Laponite-Incorporated UiO-66-NH2-Polyethylene Oxide Composite Membranes for Protection against Chemical Warfare Agent Simulants

Browe, Matthew A.; Landers, John; Tovar, Trenton M.; Mahle, John J.; Balboa, Alex; Gordon, Wesley O.; Fukuto, Masafumi; Karwacki, Christopher J.

doi:10.1021/acsami.1c00397

Laponite-Incorporated UiO-66-NH2-Polyethylene Oxide Composite Membranes for Protection against Chemical Warfare Agent Simulants

Journal Article · Fri Feb 19 00:00:00 EST 2021 · ACS Applied Materials and Interfaces

DOI:https://doi.org/10.1021/acsami.1c00397· OSTI ID:1778803

^[1]; ^[2]; Tovar, Trenton M. ^[2]; Mahle, John J. ^[1]; Balboa, Alex ^[1]; ^[1]; Fukuto, Masafumi ^[3]; Karwacki, Christopher J. ^[1]

US Dept. of Homeland Security (DHS), Aberdeen Proving Ground, MD (United States). DEVCOM Chemical Biological Center
US Dept. of Homeland Security (DHS), Aberdeen Proving Ground, MD (United States). DEVCOM Chemical Biological Center; National Research Council, Washington, DC (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)

A strategy is developed to enhance the barrier protection of polyethylene oxide (PEO)-metal–organic framework (MOF) composite films against chemical warfare agent simulants. To achieve enhanced protection, an impermeable high-aspect-ratio filler in the form of Laponite RD (LRD) clay platelets was incorporated into a composite PEO film containing MOF UiO-66-NH₂. The inclusion of the platelets aids in mitigating permeation of inert hydrocarbons (octane) and toxic chemicals (2-chloroethyl ethyl sulfide, 2-CEES) of dimensions/chemistry similar to prominent vesicant threats while still maintaining high water vapor transport rates (WVTR). By utilizing small-angle neutron scattering, small-angle X-ray scattering, and wide-angle X-ray scattering, the LRD platelet alignment of the films was determined, and the structure of the films was correlated with performance as a barrier material. Performance of the membranes against toxic chemical threats was assessed using permeation testing of octane and 2-CEES, a common simulant for the vesicant mustard gas, and breathability of the membranes was assessed using WVTR measurements. To assess their robustness, chemical exposure (in situ diffuse reflectance infrared Fourier transform spectroscopy) and mechanical (tensile strength) measurements were also performed. It was demonstrated that the barrier performance of the film upon inclusion of the LRD platelets exceeds that of other MOF-polymer composites found in the literature and that this approach establishes a new path for improving permselective materials for chemical protection applications.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: SC0012704

OSTI ID:: 1778803

Alternate ID(s):: OSTI ID: 1823123

Report Number(s):: BNL--221270-2021-JAAM

Journal Information:: ACS Applied Materials and Interfaces, Journal Name: ACS Applied Materials and Interfaces Journal Issue: 8 Vol. 13; ISSN 1944-8244

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (68)

