**7. References**

272 Molecular Dynamics – Theoretical Developments and Applications in Nanotechnology and Energy

transport rates, MD studies become one of the most beneficial methods in studying MOFs. As is evident from the volume of literature cited, this area is growing rapidly. The development of quantitative information about mixture diffusion in MOFs is just beginning (section 3.2) whereas a significant number of studies have already considered single component gas diffusion in MOFs (section 3.1). Detailed understanding of mixture diffusion in MOFs will be very beneficial for design of MOF membranes, adsorbents, catalysts and sensors. Current opportunities and challenges of using MD simulations in assessing

The most significant opportunity of employing MD simulations for obtaining gas diffusivity in MOFs lies in areas where experiments for transport property of interest (transport diffusivities, energy barrier to diffusion) are challenging, not in reiterating properties that have already been addressed experimentally. Measuring diffusivity at a wide range of loadings in the pores at extreme conditions such as infinite dilute loading and/or saturation loading is experimentally difficult. MD simulations can provide information about gas diffusion in MOFs' pores under these conditions. Getting diffusivity data as a function of gas loading is crucial to design membranes, adsorbents, catalysts from MOFs that will work

As addressed in Section 5, the development of quantitative information about mixture diffusion in MOFs is just beginning. Since performing mixture MD simulations for MOFs with large frameworks and for gas mixtures at high adsorbed loadings are computationally demanding, theoretical correlations that predict mixture diffusion based on single component diffusion data are very useful. Recent research search showed that these models yield accurate results for at least simple chemical mixtures in MOFs. Testing and validation of theoretical correlations for predicting gas diffusivity in various subclasses of MOFs will

A great advantage of using MD simulations is to test hypothetical MOF structures for particular applications if the metric describing the performance of a material for the application can be directly calculated. For example, Düren and coworkers used GCMC simulations to design materials with large adsorption capacities for CH4.(Düren et al., 2004) In a similar way, MD simulations can be used to design materials with slow diffusivities for CH4 and fast diffusivities for CO2 to identify materials that will be promising in kinetic

The development of accurate classical interatomic potentials for describing gas diffusion in MOFs remains challenging. From the modeling perspective, it is important to use experimental diffusion data from a broad range of conditions to parameterize interatomic potentials whenever this is practical. However, as discussed in Section 4, the number of experimental data on gas diffusion in MOFs is very limited. Furthermore, developing potentials specific to a MOF structure is not the solution since hundreds of different MOF structures are available. Therefore, efforts to test and improve the transferability of potentials among related families of MOFs will have a great value. One of the major

be useful to widely utilize these correlations for different structures.

transport rates of gases in MOFs will be addressed below.

under a wide range of operating conditions.

separation of CO2 from CO2/CH4 mixtures.

**6.2 Challenges** 

**6.1 Opportunities** 


Recent Advances in Molecular Dynamics

Hill,New York

110, 9565-9570.

16618-16625.

*Eng. Sci.*, 55, 2923-2930.

Wiley & Sons,New York

*Eng.*, 16, 71-197.

Simulations of Gas Diffusion in Metal Organic Frameworks 275

Eddaoudi, M., Kim, J., Rosi, N., Vodak, D., Wachter, J., O'Keeffe, M.&Yaghi, O. M. (2002).

El-Kaderi, H. M., Hunt, J. R., Mendoza-Cortés, J. L., A.P. Côté, Taylor, R. E.,

Feynman, R. P.&Hibbs, A. R. (1965). *Quantum Mechanics and Path Integrals*. McGraw-

Francl, M. M., Carey, C., Chirlian, L. E.&Gange, D. M. (1996). Charges Fit to Electrostatic

Frenkel, D.&Smit, B. (2002). *Understanding Molecular Simulation: From Algorithms to* 

Frost, H., Düren, T.&Snurr, Q. (2006). Effects of Surface Area, Free Volume, and Heat of

Greathouse, J. A.&Allendorf, M. D. (2006). The Interaction of Water with MOF-5 Simulated

Greathouse, J. A.&Allendorf, M. D. (2008). Force Field Validation for Molecular Dynamics

Hayashi, H., Cote, A. P., Furukawa, H., O'Keeffe, M.&Yaghi, O. M. (2007). Zeolite A

Jhon, Y. H., Cho, M., Jeon, H. R., Park, I., Chang, R., Rowsell, J. L. C.&Kim, J. (2007).

