Nishihara Hirotomo, Hirota Tetsuya, Matsuura Kenta, Ohwada Mao, Hoshino Norihisa, Akutagawa Tomoyuki, Higuchi Takeshi, Jinnai Hiroshi, Koseki Yoshitaka, Kasai Hitoshi, Matsuo Yoshiaki, Maruyama Jun, Hayasaka Yuichiro, Konaka Hisashi, Yamada Yasuhiro, Yamaguchi Shingi, Kamiya Kazuhide, Kamimura Takuya, Nobukuni Hirofumi, Tani Fumito
Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, 2-1-1 Katahira, Aoba, Sendai, 980-8577, Japan.
PRESTO, the Japan Science and Technology Agency (JST), 4-1-8 Honcho, Kawaguchi, 332-0012, Japan.
Nat Commun. 2017 Jul 24;8(1):109. doi: 10.1038/s41467-017-00152-z.
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 (Ni-CPD). This dimer comprises two Ni-porphyrins linked by two butadiyne (diacetylene) moieties through phenyl groups. The Ni-CPD 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-N 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.
尽管最近在金属有机框架或超分子框架等有机晶体固体的碳化方面取得了进展，但将晶体有机固体转化为有序的碳质框架一直具有挑战性。在此，我们报告了一种通过含镍环状卟啉二聚体（Ni-CPD）的有机晶体碳化来获得这种有序框架的途径。该二聚体由两个镍卟啉通过两个丁二炔（二乙炔）部分通过苯基连接而成。Ni-CPD晶体在581K下热转化为结晶共价有机框架，并在873-1073K下通过随后的碳化进一步转化为具有导电性的有序碳质框架。此外，卟啉的Ni-N单元也很好地保留并嵌入到最终框架中。所得的有序碳质框架呈现出介于有机基框架和碳材料之间的中间结构，具有有利的电催化作用。这一原理使得能够对三维碳质框架进行化学分子水平的结构设计。碳基材料是贵金属催化剂的有前途的替代品，但其结构通常是无序的且难以控制。在此，作者通过含镍卟啉二聚体网络的碳化获得了具有有利电催化性能的有序碳质框架。
Zotero 插件
