Sorption and Transport of Vapors in ZIF-11: Adsorption, Diffusion, and Linker Flexibility

Pimentel, Brian R.; Jue, Melinda L.; Zhou, Er-Kang; Verploegh, Ross J.; Leisen, Johannes; Sholl, David S.; Lively, Ryan P.

doi:10.1021/acs.jpcc.9b02192

Title: Sorption and Transport of Vapors in ZIF-11: Adsorption, Diffusion, and Linker Flexibility

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Abstract

The adsorption and diffusion of alcohol and hydrocarbon vapors in zeolitic imidazolate frameworks (ZIF)-11 are reported as a function of loading at 308 K. The hydrophobicity of the benzimidazole linkers provides moderate ideal adsorbed solution theory selectivities for adsorptive alcohol/water separations until high relative humidity conditions. Sorbates well beyond the crystallographic pore aperture are admitted into the framework at decreasing diffusivities with increasing molecular size. The diffusion of methane is also observed as a function of temperature, revealing a nonconstant activation energy of diffusion, which is linked to the temperature-dependent flexibility of the ligands comprising the six- and eight-membered aperture rings, as revealed through solid-state NMR. Compared to ZIF-8, ZIF-11 surprisingly demonstrates higher diffusivities and lower activation energies despite the smaller crystallographic aperture size. This phenomenon is explained via molecular dynamics simulations that highlight the greater flexibility of the benzimidazole linker in ZIF-11 relative to the 2-methylimidazolate linker in ZIF-8 and specifies the importance of structural flexibility in identifying diffusionally-selective materials.

Authors:

^[1]; Jue, Melinda L. ^[1]; Zhou, Er-Kang ^[1]; Verploegh, Ross J. ^[1]; Leisen, Johannes ^[1];

^[1];

^[1]

Georgia Inst. of Technology, Atlanta, GA (United States)

Publication Date:: Tue Apr 30 00:00:00 EDT 2019

Research Org.:: Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

Sponsoring Org.:: USDOE National Nuclear Security Administration (NNSA)

OSTI Identifier:: 1527278

Report Number(s):: LLNL-JRNL-769244
Journal ID: ISSN 1932-7447; 960065

Grant/Contract Number:: AC52-07NA27344

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Physical Chemistry. C

Additional Journal Information:: Journal Volume: 123; Journal Issue: 20; Journal ID: ISSN 1932-7447

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 36 MATERIALS SCIENCE

Citation Formats


                    Pimentel, Brian R., Jue, Melinda L., Zhou, Er-Kang, Verploegh, Ross J., Leisen, Johannes, Sholl, David S., and Lively, Ryan P. Sorption and Transport of Vapors in ZIF-11: Adsorption, Diffusion, and Linker Flexibility.  United States: N. p., 2019. 
Web.  doi:10.1021/acs.jpcc.9b02192.

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                    Pimentel, Brian R., Jue, Melinda L., Zhou, Er-Kang, Verploegh, Ross J., Leisen, Johannes, Sholl, David S., & Lively, Ryan P. Sorption and Transport of Vapors in ZIF-11: Adsorption, Diffusion, and Linker Flexibility.  United States.  https://doi.org/10.1021/acs.jpcc.9b02192

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                    Pimentel, Brian R., Jue, Melinda L., Zhou, Er-Kang, Verploegh, Ross J., Leisen, Johannes, Sholl, David S., and Lively, Ryan P. Tue .  
"Sorption and Transport of Vapors in ZIF-11: Adsorption, Diffusion, and Linker Flexibility".  United States.  https://doi.org/10.1021/acs.jpcc.9b02192.  https://www.osti.gov/servlets/purl/1527278.

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@article{osti_1527278,

  title        = {Sorption and Transport of Vapors in ZIF-11: Adsorption, Diffusion, and Linker Flexibility},

  author       = {Pimentel, Brian R. and Jue, Melinda L. and Zhou, Er-Kang and Verploegh, Ross J. and Leisen, Johannes and Sholl, David S. and Lively, Ryan P.},

  abstractNote = {The adsorption and diffusion of alcohol and hydrocarbon vapors in zeolitic imidazolate frameworks (ZIF)-11 are reported as a function of loading at 308 K. The hydrophobicity of the benzimidazole linkers provides moderate ideal adsorbed solution theory selectivities for adsorptive alcohol/water separations until high relative humidity conditions. Sorbates well beyond the crystallographic pore aperture are admitted into the framework at decreasing diffusivities with increasing molecular size. The diffusion of methane is also observed as a function of temperature, revealing a nonconstant activation energy of diffusion, which is linked to the temperature-dependent flexibility of the ligands comprising the six- and eight-membered aperture rings, as revealed through solid-state NMR. Compared to ZIF-8, ZIF-11 surprisingly demonstrates higher diffusivities and lower activation energies despite the smaller crystallographic aperture size. This phenomenon is explained via molecular dynamics simulations that highlight the greater flexibility of the benzimidazole linker in ZIF-11 relative to the 2-methylimidazolate linker in ZIF-8 and specifies the importance of structural flexibility in identifying diffusionally-selective materials.},

  doi          = {10.1021/acs.jpcc.9b02192},

  journal      = {Journal of Physical Chemistry. C},

  number       = 20,

  volume       = 123,

  place        = {United States},

  year         = {Tue Apr 30 00:00:00 EDT 2019},

  month        = {Tue Apr 30 00:00:00 EDT 2019}

}

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