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Coordination‐Induced N−H Bond Splitting of Ammonia and Primary Amine of Cu I −MOFs
Author(s) -
Gao Kuan,
Huang Chao,
Qiao Yan,
Wang Shasha,
Wu Jie,
Hou Hongwei
Publication year - 2021
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202100781
Subject(s) - ammonia , amine gas treating , chemistry , crystallography , dissociation (chemistry) , single crystal , crystal structure , inorganic chemistry , crystal (programming language) , bond dissociation energy , organic chemistry , computer science , programming language
We report a porous three‐dimensional anionic tetrazolium based Cu I −MOF 1 , which is capable of cleaving the N−H bond of ammonia and primary amine, as well as the O−H bond of H 2 O along with spontaneous H 2 evolution. In the gas‐solid phase reaction of 1 with ammonia and water vapor, Cu I −MOF 1 was gradually oxidized to NH 2 −Cu II −MOF and OH−Cu II −MOF, through single‐crystal‐to‐single‐crystal (SCSC) structural transformations, which was confirmed by XPS, PXRD and X‐ray single‐crystal diffraction. Density functional theory (DFT) demonstrated that Cu I −MOF could lower N−H bond dissociation free energy of ammonia through coordination‐induced bond weakening and promote H 2 evolution by the reduction potential of 1 . To our knowledge, this is the first example of MOFs that activate ammonia and amine in gas‐solid manner.