Coordination-Induced N?H Bond Splitting of Ammonia and Primary Amine of CuI?MOFs |
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| Authors: | Kuan Gao Dr Chao Huang Yan Qiao Shasha Wang Prof Jie Wu Prof Hongwei Hou |
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| Institution: | 1. Green Catalysis Center and College of Chemistry, Zhengzhou University, 45001 Zhengzhou, P. R. China;2. Center for Advanced Materials Research, Henan Key Laboratory of Functional Salt Materials, Zhongyuan University of Technology, 45001 Zhengzhou, P. R. China;3. Pathophysiology Department, Basic Medical College of Zhengzhou University, 45001 Zhengzhou, P. R. China |
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| Abstract: | We report a porous three-dimensional anionic tetrazolium based CuI?MOF 1 , which is capable of cleaving the N?H bond of ammonia and primary amine, as well as the O?H bond of H2O along with spontaneous H2 evolution. In the gas-solid phase reaction of 1 with ammonia and water vapor, CuI?MOF 1 was gradually oxidized to NH2?CuII?MOF and OH?CuII?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 CuI?MOF could lower N?H bond dissociation free energy of ammonia through coordination-induced bond weakening and promote H2 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. |
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| Keywords: | coordination-induced bond weakening gas-solid phase oxidation of NH3 SC to SC |
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