Design Requirements for Metal-Organic Frameworks as Hydrogen Storage Materials

Storing an acceptable density of hydrogen in porous materials by physisorption at room temperature and reasonable pressures is a challenging problem. Metal-organic frameworks (MOFs) are a new class of nanoporous materials that have shown early promise for meeting this goal. They have extremely large specific surface areas, but the heats of adsorption to date are too low to provide significant storage at room temperature. In this work, molecular simulations are used to provide guidelines for the design of MOFs for hydrogen storage. To learn how much the heat of adsorption must be increased to meet current targets, we artificially increase the hydrogen/MOF Lennard-Jones attraction. The correlation of the amount of hydrogen adsorbed with the heat of adsorption, the surface area, and the free volume is revisited. We also review the distinction between excess and absolute adsorption and show that comparing the density of hydrogen within the free volume of materials provides useful insight. The simulation resul...

[1]  D. Lévesque,et al.  Hydrogen adsorption in the NaA zeolite: A comparison between numerical simulations and experiments , 2000 .

[2]  J. Hupp,et al.  Microporous pillared paddle-wheel frameworks based on mixed-ligand coordination of zinc ions. , 2005, Inorganic chemistry.

[3]  A. Züttel,et al.  Hydrogen-storage materials for mobile applications , 2001, Nature.

[4]  Ulrich Müller,et al.  Hydrogen Adsorption in Metal–Organic Frameworks: Cu‐MOFs and Zn‐MOFs Compared , 2006 .

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

[6]  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.

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

[8]  Jeffrey R. Long,et al.  Strong H2 Binding and Selective Gas Adsorption within the Microporous Coordination Solid Mg3(O2C-C10H6-CO2)3 , 2005 .

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

[10]  Craig M. Brown,et al.  Hydrogen storage in a microporous metal-organic framework with exposed Mn2+ coordination sites. , 2006, Journal of the American Chemical Society.

[11]  C. Janiak.  Engineering coordination polymers towards applications , 2003 .

[12]  J. Dentzer,et al.  Hydrogen storage in activated carbon materials: Role of the nanoporous texture , 2004 .

[13]  S. Bhatia,et al.  Optimum conditions for adsorptive storage. , 2006, Langmuir : the ACS journal of surfaces and colloids.

[14]  G. Spoto,et al.  Theoretical maximal storage of hydrogen in zeolitic frameworks. , 2005, Physical chemistry chemical physics : PCCP.

[15]  M. Hirscher,et al.  Hydrogen storage in metal–organic frameworks , 2007 .

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

[17]  Joseph T Hupp,et al.  Chemical reduction of metal-organic framework materials as a method to enhance gas uptake and binding. , 2007, Journal of the American Chemical Society.

[18]  Hyunuk Kim,et al.  Synthesis, X-ray crystal structures, and gas sorption properties of pillared square grid nets based on paddle-wheel motifs: implications for hydrogen storage in porous materials. , 2005, Chemistry.

[19]  S. L. Mayo,et al.  DREIDING: A generic force field for molecular simulations , 1990 .

[20]  Susumu Kitagawa,et al.  Functional porous coordination polymers. , 2004, Angewandte Chemie.

[21]  C. A. T. Seldam,et al.  Virial coefficients of hydrogen and deuterium at temperatures between −175°C and +150°C. Conclusions from the second virial coefficient with regards to the intermolecular potential , 1960 .

[22]  J. Johnson,et al.  Adsorption of gases in metal organic materials: comparison of simulations and experiments. , 2005, The journal of physical chemistry. B.

[23]  P. Bénard,et al.  Hydrogen adsorption measurements and modeling on metal-organic frameworks and single-walled carbon nanotubes. , 2006, Langmuir : the ACS journal of surfaces and colloids.

[24]  Paul A. Anderson,et al.  Hydrogen adsorption in zeolites a, x, y and rho , 2003 .

[25]  Lev Sarkisov,et al.  Design of new materials for methane storage. , 2004, Langmuir : the ACS journal of surfaces and colloids.

[26]  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.

[27]  M. O'keeffe,et al.  Design and synthesis of an exceptionally stable and highly porous metal-organic framework , 1999, Nature.

[28]  Randall Q. Snurr,et al.  Object-oriented Programming Paradigms for Molecular Modeling , 2003 .

[29]  Omar M Yaghi,et al.  Strategies for hydrogen storage in metal--organic frameworks. , 2005, Angewandte Chemie.

[30]  R. T. Yang,et al.  Hydrogen storage in metal-organic frameworks by bridged hydrogen spillover. , 2006, Journal of the American Chemical Society.

[31]  Qing Min Wang,et al.  Nanopore Structure and Sorption Properties of Cu-BTC Metal-Organic Framework , 2003 .

[32]  K. D. de Jong,et al.  Hydrogen storage using physisorption – materials demands , 2001 .

[33]  S. Nguyen,et al.  Prospects for nanoporous metal-organic materials in advanced separations processes , 2004 .

[34]  A. Cheetham,et al.  Hydrogen adsorption in nanoporous nickel(II) phosphates. , 2003, Journal of the American Chemical Society.

[35]  Stuart L James,et al.  Metal-organic frameworks. , 2003, Chemical Society reviews.

[36]  Michael O'Keeffe,et al.  Reticular synthesis and the design of new materials , 2003, Nature.

[37]  Andreas Züttel,et al.  Materials for hydrogen storage , 2003 .

[38]  V. Simonyan,et al.  Molecular simulation of hydrogen adsorption in charged single-walled carbon nanotubes , 1999 .

[39]  Ian D. Williams,et al.  A chemically functionalizable nanoporous material (Cu3(TMA)2(H2O)3)n , 1999 .

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

[41]  Sridhar Komarneni,et al.  Porous Adsorbents for Vehicular Natural Gas Storage: A Review , 1998 .

[42]  W. Goddard,et al.  UFF, a full periodic table force field for molecular mechanics and molecular dynamics simulations , 1992 .

[43]  Randall Q. Snurr,et al.  Prediction of adsorption of aromatic hydrocarbons in silicalite from grand canonical Monte Carlo simulations with biased insertions , 1993 .

[44]  M. Fichtner.  Nanotechnological Aspects in Materials for Hydrogen Storage , 2005 .

[45]  Wenbin Lin,et al.  Highly interpenetrated metal-organic frameworks for hydrogen storage. , 2004, Angewandte Chemie.

[46]  Alan L. Myers,et al.  Adsorption in Porous Materials at High Pressure: Theory and Experiment , 2002 .

[47]  Jaheon Kim,et al.  Grand canonical Monte Carlo simulation study on the catenation effect on hydrogen adsorption onto the interpenetrating metal-organic frameworks. , 2006, The journal of physical chemistry. B.