Origin of the Strong Interaction between Polar Molecules and Copper(II) Paddle-Wheels in Metal Organic Frameworks
Abstract
The copper paddle-wheel is the building unit of many metal organic frameworks. Because of the ability of the copper cations to attract polar molecules, copper paddle-wheels are promising for carbon dioxide adsorption and separation. They have therefore been studied extensively, both experimentally and computationally. In this work we investigate the copper–CO2 interaction in HKUST-1 and in two different cluster models of HKUST-1: monocopper Cu(formate)2 and dicopper Cu2(formate)4. We show that density functional theory methods severely underestimate the interaction energy between copper paddle-wheels and CO2, even including corrections for the dispersion forces. In contrast, a multireference wave function followed by perturbation theory to second order using the CASPT2 method correctly describes this interaction. The restricted open-shell Møller–Plesset 2 method (ROS-MP2, equivalent to (2,2) CASPT2) was also found to be adequate in describing the system and used to develop a novel force field. Our parametrization is able to predict the experimental CO2 adsorption isotherms in HKUST-1, and it is shown to be transferable to other copper paddle-wheel systems.
- Authors:
-
- Laboratory of Molecular Simulation, Institut des Sciences et Ingeénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne (EPFL), Rue de l’Industrie 17, CH-1951 Sion, Valais, Switzerland
- Department of Chemistry, Chemical Theory Center, and Minnesota Supercomputing Institute, University of Minnesota, Minneapolis, Minnesota 55455, United States
- Publication Date:
- Research Org.:
- Univ. of Minnesota, Minneapolis, MN (United States); Federal Inst. of Technology (EPFL), Lausanne (Switzerland); Energy Frontier Research Centers (EFRC) (United States). Energy Frontier Research Center for Inorganometallic Catalyst Design (ICDC)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); Swiss National Science Foundation (SNSF); European Research Council (ERC)
- OSTI Identifier:
- 1369080
- Alternate Identifier(s):
- OSTI ID: 1372320
- Grant/Contract Number:
- SC0012702; 666983
- Resource Type:
- Published Article
- Journal Name:
- Journal of Physical Chemistry. C
- Additional Journal Information:
- Journal Name: Journal of Physical Chemistry. C Journal Volume: 121 Journal Issue: 28; Journal ID: ISSN 1932-7447
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Ongari, Daniele, Tiana, Davide, Stoneburner, Samuel J., Gagliardi, Laura, and Smit, Berend. Origin of the Strong Interaction between Polar Molecules and Copper(II) Paddle-Wheels in Metal Organic Frameworks. United States: N. p., 2017.
Web. doi:10.1021/acs.jpcc.7b02302.
Ongari, Daniele, Tiana, Davide, Stoneburner, Samuel J., Gagliardi, Laura, & Smit, Berend. Origin of the Strong Interaction between Polar Molecules and Copper(II) Paddle-Wheels in Metal Organic Frameworks. United States. https://doi.org/10.1021/acs.jpcc.7b02302
Ongari, Daniele, Tiana, Davide, Stoneburner, Samuel J., Gagliardi, Laura, and Smit, Berend. Mon .
"Origin of the Strong Interaction between Polar Molecules and Copper(II) Paddle-Wheels in Metal Organic Frameworks". United States. https://doi.org/10.1021/acs.jpcc.7b02302.
@article{osti_1369080,
title = {Origin of the Strong Interaction between Polar Molecules and Copper(II) Paddle-Wheels in Metal Organic Frameworks},
author = {Ongari, Daniele and Tiana, Davide and Stoneburner, Samuel J. and Gagliardi, Laura and Smit, Berend},
abstractNote = {The copper paddle-wheel is the building unit of many metal organic frameworks. Because of the ability of the copper cations to attract polar molecules, copper paddle-wheels are promising for carbon dioxide adsorption and separation. They have therefore been studied extensively, both experimentally and computationally. In this work we investigate the copper–CO2 interaction in HKUST-1 and in two different cluster models of HKUST-1: monocopper Cu(formate)2 and dicopper Cu2(formate)4. We show that density functional theory methods severely underestimate the interaction energy between copper paddle-wheels and CO2, even including corrections for the dispersion forces. In contrast, a multireference wave function followed by perturbation theory to second order using the CASPT2 method correctly describes this interaction. The restricted open-shell Møller–Plesset 2 method (ROS-MP2, equivalent to (2,2) CASPT2) was also found to be adequate in describing the system and used to develop a novel force field. Our parametrization is able to predict the experimental CO2 adsorption isotherms in HKUST-1, and it is shown to be transferable to other copper paddle-wheel systems.},
doi = {10.1021/acs.jpcc.7b02302},
journal = {Journal of Physical Chemistry. C},
number = 28,
volume = 121,
place = {United States},
year = {Mon Jul 10 00:00:00 EDT 2017},
month = {Mon Jul 10 00:00:00 EDT 2017}
}
https://doi.org/10.1021/acs.jpcc.7b02302
Web of Science
Works referenced in this record:
A Chemically Functionalizable Nanoporous Material [Cu3(TMA)2(H2O)3]n
journal, February 1999
- Chui, Stephen S.-Y.; Lo, Samuel M.-F.; Charmant, Jonathan P. H.
