Trapping guests within a nanoporous metal-organic framework through pressure-induced amorphization.

The release of guest species from within a nanoporous metal-organic framework (MOF) has been inhibited by amorphization of the guest-loaded framework structure under applied pressure. Thermogravimetric analyses have shown that by amorphizing ZIF-8 following sorption of molecular I(2), a hazardous radiological byproduct of nuclear energy production, the pore apertures in the framework are sufficiently distorted to kinetically trap I(2) and improve I(2) retention. Pair distribution function (PDF) analysis indicates that the local structure of the captive I(2) remains essentially unchanged upon amorphization of the framework, with the amorphization occurring under the same conditions for the vacant and guest-loaded framework. The low, accessible pressure range needed to effect this change in desorption is much lower than in tradition sorbents such as zeolites, opening the possibility for new molecular capture, interim storage, or controlled release applications.

[1]  J. Grate,et al.  Facile xenon capture and release at room temperature using a metal-organic framework: a comparison with activated charcoal. , 2012, Chemical communications.

[2]  A. Cooper,et al.  A soft porous organic cage crystal with complex gas sorption behavior. , 2011, Chemistry.

[3]  M. Henry,et al.  A guest-induced reversible switching of a self-assembled H-bonded supramolecular framework. , 2011, Chemical communications.

[4]  James L. Krumhansl,et al.  Low‐Temperature Sintering Bi–Si–Zn‐Oxide Glasses for Use in Either Glass Composite Materials or Core/Shell 129I Waste Forms , 2011 .

[5]  Mark A. Rodriguez,et al.  Capture of volatile iodine, a gaseous fission product, by zeolitic imidazolate framework-8. , 2011, Journal of the American Chemical Society.

[6]  A. Cheetham,et al.  Thermal amorphization of zeolitic imidazolate frameworks. , 2011, Angewandte Chemie.

[7]  A. Cooper,et al.  On-off porosity switching in a molecular organic solid. , 2011, Angewandte Chemie.

[8]  K. Chapman,et al.  Pressure-induced amorphization and porosity modification in a metal-organic framework. , 2009, Journal of the American Chemical Society.

[9]  A. Cheetham,et al.  The effect of pressure on ZIF-8: increasing pore size with pressure and the formation of a high-pressure phase at 1.47 GPa. , 2009, Angewandte Chemie.

[10]  A. J. Blake,et al.  Cation-induced kinetic trapping and enhanced hydrogen adsorption in a modulated anionic metal–organic framework , 2009, Nature Chemistry.

[11]  R. Ewing,et al.  Nuclear Waste Management in the United States—Starting Over , 2009, Science.

[12]  Seth M. Cohen,et al.  Postsynthetic modification of metal-organic frameworks. , 2009, Chemical Society reviews.

[13]  R. Angel,et al.  Pressure-induced cooperative bond rearrangement in a zinc imidazolate framework: a high-pressure single-crystal X-ray diffraction study. , 2009, Journal of the American Chemical Society.

[14]  W. J. Weber,et al.  Materials Science of High-Level Nuclear Waste Immobilization , 2009 .

[15]  K. Chapman,et al.  Guest-dependent high pressure phenomena in a nanoporous metal-organic framework material. , 2008, Journal of the American Chemical Society.

[16]  Michael O’Keeffe,et al.  Exceptional chemical and thermal stability of zeolitic imidazolate frameworks , 2006, Proceedings of the National Academy of Sciences.

[17]  Xiao-Ming Chen,et al.  Ligand-directed strategy for zeolite-type metal-organic frameworks: zinc(II) imidazolates with unusual zeolitic topologies. , 2006, Angewandte Chemie.

[18]  K. Chapman,et al.  Selective recovery of dynamic guest structure in a nanoporous prussian blue through in situ X-ray diffraction: a differential pair distribution function analysis. , 2005, Journal of the American Chemical Society.

[19]  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 .

[20]  J. Marrot,et al.  A breathing hybrid organic-inorganic solid with very large pores and high magnetic characteristics. , 2002, Angewandte Chemie.

[21]  R. Hazen,et al.  Compressibility of sodalite and scapolite , 1988 .

[22]  Yining Huang IR spectroscopic study of the effects of high pressure on zeolites Y, A and sodalite , 1998 .

[23]  A. McGhie,et al.  Intercalation of solid C60 with iodine , 1992, Nature.

[24]  P. White,et al.  Preparation and X-ray crystal structure of Se2I4(Sb2F11)2 containing the eclipsed diselenium tetraiodide(2+) cation , 1982 .