A Porous Metal‐Organic Framework Based on Triazoledicarboxylate Ligands – Synthesis, Structure, and Gas‐Sorption Studies

A new porous metal-organic framework (MOF) {[CuL]·DMF·2H2O}n [1a, H2L = 5-(4H-1,2,4-triazol-4-yl)benzene-1,3-dicarboxylic acid; DMF = N,N-dimethylformamide] with zigzag-shaped, narrow channels was prepared by solvothermal synthesis and structurally characterized. 1a has zigzag-shaped, open channels with micropore sizes of approximately 5.6 × 4.6 A2. The (3,6)-connected network of 1a leads to an α-PbO2 (apo) topology. The adsorption properties (N2, H2, and CO2) of the desolvated sample 1c have been studied. The results show that 1c has a highly porous structure and a high adsorption capacity: the total capture of CO2 at 1 bar and 298 K is 22.01 wt.-%, and the total H2 uptake at 1 bar and 77 K is 1.46 wt.-%. This high adsorption capacity can be attributed to strong interactions between the small gas molecules and the irregularly open channels with their zigzag shape and their narrow pore size.

[1]  H. Furukawa,et al.  Incorporation of active metal sites in MOFs via in situ generated ligand deficient metal-linker complexes. , 2011, Chemical communications.

[2]  Dan Zhao,et al.  Highly Stable Porous Polymer Networks with Exceptionally High Gas‐Uptake Capacities , 2011, Advanced materials.

[3]  M. Eddaoudi,et al.  The next chapter in MOF pillaring strategies: trigonal heterofunctional ligands to access targeted high-connected three dimensional nets, isoreticular platforms. , 2011, Journal of the American Chemical Society.

[4]  Wei‐Yin Sun,et al.  pH Dependent Structural Diversity of Metal Complexes with 5-(4H-1,2,4-Triazol-4-yl)benzene-1,3-dicarboxylic Acid , 2011 .

[5]  A. J. Blake,et al.  High capacity gas storage by a 4,8-connected metal-organic polyhedral framework. , 2011, Chemical communications.

[6]  Rajamani Krishna,et al.  Metal-organic frameworks as adsorbents for hydrogen purification and precombustion carbon dioxide capture. , 2011, Journal of the American Chemical Society.

[7]  D. Zhao,et al.  Three-dimensional pillar-layered copper(II) metal-organic framework with immobilized functional OH groups on pore surfaces for highly selective CO2/CH4 and C2H2/CH4 gas sorption at room temperature. , 2011, Inorganic chemistry.

[8]  C. Su,et al.  Nanotubular metal-organic frameworks with high porosity based on T-shaped pyridyl dicarboxylate ligands. , 2011, Inorganic chemistry.

[9]  X. Bu,et al.  New three-dimensional porous metal organic framework with tetrazole functionalized aromatic carboxylic Acid: synthesis, structure, and gas adsorption properties. , 2010, Inorganic chemistry.

[10]  S. Nguyen,et al.  De novo synthesis of a metal-organic framework material featuring ultrahigh surface area and gas storage capacities. , 2010, Nature chemistry.

[11]  Randall Q. Snurr,et al.  Ultrahigh Porosity in Metal-Organic Frameworks , 2010, Science.

[12]  S. Kitagawa,et al.  Selective sorption of oxygen and nitric oxide by an electron-donating flexible porous coordination polymer , 2010, Nature Chemistry.

[13]  Jie‐Peng Zhang,et al.  Nonclassical active site for enhanced gas sorption in porous coordination polymer. , 2010, Journal of the American Chemical Society.

[14]  H. Krautscheid,et al.  Highly functionalised 3,4,5-trisubstituted 1,2,4-triazoles for future use as ligands in coordination polymers , 2010 .

[15]  J. Eckert,et al.  Exceptional stability and high hydrogen uptake in hydrogen-bonded metal-organic cubes possessing ACO and AST zeolite-like topologies. , 2009, Journal of the American Chemical Society.

[16]  Sang Soo Han,et al.  Recent advances on simulation and theory of hydrogen storage in metal-organic frameworks and covalent organic frameworks. , 2009, Chemical Society reviews.

[17]  Omar K Farha,et al.  Metal-organic framework materials as catalysts. , 2009, Chemical Society reviews.

[18]  Hong-Cai Zhou,et al.  Selective gas adsorption and separation in metal-organic frameworks. , 2009, Chemical Society reviews.

[19]  R. Snurr,et al.  Using molecular simulation to characterise metal-organic frameworks for adsorption applications. , 2009, Chemical Society reviews.

[20]  Wenbin Lin,et al.  Enantioselective catalysis with homochiral metal-organic frameworks. , 2009, Chemical Society reviews.

[21]  Mircea Dincă,et al.  Hydrogen storage in metal-organic frameworks. , 2009, Chemical Society reviews.

[22]  Wenbin Lin,et al.  Highly porous and robust 4,8-connected metal-organic frameworks for hydrogen storage. , 2009, Journal of the American Chemical Society.

