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

页码：8605 / 8609

页数：5

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