skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Adsorption of a Catalytically Accessible Polyoxometalate in a Mesoporous Channel-type Metal–Organic Framework

Abstract

A Keggin-type polyoxometalate (H3PW12O40) was incorporated into a mesoporous Zr-based MOF (NU-1000) via an impregnation method in aqueous media, resulting in the hybrid material, PW12@NU-1000. The POM@MOF composite was characterized by a suite of physical methods, indicating the retention of crystallinity and high porosity of the parent MOF. The hybrid material was also stable to leaching in aqueous media at varying pH. Finally, the material was tested as a heterogeneous catalyst for the oxidation of 2-chloroethyl ethyl sulfide using hydrogen peroxide as the oxidant. PW12@NU-1000 was shown to have a higher catalytic activity than either of the individual constituents alone.

Authors:
ORCiD logo [1]; ORCiD logo [1];  [2];  [3]; ORCiD logo [4];  [5];  [4]; ORCiD logo [1]; ORCiD logo [6]
  1. Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, United States
  2. Physical and Computational Science Directorate, PNNL, Richland, Washington 99352, United States
  3. Environmental Molecular Sciences Laboratory, PNNL, Richland, Washington 99352, United States
  4. X-ray Science Division, Advanced Photon Source, Argonne National Laboratory, Argonne, Illinois 60439-4858, United States
  5. Physical and Computational Science Directorate, PNNL, Richland, Washington 99352, United States; Materials Science and Engineering, University of Washington, Seattle, Washington 98195, United States
  6. Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, United States; Department of Chemistry, Faculty of Science, King Abdulaziz University, Jeddah, Saudi Arabia
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
Sponsoring Org.:
USDOE
OSTI Identifier:
1422311
Report Number(s):
PNNL-SA-131981
Journal ID: ISSN 0897-4756; 48583; KP1704020
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 29; Journal Issue: 12; Journal ID: ISSN 0897-4756
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
Environmental Molecular Sciences Laboratory

Citation Formats

Buru, Cassandra T., Li, Peng, Mehdi, B. Layla, Dohnalkova, Alice, Platero-Prats, Ana E., Browning, Nigel D., Chapman, Karena W., Hupp, Joseph T., and Farha, Omar K. Adsorption of a Catalytically Accessible Polyoxometalate in a Mesoporous Channel-type Metal–Organic Framework. United States: N. p., 2017. Web. doi:10.1021/acs.chemmater.7b00750.
Buru, Cassandra T., Li, Peng, Mehdi, B. Layla, Dohnalkova, Alice, Platero-Prats, Ana E., Browning, Nigel D., Chapman, Karena W., Hupp, Joseph T., & Farha, Omar K. Adsorption of a Catalytically Accessible Polyoxometalate in a Mesoporous Channel-type Metal–Organic Framework. United States. https://doi.org/10.1021/acs.chemmater.7b00750
Buru, Cassandra T., Li, Peng, Mehdi, B. Layla, Dohnalkova, Alice, Platero-Prats, Ana E., Browning, Nigel D., Chapman, Karena W., Hupp, Joseph T., and Farha, Omar K. Mon . "Adsorption of a Catalytically Accessible Polyoxometalate in a Mesoporous Channel-type Metal–Organic Framework". United States. https://doi.org/10.1021/acs.chemmater.7b00750.
@article{osti_1422311,
title = {Adsorption of a Catalytically Accessible Polyoxometalate in a Mesoporous Channel-type Metal–Organic Framework},
author = {Buru, Cassandra T. and Li, Peng and Mehdi, B. Layla and Dohnalkova, Alice and Platero-Prats, Ana E. and Browning, Nigel D. and Chapman, Karena W. and Hupp, Joseph T. and Farha, Omar K.},
abstractNote = {A Keggin-type polyoxometalate (H3PW12O40) was incorporated into a mesoporous Zr-based MOF (NU-1000) via an impregnation method in aqueous media, resulting in the hybrid material, PW12@NU-1000. The POM@MOF composite was characterized by a suite of physical methods, indicating the retention of crystallinity and high porosity of the parent MOF. The hybrid material was also stable to leaching in aqueous media at varying pH. Finally, the material was tested as a heterogeneous catalyst for the oxidation of 2-chloroethyl ethyl sulfide using hydrogen peroxide as the oxidant. PW12@NU-1000 was shown to have a higher catalytic activity than either of the individual constituents alone.},
doi = {10.1021/acs.chemmater.7b00750},
url = {https://www.osti.gov/biblio/1422311}, journal = {Chemistry of Materials},
issn = {0897-4756},
number = 12,
volume = 29,
place = {United States},
year = {2017},
month = {5}
}

