Tuning the Properties of Zr6O8 Nodes in the Metal Organic Framework UiO-66 by Selection of Node-Bound Ligands and Linkers

Wei, Ruiping; Gaggioli, Carlo Alberto; Li, Guozhu; Islamoglu, Timur; Zhang, Zhuxiu; Yu, Ping; Farha, Omar K.; Cramer, Christopher J.; Gagliardi, Laura; Yang, Dong; Gates, Bruce C.

doi:10.1021/acs.chemmater.8b05037

Tuning the Properties of Zr₆O₈ Nodes in the Metal Organic Framework UiO-66 by Selection of Node-Bound Ligands and Linkers

Journal Article · Wed Feb 06 04:00:00 EST 2019 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.8b05037· OSTI ID:1566490

Wei, Ruiping ^[1]; Gaggioli, Carlo Alberto ^[2]; ^[1]; ^[3]; Zhang, Zhuxiu ^[4]; Yu, Ping ^[1]; ^[3]; ^[2]; ^[2]; ^[1]; ^[1]

Univ. of California, Davis, CA (United States)
Univ. of Minnesota, Minneapolis, MN (United States)
Northwestern Univ., Evanston, IL (United States)
Nanjing Tech Univ. (China)

The metal organic framework (MOF) UiO-66, which incorporates Zr₆O₈ nodes, exhibits high stability under a wide range of conditions that commends it for potential applications. The MOF properties can be tuned by the choice of the groups bonded to the node defect sites and to the linkers. In this paper, we report data for UiO-66 incorporating formate, acetate, benzoate, and trifluoroacetate on the nodes and -NH₂, -OH, -NO₂, and phenyl substituents on the benzene rings of the benzene-1,4-dicarboxylic acid-derived linkers. The MOFs were characterized by IR and ¹H NMR spectroscopies, thermal gravimetric analysis, N₂ adsorption, X-ray diffraction crystallography, scanning and transmission electron microscopy, and electronic structure calculations. The ligands on the nodes were identified and quantified by ¹H NMR spectra of the MOFs digested in NaOH/D₂O solutions. Lastly, the effects of the node and linker groups on the electronic properties of the nodes have been quantified with IR spectra of the node μ₃-OH groups and by density functional theory calculations, which are in good agreement with one another.

View Accepted Manuscript (DOE)

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Energy Frontier Research Center for Inorganometallic Catalyst Design (ICDC); Univ. of Minnesota, Minneapolis, MN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: SC0012702

OSTI ID:: 1566490

Journal Information:: Chemistry of Materials, Journal Name: Chemistry of Materials Journal Issue: 5 Vol. 31; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (32)