Breaking Down Chemical Weapons by Metal-Organic Frameworks Mondal, Suvendu Sekhar; Holdt, Hans-Jürgen Angewandte Chemie International Edition, Vol. 55, Issue 1 https://doi.org/10.1002/anie.201508407	journal	November 2015
Mixed-Matrix Membranes Dechnik, Janina; Gascon, Jorge; Doonan, Christian J. Angewandte Chemie International Edition, Vol. 56, Issue 32 https://doi.org/10.1002/anie.201701109	journal	July 2017
Combination of MOFs and Zeolites for Mixed-Matrix Membranes Zornoza, Beatriz; Seoane, Beatriz; Zamaro, Juan M. ChemPhysChem, Vol. 12, Issue 15 https://doi.org/10.1002/cphc.201100583	journal	September 2011
Tuning Cell Adhesion by Incorporation of Charged Silicate Nanoparticles as Cross-Linkers to Polyethylene Oxide: Tuning Cell Adhesion by Incorporation of Charged Silicate Nanoparticles as … Schexnailder, Patrick J.; Gaharwar, Akhilesh K.; Bartlett II, Rush L. Macromolecular Bioscience, Vol. 10, Issue 12 https://doi.org/10.1002/mabi.201000053	journal	December 2010
Polymer/Clay Nanocomposites: Influence of Ionic Strength on the Structure and Adhesion Characteristics in Multilayered Films Stefanescu, Eduard A.; Stefanescu, Cristina; Donose, Bogdan C. Macromolecular Materials and Engineering, Vol. 293, Issue 9 https://doi.org/10.1002/mame.200800139	journal	September 2008
Orientation of platelets in multilayered nanocomposite polymer films Malwitz, Matthew M.; Lin-Gibson, Sheng; Hobbie, Erik K. Journal of Polymer Science Part B: Polymer Physics, Vol. 41, Issue 24 https://doi.org/10.1002/polb.10699	journal	November 2003
Electrical Double-Layer Effects on the Brownian Diffusivity and Aggregation Rate of Laponite Clay Particles Tawari, Santosh L.; Koch, Donald L.; Cohen, Claude Journal of Colloid and Interface Science, Vol. 240, Issue 1 https://doi.org/10.1006/jcis.2001.7646	journal	August 2001
Quantitative Methoden zur Bestimmung des Orientierungsgrades gedehnter Zellulosefäden, ihre Grenzen und gegenseitigen Beziehungen Hermans, P. H. Kolloid-Zeitschrift, Vol. 97, Issue 2 https://doi.org/10.1007/BF01502651	journal	November 1941
Nerve gas destruction with metal organic frameworks Glaser, John A. Clean Technologies and Environmental Policy, Vol. 18, Issue 2 https://doi.org/10.1007/s10098-016-1108-0	journal	February 2016
Colloidal properties of synthetic hectorite clay dispersions Ramsay, J. D. F. Journal of Colloid and Interface Science, Vol. 109, Issue 2 https://doi.org/10.1016/0021-9797(86)90321-8	journal	February 1986
The nature of laponite and its aqueous dispersions Thompson, Dudley W.; Butterworth, James T. Journal of Colloid and Interface Science, Vol. 151, Issue 1 https://doi.org/10.1016/0021-9797(92)90254-J	journal	June 1992
Transport phenomena through polymeric systems George, Soney C.; Thomas, Sabu Progress in Polymer Science, Vol. 26, Issue 6 https://doi.org/10.1016/S0079-6700(00)00036-8	journal	August 2001
Properties of polymer–nanoparticle composites Schmidt, Gudrun; Malwitz, Matthew M. Current Opinion in Colloid & Interface Science, Vol. 8, Issue 1 https://doi.org/10.1016/S1359-0294(03)00008-6	journal	March 2003
Selective adsorption of cationic dyes by UiO-66-NH2 Chen, Qi; He, Qinqin; Lv, Mengmeng Applied Surface Science, Vol. 327 https://doi.org/10.1016/j.apsusc.2014.11.103	journal	February 2015
Catalytic degradation of chemical warfare agents and their simulants by metal-organic frameworks Liu, Yangyang; Howarth, Ashlee J.; Vermeulen, Nicholaas A. Coordination Chemistry Reviews, Vol. 346 https://doi.org/10.1016/j.ccr.2016.11.008	journal	September 2017
Chemical stability of Laponite in aqueous media Jatav, Shweta; Joshi, Yogesh M. Applied Clay Science, Vol. 97-98 https://doi.org/10.1016/j.clay.2014.06.004	journal	August 2014
