Ultramicroporous MOF with High Concentration of Vacant CuII Sites

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• 作者：Laura J. McCormick ; Samuel G. Duyker ; Aaron W. Thornton ; Chris S. Hawes ; Matthew R. Hill ; Vanessa K. Peterson ; Stuart R. Batten ; David. R. Turner
• 刊名：Chemistry of Materials
• 出版年：2014
• 出版时间：August 12, 2014
• 年：2014
• 卷：26
• 期：15
• 页码：4640-4646
• 全文大小：418K
• ISSN：1520-5002

文摘

An ultramicroporous metal鈥搊rganic framework (MOF) is reported that contains 0.35 nm nanotube-like channels with an unprecedented concentration of vacant Cu^II coordination sites. The nonintersecting, narrow channels in [Cu₃(cdm)₄] (cdm = C(CN)₂(CONH₂)^{鈭?/sup>) align in two perpendicular directions, structurally resembling copper-doped carbon nanotubes with CuII embedded in the walls of the channels. The combination of ultramicroporosity with the exposed CuII coordination sites gives size-based selectivity of CO₂ over CH₄, based on pore-size distribution and modeling. Neutron powder diffraction and molecular dynamics simulations show the close packing of single rows of guests within the tubular nanostructure and interaction of CO₂ with the exposed metal sites.}