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Title: Unexpected Diffusion Anisotropy of Carbon Dioxide in the Metal–Organic Framework Zn2(dobpdc)

Abstract

Metal–organic frameworks are promising materials for energy-efficient gas separations, but little is known about the diffusion of adsorbates in materials featuring one-dimensional porosity at the nanoscale. An understanding of the interplay between framework structure and gas diffusion is crucial for the practical application of these materials as adsorbents or in mixed-matrix membranes, since the rate of gas diffusion within the adsorbent pores impacts the required size (and therefore cost) of the adsorbent column or membrane. In this paper, we investigate the diffusion of CO2 within the pores of Zn2(dobpdc) (dobpdc4– = 4,4'-dioxidobiphenyl-3,3'-dicarboxylate) using pulsed field gradient (PFG) nuclear magnetic resonance (NMR) spectroscopy and molecular dynamics (MD) simulations. The residual chemical shift anisotropy for pore-confined CO2 allows PFG NMR measurements of self-diffusion in different crystallographic directions, and our analysis of the entire NMR line shape as a function of the applied field gradient provides a precise determination of the self-diffusion coefficients. In addition to observing CO2 diffusion through the channels parallel to the crystallographic c axis (self-diffusion coefficient D = (5.8 ± 0.1) × 10–9 m2 s–1 at a pressure of 625 mbar CO2), we unexpectedly find that CO2 is also able to diffuse between the hexagonal channels in the crystallographicmore » ab plane (D = (1.9 ± 0.2) × 10–10 m2 s–1), despite the walls of these channels appearing impermeable by single-crystal X-ray crystallography and flexible lattice MD simulations. Finally, observation of such unexpected diffusion in the ab plane suggests the presence of defects that enable effective multidimensional CO2 transport in a metal–organic framework with nominally one-dimensional porosity.« less