Works referenced in this record:

Polyoxometalates: Building Blocks for Functional Nanoscale Systems
journal, March 2010


Main-Group Element, Organic, and Organometallic Derivatives of Polyoxometalates
journal, February 1998


Polyoxometalate clusters, nanostructures and materials: From self assembly to designer materials and devices
journal, January 2007


Catalysis by Heteropoly Acids and Multicomponent Polyoxometalates in Liquid-Phase Reactions
journal, February 1998


Distinguishing Homogeneous from Heterogeneous Water Oxidation Catalysis when Beginning with Polyoxometalates
journal, January 2014


New Heterogeneous Polyoxometalate Based Mesoporous Catalysts for Hydrogen Peroxide Mediated Oxidation Reactions
journal, January 2004


Solar-Driven Water Oxidation and Decoupled Hydrogen Production Mediated by an Electron-Coupled-Proton Buffer
journal, May 2016


Polyoxometalate water oxidation catalysts and the production of green fuel
journal, January 2012


Epoxidation of olefins with hydrogen peroxide catalyzed by polyoxometalates
journal, September 2005


Broad-Spectrum Liquid- and Gas-Phase Decontamination of Chemical Warfare Agents by One-Dimensional Heteropolyniobates
journal, April 2016


Polyoxometalate [γ-SiW10O34(H2O)2]4− on MCM-41 as catalysts for sulfide oxygenation with hydrogen peroxide
journal, October 2014


Polyoxometalate based open-frameworks (POM-OFs)
journal, January 2014


Cationic Covalent Organic Frameworks: A Simple Platform of Anionic Exchange for Porosity Tuning and Proton Conduction
journal, April 2016


A Chromium Terephthalate-Based Solid with Unusually Large Pore Volumes and Surface Area
journal, September 2005


Best Practices for the Synthesis, Activation, and Characterization of Metal–Organic Frameworks
journal, September 2016


Introduction to Metal–Organic Frameworks
journal, September 2011


Metal–organic framework materials as catalysts
journal, January 2009


Postsynthetic modification of metal–organic frameworks
journal, January 2009


Immobilization of Co-containing polyoxometalates in MIL-101(Cr): structural integrity versus chemical transformation
journal, January 2014


MIL-101 Supported Polyoxometalates: Synthesis, Characterization, and Catalytic Applications in Selective Liquid-Phase Oxidation
journal, February 2011


Building MOF bottles around phosphotungstic acid ships: One-pot synthesis of bi-functional polyoxometalate-MIL-101 catalysts
journal, January 2010


Highly Stable Crystalline Catalysts Based on a Microporous Metal−Organic Framework and Polyoxometalates
journal, February 2009


Stable polyoxometalate insertion within the mesoporous metal organic framework MIL-100(Fe)
journal, January 2011


Towards efficient polyoxometalate encapsulation in MIL-100(Cr): influence of synthesis conditions
journal, January 2012


Live encapsulation of a Keggin polyanion in NH2-MIL-101(Al) observed by in situ time resolved X-ray scattering
journal, January 2011


Immobilization of polyoxometalates in the Zr-based metal organic framework UiO-67
journal, January 2015


A Multiunit Catalyst with Synergistic Stability and Reactivity: A Polyoxometalate–Metal Organic Framework for Aerobic Decontamination
journal, October 2011


