Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: Role of Structural Defects in the Water Adsorption Properties of MOF-801

Abstract

The nanoporous and tunable nature of metal–organic frameworks (MOFs) has made them promising adsorbents for water adsorption applications such as water harvesting and adsorptive heat pumps. In these applications, water adsorption properties in MOFs play a crucial role. However, understanding their structural defects and how defects influence adsorption thermodynamics remains limited to date. In this work, by employing Monte Carlo techniques and first-principle density functional theory calculations, we investigate the effect of defects on the water adsorption properties in MOF-801 structures at an atomic level. Our calculations show that the adsorption isotherm in perfect MOF-801 (without defects) greatly deviates from that measured experimentally. With the introduction of defects with a high density, a reasonably good agreement can be achieved, suggesting that a high defect density in MOF-801 may be responsible for its hydrophilic adsorptive behaviors. Further, water adsorption properties in MOF-801 structures are found to depend on the spatial configuration of defects, and water condensation in nanoporous MOF-801 is identified to occur preferentially along the $$\langle$$110$$\rangle$$ direction. Detailed structural characteristics (accessible volume, etc.) of MOF-801 structures and the adsorption energetics of water in the frameworks are also studied and correlated with the computed adsorption isotherms. Our findings reveal important insights into the role of defects, offering a microscopic picture to help facilitate the rational design of better MOFs for water adsorption applications.

Authors:
 [1]; ORCiD logo [2];  [1]
+ Show Author Affiliations
  1. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Dept. of Materials Science and Engineering
  2. The Ohio State Univ., Columbus, OH (United States). William G. Lowrie Dept. of Chemical and Biomolecular Engineering
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Sponsoring Org.:
USDOE Office of Science (SC); National Science Foundation (NSF)
OSTI Identifier:
1483797
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 122; Journal Issue: 10; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Choi, Jongwon, Lin, Li-Chiang, and Grossman, Jeffrey C. Role of Structural Defects in the Water Adsorption Properties of MOF-801. United States: N. p., 2018. Web. doi:10.1021/acs.jpcc.8b00014.
Copy to clipboard
Choi, Jongwon, Lin, Li-Chiang, & Grossman, Jeffrey C. Role of Structural Defects in the Water Adsorption Properties of MOF-801. United States. https://doi.org/10.1021/acs.jpcc.8b00014
Copy to clipboard
Choi, Jongwon, Lin, Li-Chiang, and Grossman, Jeffrey C. Wed . "Role of Structural Defects in the Water Adsorption Properties of MOF-801". United States. https://doi.org/10.1021/acs.jpcc.8b00014. https://www.osti.gov/servlets/purl/1483797.
Copy to clipboard
@article{osti_1483797,
title = {Role of Structural Defects in the Water Adsorption Properties of MOF-801},
author = {Choi, Jongwon and Lin, Li-Chiang and Grossman, Jeffrey C.},
abstractNote = {The nanoporous and tunable nature of metal–organic frameworks (MOFs) has made them promising adsorbents for water adsorption applications such as water harvesting and adsorptive heat pumps. In these applications, water adsorption properties in MOFs play a crucial role. However, understanding their structural defects and how defects influence adsorption thermodynamics remains limited to date. In this work, by employing Monte Carlo techniques and first-principle density functional theory calculations, we investigate the effect of defects on the water adsorption properties in MOF-801 structures at an atomic level. Our calculations show that the adsorption isotherm in perfect MOF-801 (without defects) greatly deviates from that measured experimentally. With the introduction of defects with a high density, a reasonably good agreement can be achieved, suggesting that a high defect density in MOF-801 may be responsible for its hydrophilic adsorptive behaviors. Further, water adsorption properties in MOF-801 structures are found to depend on the spatial configuration of defects, and water condensation in nanoporous MOF-801 is identified to occur preferentially along the $\langle$110$\rangle$ direction. Detailed structural characteristics (accessible volume, etc.) of MOF-801 structures and the adsorption energetics of water in the frameworks are also studied and correlated with the computed adsorption isotherms. Our findings reveal important insights into the role of defects, offering a microscopic picture to help facilitate the rational design of better MOFs for water adsorption applications.},
doi = {10.1021/acs.jpcc.8b00014},
journal = {Journal of Physical Chemistry. C},
number = 10,
volume = 122,
place = {United States},
year = {Wed Feb 21 00:00:00 EST 2018},
month = {Wed Feb 21 00:00:00 EST 2018}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/acs.jpcc.8b00014
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Citation Metrics:
Cited by: 49 works
Citation information provided by
Web of Science