- Science, Vol. 283, Issue 5405, p. 1148-1150
Computational approaches to study adsorption in MOFs with unsaturated metal sites
journal, February 2014
- Fischer, Michael; Gomes, José R. B.; Jorge, Miguel
- Molecular Simulation, Vol. 40, Issue 7-9
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
Projector augmented-wave method
journal, December 1994
- Blöchl, P. E.
- Physical Review B, Vol. 50, Issue 24, p. 17953-17979
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
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
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
van der Waals density functional made accurate
journal, March 2014
- Hamada, Ikutaro
- Physical Review B, Vol. 89, Issue 12
The Cambridge Structural Database
journal, April 2016
- Groom, Colin R.; Bruno, Ian J.; Lightfoot, Matthew P.
- Acta Crystallographica Section B Structural Science, Crystal Engineering and Materials, Vol. 72, Issue 2, p. 171-179
Spin Signature of Nonlocal Correlation Binding in Metal-Organic Frameworks
journal, September 2015
- Thonhauser, T.; Zuluaga, S.; Arter, C. A.
- Physical Review Letters, Vol. 115, Issue 13
Magnetic Properties of Paddlewheels and Trinuclear Clusters with Exposed Metal Sites
journal, November 2011
- Vogiatzis, Konstantinos D.; Klopper, Wim; Mavrandonakis, Andreas
- ChemPhysChem, Vol. 12, Issue 17
QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials
journal, September 2009
- Giannozzi, Paolo; Baroni, Stefano; Bonini, Nicola
- Journal of Physics: Condensed Matter, Vol. 21, Issue 39, Article No. 395502
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
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
From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999
- Kresse, G.; Joubert, D.
- Physical Review B, Vol. 59, Issue 3, p. 1758-1775
Density matrix averaged atomic natural orbital (ANO) basis sets for correlated molecular wave functions: I. First row atoms
journal, January 1990
- Widmark, Per-Olof; Malmqvist, Per-�ke; Roos, Bj�rn O.
- Theoretica Chimica Acta, Vol. 77, Issue 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
Theoretical Determination of the Zero-Field Splitting in Copper Acetate Monohydrate
journal, July 2011
- Maurice, Rémi; Sivalingam, Kanthen; Ganyushin, Dmitry
- Inorganic Chemistry, Vol. 50, Issue 13
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
Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen
journal, January 1989
- Dunning, Thom H.
- The Journal of Chemical Physics, Vol. 90, Issue 2
Understanding CO 2 Adsorption in CuBTC MOF: Comparing Combined DFT–ab Initio Calculations with Microcalorimetry Experiments
journal, August 2011
- Grajciar, Lukáš; Wiersum, Andrew D.; Llewellyn, Philip L.
- The Journal of Physical Chemistry C, Vol. 115, Issue 36
Density-functional theory and strong interactions: Orbital ordering in Mott-Hubbard insulators
journal, August 1995
- Liechtenstein, A. I.; Anisimov, V. I.; Zaanen, J.
- Physical Review B, Vol. 52, Issue 8
Cu2(ATC)·6H2O: Design of Open Metal Sites in Porous Metal−Organic Crystals (ATC: 1,3,5,7-Adamantane Tetracarboxylate)
journal, November 2000
- Chen, Banglin; Eddaoudi, M.; Reineke, T. M.
- Journal of the American Chemical Society, Vol. 122, Issue 46, p. 11559-11560
Electron affinities of the first‐row atoms revisited. Systematic basis sets and wave functions
journal, May 1992
- Kendall, Rick A.; Dunning, Thom H.; Harrison, Robert J.
- The Journal of Chemical Physics, Vol. 96, Issue 9
[Cu3(BTC)2]: A Metal-Organic Framework Catalyst for the Friedländer Reaction
journal, September 2010
- Pérez-Mayoral, Elena; Čejka, Jiří
- ChemCatChem, Vol. 3, Issue 1
Atomic Cholesky decompositions: A route to unbiased auxiliary basis sets for density fitting approximation with tunable accuracy and efficiency
journal, April 2009
- Aquilante, Francesco; Gagliardi, Laura; Pedersen, Thomas Bondo
- The Journal of Chemical Physics, Vol. 130, Issue 15
Critic2: A program for real-space analysis of quantum chemical interactions in solids
journal, March 2014
- Otero-de-la-Roza, A.; Johnson, Erin R.; Luaña, Víctor
- Computer Physics Communications, Vol. 185, Issue 3
An Extended Charge Equilibration Method
journal, August 2012
- Wilmer, Christopher E.; Kim, Ki Chul; Snurr, Randall Q.
