Elucidating correlated defects in metal organic frameworks using theory-guided inelastic neutron scattering spectroscopy
Abstract
Metal organic frameworks (MOFs) that incorporate metal oxide cluster nodes, exemplified by UiO-66, have been widely studied, especially in terms of their deviations from the ideal, defect-free crystalline structures. Although defects such as missing linkers, missing nodes, and the presence of adventitious synthesis-derived node ligands (such as acetates and formates) have been proposed, their exact structures remain unknown. Previously, it was demonstrated that defects are correlated and span multiple unit cells. The highly specialized techniques used in these studies are not easily applicable to other MOFs. Thus, there is a need to develop new experimental and computational approaches to understand the structure and properties of defects in a wider variety of MOFs. Here, we show how low-frequency phonon modes measured by inelastic neutron scattering (INS) spectroscopy can be combined with density functional theory (DFT) simulations to provide unprecedented insights into the defect structure of UiO-66. We are able to identify and assign peaks in the fingerprint region (<100 cm–1) which correspond to phonon modes only present in certain defective topologies. Specifically, this analysis suggests that our sample of UiO-66 consists of predominantly defect-free fcu regions with smaller domains corresponding to a defective bcu topology with 4 and 2 acetate ligandsmore »
- Authors:
-
- Univ. of California, Davis, CA (United States)
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Publication Date:
- Research Org.:
- Univ. of California, Davis, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1924280
- Alternate Identifier(s):
- OSTI ID: 1897313
- Grant/Contract Number:
- SC0010419; SC0012702; AC02-05CH11231; AC52-07NA27344
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Materials Horizons
- Additional Journal Information:
- Journal Volume: 10; Journal Issue: 1; Journal ID: ISSN 2051-6347
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE
Citation Formats
Cavalcante, Lucas S. R., Dettmann, Makena A., Sours, Tyler, Yang, Dong, Daemen, Luke L., Gates, Bruce C., Kulkarni, Ambarish R., and Moulé, Adam J. Elucidating correlated defects in metal organic frameworks using theory-guided inelastic neutron scattering spectroscopy. United States: N. p., 2022.
Web. doi:10.1039/d2mh00914e.
Cavalcante, Lucas S. R., Dettmann, Makena A., Sours, Tyler, Yang, Dong, Daemen, Luke L., Gates, Bruce C., Kulkarni, Ambarish R., & Moulé, Adam J. Elucidating correlated defects in metal organic frameworks using theory-guided inelastic neutron scattering spectroscopy. United States. https://doi.org/10.1039/d2mh00914e
Cavalcante, Lucas S. R., Dettmann, Makena A., Sours, Tyler, Yang, Dong, Daemen, Luke L., Gates, Bruce C., Kulkarni, Ambarish R., and Moulé, Adam J. Mon .
"Elucidating correlated defects in metal organic frameworks using theory-guided inelastic neutron scattering spectroscopy". United States. https://doi.org/10.1039/d2mh00914e. https://www.osti.gov/servlets/purl/1924280.
