Diffusion of Small Molecules in Metal Organic Framework Materials

被引:99
作者
Canepa, Pieremanuele [1 ]
Nijem, Nour [2 ]
Chabal, Yves J. [2 ]
Thonhauser, T. [1 ]
机构
[1] Wake Forest Univ, Dept Phys, Winston Salem, NC 27109 USA
[2] Univ Texas Dallas, Dept Mat Sci & Engn, Dallas, TX 75080 USA
关键词
HIGH-CAPACITY; ADSORPTION; CO2; HYDROGEN; SITES; CENTERS;
D O I
10.1103/PhysRevLett.110.026102
中图分类号
O4 [物理学];
学科分类号
0702 ;
摘要
Ab initio simulations are combined with in situ infrared spectroscopy to unveil the molecular transport of H-2, CO2, and H2O in the metal organic framework MOF-74-Mg. Our study uncovers-at the atomistic level-the major factors governing the transport mechanism of these small molecules. In particular, we identify four key diffusion mechanisms and calculate the corresponding diffusion barriers, which are nicely confirmed by time-resolved infrared experiments. We also answer a long-standing question about the existence of secondary adsorption sites for the guest molecules, and we show how those sites affect the macroscopic diffusion properties. Our findings are important to gain a fundamental understanding of the diffusion processes in these nanoporous materials, with direct implications for the usability of MOFs in gas sequestration and storage applications. DOI: 10.1103/PhysRevLett.110.026102
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页数:5
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共 28 条
[1]   Adsorption of CO2 and CH4 on a magnesium-based metal organic framework [J].
Bao, Zongbi ;
Yu, Liang ;
Ren, Qilong ;
Lu, Xiuyang ;
Deng, Shuguang .
JOURNAL OF COLLOID AND INTERFACE SCIENCE, 2011, 353 (02) :549-556
[2]   Metal-organic frameworks with high capacity and selectivity for harmful gases [J].
Britt, David ;
Tranchemontagne, David ;
Yaghi, Omar M. .
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 2008, 105 (33) :11623-11627
[3]   Highly efficient separation of carbon dioxide by a metal-organic framework replete with open metal sites [J].
Britt, David ;
Furukawa, Hiroyasu ;
Wang, Bo ;
Glover, T. Grant ;
Yaghi, Omar M. .
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 2009, 106 (49) :20637-20640
[4]   Van der Waals density functional for general geometries -: art. no. 246401 [J].
Dion, M ;
Rydberg, H ;
Schröder, E ;
Langreth, DC ;
Lundqvist, BI .
PHYSICAL REVIEW LETTERS, 2004, 92 (24) :246401-1
[5]   Independent verification of the saturation hydrogen uptake in MOF-177 and establishment of a benchmark for hydrogen adsorption in metal-organic frameworks [J].
Furukawa, Hiroyasu ;
Miller, Michael A. ;
Yaghi, Omar M. .
JOURNAL OF MATERIALS CHEMISTRY, 2007, 17 (30) :3197-3204
[6]   QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials [J].
Giannozzi, Paolo ;
Baroni, Stefano ;
Bonini, Nicola ;
Calandra, Matteo ;
Car, Roberto ;
Cavazzoni, Carlo ;
Ceresoli, Davide ;
Chiarotti, Guido L. ;
Cococcioni, Matteo ;
Dabo, Ismaila ;
Dal Corso, Andrea ;
de Gironcoli, Stefano ;
Fabris, Stefano ;
Fratesi, Guido ;
Gebauer, Ralph ;
Gerstmann, Uwe ;
Gougoussis, Christos ;
Kokalj, Anton ;
Lazzeri, Michele ;
Martin-Samos, Layla ;
Marzari, Nicola ;
Mauri, Francesco ;
Mazzarello, Riccardo ;
Paolini, Stefano ;
Pasquarello, Alfredo ;
Paulatto, Lorenzo ;
Sbraccia, Carlo ;
Scandolo, Sandro ;
Sclauzero, Gabriele ;
Seitsonen, Ari P. ;
Smogunov, Alexander ;
Umari, Paolo ;
Wentzcovitch, Renata M. .
JOURNAL OF PHYSICS-CONDENSED MATTER, 2009, 21 (39)
[7]   MOF-74 building unit has a direct impact on toxic gas adsorption [J].
Glover, T. Grant ;
Peterson, Gregory W. ;
Schindler, Bryan J. ;
Britt, David ;
Yaghi, Omar .
CHEMICAL ENGINEERING SCIENCE, 2011, 66 (02) :163-170
[8]   A climbing image nudged elastic band method for finding saddle points and minimum energy paths [J].
Henkelman, G ;
Uberuaga, BP ;
Jónsson, H .
JOURNAL OF CHEMICAL PHYSICS, 2000, 113 (22) :9901-9904
[9]   First-principles approach to rotational-vibrational frequencies and infrared intensity for H2 adsorbed in nanoporous materials [J].
Kong, Lingzhu ;
Chabal, Yves J. ;
Langreth, David C. .
PHYSICAL REVIEW B, 2011, 83 (12)
[10]   Energetics and Dynamics of H2 Adsorbed in a Nanoporous Material at Low Temperature [J].
Kong, Lingzhu ;
Roman-Perez, Guillermo ;
Soler, Jose M. ;
Langreth, David C. .
PHYSICAL REVIEW LETTERS, 2009, 103 (09)