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

Title: Tuned Hydrogen Bonding in Rare-Earth Metal–Organic Frameworks for Design of Optical and Electronic Properties: An Exemplar Study of Y–2,5-Dihydroxyterephthalic Acid

Abstract

Organic linkers in metal–organic framework (MOF) materials exhibit differences in hydrogen bonding (H-bonding), which can alter the geometric, electronic, and optical properties of the MOF. Density functional theory (DFT) simulations were performed on a photoluminescent Y-2,5-dihydroxyterephthalic acid (DOBDC) MOF with H-bonding concentrations between 0 and 100%; the H-bonds were located on both bidentate- and monodentate-bound DOBDC linkers. At 0% H-bond concentration in the framework, the lattice parameters contracted, the density increased, and simulated X-ray diffraction patterns shifted. Comparison with published experimental data identified that Y–DOBDC MOF structures must have a degree of H-bond concentration. The concentration of H-bonds in the system shifted the calculated band gap energy from 2.25 eV at 100% to 3.00 eV at 0%. The band gap energies also indicate a distinction of H-bonds formed on bidentate-coordinated linkers compared to those on monodentate linkers. Additionally, when the calculated optical spectra are compared with experimental data, the ligand-to-ligand charge-transfer luminescence in Y–DOBDC MOFs is expected to result from an average of 20–40% H-bonding with at least 50% of the bidentate linkers containing H-bonding. Therefore, the type of H-bonding within the DOBDC linker determines the electronic structure and the optical absorption of the MOF framework structure. Tuning of themore » H-bonding in rare-earth MOFs provides an opportunity to control the specific optical and adsorption properties of the MOF framework on the basis of reactions between the linker and the environment.« less

Authors:
 [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
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); Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1601266
Report Number(s):
SAND-2020-1497J
Journal ID: ISSN 1944-8244; 683567
Grant/Contract Number:  
AC04-94AL85000
Resource Type:
Accepted Manuscript
Journal Name:
ACS Applied Materials and Interfaces
Additional Journal Information:
Journal Volume: 12; Journal Issue: 4; Journal ID: ISSN 1944-8244
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; metal−organic frameworks; density functional theory; hydrogen bonding; luminescence; optical adsorption

Citation Formats

Vogel, Dayton J., Nenoff, Tina M., and Rimsza, Jessica M.. Tuned Hydrogen Bonding in Rare-Earth Metal–Organic Frameworks for Design of Optical and Electronic Properties: An Exemplar Study of Y–2,5-Dihydroxyterephthalic Acid. United States: N. p., 2020. Web. https://doi.org/10.1021/acsami.9b20513.
Vogel, Dayton J., Nenoff, Tina M., & Rimsza, Jessica M.. Tuned Hydrogen Bonding in Rare-Earth Metal–Organic Frameworks for Design of Optical and Electronic Properties: An Exemplar Study of Y–2,5-Dihydroxyterephthalic Acid. United States. https://doi.org/10.1021/acsami.9b20513
Vogel, Dayton J., Nenoff, Tina M., and Rimsza, Jessica M.. Mon . "Tuned Hydrogen Bonding in Rare-Earth Metal–Organic Frameworks for Design of Optical and Electronic Properties: An Exemplar Study of Y–2,5-Dihydroxyterephthalic Acid". United States. https://doi.org/10.1021/acsami.9b20513. https://www.osti.gov/servlets/purl/1601266.
@article{osti_1601266,
title = {Tuned Hydrogen Bonding in Rare-Earth Metal–Organic Frameworks for Design of Optical and Electronic Properties: An Exemplar Study of Y–2,5-Dihydroxyterephthalic Acid},
author = {Vogel, Dayton J. and Nenoff, Tina M. and Rimsza, Jessica M.},
abstractNote = {Organic linkers in metal–organic framework (MOF) materials exhibit differences in hydrogen bonding (H-bonding), which can alter the geometric, electronic, and optical properties of the MOF. Density functional theory (DFT) simulations were performed on a photoluminescent Y-2,5-dihydroxyterephthalic acid (DOBDC) MOF with H-bonding concentrations between 0 and 100%; the H-bonds were located on both bidentate- and monodentate-bound DOBDC linkers. At 0% H-bond concentration in the framework, the lattice parameters contracted, the density increased, and simulated X-ray diffraction patterns shifted. Comparison with published experimental data identified that Y–DOBDC MOF structures must have a degree of H-bond concentration. The concentration of H-bonds in the system shifted the calculated band gap energy from 2.25 eV at 100% to 3.00 eV at 0%. The band gap energies also indicate a distinction of H-bonds formed on bidentate-coordinated linkers compared to those on monodentate linkers. Additionally, when the calculated optical spectra are compared with experimental data, the ligand-to-ligand charge-transfer luminescence in Y–DOBDC MOFs is expected to result from an average of 20–40% H-bonding with at least 50% of the bidentate linkers containing H-bonding. Therefore, the type of H-bonding within the DOBDC linker determines the electronic structure and the optical absorption of the MOF framework structure. Tuning of the H-bonding in rare-earth MOFs provides an opportunity to control the specific optical and adsorption properties of the MOF framework on the basis of reactions between the linker and the environment.},
doi = {10.1021/acsami.9b20513},
journal = {ACS Applied Materials and Interfaces},
number = 4,
volume = 12,
place = {United States},
year = {2020},
month = {1}
}

