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Title: Defining the Proton Topology of the Zr6 -Based Metal–Organic Framework NU-1000

Abstract

Metal–organic frameworks (MOFs) constructed from Zr6-based nodes have recently received considerable attention given their exceptional thermal, chemical, and mechanical stability. Because of this, the structural diversity of Zr6-based MOFs has expanded considerably and in turn given rise to difficulty in their precise characterization. In particular it has been difficult to assign precisely where protons (needed for charge balance) reside on some Zr6-based nodes. Elucidating the precise proton topologies in Zr6-based MOFs will have wide ranging implications in defining their chemical reactivity, acid/base characteristics, conductivity and chemical catalysis. Here we have used a combined quantum mechanical and experimental approach to elucidate the precise proton topology of the Zr6-based framework NU-1000. Lastly, our data indicate that a mixed node topology, [Zr63–O)43-OH)4(OH)4(OH2)4]8+, is preferred and simultaneously rules out five alternative node topologies.

Authors:
 [1];  [2];  [1];  [1];  [1];  [2];  [3];  [1]
  1. Univ. of Minnesota, Minneapolis, MN (United States)
  2. Northwestern Univ., Evanston, IL (United States)
  3. Northwestern Univ., Evanston, IL (United States); King Abdulaziz Univ., Jeddah (Saudi Arabia)
Publication Date:
Research Org.:
Univ. of Minnesota, Minneapolis, MN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1458981
Grant/Contract Number:  
FG02-12ER16362; SC0008688
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Physical Chemistry Letters
Additional Journal Information:
Journal Volume: 5; Journal Issue: 21; Journal ID: ISSN 1948-7185
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; node topology; density functional theory; IR spectroscopy; tautomerism

Citation Formats

Planas, Nora, Mondloch, Joseph E., Tussupbayev, Samat, Borycz, Joshua, Gagliardi, Laura, Hupp, Joseph T., Farha, Omar K., and Cramer, Christopher J. Defining the Proton Topology of the Zr6 -Based Metal–Organic Framework NU-1000. United States: N. p., 2014. Web. doi:10.1021/jz501899j.
Planas, Nora, Mondloch, Joseph E., Tussupbayev, Samat, Borycz, Joshua, Gagliardi, Laura, Hupp, Joseph T., Farha, Omar K., & Cramer, Christopher J. Defining the Proton Topology of the Zr6 -Based Metal–Organic Framework NU-1000. United States. https://doi.org/10.1021/jz501899j
Planas, Nora, Mondloch, Joseph E., Tussupbayev, Samat, Borycz, Joshua, Gagliardi, Laura, Hupp, Joseph T., Farha, Omar K., and Cramer, Christopher J. 2014. "Defining the Proton Topology of the Zr6 -Based Metal–Organic Framework NU-1000". United States. https://doi.org/10.1021/jz501899j. https://www.osti.gov/servlets/purl/1458981.
@article{osti_1458981,
title = {Defining the Proton Topology of the Zr6 -Based Metal–Organic Framework NU-1000},
author = {Planas, Nora and Mondloch, Joseph E. and Tussupbayev, Samat and Borycz, Joshua and Gagliardi, Laura and Hupp, Joseph T. and Farha, Omar K. and Cramer, Christopher J.},
abstractNote = {Metal–organic frameworks (MOFs) constructed from Zr6-based nodes have recently received considerable attention given their exceptional thermal, chemical, and mechanical stability. Because of this, the structural diversity of Zr6-based MOFs has expanded considerably and in turn given rise to difficulty in their precise characterization. In particular it has been difficult to assign precisely where protons (needed for charge balance) reside on some Zr6-based nodes. Elucidating the precise proton topologies in Zr6-based MOFs will have wide ranging implications in defining their chemical reactivity, acid/base characteristics, conductivity and chemical catalysis. Here we have used a combined quantum mechanical and experimental approach to elucidate the precise proton topology of the Zr6-based framework NU-1000. Lastly, our data indicate that a mixed node topology, [Zr6(μ3–O)4(μ3-OH)4(OH)4(OH2)4]8+, is preferred and simultaneously rules out five alternative node topologies.},
doi = {10.1021/jz501899j},
url = {https://www.osti.gov/biblio/1458981}, journal = {Journal of Physical Chemistry Letters},
issn = {1948-7185},
number = 21,
volume = 5,
place = {United States},
year = {Fri Oct 10 00:00:00 EDT 2014},
month = {Fri Oct 10 00:00:00 EDT 2014}
}

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Cited by: 206 works
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Works referenced in this record:

Hybrid porous solids past, present, future
journal, January 2008


Soft porous crystals
journal, November 2009


The Chemistry and Applications of Metal-Organic Frameworks
journal, August 2013


Catalysis by a Zinc-Porphyrin-Based Metal–Organic Framework: From Theory to Computational Design
journal, October 2012


The Mechanism of Carbon Dioxide Adsorption in an Alkylamine-Functionalized Metal–Organic Framework
journal, April 2013


Elucidating steric effects on enantioselective epoxidation catalyzed by (salen)Mn in metal-organic frameworks
journal, January 2011


De novo synthesis of a metal–organic framework material featuring ultrahigh surface area and gas storage capacities
journal, September 2010


Large-scale screening of hypothetical metal–organic frameworks
journal, November 2011


A New Zirconium Inorganic Building Brick Forming Metal Organic Frameworks with Exceptional Stability
journal, October 2008

  • 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

Synthesis, Structure, and Metalation of Two New Highly Porous Zirconium Metal–Organic Frameworks
journal, June 2012


Water Adsorption in Porous Metal–Organic Frameworks and Related Materials
journal, March 2014


