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

Title: In Situ Probes of Capture and Decomposition of Chemical Warfare Agent Simulants by Zr-Based Metal Organic Frameworks

Abstract

Recently, Zr-based metal organic frameworks (MOFs) were shown to be among the fastest catalysts of nerve-agent hydrolysis in solution. Here, we report a detailed study of the adsorption and decomposition of a nerve-agent simulant, dimethyl methylphosphonate (DMMP), on UiO-66, UiO-67, MOF-808, and NU-1000 using synchrotron-based X-ray powder diffraction, X-ray absorption, and infrared spectroscopy, which reveals key aspects of the reaction mechanism. The diffraction measurements indicate that all four MOFs adsorb DMMP (introduced at atmospheric pressures through a flow of helium or air) within the pore space. In addition, the combination of X-ray absorption and infrared spectra suggests direct coordination of DMMP to the Zr6 cores of all MOFs, which ultimately leads to decomposition to phosphonate products. Our experimental probes into the mechanism of adsorption and decomposition of chemical warfare agent simulants on Zr-based MOFs open new opportunities in rational design of new and superior decontamination materials.

Authors:
ORCiD logo [1];  [1];  [2];  [2]; ORCiD logo [3];  [4];  [3];  [5];  [3];  [4]; ORCiD logo [1]
  1. Stony Brook Univ., NY (United States). Dept. of Materials Science and Chemical Engineering
  2. U.S. Army Edgewood Chemical Biological Center APG, Aberdeen Proving Ground, MD (United States)
  3. Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States). Dept. of Chemistry
  4. Emory Univ., Atlanta, GA (United States). Dept. of Chemistry
  5. Brookhaven National Lab. (BNL), Upton, NY (United States). Dept. of Chemistry
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1349576
Report Number(s):
BNL-113713-2017-JA
Journal ID: ISSN 0002-7863; R&D Project: CO040; KC0302010
Grant/Contract Number:  
SC00112704; AC02-06CH11357; AC02-76SF00515; SC0012335
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 139; Journal Issue: 2; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Plonka, Anna M., Wang, Qi, Gordon, Wesley O., Balboa, Alex, Troya, Diego, Guo, Weiwei, Sharp, Conor H., Senanayake, Sanjaya D., Morris, John R., Hill, Craig L., and Frenkel, Anatoly I.. In Situ Probes of Capture and Decomposition of Chemical Warfare Agent Simulants by Zr-Based Metal Organic Frameworks. United States: N. p., 2016. Web. https://doi.org/10.1021/jacs.6b11373.
Plonka, Anna M., Wang, Qi, Gordon, Wesley O., Balboa, Alex, Troya, Diego, Guo, Weiwei, Sharp, Conor H., Senanayake, Sanjaya D., Morris, John R., Hill, Craig L., & Frenkel, Anatoly I.. In Situ Probes of Capture and Decomposition of Chemical Warfare Agent Simulants by Zr-Based Metal Organic Frameworks. United States. https://doi.org/10.1021/jacs.6b11373
Plonka, Anna M., Wang, Qi, Gordon, Wesley O., Balboa, Alex, Troya, Diego, Guo, Weiwei, Sharp, Conor H., Senanayake, Sanjaya D., Morris, John R., Hill, Craig L., and Frenkel, Anatoly I.. Fri . "In Situ Probes of Capture and Decomposition of Chemical Warfare Agent Simulants by Zr-Based Metal Organic Frameworks". United States. https://doi.org/10.1021/jacs.6b11373. https://www.osti.gov/servlets/purl/1349576.
@article{osti_1349576,
title = {In Situ Probes of Capture and Decomposition of Chemical Warfare Agent Simulants by Zr-Based Metal Organic Frameworks},
author = {Plonka, Anna M. and Wang, Qi and Gordon, Wesley O. and Balboa, Alex and Troya, Diego and Guo, Weiwei and Sharp, Conor H. and Senanayake, Sanjaya D. and Morris, John R. and Hill, Craig L. and Frenkel, Anatoly I.},
abstractNote = {Recently, Zr-based metal organic frameworks (MOFs) were shown to be among the fastest catalysts of nerve-agent hydrolysis in solution. Here, we report a detailed study of the adsorption and decomposition of a nerve-agent simulant, dimethyl methylphosphonate (DMMP), on UiO-66, UiO-67, MOF-808, and NU-1000 using synchrotron-based X-ray powder diffraction, X-ray absorption, and infrared spectroscopy, which reveals key aspects of the reaction mechanism. The diffraction measurements indicate that all four MOFs adsorb DMMP (introduced at atmospheric pressures through a flow of helium or air) within the pore space. In addition, the combination of X-ray absorption and infrared spectra suggests direct coordination of DMMP to the Zr6 cores of all MOFs, which ultimately leads to decomposition to phosphonate products. Our experimental probes into the mechanism of adsorption and decomposition of chemical warfare agent simulants on Zr-based MOFs open new opportunities in rational design of new and superior decontamination materials.},
doi = {10.1021/jacs.6b11373},
journal = {Journal of the American Chemical Society},
number = 2,
volume = 139,
place = {United States},
year = {2016},
month = {12}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 10 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Decontamination of chemical warfare agents
journal, December 1992