- The Journal of Physical Chemistry Letters, Vol. 3, Issue 17
Ligand design for long-range magnetic order in metal–organic frameworks
journal, January 2014
- Tiana, Davide; Hendon, Christopher H.; Walsh, Aron
- Chem. Commun., Vol. 50, Issue 90
The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals
journal, July 2007
- Zhao, Yan; Truhlar, Donald G.
- Theoretical Chemistry Accounts, Vol. 120, Issue 1-3
Modeling Carbon Dioxide Adsorption on Microporous Substrates: Comparison between Cu-BTC Metal−Organic Framework and 13X Zeolitic Molecular Sieve
journal, September 2010
- Aprea, Paolo; Caputo, Domenico; Gargiulo, Nicola
- Journal of Chemical & Engineering Data, Vol. 55, Issue 9
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
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
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
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
Enhanced Binding Affinity, Remarkable Selectivity, and High Capacity of CO2 by Dual Functionalization of a rht-Type Metal-Organic Framework
journal, December 2011
- Li, Baiyan; Zhang, Zhijuan; Li, Yi
- Angewandte Chemie International Edition, Vol. 51, Issue 6
CO 2 Capture by Metal–Organic Frameworks with van der Waals Density Functionals
journal, May 2012
- Poloni, Roberta; Smit, Berend; Neaton, Jeffrey B.
- The Journal of Physical Chemistry A, Vol. 116, Issue 20
Systematically convergent basis sets for transition metals. I. All-electron correlation consistent basis sets for the 3d elements Sc–Zn
journal, August 2005
- Balabanov, Nikolai B.; Peterson, Kirk A.
- The Journal of Chemical Physics, Vol. 123, Issue 6
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
Adsorptive separation of CO2/CH4/CO gas mixtures at high pressures
journal, July 2012
- Krishna, Rajamani
- Microporous and Mesoporous Materials, Vol. 156
Quantum-Chemical Characterization of the Properties and Reactivities of Metal–Organic Frameworks
journal, April 2015
- Odoh, Samuel O.; Cramer, Christopher J.; Truhlar, Donald G.
- Chemical Reviews, Vol. 115, Issue 12
Heteropolyacid encapsulated in Cu3(BTC)2 nanocrystals: An effective esterification catalyst
journal, August 2011
- Wee, Lik H.; Janssens, Nikki; Bajpe, Sneha R.
- Catalysis Today, Vol. 171, Issue 1
Force-Field Prediction of Materials Properties in Metal-Organic Frameworks
journal, January 2017
- Boyd, Peter G.; Moosavi, Seyed Mohamad; Witman, Matthew
- The Journal of Physical Chemistry Letters, Vol. 8, Issue 2
RASPA: molecular simulation software for adsorption and diffusion in flexible nanoporous materials
journal, February 2015
- Dubbeldam, David; Calero, Sofía; Ellis, Donald E.
- Molecular Simulation, Vol. 42, Issue 2
Evaluating metal–organic frameworks for natural gas storage
journal, January 2014
- Mason, Jarad A.; Veenstra, Mike; Long, Jeffrey R.
- Chemical Science, Vol. 5, Issue 1, p. 32-51
A complete active space SCF method (CASSCF) using a density matrix formulated super-CI approach
journal, May 1980
- Roos, Björn O.; Taylor, Peter R.; Sigbahn, Per E. M.
- Chemical Physics, Vol. 48, Issue 2
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
Metal–organic frameworks for artificial photosynthesis and photocatalysis
journal, January 2014
- Zhang, Teng; Lin, Wenbin
- Chem. Soc. Rev., Vol. 43, Issue 16
Mixed matrix membranes incorporated with size-reduced Cu-BTC for improved gas separation
journal, January 2013
- Ge, Lei; Zhou, Wei; Rudolph, Victor
- Journal of Materials Chemistry A, Vol. 1, Issue 21
Applications of metal–organic frameworks in heterogeneous supramolecular catalysis
journal, January 2014
- Liu, Jiewei; Chen, Lianfen; Cui, Hao
- Chemical Society Reviews, Vol. 43, Issue 16, p. 6011-6061
Higher-accuracy van der Waals density functional
journal, August 2010
- Lee, Kyuho; Murray, Éamonn D.; Kong, Lingzhu
- Physical Review B, Vol. 82, Issue 8
CO 2 and CH 4 Separation by Adsorption Using Cu-BTC Metal−Organic Framework
journal, August 2010
- Hamon, Lomig; Jolimaître, Elsa; Pirngruber, Gerhard D.
