Enhancing Van der Waals Interactions of Functionalized UiO‐66 with Non‐polar Adsorbates: The Unique Effect of para Hydroxyl Groups
Abstract
Abstract UiO‐66 is a highly stable metal‐organic framework (MOF) that has garnered interest for many adsorption applications. For small, nonpolar adsorbates, physisorption is dominated by weak Van der Waals interactions limiting the adsorption capacity. A common strategy to enhance the adsorption properties of isoreticular MOFs, such as UiO‐66, is to add functional groups to the organic linker. Low and high pressure O 2 isotherms were measured on UiO‐66 MOFs functionalized with electron donating and withdrawing groups. It was found that the electron donating effects of ‐NH 2 , ‐OH, and ‐OCF 3 groups enhance the uptake of O 2 . Interestingly, a significant enhancement in both the binding energy and adsorption capacity of O 2 was observed for UiO‐66‐(OH) 2 ‐p, which has two ‐OH groups para from one another. Density functional theory (DFT) simulations were used to calculate the binding energy of oxygen to each MOF, which trended with the adsorption capacity and agreed well with the heats of adsorption calculated from the Toth model fit to multi‐temperature isotherms. DFT simulations also determined the highest energy binding site to be on top of the electron π‐cloud of the aromatic ring of the ligand, with a direct trend of themore »
- Authors:
-
[2];
[1]
- Edgewood Chemical Biological Center U.S. Army Research, Development and Engineering Command 5183 Blackhawk Road Aberdeen Proving Ground MD 21020 USA
- Nanoscale Sciences Department Sandia National Laboratories Albuquerque New Mexico 87185 USA
- Publication Date:
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1415668
- Resource Type:
- Publisher's Accepted Manuscript
- Journal Name:
- Chemistry - A European Journal
- Additional Journal Information:
- Journal Name: Chemistry - A European Journal Journal Volume: 24 Journal Issue: 8; Journal ID: ISSN 0947-6539
- Publisher:
- Wiley Blackwell (John Wiley & Sons)
- Country of Publication:
- Germany
- Language:
- English
Citation Formats
Tovar, Trenton M., Iordanov, Ivan, Sava Gallis, Dorina F., and DeCoste, Jared B. Enhancing Van der Waals Interactions of Functionalized UiO‐66 with Non‐polar Adsorbates: The Unique Effect of para Hydroxyl Groups. Germany: N. p., 2018.
Web. doi:10.1002/chem.201704779.
Tovar, Trenton M., Iordanov, Ivan, Sava Gallis, Dorina F., & DeCoste, Jared B. Enhancing Van der Waals Interactions of Functionalized UiO‐66 with Non‐polar Adsorbates: The Unique Effect of para Hydroxyl Groups. Germany. https://doi.org/10.1002/chem.201704779
Tovar, Trenton M., Iordanov, Ivan, Sava Gallis, Dorina F., and DeCoste, Jared B. Thu .
"Enhancing Van der Waals Interactions of Functionalized UiO‐66 with Non‐polar Adsorbates: The Unique Effect of para Hydroxyl Groups". Germany. https://doi.org/10.1002/chem.201704779.