Jobic, H., Kärger, J.&Bée, M. (1999). Simultaneous Measurement of Self- and Transport

Jobic, H.&Theodorou, D. N. (2007). Quasi-Elastic Neutron Scattering and Molecular

Jorgensen, W. L., Maxwell, D. S.&Tirado-Rives, J. (1996). Development and Testing of the

Kapteijn, F., Moulijn, J. A.&Krishna, R. (2000). The Generalized Maxwell-Stefan Model for

Kärger, J.&Ruthven, D. (1992). *Diffusion in Zeolites and Other Microporous Materials*. John

Keil, F. J., Krishna, R.&Coppens, M. O. (2000). Modeling of Diffusion in Zeolites. *Rev. Chem.* 

by Molecular Dynamics. *J. Am. Chem. Soc.*, 128, 10678-10679.

Application in Methane Storage. *Science*, 295, 469-472.

Frameworks. *Science*, 316, 268-272.

Potentials? *J. Comput. Chem.* , 17, 367-383.

*Applications*. Academic Press,San Diego

Polymers. *J. Phys. Chem. C*, 112, 5795–5802.

Imidazolate Frameworks. *Nat. Mater.*, 6, 501-506.

James, S. J. (2003). Metal Organic Frameworks. *Chem. Soc. Rev.*, 32, 276-288.

Diffusivities in Zeolites *Phys. Rev. Lett.*, 82, 4260-4263.

Zeolites. *Micropor. Mesopor. Mater.*, 102, 21-50.

Liquids. *J. Am. Chem. Soc.*, 118, 11225-11236.

Systematic Design of Pore Size and Functionality in Isoreticular MOFs and Their

M.O'Keeffe&Yaghi, O. M. (2007). Designed Synthesis of 3D Covalent Organic

Potentials. II. Can Atomic Charges Be Unambiguously Fit to Electrostatic

Adsorption on Hydrogen Uptake in Metal-Organic Frameworks. *J. Phys. Chem. B*,

Simulations of IRMOF-1 and Other Isoreticular Zinc Carboxylate Coordination

Simulation of Methane Adsorption and Diffusion within Alkoxy-Functionalized IRMOFs Exhibiting Severely Disordered Crystal Structures. *J. Phys. Chem. C*, 111,

Dynamics Simulation as Complementary Techniques for Studying Diffusion in

Opls All-Atom Force Field on Conformational Energetics and Properties of Organic

Diffusion in Zeolites: Sorbate Molecules with Different Saturation Loadings. *Chem.* 


Babarao, R.&Jiang, J. (2008). Diffusion and Separation of CO2 and CH4 in Silicalite, C168

Banerjee, R., Phan, A., Wang, B., Knobler, C., Furukawa, H., O'Keeffe, M.&Yaghi, O. M.

Banerjee, R., Furukawa, H., Britt, D., Knobler, C., O'Keeffe, M.&Yaghi, O. M. (2009). Control

Bär, N.-K., Ernst, H., Jobic, H.&Kärger, J. (1999). Combined Quasi-Elastic Neutron Scattering

Battisti, A., Taioli, S.&Garberoglio, G. (2011). Zeolitic Imidazolate Frameworks for

Bordiga, S., Vitillo, J. G., Ricchiardi, G., Regli, L., Cocina, D., Zecchina, A., Bj.Arstad,

Buch, V. (1994). Path-Integral Simulations of Mixed Para-D-2 and Ortho-D-2 Clusters - the

Chmelik, C., Kärger, J., Wiebcke, M., Caro, J., van Baten, J. M.&Krishna, R. (2009).