@article{osti_1924280,
title = {Elucidating correlated defects in metal organic frameworks using theory-guided inelastic neutron scattering spectroscopy},
author = {Cavalcante, Lucas S. R. and Dettmann, Makena A. and Sours, Tyler and Yang, Dong and Daemen, Luke L. and Gates, Bruce C. and Kulkarni, Ambarish R. and Moulé, Adam J.},
abstractNote = {Metal organic frameworks (MOFs) that incorporate metal oxide cluster nodes, exemplified by UiO-66, have been widely studied, especially in terms of their deviations from the ideal, defect-free crystalline structures. Although defects such as missing linkers, missing nodes, and the presence of adventitious synthesis-derived node ligands (such as acetates and formates) have been proposed, their exact structures remain unknown. Previously, it was demonstrated that defects are correlated and span multiple unit cells. The highly specialized techniques used in these studies are not easily applicable to other MOFs. Thus, there is a need to develop new experimental and computational approaches to understand the structure and properties of defects in a wider variety of MOFs. Here, we show how low-frequency phonon modes measured by inelastic neutron scattering (INS) spectroscopy can be combined with density functional theory (DFT) simulations to provide unprecedented insights into the defect structure of UiO-66. We are able to identify and assign peaks in the fingerprint region (<100 cm–1) which correspond to phonon modes only present in certain defective topologies. Specifically, this analysis suggests that our sample of UiO-66 consists of predominantly defect-free fcu regions with smaller domains corresponding to a defective bcu topology with 4 and 2 acetate ligands bound to the Zr6O8 nodes. Importantly, the INS/DFT approach provides detailed structural insights (e.g., relative positions and numbers of acetate ligands) that are not accessible with microscopy-based techniques. Furthermore, the quantitative agreement between DFT simulations and the experimental INS spectrum combined with the relative simplicity of sample preparation, suggests that this methodology may become part of the standard and preferred protocol for the characterization of MOFs, and, in particular, for elucidating the structure defects in these materials.},
doi = {10.1039/d2mh00914e},
journal = {Materials Horizons},
number = 1,
volume = 10,
place = {United States},
year = {Mon Oct 31 00:00:00 EDT 2022},
month = {Mon Oct 31 00:00:00 EDT 2022}
}
Works referenced in this record:
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
Sub-Ambient Temperature Direct Air Capture of CO2 using Amine-Impregnated MIL-101(Cr) Enables Ambient Temperature CO2 Recovery
journal, February 2022
- Rim, Guanhe; Kong, Fanhe; Song, Mingyu
- JACS Au, Vol. 2, Issue 2
Tackling the Defect Conundrum in UiO-66: A Mixed-Linker Approach to Engineering Missing Linker Defects
journal, November 2017
- Bueken, Bart; Van Velthoven, Niels; Krajnc, Andraž
- Chemistry of Materials, Vol. 29, Issue 24
Defect-Engineered Metal-Organic Frameworks
journal, June 2015
- Fang, Zhenlan; Bueken, Bart; De Vos, Dirk E.
- Angewandte Chemie International Edition, Vol. 54, Issue 25
Defects in Metal–Organic Frameworks: Challenge or Opportunity?
journal, August 2015
- Sholl, David S.; Lively, Ryan P.
- The Journal of Physical Chemistry Letters, Vol. 6, Issue 17
Defective Metal-Organic Frameworks
journal, January 2018
- Dissegna, Stefano; Epp, Konstantin; Heinz, Werner R.
- Advanced Materials, Vol. 30, Issue 37
Tailoring the Properties of UiO-66 through Defect Engineering: A Review
journal, August 2019
- Feng, Yi; Chen, Qian; Jiang, Minqi
- Industrial & Engineering Chemistry Research, Vol. 58, Issue 38
Switching on the Photocatalysis of Metal–Organic Frameworks by Engineering Structural Defects
journal, August 2019
- Ma, Xing; Wang, Li; Zhang, Qun
- Angewandte Chemie International Edition, Vol. 58, Issue 35
Metal-organic framework functionalization and design strategies for advanced electrochemical energy storage devices
journal, July 2019
- Baumann, Avery E.; Burns, David A.; Liu, Bingqian
- Communications Chemistry, Vol. 2, Issue 1
Lithiated Defect Sites in Zr Metal–Organic Framework for Enhanced Sulfur Utilization in Li–S Batteries
journal, December 2018
- Baumann, Avery E.; Burns, David A.; Díaz, José C.
- ACS Applied Materials & Interfaces, Vol. 11, Issue 2
Defect Engineering in Metal‒Organic Frameworks as Futuristic Options for Purification of Pollutants in an Aqueous Environment
journal, August 2021
- Cao, Yuhua; Mi, Xin; Li, Xiang
- Frontiers in Chemistry, Vol. 9
Defective Metal–Organic Framework-808@Polyaniline Composite Materials for High Capacitance Retention Supercapacitor Electrodes
journal, January 2022
- Ferhi, Najmeddine; Desalegn Assresahegn, Birhanu; Ardila-Suarez, Carolina
- ACS Applied Energy Materials, Vol. 5, Issue 1
Defects as catalytic sites for the oxygen evolution reaction in Earth-abundant MOF-74 revealed by DFT
journal, January 2021
- Morales-Vidal, Jordi; García-Muelas, Rodrigo; Ortuño, Manuel A.
