skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Tuning Binding Tendencies of Small Molecules in Metal–Organic Frameworks with Open Metal Sites by Metal Substitution and Linker Functionalization

Abstract

Metal-organic frameworks (MOFs) with open metal sites (OMS) are known to be selective for ethylene relative to ethane. In practical applications of this separation, the presence of other small molecules such as H2O, CO, and C2H2 may affect the suitability of sorbents. We used density functional theory (DFT) calculations to compute the binding energies of H2O, CO, C2H2, C2H4, and C2H6 in M-BTC (BTC = 1,3,5-benzenetricarboxylic acid) with 12 different metals forming OMS (M = Mg, Ti, V, Cr, Mo, Mn, Fe, Ru, Co, Ni, Cu, and Zn). To probe the generality of these results for MOFs containing other ligands, we performed similar calculations for metal-substituted MOFs based on four more materials with dimeric Cu sites. Here, our results provide useful insights into the variations in binding energies that are achievable by metal substitution in this broad class of MOFs, as well as pointing towards feasible adsorption-based separation strategies for complex molecular mixtures. Zn OMS MOFs were predicted to have the highest C2H4/C2H6 selectivity, but the strong binding energy of solvents and other small molecules in these materials may create practical challenges. Finally, we used DFT calculations to examine whether functionalizing linkers in these materials with electron withdrawing (-fluorine) andmore » donating (-methyl) groups offer a useful way to tune molecular binding energies on OMS in these materials.« less

Authors:
 [1];  [1];  [1];  [1]; ORCiD logo [1]
  1. Georgia Inst. of Technology, Atlanta, GA (United States). School of Chemical and Biomolecular Engineering
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Understanding and Control of Acid Gas-induced Evolution of Materials for Energy (UNCAGE-ME); Georgia Institute of Technology, Atlanta, GA (United States); Univ. of Minnesota, Minneapolis, MN (United States). Nanoporous Materials Genome Center
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); Dow Chemical Company
OSTI Identifier:
1491719
Grant/Contract Number:  
SC0008688; FG02-17ER16362; SC0012577
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 122; Journal Issue: 48; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

You, Wenqin, Liu, Yang, Howe, Joshua D., Tang, Dai, and Sholl, David S. Tuning Binding Tendencies of Small Molecules in Metal–Organic Frameworks with Open Metal Sites by Metal Substitution and Linker Functionalization. United States: N. p., 2018. Web. doi:10.1021/acs.jpcc.8b08855.
You, Wenqin, Liu, Yang, Howe, Joshua D., Tang, Dai, & Sholl, David S. Tuning Binding Tendencies of Small Molecules in Metal–Organic Frameworks with Open Metal Sites by Metal Substitution and Linker Functionalization. United States. doi:https://doi.org/10.1021/acs.jpcc.8b08855
You, Wenqin, Liu, Yang, Howe, Joshua D., Tang, Dai, and Sholl, David S. Mon . "Tuning Binding Tendencies of Small Molecules in Metal–Organic Frameworks with Open Metal Sites by Metal Substitution and Linker Functionalization". United States. doi:https://doi.org/10.1021/acs.jpcc.8b08855. https://www.osti.gov/servlets/purl/1491719.
@article{osti_1491719,
title = {Tuning Binding Tendencies of Small Molecules in Metal–Organic Frameworks with Open Metal Sites by Metal Substitution and Linker Functionalization},
author = {You, Wenqin and Liu, Yang and Howe, Joshua D. and Tang, Dai and Sholl, David S.},
abstractNote = {Metal-organic frameworks (MOFs) with open metal sites (OMS) are known to be selective for ethylene relative to ethane. In practical applications of this separation, the presence of other small molecules such as H2O, CO, and C2H2 may affect the suitability of sorbents. We used density functional theory (DFT) calculations to compute the binding energies of H2O, CO, C2H2, C2H4, and C2H6 in M-BTC (BTC = 1,3,5-benzenetricarboxylic acid) with 12 different metals forming OMS (M = Mg, Ti, V, Cr, Mo, Mn, Fe, Ru, Co, Ni, Cu, and Zn). To probe the generality of these results for MOFs containing other ligands, we performed similar calculations for metal-substituted MOFs based on four more materials with dimeric Cu sites. Here, our results provide useful insights into the variations in binding energies that are achievable by metal substitution in this broad class of MOFs, as well as pointing towards feasible adsorption-based separation strategies for complex molecular mixtures. Zn OMS MOFs were predicted to have the highest C2H4/C2H6 selectivity, but the strong binding energy of solvents and other small molecules in these materials may create practical challenges. Finally, we used DFT calculations to examine whether functionalizing linkers in these materials with electron withdrawing (-fluorine) and donating (-methyl) groups offer a useful way to tune molecular binding energies on OMS in these materials.},
doi = {10.1021/acs.jpcc.8b08855},
journal = {Journal of Physical Chemistry. C},
number = 48,
volume = 122,
place = {United States},
year = {2018},
month = {11}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 5 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Seven chemical separations to change the world
journal, April 2016

