An Adsorption Study of CH4 on ZSM-5, MOR, and ZSM-12 Zeolites

Zhang, Yiwei; Yu, JingYe; Yeh, Yu-Hao; Gorte, Raymond. J.; Rangarajan, Srinivas; Mavrikakis, Manos

doi:10.1021/acs.jpcc.5b09571

An Adsorption Study of CH₄ on ZSM-5, MOR, and ZSM-12 Zeolites

Journal Article · Mon Dec 07 00:00:00 EST 2015 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.5b09571· OSTI ID:1387606

Zhang, Yiwei ^[1]; Yu, JingYe ^[2]; Yeh, Yu-Hao ^[2]; Gorte, Raymond. J. ^[2]; Rangarajan, Srinivas ^[3]; Mavrikakis, Manos ^[3]

Univ. of Pennsylvania, Philadelphia, PA (United States). Dept. of Chemical and Biomolecular Engineering; Southeast Univ., Nanjing (China). School of Chemistry and Chemical Engineering
Univ. of Pennsylvania, Philadelphia, PA (United States). Dept. of Chemical and Biomolecular Engineering
Univ. of Wisconsin, Madison, WI (United States). Dept. of Chemical and Biological Engineering

CH₄ adsorption was studied experimentally and theoretically on ZSM-5, MOR, and ZSM-12 zeolites using calorimetric measurements at 195 K and plane wave DFT calculations. Differential heats measured on four different H-ZSM-5 samples were determined to be 22.5 ± 1 kJ/mol, independent of Brønsted site density or defect concentration. However, DFT calculations performed using various functionals and on the most stable Brønsted site indicated that CH4 should bind to this site by an additional 1–7 kJ/mol, a discrepancy that is due to the inability of standard DFT methods to capture hydrogen-bonding effects accurately with CH₄. Differential heats for CH₄ in MOR were 30±1 kJ/mol at low coverages, falling to 25 kJ/mol for coverages above one molecule per 8-membered-ring side pocket, while differential heats on ZSM-12 were initially 22.5 kJ/mol, decreasing to 21 kJ/mol with coverage. DFT calculations on the siliceous form of the zeolites were able to predict these values within 5 kJ/mol in most cases. The results indicate that CH₄ is an excellent probe molecule for characterizing the pore structure of zeolites.

View Accepted Manuscript (DOE)

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Catalysis Center for Energy Innovation (CCEI)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: SC0001004

OSTI ID:: 1387606

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 52 Vol. 119; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (46)