  • Yang, Yu Chu; Baker, James A.; Ward, J. Richard
  • Chemical Reviews, Vol. 92, Issue 8
  • DOI: 10.1021/cr00016a003

Catalytic methods for the destruction of chemical warfare agents under ambient conditions
journal, January 2008

  • Smith, Bryan M.
  • Chem. Soc. Rev., Vol. 37, Issue 3, p. 470-478
  • DOI: 10.1039/B705025A

Effect of Adsorbed Water and Surface Hydroxyls on the Hydrolysis of VX, GD, and HD on Titania Materials The Development of Self-Decontaminating Paints
journal, February 2012

  • Wagner, George W.; Peterson, Gregory W.; Mahle, John J.
  • Industrial & Engineering Chemistry Research, Vol. 51, Issue 9, p. 3598-3603
  • DOI: 10.1021/ie202063p

Reactions of VX, GD, and HD with Zr(OH)4 Near Instantaneous Decontamination of VX
journal, May 2012

  • Bandosz, Teresa J.; Laskoski, Matt; Mahle, John
  • The Journal of Physical Chemistry C, Vol. 116, Issue 21, p. 11606-11614
  • DOI: 10.1021/jp3028879

Nerve Agent Degradation with Polyoxoniobates: Nerve Agent Degradation with Polyoxoniobates
journal, April 2014

  • Kinnan, Mark K.; Creasy, William R.; Fullmer, Lauren B.
  • European Journal of Inorganic Chemistry, Vol. 2014, Issue 14
  • DOI: 10.1002/ejic.201400016

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

  • Guo, Weiwei; Lv, Hongjin; Sullivan, Kevin P.
  • Angewandte Chemie International Edition, Vol. 55, Issue 26
  • DOI: 10.1002/anie.201601620

Textile/Metal-Organic-Framework Composites as Self-Detoxifying Filters for Chemical-Warfare Agents
journal, May 2015

  • López-Maya, Elena; Montoro, Carmen; Rodríguez-Albelo, L. Marleny
  • Angewandte Chemie International Edition, Vol. 54, Issue 23
  • DOI: 10.1002/anie.201502094

Breaking Down Chemical Weapons by Metal-Organic Frameworks
journal, November 2015

  • Mondal, Suvendu Sekhar; Holdt, Hans-Jürgen
  • Angewandte Chemie International Edition, Vol. 55, Issue 1
  • DOI: 10.1002/anie.201508407

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

  • Mondloch, Joseph E.; Katz, Michael J.; Isley III, William C.
  • Nature Materials, Vol. 14, Issue 5
  • DOI: 10.1038/nmat4238

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

  • Moon, Su-Young; Liu, Yangyang; Hupp, Joseph T.
  • Angewandte Chemie International Edition, Vol. 54, Issue 23
  • DOI: 10.1002/anie.201502155