- Catalysis Science & Technology, Vol. 11, Issue 4
Opening catalytic sites in the copper-triazoles framework via defect chemistry for switching on the proton reduction
journal, July 2021
- Wang, Zhao-Di; Zang, Ying; Liu, Zhi-Juan
- Applied Catalysis B: Environmental, Vol. 288
Interplay between defects, disorder and flexibility in metal-organic frameworks
journal, December 2016
- Bennett, Thomas D.; Cheetham, Anthony K.; Fuchs, Alain H.
- Nature Chemistry, Vol. 9, Issue 1
Defects and disorder in metal organic frameworks
journal, January 2016
- Cheetham, Anthony K.; Bennett, Thomas D.; Coudert, François-Xavier
- Dalton Transactions, Vol. 45, Issue 10
Effect of Defects on the Mechanical Deformation Mechanisms of Metal–Organic Framework-5: A Molecular Dynamics Investigation
journal, February 2018
- Zheng, Bin; Fu, Fang; Wang, Lian Li
- The Journal of Physical Chemistry C, Vol. 122, Issue 8
Enhancing Electrical Conductivity of Semiconducting MOFs via Defect Healing
journal, September 2021
- Choi, Ji Yong; Park, Jihye
- ACS Applied Electronic Materials, Vol. 3, Issue 9
Tunable Electrical Conductivity in Metal-Organic Framework Thin-Film Devices
journal, December 2013
- Talin, A. Alec; Centrone, Andrea; Ford, Alexandra C.
- Science, Vol. 343, Issue 6166, p. 66-69
Defect Engineering in a Metal–Organic Framework System to Achieve Super-Protonic Conductivity
journal, July 2022
- Basu, Olivia; Mukhopadhyay, Subhabrata; Laha, Subhajit
- Chemistry of Materials, Vol. 34, Issue 15
Influence of Missing Linker Defects on the Thermal Conductivity of Metal–Organic Framework HKUST-1
journal, December 2020
- Islamov, Meiirbek; Babaei, Hasan; Wilmer, Christopher E.
- ACS Applied Materials & Interfaces, Vol. 12, Issue 50
White Light Emission Properties of Defect Engineered Metal–Organic Frameworks by Encapsulation of Eu3+ and Tb3+
journal, October 2019
- Jena, Himanshu Sekhar; Kaczmarek, Anna M.; Krishnaraj, Chidharth
- Crystal Growth & Design, Vol. 19, Issue 11
Band gap modulation in zirconium-based metal–organic frameworks by defect engineering
journal, January 2019
- Taddei, Marco; Schukraft, Giulia M.; Warwick, Michael E. A.
- Journal of Materials Chemistry A, Vol. 7, Issue 41
Growth of centimeter-sized [(CH 3 ) 2 NH 2 ][Mn(HCOO) 3 ] hybrid formate perovskite single crystals and Raman evidence of pressure-induced phase transitions
journal, January 2017
- Xin, Lipeng; Fan, Zhen; Li, Guanghui
- New Journal of Chemistry, Vol. 41, Issue 1
Growth of a dense gadolinium metal–organic framework on oxide-free silicon for cryogenic local refrigeration
journal, January 2019
- Lorusso, Giulia; Natividad, Eva; Evangelisti, Marco
- Materials Horizons, Vol. 6, Issue 1
Hypophosphite hybrid perovskites: a platform for unconventional tilts and shifts
journal, January 2018
- Wu, Yue; Binford, Trevor; Hill, Joshua A.