- Industrial & Engineering Chemistry Research, Vol. 49, Issue 16
Improving Carbon Dioxide Storage Capacity of Metal Organic Frameworks by Lithium Alkoxide Functionalization: A Molecular Simulation Study
journal, May 2016
- Hu, Jianbo; Liu, Jing; Liu, Yang
- The Journal of Physical Chemistry C, Vol. 120, Issue 19
Ab initio Study of the Interactions between CO 2 and N-Containing Organic Heterocycles
journal, February 2009
- Vogiatzis, Konstantinos D.; Mavrandonakis, Andreas; Klopper, Wim
- ChemPhysChem, Vol. 10, Issue 2
Comment on “Comment on Dunning's correlation-consistent basis sets”
journal, September 1996
- Davidson, Ernest R.
- Chemical Physics Letters, Vol. 260, Issue 3-4
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
Gas Storage in Nanoporous Materials
journal, June 2008
- Morris, Russell E.; Wheatley, Paul S.
- Angewandte Chemie International Edition, Vol. 47, Issue 27
Computational Chemistry Methods for Nanoporous Materials
journal, September 2016
- Evans, Jack D.; Fraux, Guillaume; Gaillac, Romain
- Chemistry of Materials, Vol. 29, Issue 1
Dispersion-Corrected Mean-Field Electronic Structure Methods
journal, April 2016
- Grimme, Stefan; Hansen, Andreas; Brandenburg, Jan Gerit
- Chemical Reviews, Vol. 116, Issue 9
Adsorption of CO, CO2 and CH4 on Cu-BTC and MIL-101 metal organic frameworks: Effect of open metal sites and adsorbate polarity
journal, April 2012
- Chowdhury, Pradip; Mekala, Samuel; Dreisbach, Frieder
- Microporous and Mesoporous Materials, Vol. 152
Perspective: Advances and challenges in treating van der Waals dispersion forces in density functional theory
journal, September 2012
- Klimeš, Jiří; Michaelides, Angelos
- The Journal of Chemical Physics, Vol. 137, Issue 12
Exact decoupling of the Dirac Hamiltonian. II. The generalized Douglas–Kroll–Hess transformation up to arbitrary order
journal, January 2004
- Reiher, Markus; Wolf, Alexander
- The Journal of Chemical Physics, Vol. 121, Issue 22
Restoring the Density-Gradient Expansion for Exchange in Solids and Surfaces
journal, April 2008
- Perdew, John P.; Ruzsinszky, Adrienn; Csonka, Gábor I.
- Physical Review Letters, Vol. 100, Issue 13
Ligand-Assisted Enhancement of CO 2 Capture in Metal–Organic Frameworks
journal, April 2012
- Poloni, Roberta; Smit, Berend; Neaton, Jeffrey B.
- Journal of the American Chemical Society, Vol. 134, Issue 15
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
Vapor–liquid equilibria of mixtures containing alkanes, carbon dioxide, and nitrogen
journal, July 2001
- Potoff, Jeffrey J.; Siepmann, J. Ilja
- AIChE Journal, Vol. 47, Issue 7, p. 1676-1682
Second-order perturbation theory with a CASSCF reference function
journal, July 1990
- Andersson, Kerstin.; Malmqvist, Per Aake.; Roos, Bjoern O.
- The Journal of Physical Chemistry, Vol. 94, Issue 14
Cu3(BTC)2: CO oxidation over MOF based catalysts
journal, January 2011
- Ye, Jing-yun; Liu, Chang-jun
- Chemical Communications, Vol. 47, Issue 7
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
Exceptional gravimetric and volumetric CO 2 uptake in a palladated NbO-type MOF utilizing cooperative acidic and basic, metal–CO 2 interactions
journal, January 2016
- Spanopoulos, I.; Bratsos, I.; Tampaxis, C.
- Chemical Communications, Vol. 52, Issue 69
Oxidation energies of transition metal oxides within the framework
journal, May 2006
- Wang, Lei; Maxisch, Thomas; Ceder, Gerbrand
- Physical Review B, Vol. 73, Issue 19
The calculation of small molecular interactions by the differences of separate total energies. Some procedures with reduced errors
journal, October 1970
- Boys, S.F.; Bernardi, F.
- Molecular Physics, Vol. 19, Issue 4, p. 553-566
Molcas 8: New capabilities for multiconfigurational quantum chemical calculations across the periodic table : Molcas 8
journal, November 2015
- Aquilante, Francesco; Autschbach, Jochen; Carlson, Rebecca K.
- Journal of Computational Chemistry, Vol. 37, Issue 5
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
Benchmark Calculations of Interaction Energies in Noncovalent Complexes and Their Applications
journal, March 2016
- Řezáč, Jan; Hobza, Pavel
- Chemical Reviews, Vol. 116, Issue 9