  • Sholl, David S.; Lively, Ryan P.
  • Nature, Vol. 532, Issue 7600
  • DOI: 10.1038/532435a

Hydrocarbon Separations in Metal–Organic Frameworks
journal, September 2013

  • Herm, Zoey R.; Bloch, Eric D.; Long, Jeffrey R.
  • Chemistry of Materials, Vol. 26, Issue 1
  • DOI: 10.1021/cm402897c

Modeling Adsorption in Metal–Organic Frameworks with Open Metal Sites: Propane/Propylene Separations
journal, May 2012

  • Fischer, Michael; Gomes, José R. B.; Fröba, Michael
  • Langmuir, Vol. 28, Issue 22
  • DOI: 10.1021/la301215y

Metal–organic frameworks with potential for energy-efficient adsorptive separation of light hydrocarbons
journal, January 2012

  • He, Yabing; Krishna, Rajamani; Chen, Banglin
  • Energy & Environmental Science, Vol. 5, Issue 10
  • DOI: 10.1039/c2ee22858k

Hydrocarbon Separations in a Metal-Organic Framework with Open Iron(II) Coordination Sites
journal, March 2012


Screening of Copper Open Metal Site MOFs for Olefin/Paraffin Separations Using DFT-Derived Force Fields
journal, September 2016

  • Kulkarni, Ambarish R.; Sholl, David S.
  • The Journal of Physical Chemistry C, Vol. 120, Issue 40
  • DOI: 10.1021/acs.jpcc.6b07493

Ethene/Ethane and Propene/Propane Separation via the Olefin and Paraffin Selective Metal–Organic Framework Adsorbents CPO-27 and ZIF-8
journal, June 2013

  • Böhme, Ulrike; Barth, Benjamin; Paula, Carolin
  • Langmuir, Vol. 29, Issue 27
  • DOI: 10.1021/la401471g

High Propene/Propane Selectivity in Isostructural Metal-Organic Frameworks with High Densities of Open Metal Sites
journal, January 2012

  • Bae, Youn-Sang; Lee, Chang Yeon; Kim, Ki Chul
  • Angewandte Chemie International Edition, Vol. 51, Issue 8, p. 1857-1860
  • DOI: 10.1002/anie.201107534

Adsorption of Ethane, Ethylene, Propane, and Propylene on a Magnesium-Based Metal–Organic Framework
journal, November 2011

  • Bao, Zongbi; Alnemrat, Sufian; Yu, Liang
  • Langmuir, Vol. 27, Issue 22
  • DOI: 10.1021/la2030473

Metallo-organic molecular sieve for gas separation and purification
journal, September 2002

  • Min Wang, Qing; Shen, Dongmin; Bülow, Martin
  • Microporous and Mesoporous Materials, Vol. 55, Issue 2, p. 217-230
  • DOI: 10.1016/S1387-1811(02)00405-5

Small-Molecule Adsorption in Open-Site Metal–Organic Frameworks: A Systematic Density Functional Theory Study for Rational Design
journal, January 2015