Introduction to Metal–Organic Frameworks
journal, September 2011

  • Zhou, Hong-Cai; Long, Jeffrey R.; Yaghi, Omar M.
  • Chemical Reviews, Vol. 112, Issue 2, p. 673-674
  • DOI: 10.1021/cr300014x

Review and Analysis of Molecular Simulations of Methane, Hydrogen, and Acetylene Storage in Metal–Organic Frameworks
journal, September 2011

  • Getman, Rachel B.; Bae, Youn-Sang; Wilmer, Christopher E.
  • Chemical Reviews, Vol. 112, Issue 2, p. 703-723
  • DOI: 10.1021/cr200217c

Hydrogen Storage in Metal–Organic Frameworks
journal, September 2011

  • Suh, Myunghyun Paik; Park, Hye Jeong; Prasad, Thazhe Kootteri
  • Chemical Reviews, Vol. 112, Issue 2, p. 782-835
  • DOI: 10.1021/cr200274s

Carbon Dioxide Capture in Metal–Organic Frameworks
journal, September 2011

  • Sumida, Kenji; Rogow, David L.; Mason, Jarad A.
  • Chemical Reviews, Vol. 112, Issue 2, p. 724-781
  • DOI: 10.1021/cr2003272

Light Hydrocarbon Adsorption Mechanisms in Two Calcium-Based Microporous Metal Organic Frameworks
journal, February 2016


Metal–organic framework with optimally selective xenon adsorption and separation
journal, June 2016

  • Banerjee, Debasis; Simon, Cory M.; Plonka, Anna M.
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms11831

Metal–Organic Frameworks for Air Purification of Toxic Chemicals
journal, April 2014

  • DeCoste, Jared B.; Peterson, Gregory W.
  • Chemical Reviews, Vol. 114, Issue 11
  • DOI: 10.1021/cr4006473

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

  • Furukawa, H.; Cordova, K. E.; O'Keeffe, M.
  • Science, Vol. 341, Issue 6149, p. 1230444-1230444
  • DOI: 10.1126/science.1230444

Metal–organic framework materials as catalysts
journal, January 2009

  • Lee, JeongYong; Farha, Omar K.; Roberts, John
  • Chemical Society Reviews, Vol. 38, Issue 5, p. 1450-1459
  • DOI: 10.1039/b807080f

Towards metal–organic framework based field effect chemical sensors: UiO-66-NH 2 for nerve agent detection
journal, January 2016

  • Stassen, I.; Bueken, B.; Reinsch, H.
  • Chemical Science, Vol. 7, Issue 9
  • DOI: 10.1039/C6SC00987E

Zr-based metal–organic frameworks: design, synthesis, structure, and applications
journal, January 2016

  • Bai, Yan; Dou, Yibo; Xie, Lin-Hua
  • Chemical Society Reviews, Vol. 45, Issue 8
  • DOI: 10.1039/C5CS00837A

Are Zr 6 -based MOFs water stable? Linker hydrolysis vs. capillary-force-driven channel collapse
journal, January 2014

  • Mondloch, Joseph E.; Katz, Michael J.; Planas, Nora
  • Chemical Communications, Vol. 50, Issue 64
  • DOI: 10.1039/C4CC02401J

Tuned to Perfection: Ironing Out the Defects in Metal–Organic Framework UiO-66
journal, July 2014

  • Shearer, Greig C.; Chavan, Sachin; Ethiraj, Jayashree
  • Chemistry of Materials, Vol. 26, Issue 14
  • DOI: 10.1021/cm501859p

Effective, Facile, and Selective Hydrolysis of the Chemical Warfare Agent VX Using Zr 6 -Based Metal–Organic Frameworks
journal, October 2015


Tailoring the Pore Size and Functionality of UiO-Type Metal–Organic Frameworks for Optimal Nerve Agent Destruction
journal, October 2015


X-ray absorption spectroscopies: useful tools to understand metallorganic frameworks structure and reactivity
journal, January 2010

  • Bordiga, Silvia; Bonino, Francesca; Lillerud, Karl Petter
  • Chemical Society Reviews, Vol. 39, Issue 12
  • DOI: 10.1039/c0cs00082e