Electronic Effects of Linker Substitution on Lewis Acid Catalysis with Metal-Organic Frameworks Vermoortele, Frederik; Vandichel, Matthias; Van de Voorde, Ben Angewandte Chemie International Edition, Vol. 51, Issue 20 https://doi.org/10.1002/anie.201108565	journal	April 2012
Presence versus Proximity: The Role of Pendant Amines in the Catalytic Hydrolysis of a Nerve Agent Simulant Islamoglu, Timur; Ortuño, Manuel A.; Proussaloglou, Emmanuel Angewandte Chemie International Edition, Vol. 57, Issue 7 https://doi.org/10.1002/anie.201712645	journal	January 2018
Functionality proportion and corresponding stability study of multivariate metal-organic frameworks Li, Jie; Wang, Yecheng; Yu, Yan Chinese Chemical Letters, Vol. 29, Issue 6 https://doi.org/10.1016/j.cclet.2017.12.026	journal	June 2018
When defects turn into virtues: The curious case of zirconium-based metal-organic frameworks Taddei, Marco Coordination Chemistry Reviews, Vol. 343 https://doi.org/10.1016/j.ccr.2017.04.010	journal	July 2017
Postsynthetic Tuning of Metal–Organic Frameworks for Targeted Applications Islamoglu, Timur; Goswami, Subhadip; Li, Zhanyong Accounts of Chemical Research, Vol. 50, Issue 4 https://doi.org/10.1021/acs.accounts.6b00577	journal	February 2017
Defect Engineering: Tuning the Porosity and Composition of the Metal–Organic Framework UiO-66 via Modulated Synthesis Shearer, Greig C.; Chavan, Sachin; Bordiga, Silvia Chemistry of Materials, Vol. 28, Issue 11 https://doi.org/10.1021/acs.chemmater.6b00602	journal	May 2016
Metal–Organic Frameworks for Heterogeneous Basic Catalysis Zhu, Li; Liu, Xiao-Qin; Jiang, Hai-Long Chemical Reviews, Vol. 117, Issue 12 https://doi.org/10.1021/acs.chemrev.7b00091	journal	May 2017
From Transition Metals to Lanthanides to Actinides: Metal-Mediated Tuning of Electronic Properties of Isostructural Metal–Organic Frameworks Islamoglu, Timur; Ray, Debmalya; Li, Peng Inorganic Chemistry, Vol. 57, Issue 21 https://doi.org/10.1021/acs.inorgchem.8b01748	journal	October 2018
Effect of Benzoic Acid as a Modulator in the Structure of UiO-66: An Experimental and Computational Study Atzori, Cesare; Shearer, Greig C.; Maschio, Lorenzo The Journal of Physical Chemistry C, Vol. 121, Issue 17 https://doi.org/10.1021/acs.jpcc.7b00483	journal	April 2017
Characterization of Undercoordinated Zr Defect Sites in UiO-66 with Vibrational Spectroscopy of Adsorbed CO Driscoll, Darren M.; Troya, Diego; Usov, Pavel M. The Journal of Physical Chemistry C, Vol. 122, Issue 26 https://doi.org/10.1021/acs.jpcc.8b03283	journal	May 2018
Molecular Rhodium Complexes Supported on the Metal-Oxide-Like Nodes of Metal Organic Frameworks and on Zeolite HY: Catalysts for Ethylene Hydrogenation and Dimerization Bernales, Varinia; Yang, Dong; Yu, Jun ACS Applied Materials & Interfaces, Vol. 9, Issue 39 https://doi.org/10.1021/acsami.7b03858	journal	April 2017
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 Yang, Dong; Odoh, Samuel O.; Borycz, Joshua ACS Catalysis, Vol. 6, Issue 1 https://doi.org/10.1021/acscatal.5b02243	journal	December 2015
Catalytic Zirconium/Hafnium-Based Metal–Organic Frameworks Rimoldi, Martino; Howarth, Ashlee J.; DeStefano, Matthew R. ACS Catalysis, Vol. 7, Issue 2 https://doi.org/10.1021/acscatal.6b02923	journal	December 2016
Catalysis by Metal Organic Frameworks: Perspective and Suggestions for Future Research Yang, Dong; Gates, Bruce C. ACS Catalysis, Vol. 9, Issue 3 https://doi.org/10.1021/acscatal.8b04515	journal	January 2019
Engineering Metal Organic Frameworks for Heterogeneous Catalysis Corma, A.; García, H.; Llabrés i Xamena, F. X. Chemical Reviews, Vol. 110, Issue 8, p. 4606-4655 https://doi.org/10.1021/cr9003924	journal	August 2010
Computational Thermochemistry: Scale Factor Databases and Scale Factors for Vibrational Frequencies Obtained from Electronic Model Chemistries Alecu, I. M.; Zheng, Jingjing; Zhao, Yan Journal of Chemical Theory and Computation, Vol. 6, Issue 9 https://doi.org/10.1021/ct100326h	journal	August 2010
Unusual and Highly Tunable Missing-Linker Defects in Zirconium Metal–Organic Framework UiO-66 and Their Important Effects on Gas Adsorption Wu, Hui; Chua, Yong Shen; Krungleviciute, Vaiva Journal of the American Chemical Society, Vol. 135, Issue 28 https://doi.org/10.1021/ja404514r	journal	May 2013