Figures / Tables:

Figure 1 Figure 1: Five MOF-801 defect structures with different defect densities and/or spatial configurations considered in this work. Green polyhedra represent the metal clusters, while missing linkers are highlighted in red. The relative position of the missing linkers is schematically illustrated in cubic boxes. The first number in the structure namemore » indicates how many linkers were removed per unit cell (e.g., def2: a MOF-801 structure with two missing linkers per unit cell). Additionally, the notations after the underscore refer to different relative configurations of the defects (i.e., par: defects are perpendicular to each other and located in different planes, 90: defects are perpendicular to each other and located in the same plane, 180: defects are in parallel and located in the same plane).« less
All figures and tables (6 total)
Save / Share:
Export Metadata
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:

Design and synthesis of an exceptionally stable and highly porous metal-organic framework
journal, November 1999

  • Li, Hailian; Eddaoudi, Mohamed; M., O'Keeffe
  • Nature, Vol. 402, Issue 6759, p. 276-279
  • DOI: 10.1038/46248

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
  • DOI: 10.1039/b807080f

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
  • DOI: 10.1021/cr200324t

Synthesis of Metal-Organic Frameworks (MOFs): Routes to Various MOF Topologies, Morphologies, and Composites
journal, September 2011

  • Stock, Norbert; Biswas, Shyam
  • Chemical Reviews, Vol. 112, Issue 2
  • DOI: 10.1021/cr200304e

Selective gas adsorption and separation in metal–organic frameworks
journal, January 2009

  • Li, Jian-Rong; Kuppler, Ryan J.; Zhou, Hong-Cai
  • Chemical Society Reviews, Vol. 38, Issue 5, p. 1477-1504
  • DOI: 10.1039/b802426j

The Chemistry and Applications of Metal-Organic Frameworks
journal, August 2013

  • Furukawa, H.; Cordova, K. E.; O'Keeffe, M.
  • Science, Vol. 341, Issue 6149, p. 1230444-1230444
  • DOI: 10.1126/science.1230444

Metal–Organic Framework Materials with Ultrahigh Surface Areas: Is the Sky the Limit?
journal, August 2012

  • Farha, Omar K.; Eryazici, Ibrahim; Jeong, Nak Cheon
  • Journal of the American Chemical Society, Vol. 134, Issue 36, p. 15016-15021
  • DOI: 10.1021/ja3055639

Large-Scale Computational Screening of Zeolites for Ethane/Ethene Separation
journal, August 2012

  • Kim, Jihan; Lin, Li-Chiang; Martin, Richard L.
  • Langmuir, Vol. 28, Issue 32
  • DOI: 10.1021/la302230z

Carbon Dioxide Capture: Prospects for New Materials
journal, July 2010

  • D'Alessandro, Deanna M.; Smit, Berend; Long, Jeffrey R.
  • Angewandte Chemie International Edition, Vol. 49, Issue 35, p. 6058-6082
  • DOI: 10.1002/anie.201000431

Water harvesting from air with metal-organic frameworks powered by natural sunlight
journal, April 2017

MOFs as Adsorbents for Low Temperature Heating and Cooling Applications
journal, March 2009

  • Henninger, Stefan K.; Habib, Hesham A.; Janiak, Christoph
  • Journal of the American Chemical Society, Vol. 131, Issue 8
  • DOI: 10.1021/ja808444z