Modeling mass transport in dense polymer membranes: cooperative synergy among multiple scale approaches Minelli, Matteo; Sarti, Giulio C. Current Opinion in Chemical Engineering, Vol. 28 https://doi.org/10.1016/j.coche.2020.01.004	journal	June 2020
Flocculated Laponite–PEG/PEO dispersions with monovalent salt, a SAXS and simulation study Thuresson, A.; Segad, M.; Turesson, M. Journal of Colloid and Interface Science, Vol. 466 https://doi.org/10.1016/j.jcis.2015.12.033	journal	March 2016
Functionalized metal organic framework-polyimide mixed matrix membranes for CO2/CH4 separation Nik, Omid Ghaffari; Chen, Xiao Yuan; Kaliaguine, Serge Journal of Membrane Science, Vol. 413-414 https://doi.org/10.1016/j.memsci.2012.04.003	journal	September 2012
Non-ideal effects in organic–inorganic materials for gas separation membranes Moore, Theodore T.; Koros, William J. Journal of Molecular Structure, Vol. 739, Issue 1-3 https://doi.org/10.1016/j.molstruc.2004.05.043	journal	April 2005
Melt-compounded salt-containing poly(ethylene oxide)/clay nanocomposites for polymer electrolyte membranes Loyens, Wendy; Maurer, Frans H. J.; Jannasch, Patric Polymer, Vol. 46, Issue 18 https://doi.org/10.1016/j.polymer.2005.06.006	journal	August 2005
Structure and thermal properties of multilayered Laponite/PEO nanocomposite films Stefanescu, Eduard A.; Schexnailder, Patrick J.; Dundigalla, Avinash Polymer, Vol. 47, Issue 21 https://doi.org/10.1016/j.polymer.2006.08.051	journal	October 2006
Diffusion in polymeric systems–A review on free volume theory Sharma, Jyoti; Tewari, Kshitij; Arya, Raj Kumar Progress in Organic Coatings, Vol. 111 https://doi.org/10.1016/j.porgcoat.2017.05.004	journal	October 2017
Mixed matrix membranes (MMMs) comprising organic polymers with dispersed inorganic fillers for gas separation Chung, Tai-Shung; Jiang, Lan Ying; Li, Yi Progress in Polymer Science, Vol. 32, Issue 4, p. 483-507 https://doi.org/10.1016/j.progpolymsci.2007.01.008	journal	April 2007
Synthesis of polymer/Laponite nanocomposite latex particles via emulsion polymerization using silylated and cation-exchanged Laponite clay platelets Negrete-Herrera, Norma; Putaux, Jean-Luc; Bourgeat-Lami, Elodie Progress in Solid State Chemistry, Vol. 34, Issue 2-4 https://doi.org/10.1016/j.progsolidstchem.2005.11.040	journal	July 2006
Conductivity and FTIR studies on PEO–LiX [X: CF3SO3−, SO42−] polymer electrolytes Ramesh, S.; Yuen, Tai Fung; Shen, Chia Jun Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, Vol. 69, Issue 2 https://doi.org/10.1016/j.saa.2007.05.029	journal	February 2008
Performance studies of mixed matrix membranes for gas separation: A review Aroon, M. A.; Ismail, A. F.; Matsuura, T. Separation and Purification Technology, Vol. 75, Issue 3 https://doi.org/10.1016/j.seppur.2010.08.023	journal	November 2010
Uncovering the Role of Metal–Organic Framework Topology on the Capture and Reactivity of Chemical Warfare Agents Son, Florencia A.; Wasson, Megan C.; Islamoglu, Timur Chemistry of Materials, Vol. 32, Issue 11 https://doi.org/10.1021/acs.chemmater.0c00986	journal	May 2020
Alkane–OH Hydrogen Bond Formation and Diffusion Energetics of n -Butane within UiO-66 Sharp, Conor H.; Abelard, Joshua; Plonka, Anna M. The Journal of Physical Chemistry C, Vol. 121, Issue 16 https://doi.org/10.1021/acs.jpcc.7b01351	journal	April 2017
Benzene, Toluene, and Xylene Transport through UiO-66: Diffusion Rates, Energetics, and the Role of Hydrogen Bonding Grissom, Tyler G.; Sharp, Conor H.; Usov, Pavel M. The Journal of Physical Chemistry C, Vol. 122, Issue 28 https://doi.org/10.1021/acs.jpcc.8b03356	journal	June 2018