[23]  Alexander J. Blake,et al.  High capacity hydrogen adsorption in Cu(II) tetracarboxylate framework materials: the role of pore size, ligand functionalization, and exposed metal sites. , 2009, Journal of the American Chemical Society.

[24]  S. Qiu,et al.  "Twin copper source" growth of metal-organic framework membrane: Cu(3)(BTC)(2) with high permeability and selectivity for recycling H(2). , 2009, Journal of the American Chemical Society.

[25]  A Alec Talin,et al.  Stress-induced chemical detection using flexible metal-organic frameworks. , 2008, Journal of the American Chemical Society.

[26]  C. Serre,et al.  Prediction of the conditions for breathing of metal organic framework materials using a combination of X-ray powder diffraction, microcalorimetry, and molecular simulation. , 2008, Journal of the American Chemical Society.

[27]  Wenbin Lin,et al.  Nanoscale coordination polymers for platinum-based anticancer drug delivery. , 2008, Journal of the American Chemical Society.

[28]  Dan Zhao,et al.  The current status of hydrogen storage in metal–organic frameworks , 2008 .

[29]  Jianwen Jiang,et al.  Molecular screening of metal-organic frameworks for CO2 storage. , 2008, Langmuir : the ACS journal of surfaces and colloids.

[30]  Michael J. Zaworotko,et al.  Supermolecular building blocks (SBBs) for the design and synthesis of highly porous metal-organic frameworks. , 2008, Journal of the American Chemical Society.

[31]  Qingyuan Yang,et al.  Computational Study of CO2 Storage in Metal-Organic Frameworks , 2008 .

[32]  Randall Q. Snurr,et al.  Design Requirements for Metal-Organic Frameworks as Hydrogen Storage Materials , 2007 .

[33]  I. Cabria,et al.  The optimum average nanopore size for hydrogen storage in carbon nanoporous materials , 2007 .

[34]  Krista S. Walton,et al.  Applicability of the BET method for determining surface areas of microporous metal-organic frameworks. , 2007, Journal of the American Chemical Society.

[35]  S. Kitagawa,et al.  A flexible interpenetrating coordination framework with a bimodal porous functionality. , 2007, Nature materials.

[36]  Sean Parkin,et al.  Framework-catenation isomerism in metal-organic frameworks and its impact on hydrogen uptake. , 2007, Journal of the American Chemical Society.

[37]  Hong-Cai Zhou,et al.  A metal-organic framework with entatic metal centers exhibiting high gas adsorption affinity. , 2006, Journal of the American Chemical Society.

[38]  J. Long,et al.  Microporous metal-organic frameworks incorporating 1,4-benzeneditetrazolate: syntheses, structures, and hydrogen storage properties. , 2006, Journal of the American Chemical Society.

[39]  Randall Q Snurr,et al.  Effects of surface area, free volume, and heat of adsorption on hydrogen uptake in metal-organic frameworks. , 2006, The journal of physical chemistry. B.

[40]  Daofeng Sun,et al.  An interweaving MOF with high hydrogen uptake. , 2006, Journal of the American Chemical Society.

[41]  R. T. Yang,et al.  Significantly enhanced hydrogen storage in metal-organic frameworks via spillover. , 2006, Journal of the American Chemical Society.

[42]  Omar M Yaghi,et al.  Effects of functionalization, catenation, and variation of the metal oxide and organic linking units on the low-pressure hydrogen adsorption properties of metal-organic frameworks. , 2006, Journal of the American Chemical Society.

[43]  W. Goddard,et al.  Nanopores of carbon nanotubes as practical hydrogen storage media , 2005 .

[44]  Michael O'Keeffe,et al.  Porous, Crystalline, Covalent Organic Frameworks , 2005, Science.

[45]  Omar M Yaghi,et al.  Hydrogen sorption in functionalized metal-organic frameworks. , 2004, Journal of the American Chemical Society.

[46]  Michael O'Keeffe,et al.  A route to high surface area, porosity and inclusion of large molecules in crystals , 2004, Nature.

[47]  Michael O'Keeffe,et al.  Hydrogen Storage in Microporous Metal-Organic Frameworks , 2003, Science.

[48]  Anthony L. Spek,et al.  Journal of , 1993 .

[49]  Gérard Férey,et al.  Very Large Breathing Effect in the First Nanoporous Chromium(III)-Based Solids: MIL-53 or CrIII(OH)·{O2C−C6H4−CO2}·{HO2C−C6H4−CO2H}x·H2Oy , 2002 .

[50]  Michael O'Keeffe,et al.  Systematic Design of Pore Size and Functionality in Isoreticular MOFs and Their Application in Methane Storage , 2002, Science.

[51]  Bin Chen,et al.  Interwoven Metal-Organic Framework on a Periodic Minimal Surface with Extra-Large Pores , 2001, Science.

[52]  James R. Morris,et al.  Theoretical investigation of the effect of graphite interlayer spacing on hydrogen absorption , 2007 .