Water Adsorption Characteristics of MIL-101 for Heat-Transformation Applications of MOFs
journal, December 2010

  • Ehrenmann, Johannes; Henninger, Stefan K.; Janiak, Christoph
  • European Journal of Inorganic Chemistry, Vol. 2011, Issue 4
  • DOI: 10.1002/ejic.201001156

Characterization of Adsorption Enthalpy of Novel Water-Stable Zeolites and Metal-Organic Frameworks
journal, January 2016

  • Kim, Hyunho; Cho, H. Jeremy; Narayanan, Shankar
  • Scientific Reports, Vol. 6, Issue 1
  • DOI: 10.1038/srep19097

Metal–Organic Frameworks in Adsorption-Driven Heat Pumps: The Potential of Alcohols as Working Fluids
journal, November 2015

Adsorption-Driven Heat Pumps: The Potential of Metal–Organic Frameworks
journal, October 2015

  • de Lange, Martijn F.; Verouden, Karlijn J. F. M.; Vlugt, Thijs J. H.
  • Chemical Reviews, Vol. 115, Issue 22
  • DOI: 10.1021/acs.chemrev.5b00059

Defect-Engineered Metal-Organic Frameworks
journal, June 2015

  • Fang, Zhenlan; Bueken, Bart; De Vos, Dirk E.
  • Angewandte Chemie International Edition, Vol. 54, Issue 25
  • DOI: 10.1002/anie.201411540

Excavating hidden adsorption sites in metal-organic frameworks using rational defect engineering
journal, November 2017

Disclosing the Complex Structure of UiO-66 Metal Organic Framework: A Synergic Combination of Experiment and Theory
journal, April 2011

  • Valenzano, Loredana; Civalleri, Bartolomeo; Chavan, Sachin
  • Chemistry of Materials, Vol. 23, Issue 7, p. 1700-1718
  • DOI: 10.1021/cm1022882

Correlated defect nanoregions in a metal–organic framework
journal, June 2014

  • Cliffe, Matthew J.; Wan, Wei; Zou, Xiaodong
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms5176

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
  • DOI: 10.1021/cm501859p

Defect Control To Enhance Proton Conductivity in a Metal–Organic Framework
journal, March 2015

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
  • DOI: 10.1021/ja404514r

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
  • DOI: 10.1021/ja8057953

Using water adsorption measurements to access the chemistry of defects in the metal–organic framework UiO-66
journal, January 2017

  • Dissegna, Stefano; Hardian, Rifan; Epp, Konstantin
  • CrystEngComm, Vol. 19, Issue 29
  • DOI: 10.1039/c7ce00224f

Modulated synthesis of Zr-fumarate MOF
journal, April 2012

Water Adsorption in Porous Metal–Organic Frameworks and Related Materials
journal, March 2014

  • Furukawa, Hiroyasu; Gándara, Felipe; Zhang, Yue-Biao
  • Journal of the American Chemical Society, Vol. 136, Issue 11, p. 4369-4381
  • DOI: 10.1021/ja500330a

RASPA: molecular simulation software for adsorption and diffusion in flexible nanoporous materials
journal, February 2015

DREIDING: a generic force field for molecular simulations
journal, December 1990

  • Mayo, Stephen L.; Olafson, Barry D.; Goddard, William A.
  • The Journal of Physical Chemistry, Vol. 94, Issue 26, p. 8897-8909
  • DOI: 10.1021/j100389a010

UFF, a full periodic table force field for molecular mechanics and molecular dynamics simulations
journal, December 1992

  • Rappe, A. K.; Casewit, C. J.; Colwell, K. S.
  • Journal of the American Chemical Society, Vol. 114, Issue 25, p. 10024-10035
  • DOI: 10.1021/ja00051a040

Electrostatic Potential Derived Atomic Charges for Periodic Systems Using a Modified Error Functional
journal, August 2009

  • Campañá, Carlos; Mussard, Bastien; Woo, Tom K.
  • Journal of Chemical Theory and Computation, Vol. 5, Issue 10
  • DOI: 10.1021/ct9003405