Chui, S. S. Y., Lo, S. M. F., Charmant, J. P. H., Orpen, A. G.&Williams, I. D. (1999). A

Ciccotti, G., Ferrario, M.&Ryckaert, J.-P. (1982). Molecular-Dynamics of Rigid Systems in Cartesian Coordinates: A General Formulation. *Mol. Phys.*, 47, 1253-1264. Clark, L. A., Gupta, A.&Snurr, R. Q. (1998). Siting and segregation effects of simple molecules in zeolites MFI, MOR, and BOG. *J. Phys. Chem. B* 102, 6720-6731. Darkrim, F.&Levesque, D. (1998). Monte Carlo Simulations of Hydrogen Adsorption in

Dietzel, P. D. C., Morita, Y., Blom, R.&Fjellvag, H. (2005). An in Situ High-Temperature

Dietzel, P. D. C., Panella, B., Hirscher, M., Blom, R.&Fjellvag, H. (2006). Hydrogen

Cylindrical Cavities of the Desolvated Framework *Chem. Commun.*, 959-961. Düren, T., Sarkisov, L., Yaghi, O. M.&Snurr, R. Q. (2004). Design of New Materials for

Eddaoudi, M., Li, H.&Yaghi, O. M. (2000). Highly Porous and Stable Metal-Organic

Single-Crystal Investigation of a Dehydrated Melal-Organic Framework Compound and Field-Induced Magnetization of One-Dimensional Metaloxygen

Adsorption in a Nickel Based Coordination Polymer with Open Metal Sites in the

Frameworks: Structure Design and Sorption Properties. *J. Am. Chem. Soc.*, 122, 1391-

Single-Walled Carbon Nanotubes. *J. Chem. Phys.*, 109, 4981-4985.

Chains. *Angew. Chem. Int. Ed. Eng.*, 44, 6354-6358.

Methane Storage. *Langmuir*, 20, 2683-2689.

Simulation. *Langmuir*, 24, 5474-5484.

3877.

83.

22-32.

1397.

*Science*, 283, 1148-1150.

Application to CO2 Capture. *Science*, 319, 939-943.

Investigation. *Micropor. Mesopor. Mater.*, 143, 46-53.

Orientational Effects. *J. Chem. Phys.*, 100, 7610-7629.

MOF-5. *J. Phys. Chem. B*, 109, 18237-18242.

Schwarzite and IRMOF-1: A Comparative Study from Molecualr Dynamics

(2008). High-Throughput Synthesis of Zeolitic Imidazolate Frameworks and

of Pore Size and Functionality in Isoreticular Zeolitic Imidazolate Frameworks and Their Carbon Dioxide Selective Capture Properties. *J. Am. Chem. Soc.*, 131, 3875-

and NMR Study of Hydrogen Diffusion in Zeolites. *Magn. Reson. Chem.*, 37, 79-

Separation of Binary Mixtures of CO2, CH4, N2 and H2: A Computer Simulation

Bjørgen, M., Hafizovic, J.&Lillerud, K. P. (2005). Interaction of Hydrogen with

Adsorption and Diffusion of Alkanes in CuBTC Crystals Investigated Using Infra-Red Microscopy and Molecular Simulations. *Micropor. Mesopor. Mater.*, 117,

Chemically Functionalizable Nanoporous Material [Cu-3(Tma)(2)(H2O)(3)](N).


Recent Advances in Molecular Dynamics

276-279.

10, 3244-3249.

8921.

636.

127, 17998-17999.

