Hydrogen Storage and Selective, Reversible O2 Adsorption in a Metal-Organic Framework with Open Chromium(II) Sites

被引：103
作者：
Bloch, Eric D. [1 ]
Queen, Wendy L. [2 ]
Hudson, Matthew R. [3 ]
Mason, Jarad A. [1 ]
Xiao, Dianne J. [1 ]
Murray, Leslie J. [4 ]
Flacau, Roxana [5 ]
Brown, Craig M. [3 ,6 ]
Long, Jeffrey R. [1 ,7 ,8 ]
机构：
[1] Univ Calif Berkeley, Dept Chem, Berkeley, CA 94720 USA
[2] EPFL, Inst Sci & Ingn Chim, CH-1051 Sion, Switzerland
[3] NIST, Ctr Neutron Res, Gaithersburg, MD 20899 USA
[4] Univ Florida, Dept Chem, Gainesville, FL 32611 USA
[5] CNR, Chalk River Labs, Canadian Neutron Beam Ctr, Chalk River, ON K0J 1P0, Canada
[6] Univ Delaware, Dept Chem Engn, Newark, DE 19716 USA
[7] Univ Calif Berkeley, Dept Chem & Biomol Engn, Berkeley, CA 94720 USA
[8] Lawrence Berkeley Natl Lab, Div Mat Sci, Berkeley, CA USA
来源：
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2016年 / 55卷 / 30期
基金：
美国国家科学基金会;
关键词：
air separation; chromium; metal-organic frameworks; neutron diffraction; superoxides; IRON(II) COORDINATION SITES; CARBON-DIOXIDE CAPTURE; CHROMIUM(III)-SUPEROXO COMPLEX; DRUG-DELIVERY; HIGH-CAPACITY; LEWIS-ACID; CATALYSIS; BINDING; CO; SEPARATIONS;
D O I：
10.1002/anie.201602950
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
A chromium(II)-based metal-organic framework Cr-3[(Cr4Cl)(3)(BTT)(8)](2) (Cr-BTT; BTT3 = 1,3,5-benzenetristetrazolate), featuring coordinatively unsaturated, redox-active Cr2+ 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 (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.
引用
收藏
页码：8605 / 8609
页数：5
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