Advanced X-ray absorption and emission spectroscopy: in situ catalytic studies
journal, January 2010

  • Singh, Jagdeep; Lamberti, Carlo; van Bokhoven, Jeroen A.
  • Chemical Society Reviews, Vol. 39, Issue 12
  • DOI: 10.1039/c0cs00054j

H 2 storage in isostructural UiO-67 and UiO-66 MOFs
journal, January 2012

  • Chavan, Sachin; Vitillo, Jenny G.; Gianolio, Diego
  • Phys. Chem. Chem. Phys., Vol. 14, Issue 5
  • DOI: 10.1039/C1CP23434J

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
  • DOI: 10.1021/ja4050828

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

  • Furukawa, Hiroyasu; Gándara, Felipe; Zhang, Yue-Biao
  • Journal of the American Chemical Society, Vol. 136, Issue 11, p. 4369-4381
  • DOI: 10.1021/ja500330a

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

  • Valenzano, Loredana; Civalleri, Bartolomeo; Chavan, Sachin
  • Chemistry of Materials, Vol. 23, Issue 7, p. 1700-1718
  • DOI: 10.1021/cm1022882

Reaction Mechanism of Nerve-Agent Hydrolysis with the Cs 8 Nb 6 O 19 Lindqvist Hexaniobate Catalyst
journal, July 2016

  • Chapleski, Robert C.; Musaev, Djamaladdin G.; Hill, Craig L.
  • The Journal of Physical Chemistry C, Vol. 120, Issue 30
  • DOI: 10.1021/acs.jpcc.6b05528

Reaction Mechanism of Nerve-Agent Decomposition with Zr-Based Metal Organic Frameworks
journal, December 2016


    Works referencing / citing this record:

    Presence versus Proximity: The Role of Pendant Amines in the Catalytic Hydrolysis of a Nerve Agent Simulant
    journal, January 2018

    • Islamoglu, Timur; Ortuño, Manuel A.; Proussaloglou, Emmanuel
    • Angewandte Chemie, Vol. 130, Issue 7
    • DOI: 10.1002/ange.201712645

    Direct ink writing of catalytically active UiO-66 polymer composites
    journal, January 2019

    • Young, Adam J.; Guillet-Nicolas, Rémy; Marshall, Ellis S.
    • Chemical Communications, Vol. 55, Issue 15
    • DOI: 10.1039/c8cc10018g

    Fast and selective fluoride ion conduction in sub-1-nanometer metal-organic framework channels
    journal, June 2019


    Construction and characterization of BiOI/NH2-MIL-125(Ti) heterostructures with excellent visible-light photocatalytic activity
    journal, January 2019

    • Han, Li; Zhang, Xiaomin; Wu, Deyong
    • Journal of Materials Science: Materials in Electronics, Vol. 30, Issue 4
    • DOI: 10.1007/s10854-018-00660-8

    Defective Metal-Organic Frameworks
    journal, January 2018

    • Dissegna, Stefano; Epp, Konstantin; Heinz, Werner R.
    • Advanced Materials, Vol. 30, Issue 37
    • DOI: 10.1002/adma.201704501

    Incorporation of Functional Groups Expands the Applications of UiO-67 for Adsorption, Catalysis and Thiols Detection
    journal, July 2018


    Nanomaterials with enzyme-like characteristics (nanozymes): next-generation artificial enzymes (II)
    journal, January 2019

    • Wu, Jiangjiexing; Wang, Xiaoyu; Wang, Quan
    • Chemical Society Reviews, Vol. 48, Issue 4
    • DOI: 10.1039/c8cs00457a

    Introduction to chemical warfare agents, relevant simulants and modern neutralisation methods
    journal, January 2019

    • Picard, Baptiste; Chataigner, Isabelle; Maddaluno, Jacques
    • Organic & Biomolecular Chemistry, Vol. 17, Issue 27
    • DOI: 10.1039/c9ob00802k

    A highly emissive and stable zinc( ii ) metal–organic framework as a host–guest chemopalette for approaching white-light-emission
    journal, January 2017