An Exceptionally Stable, Porphyrinic Zr Metal–Organic Framework Exhibiting pH-Dependent Fluorescence
journal, September 2013


Unusual and Highly Tunable Missing-Linker Defects in Zirconium Metal–Organic Framework UiO-66 and Their Important Effects on Gas Adsorption
journal, May 2013


CH4 storage and CO2 capture in highly porous zirconium oxide based metal–organic frameworks
journal, January 2012


Electronic Effects of Linker Substitution on Lewis Acid Catalysis with Metal-Organic Frameworks
journal, April 2012


A mixed dicarboxylate strut approach to enhancing catalytic activity of a de novo urea derivative of metal–organic framework UiO-67
journal, January 2013


Synthesis Modulation as a Tool To Increase the Catalytic Activity of Metal–Organic Frameworks: The Unique Case of UiO-66(Zr)
journal, July 2013


Simple and Compelling Biomimetic Metal-Organic Framework Catalyst for the Degradation of Nerve Agent Simulants
journal, November 2013


Highly porous and stable metal–organic frameworks for uranium extraction
journal, January 2013


Effective Mercury Sorption by Thiol-Laced Metal–Organic Frameworks: in Strong Acid and the Vapor Phase
journal, May 2013


Ionic Conductivity in the Metal-Organic Framework UiO-66 by Dehydration and Insertion of Lithium tert -Butoxide
journal, March 2013


Integration of accessible secondary metal sites into MOFs for H 2 S removal
journal, January 2014


Zirconium-Metalloporphyrin PCN-222: Mesoporous Metal-Organic Frameworks with Ultrahigh Stability as Biomimetic Catalysts
journal, August 2012


Biomimetic Catalysis of a Porous Iron-Based Metal–Metalloporphyrin Framework
journal, November 2012


Vapor-Phase Metalation by Atomic Layer Deposition in a Metal–Organic Framework
journal, May 2013

  • 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

Perfluoroalkane Functionalization of NU-1000 via Solvent-Assisted Ligand Incorporation: Synthesis and CO2 Adsorption Studies
journal, October 2013

  • 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

Versatile functionalization of the NU-1000 platform by solvent-assisted ligand incorporation
journal, January 2014


Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996


Ab initiomolecular dynamics for liquid metals
journal, January 1993


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


Generalized Gradient Approximation Made Simple
journal, October 1996


Rationale for mixing exact exchange with density functional approximations
journal, December 1996


A new local density functional for main-group thermochemistry, transition metal bonding, thermochemical kinetics, and noncovalent interactions
journal, November 2006


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
journal, May 2009

  • 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

Charge Model 5: An Extension of Hirshfeld Population Analysis for the Accurate Description of Molecular Interactions in Gaseous and Condensed Phases
journal, February 2012

  • 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

Computational exploration of newly synthesized zirconium metal–organic frameworks UiO-66, -67, -68 and analogues
journal, January 2014


Disclosing the Complex Structure of UiO-66 Metal Organic Framework: A Synergic Combination of Experiment and Theory
journal, April 2011


Works referencing / citing this record:

A porous proton-relaying metal-organic framework material that accelerates electrochemical hydrogen evolution
journal, September 2015


The effects of active site and support on hydrogen elimination over transition-metal-functionalized yttria-decorated metal–organic frameworks
journal, January 2019


Secondary building units as the turning point in the development of the reticular chemistry of MOFs
journal, October 2018


Scalable synthesis and post-modification of a mesoporous metal-organic framework called NU-1000
journal, December 2015


MOFs vs. zeolites: carbonyl activation with M( iv ) catalytic sites
journal, January 2017


Synthesis and proton conductivity of two novel molybdate polymers
journal, January 2018


Non-3d Metal Modulation of a Cobalt Imidazolate Framework for Excellent Electrocatalytic Oxygen Evolution in Neutral Media
journal, December 2018


Water-stable 2-D Zr MOFs with exceptional UO 2 2+ sorption capability
journal, January 2020


Electronic effects due to organic linker-metal surface interactions: implications on screening of MOF-encapsulated catalysts
journal, January 2020


Cooperative Cluster Metalation and Ligand Migration in Zirconium Metal-Organic Frameworks
journal, October 2015


Defect engineering of UiO-66 for CO 2 and H 2 O uptake – a combined experimental and simulation study
journal, January 2016


Instantaneous Hydrolysis of Nerve-Agent Simulants with a Six-Connected Zirconium-Based Metal-Organic Framework
journal, May 2015


Destruction of chemical warfare agents using metal–organic frameworks
journal, March 2015


Single-site metal–organic framework catalysts for the oxidative coupling of arenes via C–H/C–H activation
journal, January 2019


Water stabilization of Zr 6 -based metal–organic frameworks via solvent-assisted ligand incorporation
journal, January 2015


Acceptorless dehydrogenative coupling reactions with alcohols over heterogeneous catalysts
journal, January 2018


Instantaneous Hydrolysis of Nerve-Agent Simulants with a Six-Connected Zirconium-Based Metal-Organic Framework
journal, May 2015


Cooperative Cluster Metalation and Ligand Migration in Zirconium Metal-Organic Frameworks
journal, October 2015


Computational Approach to Molecular Catalysis by 3d Transition Metals: Challenges and Opportunities
journal, October 2018


Stable Metal–Organic Frameworks with Group 4 Metals: Current Status and Trends
journal, February 2018


A porous proton-relaying metal-organic framework material that accelerates electrochemical hydrogen evolution
journal, September 2015


Secondary building units as the turning point in the development of the reticular chemistry of MOFs
journal, October 2018