Node-Accessible Zirconium MOFs

Lu, Zhiyong; Liu, Jian; Zhang, Xuan; Liao, Yijun; Wang, Rui; Zhang, Kun; Lyu, Jiafei; Farha, Omar K.; Hupp, Joseph T.

doi:10.1021/jacs.0c09782

Title: Node-Accessible Zirconium MOFs

Journal Article · Wed Dec 02 00:00:00 EST 2020 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.0c09782· OSTI ID:1771301

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Hohai Univ., Nanjing (China); Northwestern Univ., Evanston, IL (United States)
Northwestern Univ., Evanston, IL (United States)
Northwestern Univ., Evanston, IL (United States); Nanjing Univ. of Science & Technology (China)
Northwestern Univ., Evanston, IL (United States); Tianjin Univ. (China)

High-stability, zirconium-based metal–organic frameworks are attractive as heterogeneous catalysts and as model supports for uniform arrays of subsequently constructed heterogeneous catalysts—for example, MOF-node-grafted metal–oxy and metal–sulfur clusters. For hexa-Zr(IV)-MOFs characterized by nodes that are less than 12-connected, sites not used for linkers are ideally occupied by reactive and displaceable OH/H₂O pairs. Here, the desired pairs are ideal for grafting the aforementioned catalytic clusters, while aqua-ligand lability renders them effective for exposing highly Lewis-acidic Zr(IV) sites (catalytic sites) to candidate reactants. New single-crystal X-ray studies of an eight-connected Zr-MOF, NU-1000, reveal that conventional activation fully removes modulator ligands, but replaces them with three node-blocking formate ligands (from solvent decomposition) and only one OH/H₂O pair, not four—a largely overlooked complication that now appears to be general for Zr-MOFs. Here we describe an alternative activation protocol that effectively removes modulators, avoids formate, and installs the full complement of terminal OH/H₂O pairs. It does so via an unusual isolatable intermediate featuring eight aqua ligands and four non-ligated chlorides—again as supported by single-crystal X-ray data. We find that complete replacement of node-blocking modulators/formate with the originally envisioned OH/OH₂ pairs has striking consequences; here we touch upon just three. First, elimination of unrecognized formate renders aqua ligands much more thermally labile, enabling open Zr(IV) sites to be obtained at lower temperature. Second, in the absence of formate, which otherwise links and locks pairs of node Zr(IV) ions, reversible removal of aqua ligands engenders reversible contraction of MOF meso- and micropores, as evidenced by X-ray diffraction. Third, formate replacement with OH/OH₂ pairs renders NU-1000 ca.10× more active for catalytic hydrolytic degradation of a representative simulant of G-type chemical warfare agents.

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Research Organization:: Univ. of Minnesota, Minneapolis, MN (United States)

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

Grant/Contract Number:: SC0012702

OSTI ID:: 1771301

Journal Information:: Journal of the American Chemical Society, Vol. 142, Issue 50; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (55)

