Tuning the adsorption properties of UiO-66 via ligand functionalization.

UiO-66 is one of the few known water-stable MOFs that are readily amenable to direct ligand substitution. In this work, UiO-66 has been synthesized with amino-, nitro-, methoxy-, and naphthyl-substituted ligands to impart polar, basic, and hydrophobic characteristics. Pure-component CO(2), CH(4), N(2), and water vapor adsorption isotherms were measured in the materials to study the effect of the functional group on the adsorption behavior. Heats of adsorption were calculated for each pure gas on each material. The results indicate that the amino-functionalized material possesses the best adsorption properties for each pure gas due to a combination of polarity and small functional group size. The naphthyl-functionalized material exhibits a good combination of inhibited water vapor adsorption and high selectivity for CO(2) over CH(4) and N(2).

[1]  David S. Sholl,et al.  Identification of Metal–Organic Framework Materials for Adsorption Separation of Rare Gases: Applicability of Ideal Adsorbed Solution Theory (IAST) and Effects of Inaccessible Framework Regions , 2012 .

[2]  Carlo Lamberti,et al.  A new zirconium inorganic building brick forming metal organic frameworks with exceptional stability. , 2008, Journal of the American Chemical Society.

[3]  Kimoon Kim,et al.  Rigid and flexible: a highly porous metal-organic framework with unusual guest-dependent dynamic behavior. , 2004, Angewandte Chemie.

[4]  N. Champness,et al.  Hydrogen, methane and carbon dioxide adsorption in metal-organic framework materials. , 2010, Topics in current chemistry.

[5]  Vincent Guillerm,et al.  Functionalizing porous zirconium terephthalate UiO-66(Zr) for natural gas upgrading: a computational exploration. , 2011, Chemical communications.

[6]  S. Kitagawa,et al.  Effect of functional groups in MIL-101 on water sorption behavior , 2012 .

[7]  Christian J. Doonan,et al.  Multiple Functional Groups of Varying Ratios in Metal-Organic Frameworks , 2010, Science.

[8]  Gérard Férey,et al.  Effect of NH2 and CF3 functionalization on the hydrogen sorption properties of MOFs. , 2011, Dalton transactions.

[9]  Alan L. Myers,et al.  Thermodynamics of mixed‐gas adsorption , 1965 .

[10]  Seda Keskin,et al.  Can metal-organic framework materials play a useful role in large-scale carbon dioxide separations? , 2010, ChemSusChem.

[11]  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.

[12]  Krista S. Walton,et al.  Effect of Water Adsorption on Retention of Structure and Surface Area of Metal–Organic Frameworks , 2012 .

[13]  C. Serre,et al.  High uptakes of CO2 and CH4 in mesoporous metal-organic frameworks MIL-100 and MIL-101. , 2008, Langmuir : the ACS journal of surfaces and colloids.

[14]  C. Serre,et al.  Understanding the Thermodynamic and Kinetic Behavior of the CO2/CH4 Gas Mixture within the Porous Zirconium Terephthalate UiO-66(Zr): A Joint Experimental and Modeling Approach , 2011 .

[15]  A. Benin,et al.  Virtual high throughput screening confirmed experimentally: porous coordination polymer hydration. , 2009, Journal of the American Chemical Society.

[16]  François-Xavier Coudert,et al.  Water adsorption in hydrophobic MOF channels. , 2010, Physical chemistry chemical physics : PCCP.

[17]  B. Smit,et al.  Carbon dioxide capture: prospects for new materials. , 2010, Angewandte Chemie.

[18]  Duilio Cascio,et al.  Synthesis, structure, and metalation of two new highly porous zirconium metal-organic frameworks. , 2012, Inorganic chemistry.

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

[20]  P. Sozzani,et al.  Nanochannels of two distinct cross-sections in a porous Al-based coordination polymer. , 2008, Journal of the American Chemical Society.

[21]  H. Kita,et al.  Syntheses, crystal structures, and water adsorption behaviors of jungle-gym-type porous coordination polymers containing nitro moieties , 2009 .

[22]  C. Serre,et al.  Direct covalent post-synthetic chemical modification of Cr-MIL-101 using nitrating acid. , 2011, Chemical communications.

[23]  Elsje Alessandra Quadrelli,et al.  Synthesis and Stability of Tagged UiO-66 Zr-MOFs , 2010 .

[24]  Seth M Cohen,et al.  Isoreticular synthesis and modification of frameworks with the UiO-66 topology. , 2010, Chemical communications.

[25]  Kenji Sumida,et al.  Carbon dioxide capture in metal-organic frameworks. , 2012, Chemical reviews.

[26]  Seth M. Cohen,et al.  Postsynthetic ligand exchange as a route to functionalization of ‘inert’ metal–organic frameworks , 2012 .

[27]  D. Zhao,et al.  Significantly Enhanced CO2/CH4 Separation Selectivity within a 3D Prototype Metal–Organic Framework Functionalized with OH Groups on Pore Surfaces at Room Temperature , 2011 .

[28]  C. Serre,et al.  An evaluation of UiO-66 for gas-based applications. , 2011, Chemistry, an Asian journal.

[29]  Y. Chabal,et al.  Enhancing gas adsorption and separation capacity through ligand functionalization of microporous metal-organic framework structures. , 2011, Chemistry.

[30]  S. Deng,et al.  Adsorption of CO2 and CH4 on a magnesium-based metal organic framework. , 2011, Journal of colloid and interface science.

[31]  Stefan Kaskel,et al.  Characterization of metal-organic frameworks by water adsorption , 2009 .

[32]  A. Schneemann,et al.  Zinc-1,4-benzenedicarboxylate-bipyridine frameworks – linker functionalization impacts network topology during solvothermal synthesis , 2012 .