Simulations of Gas Diffusion in Metal Organic Frameworks 277

Li, H., Eddaoudi, M., O'Keeffe, M.&Yaghi, O. M. (1999). Design and Synthesis of an

Lii, J.-H., Allinger, N. L.&Yuh, Y. H. (1989). Molecular Mechanics. The MM3 Force Field for

Liu, B., Yang, Q., Xue, C., Zhong, C.&Smit, B. (2008a). Molecular Simulation of Hydrogen

Liu, D., Zheng, C., Yang, Q.&Zhong, C. (2009). Understanding the Adsorption and Diffusion

Liu, J., Lee, J. Y., Pan, L., Obermyer, R. T., Simizu, S., Zande, B., Li, J., Sankar, S. G.&Johnson,

Loiseau, T., Serre, C., Huguenard, C., Fink, G., Taulelle, F., Henry, M., Bataille, T.&Ferey, G.

Martin, M. G.&Siepmann, J. I. (1997). Predicting Multicomponent Phase Equilibria and Free

Martyna, G. J., Tuckerman, M. E.&Klein, M. L. (1992). Nose-Hoover Chains: The Canonical

Martyna, G. J., Tuckerman, E., Tobias, D. J.&Klein, M. L. (1996). Explicit Reversible Integration Algorithms for Extended Systems. *Mol. Phys.*, 87, 1117-1157. Mayo, S. L., Olafson, B. D.&Goddard, W. A. (1990). Dreiding: A Generic Force Field for

Millward, A. R.&Yaghi, O. M. (2005). Metal-Organic Frameworks with Exceptionally High

Mueller, U., Schubert, M., Teich, F., Puetter, H., Schierle-Arndt, K.&Pastré, J. (2006). Metal

Narehood, D. G., Pearce, J. V., Eklund, P. C., Sokol, P. E., Lechner, R. E., Pieper, J., Copley, J.

Pan, L., Sander, M. B., Huang, X. Y., Li, J., Smith, M., Bittner, E., Bockrath, B.&Johnson, J. K.

Pantatosaki, E., Pazzona, E. G., Megariotis, G.&Papadopoulos, G. K. (2010). Atmic

within Zeolite Imidazolate Framework-8. *J. Phys. Chem. B*, 114, 2493-2503. Park, K. S., Ni, Z., Cote, A. P., Choi, J. Y., Huang, R. D., Uribe-Romo, F. J., Chae, H.

Capacity for Storage of Carbon Dioxide at Room Temperature. *J. Am. Chem. Soc.*,

Organic Frameworks-Prospective Industrial Applications. *J. Mater. Chem.*, 16, 626-

(2004). Microporous Metal Organic Materials: Promising Candidates as Sorbents

Simulation Studies on the Dynamics and Thermodynamics of Nonpolar Molecules

K., O'Keeffe, M.&Yaghi, O. M. (2006). Exceptional Chemical and Thermal Stability

Ensemble Via Continuous Dynamics. *J. Chem. Phys.*, 97, 2635-2643.

Framework Material:[Zn(Bdc)(Ted)0.5]. *J. Phys. Chem. C*, 112, 2911-2917. Liu, J., Keskin, S., Sholl, D.&Johnson, J. K. (2011). Molecular Simulations and Theoretical

Hydrocarbons. *J. Am. Chem. Soc.* 111, 8551-8566.

ZIF-68 and ZIF-70. *J. Phys. Chem. C*, 115, 12560-12566.

(Mil-53) Upon Hydration. *Chem.-Eur. J.*, 10, 1373-1382.

Molecular Simulations. *J. Phys. Chem. C*, 94, 8897-8909.

R. D.&Cook, J. C. (2003). *Phys. Rev. B*, 67, 205409-205415.

for Hydrogen Storage *J. Am. Chem. Soc.*, 126, 1308-1309.

Study. *J. Phys. Chem. C*, 113, 5004-5009.

