AJAC  Vol.4 No.10 C , October 2013
Adsorption Enthalpy Calculations of Hydrogen Adsorption at Ambient Temperature and Pressures Exceeding 300 bar
Abstract: Hydrogen adsorption isotherms were measured at ambient temperature to pressures exceeding 300 bar for three benchmark adsorbents: two metal-organic frameworks, Cu3(btc)2 (btc = 1,3,5-benzenetricarboxylate) and Zn4O(btb)2 (btb = 1,3,5-benzenetribenzoate), and the activated carbon MSC-30. The Dubinin-Astakhov model was applied to calculated absolute adsorption isotherms as a function of the fugacity to determine the adsorption enthalpy at ambient temperature. Comparisons of the calculated enthalpies and the surface excess concentration (excess adsorption per square meter of surface) show that Zn4O(btb)2 has an adsorption enthalpy comparable to MSC-30, but that the spacing between adsorbed molecules is much larger.
Cite this paper: M. Beckner and A. Dailly, "Adsorption Enthalpy Calculations of Hydrogen Adsorption at Ambient Temperature and Pressures Exceeding 300 bar," American Journal of Analytical Chemistry, Vol. 4 No. 10, 2013, pp. 8-16. doi: 10.4236/ajac.2013.410A3002.

[1]   G. Thomas, “Overview of Storage Development DOE Hydrogen Program,” 2000.

[2]   U. Eberle, B. Müller and R. von Helmolt, “Fuel Cell Electric Vehicles and Hydrogen Infrastructure: Status 2012,” Energy & Environmental Science, Vol. 5, No. 10, 2012, pp. 8780-8798.

[3]   “How FCX Clarity FCEV Works,” 2013.

[4]   J. Burress, M. Kraus, M. Beckner, R. Cepel, G. Suppes, C. Wexler and P. Pfeifer, “Hydrogen Storage in Engineered Carbon Nanospaces,” Nanotechnology, Vol. 20, No. 20, 2009, Article ID: 204026.

[5]   L. J. Murray, M. Dinca and J. R. Long, “Hydrogen Storage in Metal-organic Frameworks,” Chemical Society Reviews, Vol. 38, No. 5, 2009, pp. 1294-1314.

[6]   L. Firlej, S. Roszak, B. Kuchta, P. Pfeifer and C. Wexler, “Enhanced Hydrogen Adsorption in Boron Substituted Carbon Nanospaces,” Journal of Chemical Physics, Vol. 131, No. 16, 2009, Article ID:164702.

[7]   J. Romanos, M. Beckner, T. Rash, L. Firlej, B. Kuchta, P. Yu, G. Suppes, C. Wexler and P. Pfeifer, “Nanospace Engineering of KOH Activated Carbon,” Nanotechnology, Vol. 23, No. 1, 2012, Article ID: 015401.

[8]   H. Deng, S. Grunder, K. E. Cordova, C. Valente, H. Furukawa, M. Hmadeh, F. Gándara, A. C. Whalley, Z. Liu, S. Asahina, H. Kazumori, M. O’Keeffe, O. Terasaki, J. F. Stoddart and O. M. Yaghi, “Large-Pore Apertures in a Series of Metal-Organic Frameworks,” Science, Vol. 336, No. 6084, 2012, pp. 1018-1023.

[9]   D. J. Collins and H.-C. Zhou, “Hydrogen Storage in Metal-Organic Frameworks,” Journal of Materials Chemistry, Vol. 17, No. 30, 2007, pp. 3154-3160.

[10]   M. Dinca, A. Dailly, Y. Liu, C. M. Brown, D. A. Neumann and J. R. Long, “Hydrogen Storage in a Microporous Metal-Organic Framework with Exposed Mn2+ Coordination Sites,” Journal of the American Chemical Society, Vol. 128, No. 51, 2006, pp. 16876-16883.

[11]   Y. Ferro, F. Marinelli, A. Allouche and C. Brosset, “Density Functional Theory Investigation of H Adsorption on the Basal Plane of Boron-Doped Graphite,” The Journal of Chemical Physics, Vol. 118, No. 12, 2003, pp. 5650-5657.