Development of an improved four-site water model for biomolecular simulations: TIP4P-Ew
journal, May 2004

  • Horn, Hans W.; Swope, William C.; Pitera, Jed W.
  • The Journal of Chemical Physics, Vol. 120, Issue 20
  • DOI: 10.1063/1.1683075

Characterization of the TIP4P-Ew water model: Vapor pressure and boiling point
journal, November 2005

  • Horn, Hans W.; Swope, William C.; Pitera, Jed W.
  • The Journal of Chemical Physics, Vol. 123, Issue 19
  • DOI: 10.1063/1.2085031

Force-Field Development from Electronic Structure Calculations with Periodic Boundary Conditions: Applications to Gaseous Adsorption and Transport in Metal–Organic Frameworks
journal, March 2014

  • Lin, Li-Chiang; Lee, Kyuho; Gagliardi, Laura
  • Journal of Chemical Theory and Computation, Vol. 10, Issue 4
  • DOI: 10.1021/ct500094w

Effect of Water Adsorption on Retention of Structure and Surface Area of Metal–Organic Frameworks
journal, April 2012

  • Schoenecker, Paul M.; Carson, Cantwell G.; Jasuja, Himanshu
  • Industrial & Engineering Chemistry Research, Vol. 51, Issue 18
  • DOI: 10.1021/ie202325p

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
  • DOI: 10.1016/j.ces.2010.10.002

Polar Group and Defect Engineering in a Metal-Organic Framework: Synergistic Promotion of Carbon Dioxide Sorption and Conversion
journal, February 2015

Synthesis Modulation as a Tool To Increase the Catalytic Activity of Metal–Organic Frameworks: The Unique Case of UiO-66(Zr)
journal, July 2013

  • Vermoortele, Frederik; Bueken, Bart; Le Bars, Gaëlle
  • Journal of the American Chemical Society, Vol. 135, Issue 31
  • DOI: 10.1021/ja405078u

Ab initio carbon capture in open-site metal–organic frameworks
journal, August 2012

  • Dzubak, Allison L.; Lin, Li-Chiang; Kim, Jihan
  • Nature Chemistry, Vol. 4, Issue 10
  • DOI: 10.1038/nchem.1432

Prediction of CO 2 Adsorption Properties in Zeolites Using Force Fields Derived from Periodic Dispersion-Corrected DFT Calculations
journal, May 2012

  • Fang, Hanjun; Kamakoti, Preeti; Zang, Ji
  • The Journal of Physical Chemistry C, Vol. 116, Issue 19
  • DOI: 10.1021/jp302433b

CO 2 Adsorption in Fe 2 (dobdc): A Classical Force Field Parameterized from Quantum Mechanical Calculations
journal, May 2014

  • Borycz, Joshua; Lin, Li-Chiang; Bloch, Eric D.
  • The Journal of Physical Chemistry C, Vol. 118, Issue 23
  • DOI: 10.1021/jp500313j

Multiscale Modeling of Water in Mg-MOF-74: From Electronic Structure Calculations to Adsorption Isotherms
journal, July 2014

  • Rudenko, A. N.; Bendt, S.; Keil, F. J.
  • The Journal of Physical Chemistry C, Vol. 118, Issue 29
  • DOI: 10.1021/jp503778m

Prediction of Water Adsorption in Copper-Based Metal–Organic Frameworks Using Force Fields Derived from Dispersion-Corrected DFT Calculations
journal, April 2013

  • Zang, Ji; Nair, Sankar; Sholl, David S.
  • The Journal of Physical Chemistry C, Vol. 117, Issue 15
  • DOI: 10.1021/jp310497u

Force Field Development from Periodic Density Functional Theory Calculations for Gas Separation Applications Using Metal–Organic Frameworks
journal, June 2016