Selective Carbonylation of Dimethyl Ether to Methyl Acetate Catalyzed by Acidic Zeolites Cheung, Patricia; Bhan, Aditya; Sunley, Glenn J. Angewandte Chemie International Edition, Vol. 45, Issue 10 https://doi.org/10.1002/anie.200503898	journal	February 2006
Density Functional Theory and Hydrogen Bonds: Are We There Yet? Boese, A. Daniel ChemPhysChem, Vol. 16, Issue 5 https://doi.org/10.1002/cphc.201402786	journal	February 2015
Semiempirical GGA-type density functional constructed with a long-range dispersion correction Grimme, Stefan Journal of Computational Chemistry, Vol. 27, Issue 15, p. 1787-1799 https://doi.org/10.1002/jcc.20495	journal	January 2006
The adsorption of methane on H-ZSM-5 zeolite Papp, H.; Hinsen, W.; Do, N. T. Thermochimica Acta, Vol. 82, Issue 1 https://doi.org/10.1016/0040-6031(84)87282-2	journal	December 1984
Synthesis and characterization of defect-free crystals of MFI-type zeolites Axon, Sean A.; Klinowski, Jacek Applied Catalysis A: General, Vol. 81, Issue 1 https://doi.org/10.1016/0926-860X(92)80258-E	journal	January 1992
Heats of adsorption for ammonia and pyridine in H-ZSM-5: evidence for identical Brønsted-acid sites Parrillo, D. J.; Lee, C.; Gorte, R. J. Applied Catalysis A: General, Vol. 110, Issue 1 https://doi.org/10.1016/0926-860X(94)80106-1	journal	March 1994
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set Kresse, G.; Furthmüller, J. Computational Materials Science, Vol. 6, Issue 1, p. 15-50 https://doi.org/10.1016/0927-0256(96)00008-0	journal	July 1996
Design parameters for the construction and operation of heat-flow calorimeters Parrillo, D. J.; Gorte, R. J. Thermochimica Acta, Vol. 312, Issue 1-2 https://doi.org/10.1016/S0040-6031(97)00446-2	journal	March 1998
Alkane sorption in molecular sieves: The contribution of ordering, intermolecular interactions, and sorption on Brønsted acid sites Eder, Florian; Lercher, Johannes A. Zeolites, Vol. 18, Issue 1 https://doi.org/10.1016/S0144-2449(96)00127-3	journal	January 1997
A calorimetric investigation of CO, N2, and O2 in alkali-exchanged MFI Savitz, S.; Myers, A. L.; Gorte, R. J. Microporous and Mesoporous Materials, Vol. 37, Issue 1-2 https://doi.org/10.1016/S1387-1811(99)00190-0	journal	May 2000
Periodic, vdW-corrected density functional theory investigation of the effect of Al siting in H-ZSM-5 on chemisorption properties and site-specific acidity Ghorbanpour, Arian; Rimer, Jeffrey D.; Grabow, Lars C. Catalysis Communications, Vol. 52 https://doi.org/10.1016/j.catcom.2014.04.005	journal	July 2014
Embedded cluster (QM/MM) investigation of C6 diene cyclization in HZSM-5 Joshi, Y.; Thomson, K. Journal of Catalysis, Vol. 230, Issue 2 https://doi.org/10.1016/j.jcat.2004.12.016	journal	March 2005
Observation of a compensation relation for n-hexane adsorption in zeolites with different structures: implications for catalytic activity Ramachandran, C.; Williams, B.; Vanbokhoven, J. Journal of Catalysis, Vol. 233, Issue 1 https://doi.org/10.1016/j.jcat.2005.04.017	journal	July 2005
The role of spatial constraints and entropy in the adsorption and transformation of hydrocarbons catalyzed by zeolites Bučko, Tomáš; Hafner, Jürgen Journal of Catalysis, Vol. 329 https://doi.org/10.1016/j.jcat.2015.04.015	journal	September 2015
Accurate Adsorption Thermodynamics of Small Alkanes in Zeolites. Ab initio Theory and Experiment for H-Chabazite Piccini, GiovanniMaria; Alessio, Maristella; Sauer, Joachim The Journal of Physical Chemistry C, Vol. 119, Issue 11 https://doi.org/10.1021/acs.jpcc.5b01739	journal	March 2015
Predicting Methane Storage in Open-Metal-Site Metal–Organic Frameworks Koh, Hyun Seung; Rana, Malay Kumar; Wong-Foy, Antek G. The Journal of Physical Chemistry C, Vol. 119, Issue 24 https://doi.org/10.1021/acs.jpcc.5b02768	journal	June 2015
Review and Analysis of Molecular Simulations of Methane, Hydrogen, and Acetylene Storage in Metal–Organic Frameworks Getman, Rachel B.; Bae, Youn-Sang; Wilmer, Christopher E. Chemical Reviews, Vol. 112, Issue 2, p. 703-723 https://doi.org/10.1021/cr200217c	journal	September 2011
Performance of Several Density Functional Theory Methods on Describing Hydrogen-Bond Interactions Rao, Li; Ke, Hongwei; Fu, Gang Journal of Chemical Theory and Computation, Vol. 5, Issue 1 https://doi.org/10.1021/ct800237n	journal	December 2008
Characterization of acidity in H-ZSM-5, H-ZSM-12, H-Mordenite, and H-Y using microcalorimetry Parrillo, D. J.; Gorte, R. J. The Journal of Physical Chemistry, Vol. 97, Issue 34 https://doi.org/10.1021/j100136a023	journal	August 1993
Acidity Differences between Inorganic Solids Induced by Their Framework Structure. A Combined Quantum Mechanics/Molecular Mechanics ab Initio Study on Zeolites Brändle, Martin; Sauer, Joachim Journal of the American Chemical Society, Vol. 120, Issue 7 https://doi.org/10.1021/ja9729037	journal	February 1998
On the Accuracy of DFT for Describing Hydrogen Bonds: Dependence on the Bond Directionality Ireta, Joel; Neugebauer, Jörg; Scheffler, Matthias The Journal of Physical Chemistry A, Vol. 108, Issue 26 https://doi.org/10.1021/jp0377073	journal	July 2004
Adsorption and Vibrational Spectroscopy of CO on Mordenite: Ab initio Density-Functional Study Bučko, T.; Hafner, J.; Benco, L. The Journal of Physical Chemistry B, Vol. 109, Issue 15 https://doi.org/10.1021/jp050151u	journal	April 2005