Microscopic Model of the Metal–Organic Framework/Polymer Interface: A First Step toward Understanding the Compatibility in Mixed Matrix Membranes Semino, Rocio; Ramsahye, Naseem A.; Ghoufi, Aziz ACS Applied Materials & Interfaces, Vol. 8, Issue 1 https://doi.org/10.1021/acsami.5b10150	journal	December 2015
Tailoring the Adsorption and Reaction Chemistry of the Metal–Organic Frameworks UiO-66, UiO-66-NH ₂ , and HKUST-1 via the Incorporation of Molecular Guests Ploskonka, Ann M.; DeCoste, Jared B. ACS Applied Materials & Interfaces, Vol. 9, Issue 25 https://doi.org/10.1021/acsami.7b06274	journal	June 2017
MOFwich: Sandwiched Metal–Organic Framework-Containing Mixed Matrix Composites for Chemical Warfare Agent Removal Peterson, Gregory W.; Lu, Annie X.; Hall, Morgan G. ACS Applied Materials & Interfaces, Vol. 10, Issue 8 https://doi.org/10.1021/acsami.7b19365	journal	February 2018
Flexible SIS/HKUST-1 Mixed Matrix Composites as Protective Barriers against Chemical Warfare Agent Simulants Peterson, Gregory W.; Browe, Matthew A.; Durke, Erin M. ACS Applied Materials & Interfaces, Vol. 10, Issue 49 https://doi.org/10.1021/acsami.8b16227	journal	November 2018
Poly(ethylene oxide)-silicate intercalation materials Aranda, Pilar; Ruiz-Hitzky, Eduardo Chemistry of Materials, Vol. 4, Issue 6 https://doi.org/10.1021/cm00024a048	journal	November 1992
Crystallization Behavior of Poly(ethylene oxide) in the Presence of Na ⁺ Montmorillonite Fillers Strawhecker, K. E.; Manias, E. Chemistry of Materials, Vol. 15, Issue 4 https://doi.org/10.1021/cm0212865	journal	February 2003
“Hairy” Plates: Poly(ethylene oxide)- b -polyisoprene Copolymers in the Presence of Laponite Clay Gournis, D.; Floudas, G. Chemistry of Materials, Vol. 16, Issue 9 https://doi.org/10.1021/cm035267m	journal	March 2004
Disclosing the Complex Structure of UiO-66 Metal Organic Framework: A Synergic Combination of Experiment and Theory Valenzano, Loredana; Civalleri, Bartolomeo; Chavan, Sachin Chemistry of Materials, Vol. 23, Issue 7, p. 1700-1718 https://doi.org/10.1021/cm1022882	journal	April 2011
Synthesis and Stability of Tagged UiO-66 Zr-MOFs Kandiah, Mathivathani; Nilsen, Merete Hellner; Usseglio, Sandro Chemistry of Materials, Vol. 22, Issue 24 https://doi.org/10.1021/cm102601v	journal	December 2010
Metal–Organic Frameworks for Air Purification of Toxic Chemicals DeCoste, Jared B.; Peterson, Gregory W. Chemical Reviews, Vol. 114, Issue 11 https://doi.org/10.1021/cr4006473	journal	April 2014
Effect of Water Adsorption on Retention of Structure and Surface Area of Metal–Organic Frameworks Schoenecker, Paul M.; Carson, Cantwell G.; Jasuja, Himanshu Industrial & Engineering Chemistry Research, Vol. 51, Issue 18 https://doi.org/10.1021/ie202325p	journal	April 2012
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
Scalable and Template-Free Aqueous Synthesis of Zirconium-Based Metal–Organic Framework Coating on Textile Fiber Ma, Kaikai; Islamoglu, Timur; Chen, Zhijie Journal of the American Chemical Society, Vol. 141, Issue 39 https://doi.org/10.1021/jacs.9b07301	journal	September 2019
Fast Calculation of van der Waals Volume as a Sum of Atomic and Bond Contributions and Its Application to Drug Compounds Zhao, Yuan H.; Abraham, Michael H.; Zissimos, Andreas M. The Journal of Organic Chemistry, Vol. 68, Issue 19 https://doi.org/10.1021/jo034808o	journal	September 2003
Adsorption of 2-Chloroethyl Ethyl Sulfide on Silica: Binding Mechanism and Energy of a Bifunctional Hydrogen-Bond Acceptor at the Gas–Surface Interface Abelard, Joshua; Wilmsmeyer, Amanda R.; Edwards, Angela C. The Journal of Physical Chemistry C, Vol. 119, Issue 1 https://doi.org/10.1021/jp509516x	journal	December 2014
Tuning the Adsorption Properties of UiO-66 via Ligand Functionalization Cmarik, Gregory E.; Kim, Min; Cohen, Seth M. Langmuir, Vol. 28, Issue 44 https://doi.org/10.1021/la3035352	journal	October 2012