  • Mercado, Rocio; Vlaisavljevich, Bess; Lin, Li-Chiang
  • The Journal of Physical Chemistry C, Vol. 120, Issue 23
  • DOI: 10.1021/acs.jpcc.6b03393

Continuous Fractional Component Monte Carlo:  An Adaptive Biasing Method for Open System Atomistic Simulations
journal, May 2007

  • Shi, Wei; Maginn, Edward J.
  • Journal of Chemical Theory and Computation, Vol. 3, Issue 4
  • DOI: 10.1021/ct7000039

Computational Study of Water Adsorption in the Hydrophobic Metal–Organic Framework ZIF-8: Adsorption Mechanism and Acceleration of the Simulations
journal, October 2017

  • Zhang, Hongda; Snurr, Randall Q.
  • The Journal of Physical Chemistry C, Vol. 121, Issue 43
  • DOI: 10.1021/acs.jpcc.7b06405

Calculating Geometric Surface Areas as a Characterization Tool for Metal−Organic Frameworks
journal, October 2007

  • Düren, Tina; Millange, Franck; Férey, Gérard
  • The Journal of Physical Chemistry C, Vol. 111, Issue 42
  • DOI: 10.1021/jp074723h

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
  • DOI: 10.1038/nchem.1192

Mail-Order Metal–Organic Frameworks (MOFs): Designing Isoreticular MOF-5 Analogues Comprising Commercially Available Organic Molecules
journal, April 2013

  • Martin, Richard L.; Lin, Li-Chiang; Jariwala, Kuldeep
  • The Journal of Physical Chemistry C, Vol. 117, Issue 23
  • DOI: 10.1021/jp401920y

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
  • DOI: 10.1021/ja071174k

Application of Consistency Criteria To Calculate BET Areas of Micro- And Mesoporous Metal–Organic Frameworks
journal, December 2015

  • Gómez-Gualdrón, Diego A.; Moghadam, Peyman Z.; Hupp, Joseph T.
  • Journal of the American Chemical Society, Vol. 138, Issue 1
  • DOI: 10.1021/jacs.5b10266

Assessing the Surface Area of Porous Solids: Limitations, Probe Molecules, and Methods
journal, November 2016

In silico screening of carbon-capture materials
journal, May 2012

  • Lin, Li-Chiang; Berger, Adam H.; Martin, Richard L.
  • Nature Materials, Vol. 11, Issue 7
  • DOI: 10.1038/nmat3336

Structure–property relationships of porous materials for carbon dioxide separation and capture
journal, January 2012

  • Wilmer, Christopher E.; Farha, Omar K.; Bae, Youn-Sang
  • Energy & Environmental Science, Vol. 5, Issue 12, p. 9849-9856
  • DOI: 10.1039/c2ee23201d
    Sort by:
    [ × clear filter / sort ]

    Works referencing / citing this record:

    The Origin of the Reproduction of Different Nitrogen Uptakes in Covalent Organic Frameworks (COFs)
    journal, January 2019

    • Guan, Yiran; Li, Wenliang; Wang, Hailong
    • Chemistry - A European Journal, Vol. 25, Issue 9
    • DOI: 10.1002/chem.201805117

    Dipeptide-functionalized MIL-101(Fe) as efficient material for ibuprofen delivery: Dipeptide functionalized MIL-101(Fe) for Ibuprofen delivery
    journal, September 2018

    • Rajab Asadi, Fatemeh; Hamzavi, Seyedeh Fazileh; Shahverdizadeh, Gholam Hossein
    • Applied Organometallic Chemistry, Vol. 32, Issue 12
    • DOI: 10.1002/aoc.4552
      Sort by:
      [ × clear filter / sort ]

      Figures / Tables found in this record:

      Figure 1 (p. 8)figure
      Figure 2 (p. 11)figure
      Figure 3 (p. 12)figure
      Figure 4 (p. 14)figure
      Figure 5 (p. 18)figure
      Figure 6 (p. 20)figure
        [ × clear filter / sort ]
        Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.

        Similar Records in DOE PAGES and OSTI.GOV collections: