Coordination‐Induced N−H Bond Splitting of Ammonia and Primary Amine of Cu^I−MOFs.

Gao, Kuan; Huang, Chao; Qiao, Yan; Wang, Shasha; Wu, Jie; Hou, Hongwei

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.

DENSITY functional theory; AMINES; AMMONIA; REDUCTION potential

Chemistry - A European Journal, 2021, Vol 27, Issue 37, p9499

0947-6539

Academic Journal

10.1002/chem.202100781