Exceptionally Stable and Highly Porous Metal-Organic Framework. *Nature*, 402,

Diffusion in Interpenetrated Metal-Organic Frameworks. *Phys. Chem. Chem. Phys.*,

of Carbon Dioxide in Zeolitic Imidazolate Frameworks: A Molecular Simulation

J. K. (2008b). Adsorption and Diffusion of Hydrogen in a New Metal Organic

Predictions for Adsorption and Diffusion of CH4/H2 and CO2/CH4 Mixtures in

(2004). A Rationale for the Large Breathing of the Porous Aluminum Terephthalate

Energies of Transfer for Alkanes by Molecular Simulation. *J. Am. Chem. Soc.*, 119,


Keskin, S.&Sholl, D. S. (2007). Screening Metal-Organic Framework Materials for

Keskin, S., Liu, J., Johnson, J. K.&Sholl, D. S. (2008). Testing the Accuracy of Correlations for

Keskin, S.&Sholl, D. S. (2009b). Efficient Methods for Screening of Metal Organic Framework

Keskin, S., Liu, J., Johnson, J. K.&Sholl, D. S. (2009a). Atomically-Detailed Models of Gas

Keskin, S., Liu, J., Rankin, R. B., Johnson, J. K.&Sholl, D. S. (2009b). Progress, Opportunities,

Keskin, S. (2010a). Comparing Performance of CPO and IRMOF Membranes for Gas Separations Using Atomistic Models. *Ind. Eng. Chem. Res.*, 49, 11689-11696. Keskin, S. (2010b). Molecular Simulation Study of CH4/H2 Mixture Separations Using Metal

Keskin, S. (2011a). Atomistic Simulations for Adsorption, Diffusion, and Separation of Gas Mixtures in Zeolite Imidazolate Frameworks. *J. Phys. Chem. C*, 115, 800-807. Keskin, S. (2011b). High CO2 Selectivity of A Microporous Metal-Imidazolate Framework: A

Keskin, S.&Kizilel, S. (2011). Biomedical Applications of Metal Organic Frameworks. *Ind.* 

Kitagawa, S., Kitaura, R.&Noro, S. (2004). Functional Porous Coordination Polymers. *Angew.* 

Krishna, R.&van den Broeke, L. J. P. (1995). The Maxwell-Stefan Description of Mass

Krishna, R.&Paschek, D. (2002). Self-Diffusivities in Multicomponent Mixtures in Zeolites

Krishna, R.&van Baten, J. M. (2011). In Silico Screening of Metal-Organic Frameworks in

Lee, T. B., Jung, D. H., Kim, D., Kim, J., Choi, K.&Choi, S.-H. (2009). Molecular Dynamics

Simulation Study on the Hydrogen Adsorption and Diffusion in Non-Interpenetrating and Interpenetrating IRMOFs. *Catalysis Today*, 146, 216-222. Li, H., Eddaoudi, M., Groy, T. L.&Yaghi, O. M. (1998). Establishing Microporosity in Open

Metal-Organic Frameworks: Gas Sorption Isotherms for Zn(Bdc) (Bdc = 1,4-

Molecular Simulation Study. *Ind. Eng. Chem. Res.*, 50, 8230-8236.

Transport across Zeolite Membranes. *Chem. Eng. J.* , 57, 155-162.

Separation Applications. *Phys. Chem. Chem. Phys.*, 13, 10593-10616.

Benzenedicarboxylate). *J. Am. Chem. Soc.*, 120, 8571-8572.

Mixtures in MOF-5. *Ind. Eng. Chem. Res.*, 48, 914-922.

14055-14059.

11786-11795.

*Res.*, 48, 2355-2371.

*Eng. Chem. Res.*, 50, 1799-1812.

*Chem. Int. Ed.*, 43, 2334–2375.

*Phys. Chem. Chem. Phys.*, 4, 1891-1898.

106.

13054.

