Synthesis of ordered carbonaceous frameworks from organic crystals

Hirotomo Nishihara; Tetsuya Hirota; Kenta Matsuura; Mao Ohwada; Norihisa Hoshino; Tomoyuki Akutagawa; Takeshi Higuchi; Hiroshi Jinnai; Yoshitaka Koseki; Hitoshi Kasai; Yoshiaki Matsuo; Jun Maruyama; Yuichiro Hayasaka; Hisashi Konaka; Yasuhiro Yamada; Shingi Yamaguchi; Kazuhide Kamiya; Takuya Kamimura; Hirofumi Nobukuni; Fumito Tani

doi:10.1038/s41467-017-00152-z

Synthesis of ordered carbonaceous frameworks from organic crystals

Nat Commun. 2017 Jul 24;8(1):109. doi: 10.1038/s41467-017-00152-z.

Authors

Hirotomo Nishihara^{1

2}, Tetsuya Hirota³, Kenta Matsuura³, Mao Ohwada³, Norihisa Hoshino³, Tomoyuki Akutagawa³, Takeshi Higuchi³, Hiroshi Jinnai³, Yoshitaka Koseki³, Hitoshi Kasai³, Yoshiaki Matsuo⁴, Jun Maruyama⁵, Yuichiro Hayasaka⁶, Hisashi Konaka⁷, Yasuhiro Yamada⁸, Shingi Yamaguchi⁹, Kazuhide Kamiya^{10

11}, Takuya Kamimura¹², Hirofumi Nobukuni¹², Fumito Tani¹³

Affiliations

¹ Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, 2-1-1 Katahira, Aoba, Sendai, 980-8577, Japan. hirotomo.nishihara.b1@tohoku.ac.jp.
² PRESTO, the Japan Science and Technology Agency (JST), 4-1-8 Honcho, Kawaguchi, 332-0012, Japan. hirotomo.nishihara.b1@tohoku.ac.jp.
³ Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, 2-1-1 Katahira, Aoba, Sendai, 980-8577, Japan.
⁴ Department of Materials Science and Chemistry, Graduate School of Engineering, University of Hyogo, 2167 Shosha Himeji, Hyogo, 671-2280, Japan.
⁵ Research Division of Environmental Technology, Osaka Research Institute of Industrial Science and Technology, 1-6-50, Morinomiya, Joto-ku, Osaka, 536-8553, Japan.
⁶ The Electron Microscopy Centre, Tohoku University, 2-1-1 Katahira, Aoba, Sendai, 980-8577, Japan.
⁷ Application & Software Development Department, X-ray Instrument Divistion, Rigaku Corporation, 3-9-12 Matsubara-cho, Akishima-shi, Tokyo, 196-8666, Japan.
⁸ Graduate School of Engineering, Chiba University, 1-33 Yayoi, Inage, Chiba, 263-8522, Japan.
⁹ Department of Applied Chemistry, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 113-8656, Japan.
¹⁰ PRESTO, the Japan Science and Technology Agency (JST), 4-1-8 Honcho, Kawaguchi, 332-0012, Japan.
¹¹ Research Center for Solar Energy Chemistry, Osaka University, 1-3 Machikaneyama, Toyonaka, Osaka, 560-8531, Japan.
¹² Institute for Materials Chemistry and Engineering, Kyushu University, 744 Motooka, Nishi-ku, Fukuoka, 819-0395, Japan.
¹³ Institute for Materials Chemistry and Engineering, Kyushu University, 744 Motooka, Nishi-ku, Fukuoka, 819-0395, Japan. tanif@ms.ifoc.kyushu-u.ac.jp.

Abstract

Despite recent advances in the carbonization of organic crystalline solids like metal-organic frameworks or supramolecular frameworks, it has been challenging to convert crystalline organic solids into ordered carbonaceous frameworks. Herein, we report a route to attaining such ordered frameworks via the carbonization of an organic crystal of a Ni-containing cyclic porphyrin dimer (Ni₂-CPD_Py). This dimer comprises two Ni-porphyrins linked by two butadiyne (diacetylene) moieties through phenyl groups. The Ni₂-CPD_Py crystal is thermally converted into a crystalline covalent-organic framework at 581 K and is further converted into ordered carbonaceous frameworks equipped with electrical conductivity by subsequent carbonization at 873-1073 K. In addition, the porphyrin's Ni-N₄ unit is also well retained and embedded in the final framework. The resulting ordered carbonaceous frameworks exhibit an intermediate structure, between organic-based frameworks and carbon materials, with advantageous electrocatalysis. This principle enables the chemical molecular-level structural design of three-dimensional carbonaceous frameworks.Carbon-based materials are promising alternatives to noble metal catalysts, but their structures are typically disordered and difficult to control. Here, the authors obtain ordered carbonaceous frameworks with advantageous electrocatalytic properties via the carbonization of nickel-containing porphyrin dimer networks.

Publication types

Research Support, Non-U.S. Gov't