Modulated Synthesis of Zr-Based Metal-Organic Frameworks: From Nano to Single Crystals Schaate, Andreas; Roy, Pascal; Godt, Adelheid Chemistry - A European Journal, Vol. 17, Issue 24 https://doi.org/10.1002/chem.201003211	journal	May 2011
Synthesis, Structure, and Metalation of Two New Highly Porous Zirconium Metal–Organic Frameworks Morris, William; Volosskiy, Boris; Demir, Selcuk Inorganic Chemistry, Vol. 51, Issue 12, p. 6443-6445 https://doi.org/10.1021/ic300825s	journal	June 2012
Pore-Templated Growth of Catalytically Active Gold Nanoparticles within a Metal–Organic Framework Goswami, Subhadip; Noh, Hyunho; Redfern, Louis R. Chemistry of Materials, Vol. 31, Issue 5 https://doi.org/10.1021/acs.chemmater.8b04983	journal	February 2019
Identification of the strong Brønsted acid site in a metal–organic framework solid acid catalyst Trickett, Christopher A.; Osborn Popp, Thomas M.; Su, Ji Nature Chemistry, Vol. 11, Issue 2 https://doi.org/10.1038/s41557-018-0171-z	journal	November 2018
Construction of Ultrastable Porphyrin Zr Metal–Organic Frameworks through Linker Elimination Feng, Dawei; Chung, Wan-Chun; Wei, Zhangwen Journal of the American Chemical Society, Vol. 135, Issue 45 https://doi.org/10.1021/ja408084j	journal	October 2013
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
Redox-Mediator-Assisted Electrocatalytic Hydrogen Evolution from Water by a Molybdenum Sulfide-Functionalized Metal–Organic Framework Noh, Hyunho; Kung, Chung-Wei; Otake, Ken-ichi ACS Catalysis, Vol. 8, Issue 10 https://doi.org/10.1021/acscatal.8b02921	journal	September 2018
A New Class of Metal-Cyclam-Based Zirconium Metal–Organic Frameworks for CO ₂ Adsorption and Chemical Fixation Zhu, Jie; Usov, Pavel M.; Xu, Wenqian Journal of the American Chemical Society, Vol. 140, Issue 3 https://doi.org/10.1021/jacs.7b10643	journal	January 2018
Introducing Nonstructural Ligands to Zirconia-like Metal–Organic Framework Nodes To Tune the Activity of Node-Supported Nickel Catalysts for Ethylene Hydrogenation Liu, Jian; Li, Zhanyong; Zhang, Xuan ACS Catalysis, Vol. 9, Issue 4 https://doi.org/10.1021/acscatal.8b04828	journal	March 2019
Evaluation of Brønsted acidity and proton topology in Zr- and Hf-based metal–organic frameworks using potentiometric acid–base titration Klet, Rachel C.; Liu, Yangyang; Wang, Timothy C. Journal of Materials Chemistry A, Vol. 4, Issue 4 https://doi.org/10.1039/C5TA07687K	journal	January 2016
Synergistic Assembly of Heavy Metal Clusters and Luminescent Organic Bridging Ligands in Metal–Organic Frameworks for Highly Efficient X-ray Scintillation Wang, Cheng; Volotskova, Olga; Lu, Kuangda Journal of the American Chemical Society, Vol. 136, Issue 17 https://doi.org/10.1021/ja500671h	journal	April 2014
Activation of metal–organic framework materials Mondloch, Joseph E.; Karagiaridi, Olga; Farha, Omar K. CrystEngComm, Vol. 15, Issue 45 https://doi.org/10.1039/c3ce41232f	journal	January 2013
Superactivity of MOF-808 toward Peptide Bond Hydrolysis Ly, Hong Giang T.; Fu, Guangxia; Kondinski, Aleksandar Journal of the American Chemical Society, Vol. 140, Issue 20 https://doi.org/10.1021/jacs.8b01902	journal	April 2018
Activation of Methyltrioxorhenium for Olefin Metathesis in a Zirconium-Based Metal–Organic Framework Korzyński, Maciej D.; Consoli, Daniel F.; Zhang, Shiran Journal of the American Chemical Society, Vol. 140, Issue 22 https://doi.org/10.1021/jacs.8b02837	journal	April 2018
Green Synthesis of Zr-CAU-28: Structure and Properties of the First Zr-MOF Based on 2,5-Furandicarboxylic Acid Dreischarf, Anna C.; Lammert, Martin; Stock, Norbert Inorganic Chemistry, Vol. 56, Issue 4 https://doi.org/10.1021/acs.inorgchem.6b02969	journal	February 2017
An Exceptionally Stable, Porphyrinic Zr Metal–Organic Framework Exhibiting pH-Dependent Fluorescence Jiang, Hai-Long; Feng, Dawei; Wang, Kecheng Journal of the American Chemical Society, Vol. 135, Issue 37 https://doi.org/10.1021/ja406844r	journal	September 2013
Best Practices for the Synthesis, Activation, and Characterization of Metal–Organic Frameworks Howarth, Ashlee J.; Peters, Aaron W.; Vermeulen, Nicolaas A. Chemistry of Materials, Vol. 29, Issue 1 https://doi.org/10.1021/acs.chemmater.6b02626	journal	September 2016
