Combined Nuclear Magnetic Resonance and Molecular Dynamics Study of Methane Adsorption in M2 (dobdc) Metal–Organic Frameworks

Witherspoon, Velencia J.; Mercado, Rocío; Braun, Efrem; Mace, Amber; Bachman, Jonathan; Long, Jeffrey R.; Blümich, Bernhard; Smit, Berend; Reimer, Jeffrey A.

doi:10.1021/acs.jpcc.9b01733

Combined Nuclear Magnetic Resonance and Molecular Dynamics Study of Methane Adsorption in M₂ (dobdc) Metal–Organic Frameworks

Journal Article · Tue Apr 23 00:00:00 EDT 2019 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.9b01733· OSTI ID:1542406

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Univ. of California, Berkeley, CA (United States)
Ecole Polytechnique Federale Lausanne (Switzlerland)
RWTH Aachen Univ. (Germany)
Univ. of California, Berkeley, CA (United States); Ecole Polytechnique Federale Lausanne (Switzlerland)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

We investigate the diffusion of methane in the metal-organic frameworks M₂ (dobdc) (M = Mg, Ni, Zn; dobdc^4- = 2,5-dioxido-1,4-benzenedicarboxylate) as a function of methane loading through a combination of nuclear magnetic resonance and molecular dynamics simulations. At low gas densities, our results suggest that favorable CH₄ -CH₄ interactions lower the free energy barrier for methane hopping between coordinatively unsaturated metal sites and thus enhance the translational motion of methane down the c-axis. At higher gas densities, CH₄ -CH₄ interactions become more significant, CH₄ -CH₄ collisions become more frequent, and the gas self-diffusion begins to decrease. Lastly, we determine that the self-diffusion coefficient of methane is inversely related to the binding energy at the coordinatively unsaturated metal sites, such that diffusion is most rapid in the Zn₂(dobdc) framework.

View Accepted Manuscript (DOE)

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Center for Gas Separations Relevant to Clean Energy Technologies (CGS); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Science Foundation (NSF); Aachen-California Network of Academic Exchange (DAAD Germany)

Grant/Contract Number:: AC02-05CH11231; SC0001015

OSTI ID:: 1542406

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 19 Vol. 123; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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