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Generation of Hierarchical Porosity in Metal–Organic Frameworks by the Modulation of Cation Valence
Author(s) -
Qi ShiChao,
Qian XinYu,
He QiuXia,
Miao KangJing,
Jiang Yao,
Tan Peng,
Liu XiaoQin,
Sun LinBing
Publication year - 2019
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201903323
Subject(s) - microporous material , porosity , metal organic framework , valence (chemistry) , materials science , nanotechnology , metal , chemical engineering , adsorption , chemistry , metallurgy , organic chemistry , composite material , engineering
Hierarchically porous metal–organic frameworks (HP‐MOFs) have attracted great attention owing to their advantages over microporous MOFs in some applications. Despite many attempts, the development of a facile approach to generate HP‐MOFs remains a challenge. Herein we develop a new strategy, namely the modulation of cation valence, to create hierarchical porosity in MOFs. Some of the Cu II metal nodes in MOFs can be transformed into Cu I via reducing vapor treatment (RVT), which partially changes the coordination mode and thus breaks coordination bonds, resulting in the formation of HP‐MOF based on the original microporous MOF. Both the experimental results and the first‐principles calculation show that it is easy to tailor the amount of Cu I and subsequent hierarchical porosity by tuning the RVT duration. It is found that the resultant HP‐MOFs perform much better in the capture of aromatic sulfides than the original microporous MOF.