Membrane-Based Methane/Carbon Dioxide Separations. *J. Phys. Chem. C*, 111,

Multi-Component Mass Transport of Adsorbed Gases in Metal Organic Frameworks: Diffusion of H2/CH4 Mixtures in Cu-BTC. *Langmuir*, 24, 8254–8261. Keskin, S.&Sholl, D. S. (2009a). Assessment of a Metal-Organic Framework Membrane for

Gas Separations Using Atomically Detailed Calculations: CO2, CH4, N2, H2

Membranes for Gas Separations Using Atomically-Detailed Models. *Langmuir*, 25,

Mixture Diffusion through CuBTC Membranes. *Micropor. Mesopor. Mater.*, 125, 101-

and Challenges for Applying Atomically Detailed Modeling to Molecular Adsorption and Transport in Metal-Organic Framework Materials. *Ind. Eng. Chem.* 

Organic Framework Membranes and Composites. *J. Phys. Chem. C*, 114, 13047-


of Zeolitic Imidazolate Frameworks. *Proc. Natl. Acad. Sci. U. S. A.*, 103, 10186- 10191.

Recent Advances in Molecular Dynamics

403-411.

10132-10141.

Formulation. *Langmuir*, 19, 7977-7988.

*Phys. Lett.*, 501, 455-460.

*J. Solid State Chem.*, 178, 2420-2429.

*Phys. Chem. Chem. Phys.*, 11, 11389-11394.

Press,New York

114, 10527-10534.

468.

University Press,Delft

Simulations. *J. Phys. Chem. B*, 109, 15760-15768.

Material MOF-5. *Angew. Chem. Int. Ed.*, 45, 2123-2126.

Simulations of Gas Diffusion in Metal Organic Frameworks 279

Sholl, D. S. (2006). Understanding Macroscopic Diffusion of Adsorbed Molecules in

Skoulidas, A. I., Ackerman, D. M., Johnson, J. K.&Sholl, D. S. (2002). Rapid Transport of

Skoulidas, A. I.&Sholl, D. S. (2003). Molecular Dynamics Simulations of Self-Diffusivities,

Skoulidas, A. I., Sholl, D. S.&Krishna, R. (2003). Correlation Effects in Diffusion of CH4/CF4

Skoulidas, A. I. (2004). Molecular Dynamics Simulations of Gas Diffusion in Metal-Organic

Skoulidas, A. I.&Sholl, D. S. (2005). Self-Diffusion and Transport Diffusion of Light Gases in

Stallmach, F., Groger, S., Kunzel, V., Kärger, J., Yaghi, O. M., Hesse, M.&Muller, U. (2006).

Sun, X., Wick, C. D., Thallapallya, P. K., McGraila, B. P.&Danga, L. X. (2011). Molecular

Tafipolsky, M., Amirjalayer, S.&Schmid, R. (2007). Ab Initio Parametrized MM3 Force Field for the Metal-Organic Framework MOF-5. *J. Comput. Chem.*, 28, 1169-1176. Theodorou, D. N., Snurr, R. Q.&Bell, A. T. (1996). *Molecular Dynamics and Diffusion in* 

Uemura, K., Matsuda, R.&Kitagawa, S. (2005). Flexible Microporous Coordination Polymers

Watanabe, T., Keskin, S., Nair, S.&Sholl, D. S. (2009). Computational Identification of a

Wehring, M., Gascon, J., Dubbeldam, D., Kapteijn, F., Snurr, R. Q.&Stallmach, F. (2010). Self-

Wesselingh, J. A.&Krishna, R. (2000). *Mass Transfer in Multicomponent Mixtures*. Delft

Xiong, R., Odbadrakh, K., Michalkova, A., Luna, J. P., Petrova, T., Keffer, D. J., Nicholson, D.

Xu, Q.&Zhong, C. (2010). A General Approach for Estimating Framework Charges in Metal

Organic Frameworks. *J. Phys. Chem. C*, 114, 5035-5042.

Frameworks: Argon in CuBTC. *J. Am. Chem. Soc.*, 126, 1356-1357.

Gases in Carbon Nanotubes. *Phys. Rev. Lett.*, 89, 185901-185904.

