikigaki, “(1P-070) 基板上で積層した金属有機構造体の配

向性薄膜”, Bull. Jpn. Soc. Coord. Chem., 71, 92–94 (2018).

(Not including in this thesis)

4. K. Ikigaki, K. Okada, Y. Tokudome and M. Takahashi, “Metal-organic framework

thin films from copper hydroxide nano-assemblies”, J Sol-Gel Sci. Technol., 89, 128–

134 (2019).

DOI: 10.1007/s10971-018-4805-9

(Chapter 1)

5. K. Ikigaki, K. Okada, Y. Tokudome, T. Toyao, P. Falcaro, C. J. Doonan, M. Takahashi,

“MOF-on-MOF: Oriented growth of multiple layered thin films of metal-organic

frameworks”, Angew. Chem. Int. Ed., 58, 6886–6890 (2019).

DOI: 10.1002/anie.201901707

(Chapter 2)

6. K. Ikigaki, K. Okada, Y. Tokudome, P. Falcaro, C. Coleman, A. Tarzia, C. J. Doonan,

M. Takahashi, “Oriented growth of Covalent organic framework (COF) crystals on

metal-hydroxides thin film”, MS&T proceedings (2019).

DOI: 10.7449/2019/MST_2019_1329_1330

(Not including in this thesis)

146

7. 生垣賢, 岡田健司, 高橋雅英, “水酸化銅ナノ構造体を前駆体とした多孔性金

属錯体(PCP/MOF)”, J. Jpn. Soc. Powder Metallurgy., 67, 132–139 (2020).

DOI: 10.2497/jjspm.67.132

(Chapter 1)

8. K. Okada, M. Nakanishi, K. Ikigaki, Y. Tokudome, P. Falcaro, C. J. Doonan, M.

Takahashi, “Controlling the alignment of 1D nanochannel arrays in oriented metalorganic framework films for host-guest materials design” Chem. Sci., 11, 8005–8012

(2020).

DOI: 10.1039/D0SC02958K

(Chapter 4)

9. K. Ikigaki, K. Okada, M. Takahashi, “Epitaxial growth of Multi-layered Metalorganic framework thin films (e-MoM): fundamental growth mechanism and

crystallographic orientations” ACS Appl. Nano Mater., (2021) submitted.

(Chapter 3)

10. K. Okada, K. Ikigaki, Y. Miyazaki, Y. Tokuda, N. Tarutani, A. Tarzia, C. N. Coleman,

C. J. Doonan, M. Takahashi, “Edge-on growth of oriented covalent organic

frameworks along“molecular guidelines” on surface of copper hydroxide” J. Am.

Chem. Soc., (2021) to be submitted.

(Chapter 5)

147

Acknowledgement

The present thesis has been carried out at Doctoral course, Graduate School of

Engineering, Osaka Prefecture University, under the direction of Professor Masahide

Takahashi and Professor Kenji Okada.

First of all, the author wishes to express his sincere gratitude to Professor

Masahide Takahashi for his continuous encouragement and valuable advice all through

the duration of the present work. The author is also greatly indebted to Professor Kenji

Okada for his critical discussion, experimental directions, and sincere supports in

proceeding with present study.

The author would like to thank Prof. Yasuaki Tokudome and Dr. Arisa Fukatsu

for useful advice on synthesizing and characterizing MOF/COF thin films, and Dr.

Hiroshi Tsuda for support on TEM measurements.

The author really appreciates Dr. Naoki Tarutani (Hiroshima University), Dr.

Kazumasa Suzuki (Shiga Prefecture University), Dr. Takashi Toyao (Hokkaido

University) and Dr. Bettina Baumgartner (JSPS postdoctoral researcher) for providing an

opportunity and supporting collaborative work in Japan, giving a significantly valuable

discussion and cooperation in investigation on TEM, XPS and FT-IR analyses.

The author is grateful to Prof. Christian Doonan (The University of Adelaide in

Australia) and Prof. Paolo Falcaro (Graz University of Technology in Austria) for

providing him precious study opportunity about experimental ways in international

laboratory, encouragement and valuable cooperation in present study. Valuable

suggestions and supports from Dr. Raffaele Ricco (Graz University of Technology), Prof.

Rie Makiura (Osaka Prefecture University) are gratefully acknowledged.

Hearty thanks are made to all students of Takahashi’s Lab. for their daily

collaboration, discussions and everyday activities.

The author is grateful to grand-in-aids from the Ministry of Education, Culture,

Sports, Science and Technology (MEXT), administrated by JSPS for the financial support

(Research Fellowship for Young Scientists: DC1).

Finally, the author expresses his sincere gratitude to his parents, Hisanobu Ikigaki and

Michiko Ikigaki, for their understanding his decision, supporting his life, encouragement

and sacrifice.

Osaka, Winter 2020

148

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