  • Lee, Kyuho; Howe, Joshua D.; Lin, Li-Chiang
  • Chemistry of Materials, Vol. 27, Issue 3, p. 668-678
  • DOI: 10.1021/cm502760q

Water Adsorption on Coordinatively Unsaturated Sites in CuBTC MOF
journal, November 2010

  • Grajciar, Lukáš; Bludský, Ota; Nachtigall, Petr
  • The Journal of Physical Chemistry Letters, Vol. 1, Issue 23
  • DOI: 10.1021/jz101378z

Interaction of Small Gases with the Unsaturated Metal Centers of the HKUST-1 Metal Organic Framework
journal, July 2013

  • Supronowicz, Barbara; Mavrandonakis, Andreas; Heine, Thomas
  • The Journal of Physical Chemistry C, Vol. 117, Issue 28
  • DOI: 10.1021/jp4018037

A Viewpoint on Direct Methane Conversion to Ethane and Ethylene Using Oxidative Coupling on Solid Catalysts
journal, June 2016

  • Farrell, Brittany Lancaster; Igenegbai, Valentina Omoze; Linic, Suljo
  • ACS Catalysis, Vol. 6, Issue 7
  • DOI: 10.1021/acscatal.6b01087

Insights into the Stability of Zeolitic Imidazolate Frameworks in Humid Acidic Environments from First-Principles Calculations
journal, February 2018

  • Han, Chu; Zhang, Chenyang; Tymińska, Nina
  • The Journal of Physical Chemistry C, Vol. 122, Issue 8
  • DOI: 10.1021/acs.jpcc.7b12058

Competitive Binding of Ethylene, Water, and Carbon Monoxide in Metal–Organic Framework Materials with Open Cu Sites
journal, April 2018

  • You, Wenqin; Liu, Yang; Howe, Joshua D.
  • The Journal of Physical Chemistry C, Vol. 122, Issue 16
  • DOI: 10.1021/acs.jpcc.8b00909

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

Selective adsorption of ethylene over ethane and propylene over propane in the metal–organic frameworks M2(dobdc) (M = Mg, Mn, Fe, Co, Ni, Zn)
journal, January 2013

  • Geier, Stephen J.; Mason, Jarad A.; Bloch, Eric D.
  • Chemical Science, Vol. 4, Issue 5
  • DOI: 10.1039/c3sc00032j

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
  • DOI: 10.1021/ja1027925

Synthesis and properties of the metal-organic framework Mo3(BTC)2 (TUDMOF-1)
journal, January 2006

  • Kramer, Markus; Schwarz, Ulrich; Kaskel, Stefan
  • Journal of Materials Chemistry, Vol. 16, Issue 23
  • DOI: 10.1039/b601811d

Mixed-Valence Iron(II, III) Trimesates with Open Frameworks Modulated by Solvents
journal, September 2007

  • Xie, Linhua; Liu, Shuxia; Gao, Chaoying
  • Inorganic Chemistry, Vol. 46, Issue 19
  • DOI: 10.1021/ic062273m

Solvothermal growth of a ruthenium metal–organic framework featuring HKUST-1 structure type as thin films on oxide surfaces
journal, January 2011

  • Kozachuk, Olesia; Yusenko, Kirill; Noei, Heshmat
  • Chemical Communications, Vol. 47, Issue 30
  • DOI: 10.1039/c1cc11107h

A Chemically Functionalizable Nanoporous Material [Cu3(TMA)2(H2O)3]n
journal, February 1999


Reconciling the Discrepancies between Crystallographic Porosity and Guest Access As Exemplified by Zn-HKUST-1
journal, November 2011

  • Feldblyum, Jeremy I.; Liu, Ming; Gidley, David W.
  • Journal of the American Chemical Society, Vol. 133, Issue 45
  • DOI: 10.1021/ja2055935

Computational Screening of Functionalized UiO-66 Materials for Selective Contaminant Removal from Air
journal, September 2017

  • Demir, Hakan; Walton, Krista S.; Sholl, David S.
  • The Journal of Physical Chemistry C, Vol. 121, Issue 37
  • DOI: 10.1021/acs.jpcc.7b07079