Authors:
ORCiD logo [1];  [2];  [2]; ORCiD logo [3]; ORCiD logo [3];  [3];  [2];  [2]; ORCiD logo [4];  [5]; ORCiD logo [6];  [7]
  1. Univ. of California, Berkeley, CA (United States). Dept. of Chemistry. Dept. of Chemical and Biomolecular Engineering. Berkeley Energy and Climate Inst.
  2. Univ. of California, Berkeley, CA (United States). Dept. of Chemistry
  3. Univ. of California, Berkeley, CA (United States). Dept. of Chemical and Biomolecular Engineering
  4. Univ. of California, Berkeley, CA (United States). Dept. of Chemistry. Dept. of Chemical and Biomolecular Engineering; École Polytechnique Fedérale de Lausanne (EPFL) (Switzlerland). Inst. of Chemical Sciences and Engineering
  5. RWTH Aachen Univ. (Germany). Inst. of Technical and Macromolecular Chemistry (ITMC)
  6. Univ. of California, Berkeley, CA (United States). Dept. of Chemistry. Dept. of Chemical and Biomolecular Engineering; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division
  7. Univ. of California, Berkeley, CA (United States). Dept. of Chemical and Biomolecular Engineering; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Gas Separations Relevant to Clean Energy Technologies (CGS); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Inst. of Health (NIH) (United States)
OSTI Identifier:
1464162
Grant/Contract Number:  
AC02-05CH11231; SC0001015; GM120799; S10-RR027172
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 140; Journal Issue: 5; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Forse, Alexander C., Gonzalez, Miguel I., Siegelman, Rebecca L., Witherspoon, Velencia J., Jawahery, Sudi, Mercado, Rocio, Milner, Phillip J., Martell, Jeffrey D., Smit, Berend, Blümich, Bernhard, Long, Jeffrey R., and Reimer, Jeffrey A. Unexpected Diffusion Anisotropy of Carbon Dioxide in the Metal–Organic Framework Zn2(dobpdc). United States: N. p., 2018. Web. doi:10.1021/jacs.7b09453.
Forse, Alexander C., Gonzalez, Miguel I., Siegelman, Rebecca L., Witherspoon, Velencia J., Jawahery, Sudi, Mercado, Rocio, Milner, Phillip J., Martell, Jeffrey D., Smit, Berend, Blümich, Bernhard, Long, Jeffrey R., & Reimer, Jeffrey A. Unexpected Diffusion Anisotropy of Carbon Dioxide in the Metal–Organic Framework Zn2(dobpdc). United States. https://doi.org/10.1021/jacs.7b09453
Forse, Alexander C., Gonzalez, Miguel I., Siegelman, Rebecca L., Witherspoon, Velencia J., Jawahery, Sudi, Mercado, Rocio, Milner, Phillip J., Martell, Jeffrey D., Smit, Berend, Blümich, Bernhard, Long, Jeffrey R., and Reimer, Jeffrey A. 2018. "Unexpected Diffusion Anisotropy of Carbon Dioxide in the Metal–Organic Framework Zn2(dobpdc)". United States. https://doi.org/10.1021/jacs.7b09453. https://www.osti.gov/servlets/purl/1464162.
@article{osti_1464162,
title = {Unexpected Diffusion Anisotropy of Carbon Dioxide in the Metal–Organic Framework Zn2(dobpdc)},
author = {Forse, Alexander C. and Gonzalez, Miguel I. and Siegelman, Rebecca L. and Witherspoon, Velencia J. and Jawahery, Sudi and Mercado, Rocio and Milner, Phillip J. and Martell, Jeffrey D. and Smit, Berend and Blümich, Bernhard and Long, Jeffrey R. and Reimer, Jeffrey A.},
abstractNote = {Metal–organic frameworks are promising materials for energy-efficient gas separations, but little is known about the diffusion of adsorbates in materials featuring one-dimensional porosity at the nanoscale. An understanding of the interplay between framework structure and gas diffusion is crucial for the practical application of these materials as adsorbents or in mixed-matrix membranes, since the rate of gas diffusion within the adsorbent pores impacts the required size (and therefore cost) of the adsorbent column or membrane. In this paper, we investigate the diffusion of CO2 within the pores of Zn2(dobpdc) (dobpdc4– = 4,4'-dioxidobiphenyl-3,3'-dicarboxylate) using pulsed field gradient (PFG) nuclear magnetic resonance (NMR) spectroscopy and molecular dynamics (MD) simulations. The residual chemical shift anisotropy for pore-confined CO2 allows PFG NMR measurements of self-diffusion in different crystallographic directions, and our analysis of the entire NMR line shape as a function of the applied field gradient provides a precise determination of the self-diffusion coefficients. In addition to observing CO2 diffusion through the channels parallel to the crystallographic c axis (self-diffusion coefficient D∥ = (5.8 ± 0.1) × 10–9 m2 s–1 at a pressure of 625 mbar CO2), we unexpectedly find that CO2 is also able to diffuse between the hexagonal channels in the crystallographic ab plane (D⊥ = (1.9 ± 0.2) × 10–10 m2 s–1), despite the walls of these channels appearing impermeable by single-crystal X-ray crystallography and flexible lattice MD simulations. Finally, observation of such unexpected diffusion in the ab plane suggests the presence of defects that enable effective multidimensional CO2 transport in a metal–organic framework with nominally one-dimensional porosity.},
doi = {10.1021/jacs.7b09453},
url = {https://www.osti.gov/biblio/1464162}, journal = {Journal of the American Chemical Society},
issn = {0002-7863},
number = 5,
volume = 140,
place = {United States},
year = {Thu Jan 04 00:00:00 EST 2018},
month = {Thu Jan 04 00:00:00 EST 2018}
}

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Works referencing / citing this record:

Precise Control of Molecular Self‐Diffusion in Isoreticular and Multivariate Metal‐Organic Frameworks
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