Modulation of Self‐Assembly Enhances the Catalytic Activity of Iron Porphyrin for CO 2 Reduction
Modulation of Self‐Assembly Enhances the Catalytic Activity of Iron Porphyrin for CO 2 Reduction
复制标题
自组装调节增强铁卟啉对 CO 2 还原的催化活性
DOI：
10.1002/smll.202006150
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发表时间：
2021
期刊：
影响因子：
13.3
通讯作者：
Masaoka Shigeyuki
中科院分区：
文献类型：
--
作者：
Tasaki Masahiro;Okabe Yuki;Iwami Hikaru;Akatsuka Chiharu;Kosugi Kento;Negita Kohei;Kusaka Sinpei;Matsuda Ryotaro;Kondo Mio;Masaoka Shigeyuki
水介质中CO2的电化学还原是以环境和经济友好的方式生产附加值碳产品的重要反应。到目前为止，已经报道了用于该反应的各种基于分子的催化体系。该领域最先进的催化体系的关键特征可以总结如下：1）基于铁卟啉的支架作为催化中心，2）用于有效活化CO2分子的双核活性中心，以及3）用于CO2积累的疏水通道。本文报道了一种新的方法来构建一个具有上述三个关键亚结构的催化体系，用于CO2还原。新设计的具有非共价相互作用能力的大体积取代基的铁卟啉络合物的自组装形成具有相邻催化活性位点和疏水孔的高度有序的结晶固体。得到的结晶固体作为电催化剂用于在水介质中还原CO2。注意，没有大体积取代基的相关铁卟啉络合物不能形成具有相邻活性位点的多孔结构，并且该相关铁卟啉络合物的晶体的催化性能显著低于新开发的催化体系的催化性能。本研究为构建用于小分子转化的多孔结晶固体提供了一种新的策略。
Electrochemical reduction of CO2in aqueous media is an important reaction to produce value‐added carbon products in an environmentally and economically friendly manner. Various molecule‐based catalytic systems for the reaction have been reported thus far. The key features of state‐of‐the‐art catalytic systems in this field can be summarized as follows: 1) an iron‐porphyrin‐based scaffold as a catalytic center, 2) a dinuclear active center for the efficient activation of a CO2molecule, and 3) a hydrophobic channel for the accumulation of CO2. This article reports a novel approach to construct a catalytic system for CO2reduction with the aforementioned three key substructures. The self‐assembly of a newly designed iron‐porphyrin complex bearing bulky substituents with noncovalent interaction ability forms a highly ordered crystalline solid with adjacent catalytically active sites and hydrophobic pores. The obtained crystalline solid serves as an electrocatalyst for CO2reduction in aqueous media. Note that a relevant iron‐porphyrin complex without bulky substituents cannot form a porous structure with adjacent active sites, and the catalytic performance of the crystals of this relevant iron‐porphyrin complex is substantially lower than that of the newly developed catalytic system. The present study provides a novel strategy for constructing porous crystalline solids for small‐molecule conversions.