Proline Functionalized UiO-67 and UiO-68 Type Metal–Organic Frameworks Showing Reversed Diastereoselectivity in Aldol Addition Reactions Kutzscher, Christel; Nickerl, Georg; Senkovska, Irena Chemistry of Materials, Vol. 28, Issue 8 https://doi.org/10.1021/acs.chemmater.5b04575	journal	April 2016
Atomically Precise Growth of Catalytically Active Cobalt Sulfide on Flat Surfaces and within a Metal–Organic Framework via Atomic Layer Deposition Peters, Aaron W.; Li, Zhanyong; Farha, Omar K. ACS Nano, Vol. 9, Issue 8 https://doi.org/10.1021/acsnano.5b03429	journal	July 2015
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
Wavelength-Dependent Energy and Charge Transfer in MOF: A Step toward Artificial Porous Light-Harvesting System Li, Xinlin; Yu, Jierui; Gosztola, David J. Journal of the American Chemical Society, Vol. 141, Issue 42 https://doi.org/10.1021/jacs.9b08078	journal	September 2019
Photocatalytic Metal–Organic Frameworks for Selective 2,2,2-Trifluoroethylation of Styrenes Yu, Xiao; Cohen, Seth M. Journal of the American Chemical Society, Vol. 138, Issue 38 https://doi.org/10.1021/jacs.6b06859	journal	September 2016
Defining the Proton Topology of the Zr₆-Based Metal–Organic Framework NU-1000 Planas, Nora; Mondloch, Joseph E.; Tussupbayev, Samat The Journal of Physical Chemistry Letters, Vol. 5, Issue 21, p. 3716-3723 https://doi.org/10.1021/jz501899j	journal	October 2014
Robust Corrole-Based Metal–Organic Frameworks with Rare 9-Connected Zr/Hf-Oxo Clusters Zhao, Yanming; Qi, Shibo; Niu, Zheng Journal of the American Chemical Society, Vol. 141, Issue 36 https://doi.org/10.1021/jacs.9b07700	journal	August 2019
Biomimetic Catalysis of a Porous Iron-Based Metal–Metalloporphyrin Framework Chen, Yao; Hoang, Tran; Ma, Shengqian Inorganic Chemistry, Vol. 51, Issue 23 https://doi.org/10.1021/ic301923x	journal	November 2012
A Flexible Metal–Organic Framework with 4-Connected Zr ₆ Nodes Zhang, Yuanyuan; Zhang, Xuan; Lyu, Jiafei Journal of the American Chemical Society, Vol. 140, Issue 36 https://doi.org/10.1021/jacs.8b06789	journal	August 2018
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
Nature of active sites on UiO-66 and beneficial influence of water in the catalysis of Fischer esterification Caratelli, Chiara; Hajek, Julianna; Cirujano, Francisco G. Journal of Catalysis, Vol. 352 https://doi.org/10.1016/j.jcat.2017.06.014	journal	August 2017
Cooperative Cluster Metalation and Ligand Migration in Zirconium Metal-Organic Frameworks Yuan, Shuai; Chen, Ying-Pin; Qin, Junsheng Angewandte Chemie International Edition, Vol. 54, Issue 49 https://doi.org/10.1002/anie.201505625	journal	October 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
Identification Schemes for Metal–Organic Frameworks To Enable Rapid Search and Cheminformatics Analysis Bucior, Benjamin J.; Rosen, Andrew S.; Haranczyk, Maciej Crystal Growth & Design, Vol. 19, Issue 11 https://doi.org/10.1021/acs.cgd.9b01050	journal	September 2019
Isoreticular synthesis and modification of frameworks with the UiO-66 topology Garibay, Sergio J.; Cohen, Seth M. Chemical Communications, Vol. 46, Issue 41, p. 7700-7702 https://doi.org/10.1039/c0cc02990d	journal	January 2010
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
Metal Acetylacetonates as a Source of Metals for Aqueous Synthesis of Metal–Organic Frameworks Avci-Camur, Ceren; Perez-Carvajal, Javier; Imaz, Inhar ACS Sustainable Chemistry & Engineering, Vol. 6, Issue 11 https://doi.org/10.1021/acssuschemeng.8b03180	journal	September 2018
Postsynthetic modification of a zirconium metal–organic framework at the inorganic secondary building unit with diphenylphosphinic acid for increased photosensitizing properties and stability Hynek, J.; Ondrušová, S.; Bůžek, D. Chemical Communications, Vol. 53, Issue 61 https://doi.org/10.1039/C7CC05068B	journal	January 2017
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
Revisiting the structural homogeneity of NU-1000, a Zr-based metal–organic framework Islamoglu, Timur; Otake, Ken-ichi; Li, Peng CrystEngComm, Vol. 20, Issue 39 https://doi.org/10.1039/C8CE00455B	journal	January 2018
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
Single-Site Cobalt Catalysts at New Zr ₁₂ (μ ₃ -O) ₈ (μ ₃ -OH) ₈ (μ ₂ -OH) ₆ Metal–Organic Framework Nodes for Highly Active Hydrogenation of Nitroarenes, Nitriles, and Isocyanides Ji, Pengfei; Manna, Kuntal; Lin, Zekai Journal of the American Chemical Society, Vol. 139, Issue 20 https://doi.org/10.1021/jacs.7b02394	journal	May 2017