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

Citation Metrics:
Cited by: 3 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

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

Adsorptive removal of hazardous materials using metal-organic frameworks (MOFs): A review
journal, January 2013


Enhanced H2 Adsorption in Isostructural Metal−Organic Frameworks with Open Metal Sites: Strong Dependence of the Binding Strength on Metal Ions
journal, November 2008

  • Zhou, Wei; Wu, Hui; Yildirim, Taner
  • Journal of the American Chemical Society, Vol. 130, Issue 46, p. 15268-15269
  • DOI: 10.1021/ja807023q

A Review on Breathing Behaviors of Metal-Organic-Frameworks (MOFs) for Gas Adsorption
journal, April 2014

  • Alhamami, Mays; Doan, Huu; Cheng, Chil-Hung
  • Materials, Vol. 7, Issue 4
  • DOI: 10.3390/ma7043198

Defect and Linker Effects on the Binding of Organophosphorous Compounds in UiO-66 and Rare-Earth MOFs
journal, November 2018

  • Harvey, Jacob A.; Greathouse, Jeffery A.; Sava Gallis, Dorina F.
  • The Journal of Physical Chemistry C, Vol. 122, Issue 47
  • DOI: 10.1021/acs.jpcc.8b06198

Luminescent metal–organic frameworks
journal, January 2009

  • Allendorf, M. D.; Bauer, C. A.; Bhakta, R. K.
  • Chemical Society Reviews, Vol. 38, Issue 5
  • DOI: 10.1039/b802352m

Lanthanide metal-organic frameworks for luminescent sensing and light-emitting applications
journal, August 2014


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
  • DOI: 10.1021/acsami.7b05859

Efficient Photoluminescence via Metal–Ligand Alteration in a New MOFs Family
journal, April 2014

  • Sava Gallis, Dorina F.; Rohwer, Lauren E. S.; Rodriguez, Mark A.
  • Chemistry of Materials, Vol. 26, Issue 9, p. 2943-2951
  • DOI: 10.1021/cm500700z

Intrinsic Broad-Band White-Light Emission by a Tuned, Corrugated Metal–Organic Framework
journal, February 2012

  • Sava, Dorina F.; Rohwer, Lauren E. S.; Rodriguez, Mark A.
  • Journal of the American Chemical Society, Vol. 134, Issue 9, p. 3983-3986
  • DOI: 10.1021/ja211230p

Metal–organic framework nanosheets for fast-response and highly sensitive luminescent sensing of Fe 3+
journal, January 2016

  • Xu, Hui; Gao, Junkuo; Qian, Xuefeng
  • Journal of Materials Chemistry A, Vol. 4, Issue 28
  • DOI: 10.1039/C6TA03065C

Luminescent Properties of Metal–Organic Framework MOF-5: Relativistic Time-Dependent Density Functional Theory Investigations
journal, November 2012