Crystalline Nanoporous Materials Via Atomistic Simulations. *Acc. Chem. Res.*, 39,

Corrected Diffusivities, and Transport Diffusivities of Light Gases in Four Silica Zeolites to Assess Influences of Pore Shape and Connectivity. *J. Phys. Chem. A*, 107,

Mixtures in MFI Zeolite. A Study Linking MD Simulations with the Maxwell-Stefan

Metal-Organic Framework Materials Assessed Using Molecular Dynamics

NMR Studies on the Diffusion of Hydrocarbons in the Metal-Organic Framework

Mechanism of Hydrocarbons Binding to the Metal–Organic Framework. *Chem.* 

*Microporous Materials. In Comprehensive Supramolecular Chemistry*. Pergamon

Metal Organic Framework for High Selectivity Membrane-Based Gas Separations.

Diffusion Studies in CuBTC by PFG NMR and MD Simulations. *J. Phys. Chem. C*,

M., Fuentes-Cabrera, M. A., Lewis, J. P.&Leszczynski, J. (2010). Evaluation of Functionalized Isoreticular Metal Organic Frameworks (IRMOFs) as Smart Nanoporous Preconcentrators of RDX. *Sensors and Actuators B: Chemical*, 148, 459-


Potoff, J. J.&Siepmann, J. I. (2001). Vapor-Liquid Equilibria of Mixtures Contaning Alkanes,

Rankin, R. B., Liu, J., Kulkarni, A. D.&Johnson, J. K. (2009). Adsorption and Diffusion of

Rappe, A. K., Casewit, C. J., Colwell, K. S., Goddard, W. A.&Skiff, W. M. (1992). Application

Rowsell, J. L. C., Spencer, E. C., Eckert, J., Howard, J. A. K.&Yaghi, O. M. (2005). Gas

Sagara, T., Klassen, J.&Ganz, E. (2004). Computational Study of Hydrogen Binding by

Sagara, T., Ortony, J.&Ganz, E. (2005a). New Isoreticular Metal-Organic Framework

Sagara, T., Klassen, J., Ortony, J.&Ganz, E. (2005b). Binding Energies of Hydrogen Molecules

Salles, F., Jobic, H., Maurin, G., Koza, M. M., Llewellyn, P. L., Devic, T., Serre, C.&Ferey, G.

Salles, F., Jobic, H., Devic, T., Llewellyn, P., Serre, C., G.Ferey&Maurin, G. (2010). Self and

Salles, F., Bourrelly, S., Jobic, H., Devic, T., Guillerm, V., Llewellyn, P., Serre, C.,

Sanborn, M. J.&Snurr, R. Q. (2000). Diffusion of Binary Mixtures of CF4 and N-Alkanes in

Sarkisov, L., Düren, T.&Snurr, R. Q. (2004). Molecular Modeling of Adsorption in Novel

Seehamart, K., Chmelik, C., Krishna, R.&Fritzsche, S. (2011). Molecular Dynamics

Nanoporous Metal-Organic Materials. *Mol. Phys.*, 102, 211-221.

Ruthven, D. M. (1984). *Principles of Adsorption and Adsorption Processes.* Wiley,New York Ryan, P., Broadbelt, L. J.&Snurr, R. Q. (2008). Is Catenation Beneficial for Hydrogen Storage

in Metal-Organic Frameworks? *Chem. Commun.*, 4132-4134.

Metal-Organic Framework-5. *J. Chem. Phys.*, 121, 12543-12547.

Carbon Dioxide, and Nitrogen. *AIChE J.*, 47, 1676-1682.

10191.

16914.

10046.

1354.

214713.

014706.

245904.

Simulations. *ACS Nano*, 4, 143-152.

Faujasite. *Sep. Purif. Technol.*, 20, 1-13.

*Chem. C*, 115, 10764-10776.