@article{osti_1415668,
title = {Enhancing Van der Waals Interactions of Functionalized UiO‐66 with Non‐polar Adsorbates: The Unique Effect of para Hydroxyl Groups},
author = {Tovar, Trenton M. and Iordanov, Ivan and Sava Gallis, Dorina F. and DeCoste, Jared B.},
abstractNote = {Abstract UiO‐66 is a highly stable metal‐organic framework (MOF) that has garnered interest for many adsorption applications. For small, nonpolar adsorbates, physisorption is dominated by weak Van der Waals interactions limiting the adsorption capacity. A common strategy to enhance the adsorption properties of isoreticular MOFs, such as UiO‐66, is to add functional groups to the organic linker. Low and high pressure O 2 isotherms were measured on UiO‐66 MOFs functionalized with electron donating and withdrawing groups. It was found that the electron donating effects of ‐NH 2 , ‐OH, and ‐OCF 3 groups enhance the uptake of O 2 . Interestingly, a significant enhancement in both the binding energy and adsorption capacity of O 2 was observed for UiO‐66‐(OH) 2 ‐p, which has two ‐OH groups para from one another. Density functional theory (DFT) simulations were used to calculate the binding energy of oxygen to each MOF, which trended with the adsorption capacity and agreed well with the heats of adsorption calculated from the Toth model fit to multi‐temperature isotherms. DFT simulations also determined the highest energy binding site to be on top of the electron π‐cloud of the aromatic ring of the ligand, with a direct trend of the binding energy with low pressure adsorption capacity. Uniquely, DFT found that oxygen molecules adsorbed to UiO‐66‐(OH) 2 ‐p prefer to align parallel to the ‐OH groups on the aromatic ring. Similar effects for the electron donation of the functional groups were observed for the low pressure adsorption of N 2 , CH 4 , and CO 2 .},
doi = {10.1002/chem.201704779},
journal = {Chemistry - A European Journal},
number = 8,
volume = 24,
place = {Germany},
year = {Thu Jan 04 00:00:00 EST 2018},
month = {Thu Jan 04 00:00:00 EST 2018}
}
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1002/chem.201704779
https://doi.org/10.1002/chem.201704779
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 7 works
Citation information provided by
Web of Science
Web of Science
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Stability and degradation mechanisms of metal–organic frameworks containing the Zr6O4(OH)4 secondary building unit
journal, January 2013
- DeCoste, Jared B.; Peterson, Gregory W.; Jasuja, Himanshu
- Journal of Materials Chemistry A, Vol. 1, Issue 18
Functionalizing porous zirconium terephthalate UiO-66(Zr) for natural gas upgrading: a computational exploration
journal, January 2011
- Yang, Qingyuan; Wiersum, Andrew D.; Llewellyn, Philip L.
- Chemical Communications, Vol. 47, Issue 34
Isoreticular synthesis and modification of frameworks with the UiO-66 topology
journal, January 2010
- Garibay, Sergio J.; Cohen, Seth M.
- Chemical Communications, Vol. 46, Issue 41, p. 7700-7702
An Amine-Functionalized MIL-53 Metal−Organic Framework with Large Separation Power for CO 2 and CH 4
journal, May 2009
- Couck, Sarah; Denayer, Joeri F. M.; Baron, Gino V.
- Journal of the American Chemical Society, Vol. 131, Issue 18
Redox-Active Metal-Organic Composites for Highly Selective Oxygen Separation Applications
journal, March 2016
- Zhang, Wen; Banerjee, Debasis; Liu, Jian
- Advanced Materials, Vol. 28, Issue 18
Enhanced O 2 Selectivity versus N 2 by Partial Metal Substitution in Cu-BTC
journal, March 2015
- Sava Gallis, Dorina F.; Parkes, Marie V.; Greathouse, Jeffery A.
- Chemistry of Materials, Vol. 27, Issue 6
High Pressure Excess Isotherms for Adsorption of Oxygen and Nitrogen in Zeolites
journal, September 2011
- Wang, Yu; Helvensteijn, Bernardus; Nizamidin, Nabijan
- Langmuir, Vol. 27, Issue 17
The effect of water adsorption on the structure of the carboxylate containing metal–organic frameworks Cu-BTC, Mg-MOF-74, and UiO-66
journal, January 2013
- DeCoste, Jared B.; Peterson, Gregory W.; Schindler, Bryan J.
- Journal of Materials Chemistry A, Vol. 1, Issue 38
Multifunctional, Tunable Metal–Organic Framework Materials Platform for Bioimaging Applications
journal, June 2017
- Sava Gallis, Dorina F.; Rohwer, Lauren E. S.; Rodriguez, Mark A.
- ACS Applied Materials & Interfaces, Vol. 9, Issue 27
Assembly of Metal−Organic Frameworks from Large Organic and Inorganic Secondary Building Units: New Examples and Simplifying Principles for Complex Structures
journal, August 2001
- Kim, Jaheon; Chen, Banglin; Reineke, Theresa M.