Postsynthetic ligand exchange as a route to functionalization of ‘inert’ metal–organic frameworks
journal, January 2012

  • Kim, Min; Cahill, John F.; Su, Yongxuan
  • Chem. Sci., Vol. 3, Issue 1, p. 126-130
  • DOI: 10.1039/c1sc00394a

Proton Conductivities in Functionalized UiO-66: Tuned Properties, Thermogravimetry Mass, and Molecular Simulation Analyses
journal, November 2015

  • Yang, Fan; Huang, Hongliang; Wang, Xiayan
  • Crystal Growth & Design, Vol. 15, Issue 12
  • DOI: 10.1021/acs.cgd.5b01190

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
  • DOI: 10.1039/c1dt10115c

Caffeine Confinement into a Series of Functionalized Porous Zirconium MOFs: A Joint Experimental/Modeling Exploration
journal, May 2013

  • Devautour-Vinot, Sabine; Martineau, Charlotte; Diaby, Sekou
  • The Journal of Physical Chemistry C, Vol. 117, Issue 22
  • DOI: 10.1021/jp402916y

Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996


Projector augmented-wave method
journal, December 1994


Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/physrevlett.77.3865

A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu
journal, April 2010

  • Grimme, Stefan; Antony, Jens; Ehrlich, Stephan
  • The Journal of Chemical Physics, Vol. 132, Issue 15
  • DOI: 10.1063/1.3382344

Accurate Ab Initio Description of Adsorption on Coordinatively Unsaturated Cu 2+ and Fe 3+ Sites in MOFs
journal, December 2014

  • Grajciar, Lukáš; Nachtigall, Petr; Bludský, Ota
  • Journal of Chemical Theory and Computation, Vol. 11, Issue 1
  • DOI: 10.1021/ct500711z

Orbital-dependent density functionals: Theory and applications
journal, January 2008


Density Functional Theory in Transition-Metal Chemistry: A Self-Consistent Hubbard U Approach
journal, September 2006


Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study
journal, January 1998

  • Dudarev, S. L.; Botton, G. A.; Savrasov, S. Y.
  • Physical Review B, Vol. 57, Issue 3, p. 1505-1509
  • DOI: 10.1103/physrevb.57.1505

Oxidation energies of transition metal oxides within the GGA + U framework
journal, May 2006


First-principles Hubbard U approach for small molecule binding in metal-organic frameworks
journal, May 2016

  • Mann, Gregory W.; Lee, Kyuho; Cococcioni, Matteo
  • The Journal of Chemical Physics, Vol. 144, Issue 17
  • DOI: 10.1063/1.4947240

CW and Pulsed ESR Spectroscopy of Cupric Ions in the Metal−Organic Framework Compound Cu 3 (BTC) 2
journal, February 2008

  • Pöppl, Andreas; Kunz, Sebastian; Himsl, Dieter
  • The Journal of Physical Chemistry C, Vol. 112, Issue 7
  • DOI: 10.1021/jp7100094

Computational identification of a metal organic framework for high selectivity membrane-based CO2/CH4 separations: Cu(hfipbb)(H2hfipbb)0.5
journal, January 2009

  • Watanabe, Taku; Keskin, Seda; Nair, Sankar
  • Physical Chemistry Chemical Physics, Vol. 11, Issue 48
  • DOI: 10.1039/b918254n

Computation-Ready, Experimental Metal–Organic Frameworks: A Tool To Enable High-Throughput Screening of Nanoporous Crystals
journal, October 2014

  • Chung, Yongchul G.; Camp, Jeffrey; Haranczyk, Maciej
  • Chemistry of Materials, Vol. 26, Issue 21
  • DOI: 10.1021/cm502594j

Linker-Directed Vertex Desymmetrization for the Production of Coordination Polymers with High Porosity
journal, October 2010

  • Schnobrich, Jennifer K.; Lebel, Olivier; Cychosz, Katie A.
  • Journal of the American Chemical Society, Vol. 132, Issue 39
  • DOI: 10.1021/ja107423k