Adsorption of C2−C8 n -Alkanes in Zeolites De Moor, Bart A.; Reyniers, Marie-Françoise; Gobin, Oliver C. The Journal of Physical Chemistry C, Vol. 115, Issue 4 https://doi.org/10.1021/jp106536m	journal	September 2010
Theoretical Study of Host−Guest Interactions in the Large and Small Cavities of MOR Zeolite Models Dominguez-Soria, Victor D.; Calaminici, Patrizia; Goursot, Annick The Journal of Physical Chemistry C, Vol. 115, Issue 14 https://doi.org/10.1021/jp108815r	journal	March 2011
β-Scission of Olefins on Acidic Zeolites: A Periodic PBE-D Study in H-ZSM-5 Mazar, Mark N.; Al-Hashimi, Saleh; Cococcioni, Matteo The Journal of Physical Chemistry C, Vol. 117, Issue 45 https://doi.org/10.1021/jp403504n	journal	October 2013
Calorimetric Study of Alcohol and Nitrile Adsorption Complexes in H-ZSM-5 Lee, C. -C.; Gorte, R. J.; Farneth, W. E. The Journal of Physical Chemistry B, Vol. 101, Issue 19 https://doi.org/10.1021/jp970711s	journal	May 1997
Calorimetric Study of Adsorption of Alkanes in High-Silica Zeolites Savitz, Scott; Siperstein, Flor; Gorte, Raymond J. The Journal of Physical Chemistry B, Vol. 102, Issue 35 https://doi.org/10.1021/jp981836f	journal	August 1998
Calorimetric Investigation of CO and N ₂ for Characterization of Acidity in Zeolite H−MFI Savitz, S.; Myers, A. L.; Gorte, R. J. The Journal of Physical Chemistry B, Vol. 103, Issue 18 https://doi.org/10.1021/jp990157h	journal	May 1999
Calorimetric Heats of Adsorption and Adsorption Isotherms. 1. O ₂ , N ₂ , Ar, CO ₂ , CH ₄ , C ₂ H ₆ , and SF ₆ on Silicalite Dunne, J. A.; Mariwala, R.; Rao, M. Langmuir, Vol. 12, Issue 24 https://doi.org/10.1021/la960495z	journal	January 1996
What do we know about the acidity of solid acids? Gorte, R. J. Catalysis Letters, Vol. 62, Issue 1, p. 1-13 https://doi.org/10.1023/A:1019010013989	journal	January 1999
The materials genome in action: identifying the performance limits for methane storage Simon, Cory M.; Kim, Jihan; Gomez-Gualdron, Diego A. Energy & Environmental Science, Vol. 8, Issue 4 https://doi.org/10.1039/C4EE03515A	journal	January 2015
A thermodynamic tank model for studying the effect of higher hydrocarbons on natural gas storage in metal–organic frameworks Zhang, Hongda; Deria, Pravas; Farha, Omar K. Energy Environ. Sci., Vol. 8, Issue 5 https://doi.org/10.1039/C5EE00808E	journal	January 2015
Performance of conventional and dispersion-corrected density-functional theory methods for hydrogen bonding interaction energies DiLabio, Gino A.; Johnson, Erin R.; Otero-de-la-Roza, Alberto Physical Chemistry Chemical Physics, Vol. 15, Issue 31 https://doi.org/10.1039/c3cp51559a	journal	January 2013
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu Grimme, Stefan; Antony, Jens; Ehrlich, Stephan The Journal of Chemical Physics, Vol. 132, Issue 15 https://doi.org/10.1063/1.3382344	journal	April 2010
Van der Waals interactions between hydrocarbon molecules and zeolites: Periodic calculations at different levels of theory, from density functional theory to the random phase approximation and Møller-Plesset perturbation theory Göltl, Florian; Grüneis, Andreas; Bučko, Tomas The Journal of Chemical Physics, Vol. 137, Issue 11 https://doi.org/10.1063/1.4750979	journal	September 2012
Quantum chemical ab initio prediction of proton exchange barriers between CH ₄ and different H-zeolites Tuma, Christian; Sauer, Joachim The Journal of Chemical Physics, Vol. 143, Issue 10 https://doi.org/10.1063/1.4923086	journal	September 2015
Evaluated Gas Phase Basicities and Proton Affinities of Molecules: An Update Hunter, Edward P. L.; Lias, Sharon G. Journal of Physical and Chemical Reference Data, Vol. 27, Issue 3 https://doi.org/10.1063/1.556018	journal	May 1998
Atoms, molecules, solids, and surfaces: Applications of the generalized gradient approximation for exchange and correlation Perdew, John P.; Chevary, J. A.; Vosko, S. H. Physical Review B, Vol. 46, Issue 11 https://doi.org/10.1103/PhysRevB.46.6671	journal	September 1992
Erratum: Atoms, molecules, solids, and surfaces: Applications of the generalized gradient approximation for exchange and correlation Perdew, John P.; Chevary, J. A.; Vosko, S. H. Physical Review B, Vol. 48, Issue 7 https://doi.org/10.1103/PhysRevB.48.4978.2	journal	August 1993
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
From ultrasoft pseudopotentials to the projector augmented-wave method Kresse, G.; Joubert, D. Physical Review B, Vol. 59, Issue 3, p. 1758-1775 https://doi.org/10.1103/PhysRevB.59.1758	journal	January 1999
Improved adsorption energetics within density-functional theory using revised Perdew-Burke-Ernzerhof functionals Hammer, B.; Hansen, L. B.; Nørskov, J. K. Physical Review B, Vol. 59, Issue 11 https://doi.org/10.1103/PhysRevB.59.7413	journal	March 1999
Density functionals for surface science: Exchange-correlation model development with Bayesian error estimation Wellendorff, Jess; Lundgaard, Keld T.; Møgelhøj, Andreas Physical Review B, Vol. 85, Issue 23 https://doi.org/10.1103/PhysRevB.85.235149	journal	June 2012
Restoring the Density-Gradient Expansion for Exchange in Solids and Surfaces Perdew, John P.; Ruzsinszky, Adrienn; Csonka, Gábor I. Physical Review Letters, Vol. 100, Issue 13 https://doi.org/10.1103/PhysRevLett.100.136406	journal	April 2008
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data Momma, Koichi; Izumi, Fujio Journal of Applied Crystallography, Vol. 44, Issue 6 https://doi.org/10.1107/S0021889811038970	journal	October 2011

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