Water Adsorption in Porous Metal–Organic Frameworks and Related Materials Furukawa, Hiroyasu; Gándara, Felipe; Zhang, Yue-Biao Journal of the American Chemical Society, Vol. 136, Issue 11, p. 4369-4381 https://doi.org/10.1021/ja500330a	journal	March 2014
Site-Directed Synthesis of Cobalt Oxide Clusters in a Metal–Organic Framework Peters, Aaron W.; Otake, Kenichi; Platero-Prats, Ana E. ACS Applied Materials & Interfaces, Vol. 10, Issue 17 https://doi.org/10.1021/acsami.8b02825	journal	March 2018
Tailoring of network dimensionality and porosity adjustment in Zr- and Hf-based MOFs Bon, Volodymyr; Senkovska, Irena; Weiss, Manfred S. CrystEngComm, Vol. 15, Issue 45 https://doi.org/10.1039/c3ce41121d	journal	January 2013
Role of a Modulator in the Synthesis of Phase-Pure NU-1000 Webber, Thomas E.; Liu, Wei-Guang; Desai, Sai Puneet ACS Applied Materials & Interfaces, Vol. 9, Issue 45 https://doi.org/10.1021/acsami.7b11348	journal	November 2017
Lithium Thiophosphate Functionalized Zirconium MOFs for Li–S Batteries with Enhanced Rate Capabilities Baumann, Avery E.; Han, Xu; Butala, Megan M. Journal of the American Chemical Society, Vol. 141, Issue 44 https://doi.org/10.1021/jacs.9b09538	journal	October 2019
Chemical, thermal and mechanical stabilities of metal–organic frameworks Howarth, Ashlee J.; Liu, Yangyang; Li, Peng Nature Reviews Materials, Vol. 1, Issue 3 https://doi.org/10.1038/natrevmats.2015.18	journal	February 2016
Postsynthetic Incorporation of a Singlet Oxygen Photosensitizer in a Metal-Organic Framework for Fast and Selective Oxidative Detoxification of Sulfur Mustard Howarth, Ashlee J.; Buru, Cassandra T.; Liu, Yangyang Chemistry - A European Journal, Vol. 23, Issue 1 https://doi.org/10.1002/chem.201604972	journal	November 2016
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
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
A Modulated Hydrothermal (MHT) Approach for the Facile Synthesis of UiO-66-Type MOFs Hu, Zhigang; Peng, Yongwu; Kang, Zixi Inorganic Chemistry, Vol. 54, Issue 10 https://doi.org/10.1021/acs.inorgchem.5b00435	journal	April 2015
Toward Topology Prediction in Zr-Based Microporous Coordination Polymers: The Role of Linker Geometry and Flexibility Ma, Jialiu; Tran, Ly D.; Matzger, Adam J. Crystal Growth & Design, Vol. 16, Issue 7 https://doi.org/10.1021/acs.cgd.6b00698	journal	May 2016
Synthesis and functionalization of phase-pure NU-901 for enhanced CO ₂ adsorption: the influence of a zirconium salt and modulator on the topology and phase purity Garibay, Sergio J.; Iordanov, Ivan; Islamoglu, Timur CrystEngComm, Vol. 20, Issue 44 https://doi.org/10.1039/C8CE01454J	journal	January 2018
Application of Consistency Criteria To Calculate BET Areas of Micro- And Mesoporous Metal–Organic Frameworks Gómez-Gualdrón, Diego A.; Moghadam, Peyman Z.; Hupp, Joseph T. Journal of the American Chemical Society, Vol. 138, Issue 1 https://doi.org/10.1021/jacs.5b10266	journal	December 2015
Zr- and Hf-Based Metal–Organic Frameworks: Tracking Down the Polymorphism Bon, Volodymyr; Senkovska, Irena; Baburin, Igor A. Crystal Growth & Design, Vol. 13, Issue 3, p. 1231-1237 https://doi.org/10.1021/cg301691d	journal	February 2013
Zirconium-Metalloporphyrin PCN-222: Mesoporous Metal-Organic Frameworks with Ultrahigh Stability as Biomimetic Catalysts Feng, Dawei; Gu, Zhi-Yuan; Li, Jian-Rong Angewandte Chemie International Edition, Vol. 51, Issue 41 https://doi.org/10.1002/anie.201204475	journal	August 2012
Metal–Organic Framework-Based Catalysts with Single Metal Sites Wei, Yong-Sheng; Zhang, Mei; Zou, Ruqiang Chemical Reviews, Vol. 120, Issue 21 https://doi.org/10.1021/acs.chemrev.9b00757	journal	May 2020

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Anions
Ligands
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Metal organic frameworks
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CCDC 2030766: Experimental Crystal Structure Determination Zhiyong, Lu,; Jian, Liu,; Xuan, Zhang, https://doi.org/10.5517/ccdc.csd.cc2655l5 The current record is supplemented by this dataset	dataset	January 2020
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Title: Node-Accessible Zirconium MOFs

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