Systematic Design of Pore Size and Functionality in Isoreticular MOFs and Their Application in Methane Storage
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“Reticular” is an adjective defined in Random House Webster Unabridged Dictionary as “having the form of a net; netlike.” Isoreticular is defined as “having the same network topology.”
All IRMOFs were formulated as Zn 4 O(Link) 3 (DEF) x . [See (23) for details of elemental analyses.]
All the intensity data were collected on Bruker SMART CCD diffractometer with a graphite monochromated MoKα (λ = 0.71073 Å) radiation. Structures were solved by direct methods and successive difference Fourier syntheses with SHELXTL software package. Final R 1 values were calculated with I > 2σ( I ). Crystal data are as follows: IRMOF-2 cubic space group Fm -3 m a = 25.772(1) Å V = 17117(1) Å 3 Z = 8 R 1 = 0.0976; IRMOF-3 cubic Fm -3 m a = 25.747(1) Å V = 17067(2) Å 3 Z = 8 R 1 = 0.1160; IRMOF-4 cubic Fm -3 m a = 25.849(1) Å V = 17272(2) Å 3 Z = 8 R 1 = 0.0706; IRMOF-5 cubic Pm -3 m a = 12.882(1) Å V = 2137.6(3) Å 3 Z = 1 R 1 = 0.1181; IRMOF-6 cubic Fm -3 m a = 25.842(2) Å V = 17258(2) Å 3 Z = 8 R 1 = 0.1325; IRMOF-7 cubic Pm -3 m a = 12.914(3) Å V = 2153.9(7) Å 3 Z = 1 R 1 = 0.1957; IRMOF-8 cubic Fm -3 m a = 30.092(2) Å V = 27248(3) Å 3 Z = 8 R 1 = 0.1691; IRMOF-9 orthorhombic Pnnm a = 17.147(1) Å b = 23.322(1) Å c = 25.255(1) Å V = 10099.6(8) Å 3 Z = 4 R 1 = 0.0802; IRMOF-10 [single crystals of sufficient quality to perform a single-crystal analysis study could not be obtained but its observed x-ray powder diffraction pattern was the same as that observed for IRMOF-12 (below) and was confirmed by a simulated pattern for IRMOF-10 based on IRMOF-12 coordinates] cubic Fm -3 m a = 34.281(2) Å V = 40286(4) Å 3 Z = 8; IRMOF-11 trigonal R-3m a = 24.822(1) Å c = 56.734(3) Å V = 30272(3) Å 3 Z = 12 R 1 = 0.0963; IRMOF-12 cubic Fm -3 m a = 34.281(2) Å V = 40286(4) Å 3 Z = 8 R 1 = 0.1080; IRMOF-13 (same as treatment for IRMOF-10 but with the use of IRMOF-11) trigonal R-3m a = 24.822(1) Å c = 56.734(3) Å V = 30272(3) Å 3 Z = 12; IRMOF-14 cubic Fm -3 m a = 34.381(13) Å V = 40642(26) Å 3 Z = 8 R 1 = 0.1914; IRMOF-15 cubic Im -3 m a = 21.459(1) Å V = 9882(1) Å 3 Z = 1 R 1 = 0.1164; IRMOF-16 cubic Pm -3 m a = 21.490(1) Å V = 9925(1) Å 3 Z = 1 R 1 = 0.1845. [See (23) for details.]
M. O'Keeffe B. G. Hyde Crystal Structures I: Patterns and Symmetry (Mineralogy Society of America Washington DC 1996).
A van der Waals radius of C (1.70 Å) was used in determination of distance parameters [
K. Seki et al. U.S. patent 5 862 796 (1999).
Single crystal XRD data and elemental microanalyses for IRMOF-2 through -16 including sorption and XRD data for IRMOF-12 and -14 are available as supplementary material on Science Online at www.sciencemag.org/cgi/content/full/295/5554/469/DC1.
Supported by NSF (M.O. O.M.Y.) and DOE (O.M.Y.). We thank D. Martin (University of Michigan Material Sciences Engineering) for supplying a sample of the free R 6 -BDC acid.