- Chemical Communications, Vol. 54, Issue 30
Formation Mechanisms and Defect Engineering of Imine-Based Porous Organic Cages
journal, December 2017
- Zhu, Guanghui; Liu, Yang; Flores, Luis
- Chemistry of Materials, Vol. 30, Issue 1
Catalytic Zirconium/Hafnium-Based Metal–Organic Frameworks
journal, December 2016
- Rimoldi, Martino; Howarth, Ashlee J.; DeStefano, Matthew R.
- ACS Catalysis, Vol. 7, Issue 2
Structure and Dynamics of Zr 6 O 8 Metal–Organic Framework Node Surfaces Probed with Ethanol Dehydration as a Catalytic Test Reaction
journal, February 2018
- Yang, Dong; Ortuño, Manuel A.; Bernales, Varinia
- Journal of the American Chemical Society, Vol. 140, Issue 10
Molecular Rhodium Complexes Supported on the Metal-Oxide-Like Nodes of Metal Organic Frameworks and on Zeolite HY: Catalysts for Ethylene Hydrogenation and Dimerization
journal, April 2017
- Bernales, Varinia; Yang, Dong; Yu, Jun
- ACS Applied Materials & Interfaces, Vol. 9, Issue 39
Tuning Zr 6 Metal–Organic Framework (MOF) Nodes as Catalyst Supports: Site Densities and Electron-Donor Properties Influence Molecular Iridium Complexes as Ethylene Conversion Catalysts
journal, December 2015
- Yang, Dong; Odoh, Samuel O.; Borycz, Joshua
- ACS Catalysis, Vol. 6, Issue 1
A Structure–Activity Study of Aromatic Acid Modulators for the Synthesis of Zirconium-Based Metal–Organic Frameworks
journal, March 2022
- Chen, Faith E.; Pitt, Tristan A.; Okong’o, Diane J.
- Chemistry of Materials, Vol. 34, Issue 7
Correlated defect nanoregions in a metal–organic framework
journal, June 2014
- Cliffe, Matthew J.; Wan, Wei; Zou, Xiaodong
- Nature Communications, Vol. 5, Issue 1
Imaging defects and their evolution in a metal–organic framework at sub-unit-cell resolution
journal, May 2019
- Liu, Lingmei; Chen, Zhijie; Wang, Jianjian
- Nature Chemistry, Vol. 11, Issue 7
Exceptional Mechanical Stability of Highly Porous Zirconium Metal–Organic Framework UiO-66 and Its Important Implications
journal, March 2013
- Wu, Hui; Yildirim, Taner; Zhou, Wei
- The Journal of Physical Chemistry Letters, Vol. 4, Issue 6
Evaluation of Brønsted acidity and proton topology in Zr- and Hf-based metal–organic frameworks using potentiometric acid–base titration
journal, January 2016
- Klet, Rachel C.; Liu, Yangyang; Wang, Timothy C.
- Journal of Materials Chemistry A, Vol. 4, Issue 4
Tuning the Properties of Zr 6 O 8 Nodes in the Metal Organic Framework UiO-66 by Selection of Node-Bound Ligands and Linkers
journal, February 2019
- Wei, Ruiping; Gaggioli, Carlo Alberto; Li, Guozhu
- Chemistry of Materials, Vol. 31, Issue 5
Direct probe of the nuclear modes limiting charge mobility in molecular semiconductors
journal, January 2019
- Harrelson, Thomas F.; Dantanarayana, Varuni; Xie, Xiaoyu
- Materials Horizons, Vol. 6, Issue 1
Identifying Atomic Scale Structure in Undoped/Doped Semicrystalline P3HT Using Inelastic Neutron Scattering
journal, March 2017
- Harrelson, Thomas F.; Cheng, Yongqiang Q.; Li, Jun
- Macromolecules, Vol. 50, Issue 6
Understanding ZIF-8 Performance upon Gas Adsorption by Means of Inelastic Neutron Scattering
journal, March 2017
- Casco, Mirian E.; Fernández-Catalá, Javier; Cheng, Yongqiang
- ChemistrySelect, Vol. 2, Issue 9
Understanding the ZIF-L to ZIF-8 transformation from fundamentals to fully costed kilogram-scale production
journal, February 2022
- Deacon, Adam; Briquet, Ludovic; Malankowska, Magdalena
- Communications Chemistry, Vol. 5, Issue 1
Quantitative Hole Mobility Simulation and Validation in Substituted Acenes
journal, June 2022
- Vong, Daniel; Nematiaram, Tahereh; Dettmann, Makena A.