  • Ji, Min; Lan, Xin; Han, Zhenping
  • Inorganic Chemistry, Vol. 51, Issue 22
  • DOI: 10.1021/ic301771b

Tunable emission from a porous metal–organic framework by employing an excited-state intramolecular proton transfer responsive ligand
journal, January 2010

  • Jayaramulu, K.; Kanoo, Prakash; George, Subi J.
  • Chemical Communications, Vol. 46, Issue 42
  • DOI: 10.1039/c0cc02069a

A General Model of Sensitized Luminescence in Lanthanide-Based Coordination Polymers and Metal–Organic Framework Materials
journal, April 2017


An advanced approach for measuring acidity of hydroxyls in confined space: a FTIR study of low-temperature CO and 15 N 2 adsorption on MOF samples from the MIL-53(Al) series
journal, January 2015

  • Mihaylov, M.; Andonova, S.; Chakarova, K.
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 37
  • DOI: 10.1039/C5CP04139B

NO x Adsorption and Optical Detection in Rare Earth Metal–Organic Frameworks
journal, October 2019

  • Sava Gallis, Dorina F.; Vogel, Dayton J.; Vincent, Grace A.
  • ACS Applied Materials & Interfaces, Vol. 11, Issue 46
  • DOI: 10.1021/acsami.9b16470

Ab initiomolecular dynamics for liquid metals
journal, January 1993


Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium
journal, May 1994


Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996


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


From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999


Restoring the Density-Gradient Expansion for Exchange in Solids and Surfaces
journal, April 2008


Spectroscopically Resolved Binding Sites for the Adsorption of Sarin Gas in a Metal–Organic Framework: Insights beyond Lewis Acidity
journal, August 2019

  • Harvey, Jacob A.; McEntee, Monica L.; Garibay, Sergio J.
  • The Journal of Physical Chemistry Letters, Vol. 10, Issue 17
  • DOI: 10.1021/acs.jpclett.9b01867

Structure and electronic properties of rare earth DOBDC metal–organic-frameworks
journal, January 2019

  • Vogel, Dayton J.; Sava Gallis, Dorina F.; Nenoff, Tina M.
  • Physical Chemistry Chemical Physics, Vol. 21, Issue 41
  • DOI: 10.1039/C9CP04038B

Modelling photophysical properties of metal–organic frameworks: a density functional theory based approach
journal, January 2016

  • Wilbraham, Liam; Coudert, François-Xavier; Ciofini, Ilaria
  • Physical Chemistry Chemical Physics, Vol. 18, Issue 36
  • DOI: 10.1039/C6CP04056J

Efficient MOF-based degradation of organophosphorus compounds in non-aqueous environments
journal, January 2018

  • Sava Gallis, Dorina F.; Harvey, Jacob A.; Pearce, Charles J.
  • Journal of Materials Chemistry A, Vol. 6, Issue 7
  • DOI: 10.1039/C7TA10794C

Assessing Hubbard-corrected AM05+U and PBEsol+U density functionals for strongly correlated oxides CeO 2 and Ce 2 O 3
journal, January 2016

  • Weck, Philippe F.; Kim, Eunja
  • Physical Chemistry Chemical Physics, Vol. 18, Issue 38
  • DOI: 10.1039/C6CP05479J

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

Effect of the damping function in dispersion corrected density functional theory
journal, March 2011

  • Grimme, Stefan; Ehrlich, Stephan; Goerigk, Lars
  • Journal of Computational Chemistry, Vol. 32, Issue 7
  • DOI: 10.1002/jcc.21759

Effect of Metal in M 3 (btc) 2 and M 2 (dobdc) MOFs for O 2 /N 2 Separations: A Combined Density Functional Theory and Experimental Study
journal, March 2015

  • Parkes, Marie V.; Sava Gallis, Dorina F.; Greathouse, Jeffery A.
  • The Journal of Physical Chemistry C, Vol. 119, Issue 12
  • DOI: 10.1021/jp511789g

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
  • DOI: 10.1039/C6CP00768F