*Mater.*, 143, 125-131.

of Zeolitic Imidazolate Frameworks. *Proc. Natl. Acad. Sci. U. S. A.*, 103, 10186-

Light Gases in ZIF-68 and ZIF-70: A Simulation Study. *J. Phys. Chem. C*, 113, 16906-

of a Universal Force Field to Organic Molecules. *J. Am. Chem. Soc.*, 114, 10035-

Adsorption Sites in a Large-Pore Metal Organic Framework. *Science*, 309, 1350-

Materials for High Hydrogen Storage Capacity. *J. Chem. Phys.*, 123, 214707-

to Isoreticular Metal-Organic Framework Materials. *J. Chem. Phys.*, 123, 014701-

(2008). Experimental Evidence Supported by Simulations of a Very High H2 Diffusion in Metal Organic Framework Materials. *Phys. Rev. Lett.*, 100, 245901-

Transport Diffusivity of CO2 in the Metal−Organic Framework MIL-47(V) Explored by Quasi-Elastic Neutron Scattering Experiments and Molecular Dynamics

G.Ferey&Maurin, G. (2011). Molecular Insight into the Adsorption and Diffusion of Water in the Versatile Hydrophilic/Hydrophobic Flexible MIL-53(Cr) MOF. *J. Phys.* 

Investigation of the Self Diffusion of Binary Mixture Diffusion in the Metal Organic Framework Zn/Tbip) Accounting for the Frameowrk Flexibility. *Micropor. Mesopor.* 


Xue, C.&Zhong, C. (2009). Molecular Simulation Study of Hexane Diffusion in Dynamic Metal Organic Frameworks. *Chinese J. Chem.*, 27, 472-478.

**14** 

**Molecular Dynamic Simulation of Short** 

*Institute of Metallurgy, Russian Academy of Sciences, Ural division* 

Main concepts of Hydrogen permeability (HP) mechanism for the pure crystal metals are already stated. There are well-founded theoretical models and numerous experimental researches. As far as disordered systems (in which Hydrogen solubility is much more, than in crystal samples) are concerned, such works appear to be comparatively recent and rare. Particularly, they are devoted to Hydrogen interaction of with amorphous structures. Deficiency of similar researches is caused by thermo-temporal instability of amorphous

Unlike crystal alloy, where interstice volumes are presented discretely only by tetrahedron and octahedron cavities, small and big interstice cavities distribution in an amorphous alloy is close to Gaussian function (Polukhin and Vatolin, 1985, Polukhin et.al, 1984, 1986). Thus Hydrogen energy distribution function form in the amorphous alloys cavities is close to the main RDF peak which is approximated by Gaussian function. Inter-cavities transitions are strongly correlated, and the stationary states contribution to the Hydrogen atoms motion is

Amorfizator-elements (Si, B, C, etc.) insertion into the amorphous metals reduces number of large cavities (octahedrons) providing most energetically favourable Hydrogen migration path. It reduces metal absorption ability, as well as hydrogen diffusion motion intensity,

Amorphous alloys absorption ability of hydrogen is defined by number and size of cavities for hydrogen insertion, as well as the hydride forming elements (Ti, Zr, Hf, etc.) content in an alloy. Hydrogen diffusion factor in the amorphous alloys depends on its concentration.

Crystal and amorphous Palladium alloys are widely used in membranes for high pure Hydrogen producing. Literary data analysis shows possibility of filtering alloys production for hydrogen based on less expensive metals: V, Nb, Zr, Ta, etc., characterized by high Hydrogen solubility, which defines alloy Hydrogen permeability by diffusion factors as well as Palladium. Negative effect of these elements hydrides formation should be inhibited

**1. Introduction**

negligible.

materials structure and properties.

reducing Hydrogen permeability.

**Order and Hydrogen Diffusion in** 

**the Disordered Metal Systems** 

Eduard Pastukhov, Nikolay Sidorov, Andrey Vostrjakov and Victor Chentsov

 *Russian Federation* 