- The Journal of Physical Chemistry Letters, Vol. 13, Issue 24
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
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
Detailed Structure Analysis of Atomic Positions and Defects in Zirconium Metal–Organic Frameworks
journal, October 2014
- Øien, Sigurd; Wragg, David; Reinsch, Helge
- Crystal Growth & Design, Vol. 14, Issue 11
Active site engineering in UiO-66 type metal–organic frameworks by intentional creation of defects: a theoretical rationalization
journal, January 2015
- Vandichel, Matthias; Hajek, Julianna; Vermoortele, Frederik
- CrystEngComm, Vol. 17, Issue 2
Connecting defects and amorphization in UiO-66 and MIL-140 metal–organic frameworks: a combined experimental and computational study
journal, January 2016
- Bennett, Thomas D.; Todorova, Tanya K.; Baxter, Emma F.
- Physical Chemistry Chemical Physics, Vol. 18, Issue 3
Zirconium-containing UiO-66 as an efficient and reusable catalyst for transesterification of triglyceride with methanol
journal, September 2016
- Zhou, Fan; Lu, Ningyue; Fan, Binbin
- Journal of Energy Chemistry, Vol. 25, Issue 5
Effect of Benzoic Acid as a Modulator in the Structure of UiO-66: An Experimental and Computational Study
journal, April 2017
- Atzori, Cesare; Shearer, Greig C.; Maschio, Lorenzo
- The Journal of Physical Chemistry C, Vol. 121, Issue 17
Direct Imaging of Correlated Defect Nanodomains in a Metal–Organic Framework
journal, July 2020
- Johnstone, Duncan N.; Firth, Francesca C. N.; Grey, Clare P.
- Journal of the American Chemical Society, Vol. 142, Issue 30
Defect Termination in the UiO-66 Family of Metal–Organic Frameworks: The Role of Water and Modulator
journal, April 2021
- Tan, Kui; Pandey, Haardik; Wang, Hao
- Journal of the American Chemical Society, Vol. 143, Issue 17
Simulation of Inelastic Neutron Scattering Spectra Using OCLIMAX
journal, January 2019
- Cheng, Y. Q.; Daemen, L. L.; Kolesnikov, A. I.
- Journal of Chemical Theory and Computation, Vol. 15, Issue 3
Comparing the Expense and Accuracy of Methods to Simulate Atomic Vibrations in Rubrene
journal, November 2021
- Dettmann, Makena A.; Cavalcante, Lucas S. R.; Magdaleno, Corina
- Journal of Chemical Theory and Computation, Vol. 17, Issue 12
Davis Computational Spectroscopy Workflow—From Structure to Spectra
journal, August 2021
- Cavalcante, L. S. R.; Daemen, Luke L.; Goldman, Nir
- Journal of Chemical Information and Modeling, Vol. 61, Issue 9
First principles phonon calculations in materials science
journal, November 2015
- Togo, Atsushi; Tanaka, Isao
- Scripta Materialia, Vol. 108
Gate-opening effect in ZIF-8: the first experimental proof using inelastic neutron scattering
journal, January 2016
- Casco, M. E.; Cheng, Y. Q.; Daemen, L. L.
- Chemical Communications, Vol. 52, Issue 18
Standard Practices of Reticular Chemistry
journal, July 2020
- Gropp, Cornelius; Canossa, Stefano; Wuttke, Stefan
- ACS Central Science, Vol. 6, Issue 8