    • Cai, Hong; Xu, Li-Li; Lai, He-Yun
    • Chemical Communications, Vol. 53, Issue 56
    • DOI: 10.1039/c7cc03350h

    Sensing and capture of toxic and hazardous gases and vapors by metal–organic frameworks
    journal, January 2018

    • Wang, Hao; Lustig, William P.; Li, Jing
    • Chemical Society Reviews, Vol. 47, Issue 13
    • DOI: 10.1039/c7cs00885f

    Creation of Redox‐Active PdS x Nanoparticles Inside the Defect Pores of MOF UiO‐66 with Unique Semihydrogenation Catalytic Properties
    journal, December 2019

    • Dong, Ming‐Jie; Wang, Xuan; Wu, Chuan‐De
    • Advanced Functional Materials, Vol. 30, Issue 7
    • DOI: 10.1002/adfm.201908519

    HFIP‐Functionalized Co 3 O 4 Micro‐Nano‐Octahedra/rGO as a Double‐Layer Sensing Material for Chemical Warfare Agents
    journal, August 2019

    • Alali, Khaled Tawfik; Liu, Jingyuan; Chen, Rongrong
    • Chemistry – A European Journal, Vol. 25, Issue 51
    • DOI: 10.1002/chem.201901435

    Screening for Improved Nerve Agent Simulants and Insights into Organophosphate Hydrolysis Reactions from DFT and QSAR Modeling
    journal, May 2019

    • Mendonca, Matthew L.; Snurr, Randall Q.
    • Chemistry – A European Journal, Vol. 25, Issue 39
    • DOI: 10.1002/chem.201900655

    Structure and electronic properties of rare earth DOBDC metal–organic-frameworks
    journal, January 2019

    • Vogel, Dayton J.; Sava Gallis, Dorina F.; Nenoff, Tina M.
    • Physical Chemistry Chemical Physics, Vol. 21, Issue 41
    • DOI: 10.1039/c9cp04038b

    From IR to x-rays: gaining molecular level insights on metal-organic frameworks through spectroscopy
    journal, August 2019

    • Hanna, Lauren; Lockard, Jenny V.
    • Journal of Physics: Condensed Matter, Vol. 31, Issue 48
    • DOI: 10.1088/1361-648x/ab38da

    Assembly of the active center of organophosphorus hydrolase in metal–organic frameworks via rational combination of functional ligands
    journal, January 2017

    • Xia, Mengfan; Zhuo, Caixia; Ma, Xuejuan
    • Chem. Commun., Vol. 53, Issue 82
    • DOI: 10.1039/c7cc06270b

    High-throughput screening of solid-state catalysts for nerve agent degradation
    journal, January 2018

    • Palomba, Joseph M.; Credille, Cy V.; Kalaj, Mark
    • Chemical Communications, Vol. 54, Issue 45
    • DOI: 10.1039/c8cc03255f

    Promoting sulfur adsorption using surface Cu sites in metal–organic frameworks for lithium sulfur batteries
    journal, January 2018

    • Baumann, Avery E.; Aversa, Gabrielle E.; Roy, Anindya
    • Journal of Materials Chemistry A, Vol. 6, Issue 11
    • DOI: 10.1039/c8ta01057a

    Dynamic Interplay between Defective UiO‐66 and Protic Solvents in Activated Processes
    journal, October 2019

    • Caratelli, Chiara; Hajek, Julianna; Meijer, Evert Jan
    • Chemistry – A European Journal, Vol. 25, Issue 67
    • DOI: 10.1002/chem.201903178

    An updated roadmap for the integration of metal–organic frameworks with electronic devices and chemical sensors
    journal, January 2017

    • Stassen, Ivo; Burtch, Nicholas; Talin, Alec
    • Chemical Society Reviews, Vol. 46, Issue 11
    • DOI: 10.1039/c7cs00122c

    Novel metal–organic frameworks with high stability for selectively sensing nitroaromatics
    journal, January 2018

    • Liu, Yi; Zhao, Yue; Liu, Xiao-Hui
    • Dalton Transactions, Vol. 47, Issue 43
    • DOI: 10.1039/c8dt03551b