Prediction of the conditions for breathing of metal organic framework materials using a combination of X-ray powder diffraction, microcalorimetry, and molecular simulation

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作   者：

Llewellyn PL;  Maurin G;  Devic T;  Loera-Serna S;  Rosenbach N;  Serre C;  Bourrelly S;  Horcajada P;  Filinchuk Y;  Ferey G; 

作者机构：

Inst C Gerhardt Montpellier;  ESRF;  ENSCM;  Ctr St Jerome;  Univ Versailles St Quentin Yvelines;  Univ Aix Marseille 1;  F-78035 Versailles;  Univ Aix Marseille 2;  Univ Aix Marseille 3;  UMR 6264;  UMR 5253;  UM2;  Lab Chim Provence;  Inst Univ France;  UMR 8180;  SNBL;  F-38043 Grenoble;  CNRS;  F-13397 Marseille;  F-34095 Montpellier 05;  France;  Inst Lavoisier;  F-75005 Paris; 

关键词：

MIXTURES;  GAS-ADSORPTION;  MIL-53;  MOF-177;  SORPTION;  FLEXIBILITY;  CO2 ADSORPTION;  SEPARATION;  COORDINATION POLYMERS;  HYDROGEN STORAGE; 

期刊名称：

Journal of the American Chemical Society

i s s n：

0002-7863

年卷期：

2008 年 130 卷 38 期

页   码：

12808-12814

页   码：

摘   要：

The adsorption of C1 to C4 linear hydrocarbons in the flexible metal organic framework MIL-53(Cr) has been followed by adsorption manometry coupled with microcalorimetry and Synchrotron X-ray powder diffraction. This experimental investigation was completed by molecular modeling. In the case of methane, the solid remains rigid whatever the adsorbate amount. However for the C2-C4 series, an increasing flexibility of the structure is observed, which is ascribed first to a breathing of the material from a large pore to a narrow pore form followed by a further expansion at high pressure. The collected thermodynamic and structural information suggests that a minimum adsorption enthalpy of ca. 20 kJ mol(-1) in the initial large pore structure of MIL-53(Cr) is required to induce the structural transition "large to narrow pore". Further, the enthalpy of adsorption can be used to predict the pressure at which the structure reopens. Finally, the magnitude of the breathing can be related to the size of the probe molecule via the van der Waals volume. The above trends have been successfully verified in the case of water and carbon dioxide. This combined experimental and theoretical approach gives the first elements for the prediction of whether or not the MIL53 and similar flexible structures will respond to gas loading and what would be the pressure required and further the amplitude of the induced breathing.