Three-Dimensional Visualization in Powder Diffraction
journal, December 2007


Hybrid functionals based on a screened Coulomb potential
journal, May 2003

  • Heyd, Jochen; Scuseria, Gustavo E.; Ernzerhof, Matthias
  • The Journal of Chemical Physics, Vol. 118, Issue 18
  • DOI: 10.1063/1.1564060

Influence of the exchange screening parameter on the performance of screened hybrid functionals
journal, December 2006

  • Krukau, Aliaksandr V.; Vydrov, Oleg A.; Izmaylov, Artur F.
  • The Journal of Chemical Physics, Vol. 125, Issue 22
  • DOI: 10.1063/1.2404663

Photoabsorbance and Photovoltage of Crystalline and Amorphous Silicon Slabs with Silver Adsorbates
journal, November 2012

  • Vazhappilly, Tijo; Kilin, Dmitri S.; Micha, David A.
  • The Journal of Physical Chemistry C, Vol. 116, Issue 48
  • DOI: 10.1021/jp306845g

First-Principles Treatment of Photoluminescence in Semiconductors
journal, December 2015

  • Vogel, Dayton J.; Kilin, Dmitri S.
  • The Journal of Physical Chemistry C, Vol. 119, Issue 50
  • DOI: 10.1021/acs.jpcc.5b06434

Photoinduced Single- and Multiple-Electron Dynamics Processes Enhanced by Quantum Confinement in Lead Halide Perovskite Quantum Dots
journal, June 2017

  • Vogel, Dayton J.; Kryjevski, Andrei; Inerbaev, Talgat
  • The Journal of Physical Chemistry Letters, Vol. 8, Issue 13
  • DOI: 10.1021/acs.jpclett.6b03048

Role of Lead Vacancies for Optoelectronic Properties of Lead-Halide Perovskites
journal, December 2017

  • Vogel, Dayton J.; Inerbaev, Talgat M.; Kilin, Dmitri S.
  • The Journal of Physical Chemistry C, Vol. 122, Issue 10
  • DOI: 10.1021/acs.jpcc.7b05375

Charge Transfer, Luminescence, and Phonon Bottleneck in TiO 2 Nanowires Computed by Eigenvectors of Liouville Superoperator
journal, August 2014

  • Huang, Shuping; Kilin, Dmitri S.
  • Journal of Chemical Theory and Computation, Vol. 10, Issue 9
  • DOI: 10.1021/ct5004093

Hybrid functionals applied to rare-earth oxides: The example of ceria
journal, January 2007

  • Da Silva, Juarez L. F.; Ganduglia-Pirovano, M. Verónica; Sauer, Joachim
  • Physical Review B, Vol. 75, Issue 4
  • DOI: 10.1103/PhysRevB.75.045121

Screened hybrid density functionals for solid-state chemistry and physics
journal, January 2009

  • Janesko, Benjamin G.; Henderson, Thomas M.; Scuseria, Gustavo E.
  • Phys. Chem. Chem. Phys., Vol. 11, Issue 3
  • DOI: 10.1039/B812838C

Predicting Band Gaps with Hybrid Density Functionals
journal, October 2016

  • Garza, Alejandro J.; Scuseria, Gustavo E.
  • The Journal of Physical Chemistry Letters, Vol. 7, Issue 20
  • DOI: 10.1021/acs.jpclett.6b01807

Electronic Chemical Potentials of Porous Metal–Organic Frameworks
journal, February 2014

  • Butler, Keith T.; Hendon, Christopher H.; Walsh, Aron
  • Journal of the American Chemical Society, Vol. 136, Issue 7
  • DOI: 10.1021/ja4110073

Lattice Expansion and Contraction in Metal-Organic Frameworks by Sequential Linker Reinstallation
journal, July 2019


Estimates of the Energy of Intramolecular Hydrogen Bonds
journal, September 2006

  • Jabłoński, Mirosław; Kaczmarek, Anna; Sadlej, Andrzej J.
  • The Journal of Physical Chemistry A, Vol. 110, Issue 37
  • DOI: 10.1021/jp062759o

Strong intramolecular hydrogen bonding within the dimedone–aldehyde adducts
journal, August 2010


“Strong” Hydrogen Bonds in Chemistry and Biology
journal, October 1997