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

详细信息    查看全文

• 作者：Dr. Eric D. Bloch ; Prof. Dr. Wendy L. Queen ; Dr. Matthew R. Hudson ; Dr. Jarad A. Mason ; Dianne J. Xiao ; Prof. Dr. Leslie J. Murray ; Dr. Roxana Flacau ; Dr. Craig M. Brown and Prof. Dr. Jeffrey R. Long
• 刊名：Angewandte Chemie International Edition
• 出版年：2016
• 出版时间：July 18, 2016
• 年：2016
• 卷：55
• 期：30
• 页码：8605-8609
• 全文大小：1473K
• ISSN：1521-3773

文摘

A chromium(II)-based metal&ndash;organic framework Cr<sub>3sub>[(Cr<sub>4sub>Cl)<sub>3sub>(BTT)<sub>8sub>]<sub>2sub> (Cr-BTT; BTT<sup>3&minus;sup>=1,3,5-benzenetristetrazolate), featuring coordinatively unsaturated, redox-active Cr<sup>2+sup> cation sites, was synthesized and investigated for potential applications in H<sub>2sub> storage and O<sub>2sub> production. Low-pressure H<sub>2sub> adsorption and neutron powder diffraction experiments reveal moderately strong Cr&ndash;H<sub>2sub> interactions, in line with results from previously reported M-BTT frameworks. Notably, gas adsorption measurements also reveal excellent O<sub>2sub>/N<sub>2sub> selectivity with substantial O<sub>2sub> reversibility at room temperature, based on selective electron transfer to form Cr<sup>IIIsup> superoxide moieties. Infrared spectroscopy and powder neutron diffraction experiments were used to confirm this mechanism of selective O<sub>2sub> binding.