Vapor-Phase Metalation by Atomic Layer Deposition in a Metal–Organic Framework Mondloch, Joseph E.; Bury, Wojciech; Fairen-Jimenez, David Journal of the American Chemical Society, Vol. 135, Issue 28, p. 10294-10297 https://doi.org/10.1021/ja4050828	journal	May 2013
A New Zirconium Inorganic Building Brick Forming Metal Organic Frameworks with Exceptional Stability Cavka, Jasmina Hafizovic; Jakobsen, Søren; Olsbye, Unni Journal of the American Chemical Society, Vol. 130, Issue 42, p. 13850-13851 https://doi.org/10.1021/ja8057953	journal	October 2008
Metal–Organic Framework Nodes as Nearly Ideal Supports for Molecular Catalysts: NU-1000- and UiO-66-Supported Iridium Complexes Yang, Dong; Odoh, Samuel O.; Wang, Timothy C. Journal of the American Chemical Society, Vol. 137, Issue 23, p. 7391-7396 https://doi.org/10.1021/jacs.5b02956	journal	June 2015
Tuning the Surface Chemistry of Metal Organic Framework Nodes: Proton Topology of the Metal-Oxide-Like Zr ₆ Nodes of UiO-66 and NU-1000 Yang, Dong; Bernales, Varinia; Islamoglu, Timur Journal of the American Chemical Society, Vol. 138, Issue 46 https://doi.org/10.1021/jacs.6b08273	journal	November 2016
Structure and Dynamics of Zr ₆ O ₈ Metal–Organic Framework Node Surfaces Probed with Ethanol Dehydration as a Catalytic Test Reaction Yang, Dong; Ortuño, Manuel A.; Bernales, Varinia Journal of the American Chemical Society, Vol. 140, Issue 10 https://doi.org/10.1021/jacs.7b13330	journal	February 2018
Correlated defect nanoregions in a metal–organic framework Cliffe, Matthew J.; Wan, Wei; Zou, Xiaodong Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms5176	journal	June 2014
Destruction of chemical warfare agents using metal–organic frameworks Mondloch, Joseph E.; Katz, Michael J.; Isley III, William C. Nature Materials, Vol. 14, Issue 5 https://doi.org/10.1038/nmat4238	journal	March 2015
Exploiting parameter space in MOFs: a 20-fold enhancement of phosphate-ester hydrolysis with UiO-66-NH ₂ Katz, Michael J.; Moon, Su-Young; Mondloch, Joseph E. Chemical Science, Vol. 6, Issue 4 https://doi.org/10.1039/C4SC03613A	journal	January 2015
What can pK _a and NBO charges of the ligands tell us about the water and thermal stability of metal organic frameworks? Lu, Ping; Wu, Yong; Kang, Hong J. Mater. Chem. A, Vol. 2, Issue 38 https://doi.org/10.1039/C4TA03154G	journal	January 2014
Zr-based metal–organic frameworks: design, synthesis, structure, and applications Bai, Yan; Dou, Yibo; Xie, Lin-Hua Chemical Society Reviews, Vol. 45, Issue 8 https://doi.org/10.1039/C5CS00837A	journal	January 2016
Probing the correlations between the defects in metal–organic frameworks and their catalytic activity by an epoxide ring-opening reaction Liu, Yangyang; Klet, Rachel C.; Hupp, Joseph T. Chemical Communications, Vol. 52, Issue 50 https://doi.org/10.1039/C6CC03727E	journal	January 2016
Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy Weigend, Florian; Ahlrichs, Reinhart Physical Chemistry Chemical Physics, Vol. 7, Issue 18, p. 3297-3305 https://doi.org/10.1039/b508541a	journal	January 2005
Accurate Coulomb-fitting basis sets for H to Rn Weigend, Florian Physical Chemistry Chemical Physics, Vol. 8, Issue 9 https://doi.org/10.1039/b515623h	journal	January 2006
A new local density functional for main-group thermochemistry, transition metal bonding, thermochemical kinetics, and noncovalent interactions Zhao, Yan; Truhlar, Donald G. The Journal of Chemical Physics, Vol. 125, Issue 19, Article No. 194101 https://doi.org/10.1063/1.2370993	journal	November 2006
The Chemistry and Applications of Metal-Organic Frameworks Furukawa, H.; Cordova, K. E.; O'Keeffe, M. Science, Vol. 341, Issue 6149, p. 1230444-1230444 https://doi.org/10.1126/science.1230444	journal	August 2013

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Switching on the Photocatalysis of Metal–Organic Frameworks by Engineering Structural Defects Ma, Xing; Wang, Li; Zhang, Qun Angewandte Chemie International Edition, Vol. 58, Issue 35 https://doi.org/10.1002/anie.201907074	journal	August 2019
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Green Synthesis of a Functionalized Zirconium-Based Metal–Organic Framework for Water and Ethanol Adsorption Chen, Zhijie; Wang, Xingjie; Islamoglu, Timur Inorganics, Vol. 7, Issue 5 https://doi.org/10.3390/inorganics7050056	journal	April 2019

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