Selective CO2 adsorption in a flexible non-interpenetrated metal–organic framework
journal, January 2011

  • Kim, Tae Kyung; Suh, Myunghyun Paik
  • Chemical Communications, Vol. 47, Issue 14
  • DOI: 10.1039/c0cc05199c

An unusual case of symmetry-preserving isomerism
journal, January 2010

  • Sun, Daofeng; Ma, Shengqian; Simmons, Jason M.
  • Chemical Communications, Vol. 46, Issue 8
  • DOI: 10.1039/b920995f

Syntheses, structures and sorption properties of two framework-isomeric porous copper-coordination polymers
journal, January 2009

  • Xue, Dong-Xu; Lin, Jian-Bin; Zhang, Jie-Peng
  • CrystEngComm, Vol. 11, Issue 1
  • DOI: 10.1039/b813226g

Understanding Trends in CO 2 Adsorption in Metal–Organic Frameworks with Open-Metal Sites
journal, February 2014

  • Poloni, Roberta; Lee, Kyuho; Berger, Robert F.
  • The Journal of Physical Chemistry Letters, Vol. 5, Issue 5
  • DOI: 10.1021/jz500202x

Design of a Metal–Organic Framework with Enhanced Back Bonding for Separation of N 2 and CH 4
journal, December 2013

  • Lee, Kyuho; Isley, William C.; Dzubak, Allison L.
  • Journal of the American Chemical Society, Vol. 136, Issue 2
  • DOI: 10.1021/ja4102979

Efficient purification of ethene by an ethane-trapping metal-organic framework
journal, October 2015

  • Liao, Pei-Qin; Zhang, Wei-Xiong; Zhang, Jie-Peng
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms9697

An ethane-trapping MOF PCN-250 for highly selective adsorption of ethane over ethylene
journal, January 2018


Adsorption and separation of binary mixtures in a metal-organic framework Cu-BTC: A computational study
journal, April 2008


Impacts of Gas Impurities from Pipeline Natural Gas on Methane Storage in Metal–Organic Frameworks during Long-Term Cycling
journal, July 2017

  • Wu, Ying; Tang, Dai; Verploegh, Ross J.
  • The Journal of Physical Chemistry C, Vol. 121, Issue 29
  • DOI: 10.1021/acs.jpcc.7b03459

Adsorption of natural gas and its whole components on adsorbents
journal, September 2011


Effect of cycling operations on an adsorbed natural gas storage
journal, January 2005

  • Pupier, O.; Goetz, V.; Fiscal, R.
  • Chemical Engineering and Processing: Process Intensification, Vol. 44, Issue 1
  • DOI: 10.1016/j.cep.2004.05.005

Natural gas storage cycles: Influence of nonisothermal effects and heavy alkanes
journal, May 2006


A designed metal–organic framework based on a metal–organic polyhedron
journal, January 2008

  • Zou, Yang; Park, Mira; Hong, Seunghee
  • Chemical Communications, Issue 20
  • DOI: 10.1039/b801103f

Topological Diversity, Adsorption and Fluorescence Properties of MOFs Based on a Tetracarboxylate Ligand
journal, July 2010

  • Grünker, Ronny; Senkovska, Irena; Biedermann, Ralf
  • European Journal of Inorganic Chemistry, Vol. 2010, Issue 24
  • DOI: 10.1002/ejic.201000415

Molecular-level Insight into Unusual Low Pressure CO 2 Affinity in Pillared Metal–Organic Frameworks
journal, May 2013

  • Burtch, Nicholas C.; Jasuja, Himanshu; Dubbeldam, David
  • Journal of the American Chemical Society, Vol. 135, Issue 19
  • DOI: 10.1021/ja310770c

Control of Metal–Organic Framework Crystal Topology by Ligand Functionalization: Functionalized HKUST-1 Derivatives
journal, October 2014

  • Cai, Yang; Kulkarni, Ambarish R.; Huang, You-Gui
  • Crystal Growth & Design, Vol. 14, Issue 11
  • DOI: 10.1021/cg501285q