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Title: Record-Setting Sorbents for Reversible Water Uptake by Systematic Anion Exchanges in Metal–Organic Frameworks

Abstract

The reversible capture of water vapor at low humidity can enable transformative applications such as atmospheric water harvesting and heat transfer that uses water as a refrigerant, replacing environmentally detrimental hydro- and chloro-fluorocarbons. The driving force for these applications is governed by the relative humidity at which the pores of a porous material fill with water. Here, we demonstrate modulation of the onset of pore-filling in a family of metal-organic frameworks with record water sorption capacities by employing anion exchange. Unexpectedly, the replacement of the structural bridging Cl - with the more hydrophilic anions F - and OH - does not induce porefilling at lower relative humidity, whereas the introduction of the larger Br - results in a substantial shift toward lower relative humidity. We rationalize these results in terms of pore size modifications as well as the water hydrogen bonding structure based on detailed infrared spectroscopic measurements. Fundamentally, our data suggest that, in the presence of strong nucleation sites, the thermodynamic favorability of water pore-filling depends more strongly on the pore diameter and the interface between water in the center of the pore and water bound to the pore walls than the hydrophilicity of the pore wall itself. Onmore » the basis of these results, we report two materials that exhibit record water uptake capacities in their respective humidity regions and extended stability over 400 water adsorption-desorption cycles.« less

Authors:
ORCiD logo [1]; ORCiD logo [1];  [1];  [1]; ORCiD logo [2]; ORCiD logo [1]
  1. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Dept. of Chemistry
  2. Univ. of Oregon, Eugene, OR (United States). Dept. of Chemistry and Biochemistry
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Contributing Org.:
Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
OSTI Identifier:
1560063
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 141; Journal Issue: 35; 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

Rieth, Adam J., Wright, Ashley M., Skorupskii, Grigorii, Mancuso, Jenna L., Hendon, Christopher H., and Dincă, Mircea. Record-Setting Sorbents for Reversible Water Uptake by Systematic Anion Exchanges in Metal–Organic Frameworks. United States: N. p., 2019. Web. doi:10.1021/jacs.9b06246.
Rieth, Adam J., Wright, Ashley M., Skorupskii, Grigorii, Mancuso, Jenna L., Hendon, Christopher H., & Dincă, Mircea. Record-Setting Sorbents for Reversible Water Uptake by Systematic Anion Exchanges in Metal–Organic Frameworks. United States. doi:10.1021/jacs.9b06246.
Rieth, Adam J., Wright, Ashley M., Skorupskii, Grigorii, Mancuso, Jenna L., Hendon, Christopher H., and Dincă, Mircea. Fri . "Record-Setting Sorbents for Reversible Water Uptake by Systematic Anion Exchanges in Metal–Organic Frameworks". United States. doi:10.1021/jacs.9b06246. https://www.osti.gov/servlets/purl/1560063.
@article{osti_1560063,
title = {Record-Setting Sorbents for Reversible Water Uptake by Systematic Anion Exchanges in Metal–Organic Frameworks},
author = {Rieth, Adam J. and Wright, Ashley M. and Skorupskii, Grigorii and Mancuso, Jenna L. and Hendon, Christopher H. and Dincă, Mircea},
abstractNote = {The reversible capture of water vapor at low humidity can enable transformative applications such as atmospheric water harvesting and heat transfer that uses water as a refrigerant, replacing environmentally detrimental hydro- and chloro-fluorocarbons. The driving force for these applications is governed by the relative humidity at which the pores of a porous material fill with water. Here, we demonstrate modulation of the onset of pore-filling in a family of metal-organic frameworks with record water sorption capacities by employing anion exchange. Unexpectedly, the replacement of the structural bridging Cl- with the more hydrophilic anions F- and OH- does not induce porefilling at lower relative humidity, whereas the introduction of the larger Br- results in a substantial shift toward lower relative humidity. We rationalize these results in terms of pore size modifications as well as the water hydrogen bonding structure based on detailed infrared spectroscopic measurements. Fundamentally, our data suggest that, in the presence of strong nucleation sites, the thermodynamic favorability of water pore-filling depends more strongly on the pore diameter and the interface between water in the center of the pore and water bound to the pore walls than the hydrophilicity of the pore wall itself. On the basis of these results, we report two materials that exhibit record water uptake capacities in their respective humidity regions and extended stability over 400 water adsorption-desorption cycles.},
doi = {10.1021/jacs.9b06246},
journal = {Journal of the American Chemical Society},
issn = {0002-7863},
number = 35,
volume = 141,
place = {United States},
year = {2019},
month = {8}
}

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Figures / Tables:

Figure 1 Figure 1: Structure of Ni2X2BTDD (X = Cl, F, Br, OH). Left: View parallel to the c axis. Right: View of anion-exchanged SBUs perpendicular to the c axis and synthetic pathways.

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Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.