- Journal of the American Chemical Society, Vol. 123, Issue 34, p. 8239-8247
Adsorption and Transport of CH 4 , CO 2 , H 2 Mixtures in a Bio-MOF Material from Molecular Simulations
journal, March 2011
- Atci, Erhan; Erucar, Ilknur; Keskin, Seda
- The Journal of Physical Chemistry C, Vol. 115, Issue 14
Computational study of oxygen adsorption in metal–organic frameworks with exposed cation sites: effect of framework metal ions
journal, January 2015
- Wang, Yong; Yang, Jiangfeng; Li, Zhengjie
- RSC Advances, Vol. 5, Issue 42
Highly-Selective and Reversible O2 Binding in Cr3(1,3,5-benzenetricarboxylate)2
journal, June 2010
- Murray, Leslie J.; Dinca, Mircea; Yano, Junko
- Journal of the American Chemical Society, Vol. 132, Issue 23, p. 7856-7857
Role and effective treatment of dispersive forces in materials: Polyethylene and graphite crystals as test cases
journal, April 2009
- Barone, Vincenzo; Casarin, Maurizio; Forrer, Daniel
- Journal of Computational Chemistry, Vol. 30, Issue 6
A facile synthesis of UiO-66, UiO-67 and their derivatives
journal, January 2013
- Katz, Michael J.; Brown, Zachary J.; Colón, Yamil J.
- Chemical Communications, Vol. 49, Issue 82
Metal–organic framework materials as catalysts
journal, January 2009
- Lee, JeongYong; Farha, Omar K.; Roberts, John
- Chemical Society Reviews, Vol. 38, Issue 5, p. 1450-1459
Tuning the Adsorption Properties of UiO-66 via Ligand Functionalization
journal, October 2012
- Cmarik, Gregory E.; Kim, Min; Cohen, Seth M.
- Langmuir, Vol. 28, Issue 44
Nanopore Structure and Sorption Properties of Cu−BTC Metal−Organic Framework
journal, June 2003
- Vishnyakov, Aleksey; Ravikovitch, Peter I.; Neimark, Alexander V.
- Nano Letters, Vol. 3, Issue 6
Carbon Dioxide Capture in Metal–Organic Frameworks
journal, September 2011
- Sumida, Kenji; Rogow, David L.; Mason, Jarad A.
- Chemical Reviews, Vol. 112, Issue 2, p. 724-781
Positive effect of the fluorine moiety on the oxygen storage capacity of UiO-66 metal–organic frameworks
journal, January 2016
- Piscopo, Calogero Giancarlo; Trapani, Federica; Polyzoidis, Angelos
- New Journal of Chemistry, Vol. 40, Issue 10
Enhanced selectivity of CO2 over CH4 in sulphonate-, carboxylate- and iodo-functionalized UiO-66 frameworks
journal, January 2013
- Biswas, Shyam; Zhang, Jian; Li, Zhibao
- Dalton Transactions, Vol. 42, Issue 13
MOF-74 building unit has a direct impact on toxic gas adsorption
journal, January 2011
- Grant Glover, T.; Peterson, Gregory W.; Schindler, Bryan J.
- Chemical Engineering Science, Vol. 66, Issue 2, p. 163-170
Crystallographic Observation of Dynamic Gas Adsorption Sites and Thermal Expansion in a Breathable Fluorous Metal-Organic Framework
journal, March 2009
- Yang, Chi; Wang, Xiaoping; Omary, Mohammad A.
- Angewandte Chemie International Edition, Vol. 48, Issue 14
Computational and Experimental Studies on the Adsorption of CO, N 2 , and CO 2 on Mg-MOF-74
journal, June 2010
- Valenzano, L.; Civalleri, B.; Chavan, S.
- The Journal of Physical Chemistry C, Vol. 114, Issue 25
A General Strategy for the Synthesis of Functionalised UiO-66 Frameworks: Characterisation, Stability and CO 2 Adsorption Properties
journal, February 2013
- Biswas, Shyam; Van Der Voort, Pascal
- European Journal of Inorganic Chemistry, Vol. 2013, Issue 12
Gas Adsorption Sites in a Large-Pore Metal-Organic Framework
journal, August 2005
- Rowsell, Jesse L. C.; Spencer, Elinor C.; Eckert, Juergen
- Science, Vol. 309, Issue 5739, p. 1350-1354
Selective Binding of O 2 over N 2 in a Redox–Active Metal–Organic Framework with Open Iron(II) Coordination Sites
journal, September 2011
- Bloch, Eric D.; Murray, Leslie J.; Queen, Wendy L.
