TY - JOUR
T1 - Synthesis of ordered carbonaceous frameworks from organic crystals
AU - Nishihara, Hirotomo
AU - Hirota, Tetsuya
AU - Matsuura, Kenta
AU - Ohwada, Mao
AU - Hoshino, Norihisa
AU - Akutagawa, Tomoyuki
AU - Higuchi, Takeshi
AU - Jinnai, Hiroshi
AU - Koseki, Yoshitaka
AU - Kasai, Hitoshi
AU - Matsuo, Yoshiaki
AU - Maruyama, Jun
AU - Hayasaka, Yuichiro
AU - Konaka, Hisashi
AU - Yamada, Yasuhiro
AU - Yamaguchi, Shingi
AU - Kamiya, Kazuhide
AU - Kamimura, Takuya
AU - Nobukuni, Hirofumi
AU - Tani, Fumito
N1 - Funding Information:
This work was supported by PRESTO, JST; JSPS KAKENHI Grant Number 15KK0196; the Dynamic Alliance for Open Innovation Bridging Human, Environment and Materials; and the Network Joint Research Centre for Materials and Devices. The PXRD and XAFS measurements were performed in SPring-8 (Proposals no. 2015A1956, 2015A1666, and 2016A1750).
Publisher Copyright:
© 2017 The Author(s).
PY - 2017/12/1
Y1 - 2017/12/1
N2 - 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-CPDPy). This dimer comprises two Ni-porphyrins linked by two butadiyne (diacetylene) moieties through phenyl groups. The Ni2-CPDPy 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.
AB - 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-CPDPy). This dimer comprises two Ni-porphyrins linked by two butadiyne (diacetylene) moieties through phenyl groups. The Ni2-CPDPy 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.
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U2 - 10.1038/s41467-017-00152-z
DO - 10.1038/s41467-017-00152-z
M3 - Article
C2 - 28740078
AN - SCOPUS:85023190120
SN - 2041-1723
VL - 8
JO - Nature Communications
JF - Nature Communications
IS - 1
M1 - 109
ER -