Rolling two-dimensional covalent organic framework (COF) sheets into one-dimensional electronic and proton-conductive nanotubes
Abstract
Mimicking the interconvertible carbon allotropes of 2-dimensional (2D) graphene and 1-dimensional (1D) carbon nanotubes (CNTs), herein we report the in situ transformation of 2D π-conjugated covalent organic frameworks (COFs) sheet into 1D nanotubular structures via self-assembly the sheets at solvent interfaces. The facile “roll-sheets” self-assembly resulted in coaxial nanotubes with uniform cross-sectional diameter, which was realized for diazapyrene-based COFs but not for the corresponding pyrene COF, although both possess similar chemical structures. Upon replacing the carbon atoms at 2,7-positions of pyrene with nitrogen, contrasting optical and electronic properties were realized, reflecting the rolled structure of the conjugated 2D sheets. The nanotubes exhibited concerted electronic- and proton-conducting nature with stable conducting pathways at ambient conditions. The nitrogen centers act simultaneously as the site for charge carrier doping and proton acceptors, as evidenced by the high photo- and electrical conductivity, as well as the record proton conductivity (σ = 1.98 S cm −1 ) results. The present diazapyrene-based 1D nanotubular COF serves as a unique materials platform with electronic conduction in the wall and proton conduction in the core, respectively.
Article Details
Journal Info
Proceedings of the National Academy of Sciences
National Academy of Sciences
Authors (21)
Zhuowei Li
Department of Molecular Engineering, Kyoto University
Rajendra Prasad Paitandi
Department of Molecular Engineering, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto 615-8510, Japan
Yusuke Tsutsui
Department of Molecular Engineering, Graduate School of Engineering, Kyoto University, Kyotodaigakukatsura, Nishikyo-ku, Kyoto 615-8510, Japan
Wakana Matsuda
Department of Molecular Engineering, Kyoto University
Masaki Nobuoka
Department of Molecular Engineering, Kyoto University
Bin Chen
Samrat Ghosh
Department of Molecular Engineering, Kyoto University
Takayuki Tanaka
Department of Molecular Engineering, Graduate School of Engineering, Kyoto University, Kyotodaigakukatsura, Nishikyo-ku, Kyoto 615-8510, Japan
Masayuki Suda
Department of Molecular Engineering, Kyoto University
Tong Zhu
Hiroshi Kageyama
Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto 615-8510, Japan
Yoshihiro Miyake
Department of Molecular and Macromolecular Chemistry, Nagoya University
Hiroshi Shinokubo
Department of Molecular and Macromolecular Chemistry, Graduate School of Engineering
Makito Takagi
Graduate School of Nanobio Science, Yokohama City University
Tomomi Shimazaki
Graduate School of Nanobio Science, Yokohama City University
Masanori Tachikawa
Graduate School of Nanobio Science, Yokohama City University
Katsuaki Suzuki
Institute for Chemical Research, Kyoto University
Hironori Kaji
Institute for Chemical Research
Yasunobu Ando
Laboratory for Chemistry and Life Science, Institute of Integrated Research, Institute of Science Tokyo, 4259 Nagatsuta-cho, Midori-ku, Yokohama, Kanagawa 226-8503, Japan
Takahiro Ezaki
Research Center for Advanced Science and Technology, The University of Tokyo
Shu Seki
Department of Molecular Engineering, Graduate School of Engineering