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Hydrogen Storage and Selective, Reversible O 2 Adsorption in a Metal–Organic Framework with Open Chromium(II) Sites
Author(s) -
Bloch Eric D.,
Queen Wendy L.,
Hudson Matthew R.,
Mason Jarad A.,
Xiao Dianne J.,
Murray Leslie J.,
Flacau Roxana,
Brown Craig M.,
Long Jeffrey R.
Publication year - 2016
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201602950
Subject(s) - chromium , chemistry , adsorption , neutron diffraction , hydrogen storage , metal organic framework , infrared spectroscopy , metal , inorganic chemistry , redox , hydrogen , selectivity , powder diffraction , catalysis , crystallography , organic chemistry , crystal structure
A chromium(II)‐based metal–organic framework Cr 3 [(Cr 4 Cl) 3 (BTT) 8 ] 2 (Cr‐BTT; BTT 3− =1,3,5‐benzenetristetrazolate), featuring coordinatively unsaturated, redox‐active Cr 2+ cation sites, was synthesized and investigated for potential applications in H 2 storage and O 2 production. Low‐pressure H 2 adsorption and neutron powder diffraction experiments reveal moderately strong Cr–H 2 interactions, in line with results from previously reported M‐BTT frameworks. Notably, gas adsorption measurements also reveal excellent O 2 /N 2 selectivity with substantial O 2 reversibility at room temperature, based on selective electron transfer to form Cr III superoxide moieties. Infrared spectroscopy and powder neutron diffraction experiments were used to confirm this mechanism of selective O 2 binding.