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

Defining the Proton Topology of the Zr6-Based Metal–Organic Framework NU-1000
journal, October 2014


An Exceptionally Stable Metal–Organic Framework Supported Molybdenum(VI) Oxide Catalyst for Cyclohexene Epoxidation
journal, October 2016


Stable Metal–Organic Framework-Supported Niobium Catalysts
journal, October 2016


Metal–Organic Framework Supported Cobalt Catalysts for the Oxidative Dehydrogenation of Propane at Low Temperature
journal, November 2016


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


Toward Design Rules for Enzyme Immobilization in Hierarchical Mesoporous Metal-Organic Frameworks
journal, July 2016


High Efficiency Adsorption and Removal of Selenate and Selenite from Water Using Metal–Organic Frameworks
journal, June 2015


Efficient extraction of sulfate from water using a Zr-metal–organic framework
journal, January 2016


Mechanism of H 2 O 2 Decomposition on Transition Metal Oxide Surfaces
journal, April 2012


Hydrolytic Stability and Hydrogen Peroxide Activation of Zirconium-Based Oxoclusters: Hydrolytic Stability of Zirconium-Based Oxoclusters
journal, November 2014


Studies on the Mechanism of the Toxic Action of Organic Halogen Compounds
journal, June 1950


Evaluation of Brønsted acidity and proton topology in Zr- and Hf-based metal–organic frameworks using potentiometric acid–base titration
journal, January 2016


Rational design of efficient electrode–electrolyte interfaces for solid-state energy storage using ion soft landing
journal, April 2016


Regioselective Atomic Layer Deposition in Metal–Organic Frameworks Directed by Dispersion Interactions
journal, October 2016


Study of Guest Molecules in Metal–Organic Frameworks by Powder X-ray Diffraction: Analysis of Difference Envelope Density
journal, October 2014


Synthesis and acidic catalytic properties of ordered mesoporous alumina–tungstophosphoric acid composites
journal, January 2010


Insights into the electrochemical behaviour of composite materials: Monovacant polyoxometalates @ porous metal-organic framework
journal, January 2013


Hybrid Polyoxotungstate/MIL-101 Materials: Synthesis, Characterization, and Catalysis of H 2 O 2 -Based Alkene Epoxidation
journal, March 2010


1H, 31P NMR MAS, infrared and catalytic studies of heteropolyacid H3PW12O40 supported on MgF2
journal, January 1995


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

A study of the decomposition behaviour of 12-tungstophosphate heteropolyacid in solution
journal, October 2003


Efficient and selective oxidation of sulfur mustard using singlet oxygen generated by a pyrene-based metal–organic framework
journal, January 2016


    Works referencing / citing this record:

    Thermally induced migration of a polyoxometalate within a metal–organic framework and its catalytic effects
    journal, January 2018


    A Nanocrystalline POM@MOFs Catalyst for the Degradation of Phenol: Effective Cooperative Catalysis by Metal Nodes and POM Guests
    journal, February 2018


    Heptamolybdate: a highly active sulfide oxygenation catalyst
    journal, January 2018


    Hybridized Polyoxometalate-Based Metal-Organic Framework with Ketjenblack for the Nonenzymatic Detection of H 2 O 2
    journal, July 2018


    Construction of unprecedented pillar-layered metal organic frameworks via a dual-ligand strategy for dye degradation
    journal, January 2018


    Metal–Organic Framework Hybrid Materials and Their Applications
    journal, August 2018


    Stabilization of Formate Dehydrogenase in a Metal–Organic Framework for Bioelectrocatalytic Reduction of CO 2
    journal, June 2019


    Revisiting the structural homogeneity of NU-1000, a Zr-based metal–organic framework
    journal, January 2018


    Water-Stable Chemical-Protective Textiles via Euhedral Surface-Oriented 2D Cu-TCPP Metal-Organic Frameworks
    journal, February 2019


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


    Versatile catalysts constructed from hybrid polyoxomolybdates for simultaneously detoxifying sulfur mustard and organophosphate simulants
    journal, January 2019