[12]   T. C. M. Chung, Y. Jeong, Q. Chen, A. Kleinhammes and Y. Wu, “Synthesis of Microporous Boron-Substituted Carbon (b/c) Materials Using Polymeric Precursors for Hydrogen Physisorption,” Journal of the American Chemical Society, Vol. 130, No. 21, 2008, pp. 6668-6669.

[13]   F. Rouquerol, J. Rouquerol and K. Sing, “Adsorption by Powders & Porous Solids,” Academic Press, London, 1999.

[14]   E. Poirier, R. Chahine, P. Bénard, L. Lafi, G. DorvalDouville and P. A. Chandonia, “Hydrogen Adsorption Measurements and Modeling on Metal-Organic frameworks and Single-Walled Carbon Nanotubes,” Langmuir, Vol. 22, No. 21, 2006, pp. 8784-8789.

[15]   T. Otowa, R. Tanibata and M. Itoh, “Production and Adsorption Characteristics of MAXSORB: High-SurfaceArea Active Carbon,” Gas Separation & Purification, Vol. 7, No. 4, 1993, pp. 241-245.

[16]   T. Voskuilen, Y. Zheng and T. Pourpoint, “Development of a Sievert Apparatus for Characterization of High Pressure Hydrogen Sorption Materials,” International Journal of Hydrogen Energy, Vol. 35, No. 19, 2010, pp. 10387-10395.

[17]   T. G. Voskuilen, T. L. Pourpoint and A. M. Dailly, “Hydrogen Adsorption on Microporous Materials at Ambient Temperatures and Pressures up to 50 MPa,” Adsorption, Vol. 18, No. 3-4, 2012, pp. 239-249.

[18]   A. M. Tolmachev, “Adsorption of Gases, Vapors, and Solutions: II. Description and a Priori Calculations of Adsorption Equilibria,” Protection of Metals and Physical Chemistry of Surfaces, Vol. 46, No. 3, 2010, pp. 291-308.

[19]   A. L. Myers, “Thermodynamics of Adsorption in Porous Materials,” AIChE Journal, Vol. 48, No. 1, 2002, pp. 145-160.

[20]   E. W. Lemmon and R. T. Jacobsen, “A New Functional Form and New Fitting Techniques for Equations of State with Application to Pentafluoroethane (HFC-125),” Journal of Physical and Chemical Reference Data, Vol. 34, No. 1, 2005, pp. 69-108.

[21]   J. W. Leachman, R. T. Jacobsen, S. G. Penoncello and E. W. Lemmon, “Fundamental Equations of State for Parahydrogen, Normal Hydrogen, and Orthohydrogen,” Journal of Physical and Chemical Reference Data, Vol. 38, No. 3, 2009, pp. 721-748.

[22]   F. O. Mertens, “Determination of Absolute Adsorption in Highly Ordered Porous Media,” Surface Science, Vol. 603, No. 10-12, 2009, pp. 1979-1984.

[23]   S. Sircar, “Gibbsian Surface Excess for Gas Adsorption Revisited,” Industrial & Engineering Chemistry Research, Vol. 38, No. 10, 1999, pp. 3670-3682.

[24]   G. Aranovich and M. Donohue, “Determining Surface Areas from Linear Adsorption Isotherms at Supercritical Conditions,” Journal of Colloid and Interface Science, Vol. 194, No. 2, 1997, pp. 392-397.

[25]   D. Saha, Z. Wei and S. Deng, “Equilibrium, Kinetics and Enthalpy of Hydrogen Adsorption in MOF-177,” International Journal of Hydrogen Energy, Vol. 33, No. 24, 2008, pp. 7479-7488.

[26]   N. P. Stadie, M. Murialdo, C. C. Ahn and B. Fultz, “Anomalous Isosteric Enthalpy of Adsorption of Methane on Zeolite-templated Carbon,” Journal of the American Chemical Society, Vol. 135, No. 3, 2013, pp. 990-993.

[27]   E. Poirier and A. Dailly, “Thermodynamics of Hydrogen Adsorption in MOF-177 at Low Temperatures: Measurements and Modelling,” Nanotechnology, Vol. 20, No. 20, 2009, Article ID: 204006.

[28]   K. A. G. Amankwah and J. A. Schwarz, “A Modified Approach for Estimating Pseudo-Vapor Pressures in the Application of the Dubinin-Astakhov Equation,” Carbon, Vol. 33, No. 9, 1995, pp. 1313-1319.