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Title: Tuning the Surface Chemistry of Metal Organic Framework Nodes: Proton Topology of the Metal-Oxide-Like Zr6 Nodes of UiO-66 and NU-1000

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/jacs.6b08273· OSTI ID:1388680
 [1];  [2];  [3];  [4];  [3];  [2];  [2];  [1]
  1. Univ. of California, Davis, CA (United States)
  2. Univ. of Minnesota, Minneapolis, MN (United States)
  3. Northwestern Univ., Evanston, IL (United States)
  4. Northwestern Univ., Evanston, IL (United States); King Abdul-Aziz Univ., Jeddah (Saudi Arabia)
+ Show Author Affiliations

Some metal organic frameworks (MOFs) incorporate nodes that are nanoscale metal oxides, and the hydroxycontaining functional groups on them provide opportunities for introducing catalytic sites with precisely defined structures. Investigations have been done to understand the structures of these groups on nodes and node vacancies, because, in prospect, atomic-scale modulation of the composition, areal density, and/or siting of the groups would open up possibilities for exquisite tuning of the siting and performance of subsequently anchored catalytic units (e.g., single metal ions, pairs of metal ions, or well-defined metal-ion-containing clusters). In this work we have combined infrared (IR) spectroscopy and density functional theory (DFT) to demonstrate tuning of these sites, namely, hydrogen-bonded OH/OH2 groups on the Zr6 nodes of the MOFs UiO-66 and NU-1000 via the intermediacy of node methoxy (or ethoxy) groups formed from methanol (or ethanol). Methoxy (or ethoxy) groups on node vacancy sites are converted to a structure incorporating one vacant Zr site and one terminal OH group per face by reaction with water. Our results highlight how the combination of DFT and IR spectroscopy facilitates the determination of the identity and chemistry of the functional groups on MOF node vacancies and defect sites.

Research Organization:
Energy Frontier Research Centers (EFRC) (United States). Inorganometallic Catalyst Design (ICDC)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0012702
OSTI ID:
1388680
Journal Information:
Journal of the American Chemical Society, Vol. 138, Issue 46; Related Information: ICDC partners with University of Minnesota(lead); Argonne National Laboratory; Clemson University; Dow Chemical Company; Northwestern University; Pacific Northwest National Laboratory; University of California Davis; University of Washington; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 139 works
Citation information provided by
Web of Science

References (38)

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
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
Vanadium-Node-Functionalized UiO-66: A Thermally Stable MOF-Supported Catalyst for the Gas-Phase Oxidative Dehydrogenation of Cyclohexene journal June 2014
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
Metal–Organic Framework Nodes as Nearly Ideal Supports for Molecular Catalysts: NU-1000- and UiO-66-Supported Iridium Complexes journal June 2015
Correlated defect nanoregions in a metal–organic framework journal June 2014
Defect Engineering: Tuning the Porosity and Composition of the Metal–Organic Framework UiO-66 via Modulated Synthesis journal May 2016
Defects and disorder in metal organic frameworks journal January 2016
Brønsted Acidity in Metal–Organic Frameworks journal June 2015
Evaluation of Brønsted acidity and proton topology in Zr- and Hf-based metal–organic frameworks using potentiometric acid–base titration journal January 2016
Cooperative Cluster Metalation and Ligand Migration in Zirconium Metal-Organic Frameworks journal October 2015
Single-Site Organozirconium Catalyst Embedded in a Metal–Organic Framework journal December 2015
Gas-Phase Dimerization of Ethylene under Mild Conditions Catalyzed by MOF Materials Containing (bpy)Ni II Complexes journal October 2015
Dynamic acidity in defective UiO-66 journal January 2016
Definitive Molecular Level Characterization of Defects in UiO-66 Crystals journal August 2015
Defining the Proton Topology of the Zr6-Based Metal–Organic Framework NU-1000 journal October 2014
Versatile functionalization of the NU-1000 platform by solvent-assisted ligand incorporation journal January 2014
Perfluoroalkane Functionalization of NU-1000 via Solvent-Assisted Ligand Incorporation: Synthesis and CO2 Adsorption Studies
  • Deria, Pravas; Mondloch, Joseph E.; Tylianakis, Emmanuel
  • Journal of the American Chemical Society, Vol. 135, Issue 45, p. 16801-16804 https://doi.org/10.1021/ja408959g
journal October 2013
MOF Functionalization via Solvent-Assisted Ligand Incorporation: Phosphonates vs Carboxylates journal February 2015
Scalable synthesis and post-modification of a mesoporous metal-organic framework called NU-1000 journal December 2015
Charge Model 5: An Extension of Hirshfeld Population Analysis for the Accurate Description of Molecular Interactions in Gaseous and Condensed Phases
  • Marenich, Aleksandr V.; Jerome, Steven V.; Cramer, Christopher J.
  • Journal of Chemical Theory and Computation, Vol. 8, Issue 2, p. 527-541 https://doi.org/10.1021/ct200866d
journal February 2012
A new local density functional for main-group thermochemistry, transition metal bonding, thermochemical kinetics, and noncovalent interactions journal November 2006
Accurate Coulomb-fitting basis sets for H to Rn journal January 2006
Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy journal January 2005
Universal Solvation Model Based on Solute Electron Density and on a Continuum Model of the Solvent Defined by the Bulk Dielectric Constant and Atomic Surface Tensions
  • Marenich, Aleksandr V.; Cramer, Christopher J.; Truhlar, Donald G.
  • The Journal of Physical Chemistry B, Vol. 113, Issue 18, p. 6378-6396 https://doi.org/10.1021/jp810292n
journal May 2009
A facile synthesis of UiO-66, UiO-67 and their derivatives journal January 2013
Site Conversion of Methoxy Species on ZrO 2 journal June 1997
An in Situ Infrared Study of Dimethyl Carbonate Synthesis from Carbon Dioxide and Methanol over Zirconia journal December 2001
Reaction of methyl chloride with alumina surfaces: a study of the methoxy surface species by transmission infrared spectroscopy journal March 1988
Infrared study of methanol, formaldehyde, and formic acid adsorbed on hematite journal November 1980
Infra-red studies of reactions on oxide surfaces. Part 2.—Methanol on silica journal January 1974
Role of Hydrogen Spillover in Methanol Synthesis over Cu/ZrO2 journal July 2000
Infrared spectra of methanol, ethanol, and n-propanol journal April 1952
Computational Thermochemistry: Scale Factor Databases and Scale Factors for Vibrational Frequencies Obtained from Electronic Model Chemistries journal August 2010
Destruction of chemical warfare agents using metal–organic frameworks journal March 2015
Engineering Metal Organic Frameworks for Heterogeneous Catalysis journal August 2010
One Step Backward Is Two Steps Forward: Enhancing the Hydrolysis Rate of UiO-66 by Decreasing [OH – ] journal July 2015
Metal–Organic Framework Nodes Support Single-Site Magnesium–Alkyl Catalysts for Hydroboration and Hydroamination Reactions journal June 2016