- Journal of the American Chemical Society, Vol. 133, Issue 37
Molecular Insight into the Adsorption of H 2 S in the Flexible MIL-53(Cr) and Rigid MIL-47(V) MOFs: Infrared Spectroscopy Combined to Molecular Simulations
journal, December 2010
- Hamon, Lomig; Leclerc, Hervé; Ghoufi, Aziz
- The Journal of Physical Chemistry C, Vol. 115, Issue 5
A New Zirconium Inorganic Building Brick Forming Metal Organic Frameworks with Exceptional Stability
journal, October 2008
- Cavka, Jasmina Hafizovic; Jakobsen, Søren; Olsbye, Unni
- Journal of the American Chemical Society, Vol. 130, Issue 42, p. 13850-13851
Metal–Organic Frameworks for Separations
journal, September 2011
- Li, Jian-Rong; Sculley, Julian; Zhou, Hong-Cai
- Chemical Reviews, Vol. 112, Issue 2, p. 869-932
MOF Crystal Chemistry Paving the Way to Gas Storage Needs: Aluminum-Based soc -MOF for CH 4 , O 2 , and CO 2 Storage
journal, October 2015
- Alezi, Dalal; Belmabkhout, Youssef; Suyetin, Mikhail
- Journal of the American Chemical Society, Vol. 137, Issue 41
Tuned to Perfection: Ironing Out the Defects in Metal–Organic Framework UiO-66
journal, July 2014
- Shearer, Greig C.; Chavan, Sachin; Ethiraj, Jayashree
- Chemistry of Materials, Vol. 26, Issue 14
Metal-Organic Frameworks for Oxygen Storage
journal, October 2014
- DeCoste, Jared B.; Weston, Mitchell H.; Fuller, Patrick E.
- Angewandte Chemie International Edition, Vol. 53, Issue 51
Unusual and Highly Tunable Missing-Linker Defects in Zirconium Metal–Organic Framework UiO-66 and Their Important Effects on Gas Adsorption
journal, May 2013
- Wu, Hui; Chua, Yong Shen; Krungleviciute, Vaiva
- Journal of the American Chemical Society, Vol. 135, Issue 28
Metal–Organic Framework Materials as Chemical Sensors
journal, September 2011
- Kreno, Lauren E.; Leong, Kirsty; Farha, Omar K.
- Chemical Reviews, Vol. 112, Issue 2, p. 1105-1125
Semiempirical GGA-type density functional constructed with a long-range dispersion correction
journal, January 2006
- Grimme, Stefan
- Journal of Computational Chemistry, Vol. 27, Issue 15, p. 1787-1799
Experimental Study of CO 2 , CH 4 , and Water Vapor Adsorption on a Dimethyl-Functionalized UiO-66 Framework
journal, March 2013
- Jasuja, Himanshu; Walton, Krista S.
- The Journal of Physical Chemistry C, Vol. 117, Issue 14
Large-scale screening of hypothetical metal–organic frameworks
journal, November 2011
- Wilmer, Christopher E.; Leaf, Michael; Lee, Chang Yeon
- Nature Chemistry, Vol. 4, Issue 2, p. 83-89
Understanding Hydrogen Adsorption in Metal−Organic Frameworks with Open Metal Sites: A Computational Study
journal, January 2006
- Yang, Qingyuan; Zhong, Chongli
- The Journal of Physical Chemistry B, Vol. 110, Issue 2
Effect of NH2 and CF3 functionalization on the hydrogen sorption properties of MOFs
journal, January 2011
- Zlotea, Claudia; Phanon, Delphine; Mazaj, Matjaz
- Dalton Transactions, Vol. 40, Issue 18
Adsorption Sites and Binding Nature of CO 2 in Prototypical Metal−Organic Frameworks: A Combined Neutron Diffraction and First-Principles Study
journal, June 2010
- Wu, Hui; Simmons, Jason M.; Srinivas, Gadipelli
- The Journal of Physical Chemistry Letters, Vol. 1, Issue 13
Selective CO2 and H2 adsorption in a chiral magnesium-based metal organic framework (Mg-MOF) with open metal sites
journal, January 2010
- Mallick, Arijit; Saha, Subhadeep; Pachfule, Pradip
- Journal of Materials Chemistry, Vol. 20, Issue 41
Ab initio molecular dynamics determination of competitive O 2 vs. N 2 adsorption at open metal sites of M 2 (dobdc)
journal, January 2016
- Parkes, Marie V.; Greathouse, Jeffery A.; Hart, David B.
- Physical Chemistry Chemical Physics, Vol. 18, Issue 16
Applicability of the BET Method for Determining Surface Areas of Microporous Metal−Organic Frameworks
journal, July 2007
- Walton, Krista S.; Snurr, Randall Q.
- Journal of the American Chemical Society, Vol. 129, Issue 27