Cited By (20)

Defective Metal-Organic Frameworks journal January 2018
Untwisted restacking of two-dimensional metal-organic framework nanosheets for highly selective isomer separations journal July 2019
Creation of Active Sites in MOF‐808(Zr) by a Facile Route for Oxidative Desulfurization of Model Diesel Oil journal January 2020
Efficient transformative HCHO capture by defective NH 2 -UiO-66(Zr) at room temperature journal January 2019
Organic amines as templates: pore imprints with exactly matching sizes in a series of metal–organic frameworks journal January 2018
Geminal Coordinatively Unsaturated Sites on MOF‐808 for the Selective Uptake of Phenolics from a Real Bio‐Oil Mixture journal February 2019
Operando study of palladium nanoparticles inside UiO-67 MOF for catalytic hydrogenation of hydrocarbons journal January 2018
Fine tuning of catalytic and sorption properties of metal–organic frameworks via in situ ligand exchange journal January 2017
Dynamic Interplay between Defective UiO‐66 and Protic Solvents in Activated Processes journal October 2019
Enhancing catalytic alkane hydroxylation by tuning the outer coordination sphere in a heme-containing metal–organic framework journal January 2020
A Titanium(IV)‐Based Metal–Organic Framework Featuring Defect‐Rich Ti‐O Sheets as an Oxidative Desulfurization Catalyst journal May 2019
Accelerated proton transmission in metal–organic frameworks for the efficient reduction of CO 2 in aqueous solutions journal January 2019
Substitution-type luminescent MOF sensor with built-in capturer for selective cholesterol detection in blood serum journal January 2019
Modulator-Controlled Synthesis of Microporous STA-26, an Interpenetrated 8,3-Connected Zirconium MOF with the the-i Topology, and its Reversible Lattice Shift journal March 2018
A Titanium(IV)‐Based Metal–Organic Framework Featuring Defect‐Rich Ti‐O Sheets as an Oxidative Desulfurization Catalyst journal May 2019
Zr‐Metal‐Organic Framework Catalysts for Oxidative Desulfurization and Their Improvement by Postsynthetic Ligand Exchange journal August 2018
Band Gap Modulation in Zirconium-Based Metal-Organic Frameworks by Defect Engineering journal July 2019
Band Gap Modulation in Zirconium-Based Metal-Organic Frameworks by Defect Engineering journal May 2019
A Titanium(IV)-Based Metal-Organic Framework Featuring Defect-Rich Ti-O Sheets as an Oxidative Desulfurization Catalyst text January 2019
Engineering a Highly Defective Stable UiO-66 with Tunable Lewis- Brønsted Acidity: The Role of the Hemilabile Linker journal January 2020

Figures / Tables (7)

Scheme 1(p. 3)figure Scheme 1
Figure 1(p. 4)figure Figure 1
Figure 2(p. 4)figure Figure 2
Figure 3(p. 5)figure Figure 3
Figure 4(p. 6)figure Figure 4
Figure 5(p. 6)figure Figure 5
Scheme 2(p. 7)figure Scheme 2

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
catalysis (heterogeneous)
materials and chemistry by design
synthesis (novel materials)
alcohols
metal organic frameworks
chemical structure
infrared light
mathematical methods