Supercritical CO ₂ -Mediated Intercalation of PEO in Clay Zhao, Qian; Samulski, Edward T. Macromolecules, Vol. 36, Issue 19 https://doi.org/10.1021/ma0349682	journal	September 2003
Large Scale Structures in Nanocomposite Hydrogels Loizou, Elena; Butler, Paul; Porcar, Lionel Macromolecules, Vol. 38, Issue 6 https://doi.org/10.1021/ma047411a	journal	March 2005
Dynamic Responses in Nanocomposite Hydrogels Loizou, Elena; Butler, Paul; Porcar, Lionel Macromolecules, Vol. 39, Issue 4 https://doi.org/10.1021/ma0517547	journal	February 2006
Model Nanocomposites Based on Laponite and Poly(ethylene oxide): Preparation and Rheology Loiseau, Anthony; Tassin, Jean-François Macromolecules, Vol. 39, Issue 26 https://doi.org/10.1021/ma061324w	journal	November 2006
Shear Orientation of Viscoelastic Polymer−Clay Solutions Probed by Flow Birefringence and SANS Schmidt, Gudrun; Nakatani, Alan I.; Butler, Paul D. Macromolecules, Vol. 33, Issue 20 https://doi.org/10.1021/ma9918811	journal	October 2000
Reticular synthesis and the design of new materials Yaghi, Omar M.; O'Keeffe, Michael; Ockwig, Nathan W. Nature, Vol. 423, Issue 6941, p. 705-714 https://doi.org/10.1038/nature01650	journal	June 2003
A colloidal water-stable MOF as a broad-range fluorescent pH sensor via post-synthetic modification Aguilera-Sigalat, Jordi; Bradshaw, Darren Chem. Commun., Vol. 50, Issue 36 https://doi.org/10.1039/C4CC00659C	journal	January 2014
Exploiting parameter space in MOFs: a 20-fold enhancement of phosphate-ester hydrolysis with UiO-66-NH ₂ Katz, Michael J.; Moon, Su-Young; Mondloch, Joseph E. Chemical Science, Vol. 6, Issue 4 https://doi.org/10.1039/C4SC03613A	journal	January 2015
Removal of chlorine gas by an amine functionalized metal–organic framework via electrophilic aromatic substitution DeCoste, Jared B.; Browe, Matthew A.; Wagner, George W. Chemical Communications, Vol. 51, Issue 62 https://doi.org/10.1039/C5CC03780H	journal	January 2015
Synthesis and characterization of hydroxypropyl methylcellulose-g-poly(acrylamide)/LAPONITE® RD nanocomposites as novel magnetic- and pH-sensitive carriers for controlled drug release Mahdavinia, Gholam Reza; Ettehadi, Sanaz; Amini, Mojtaba RSC Advances, Vol. 5, Issue 55 https://doi.org/10.1039/C5RA03731J	journal	January 2015
Challenges and recent advances in MOF–polymer composite membranes for gas separation Zhang, Yuanyuan; Feng, Xiao; Yuan, Shuai Inorganic Chemistry Frontiers, Vol. 3, Issue 7 https://doi.org/10.1039/C6QI00042H	journal	January 2016
Hybridization of MOFs and polymers Kitao, Takashi; Zhang, Yuanyuan; Kitagawa, Susumu Chemical Society Reviews, Vol. 46, Issue 11 https://doi.org/10.1039/C7CS00041C	journal	January 2017
Metal–organic frameworks for the removal of toxic industrial chemicals and chemical warfare agents Bobbitt, N. Scott; Mendonca, Matthew L.; Howarth, Ashlee J. Chemical Society Reviews, Vol. 46, Issue 11 https://doi.org/10.1039/C7CS00108H	journal	January 2017
A metal–organic framework and conducting polymer based electrochemical sensor for high performance cadmium ion detection Wang, Yang; Wang, Lu; Huang, Wei Journal of Materials Chemistry A, Vol. 5, Issue 18 https://doi.org/10.1039/C7TA01066D	journal	January 2017
Synthesis and gas permselectivity of CuBTC–GO–PVDF mixed matrix membranes Feijani, Elahe Ahmadi; Mahdavi, Hossein; Tavassoli, Ahmad New Journal of Chemistry, Vol. 42, Issue 14 https://doi.org/10.1039/C8NJ00796A	journal	January 2018
The state of the field: from inception to commercialization of metal–organic frameworks Chen, Zhijie; Wasson, Megan C.; Drout, Riki J. Faraday Discussions, Vol. 225 https://doi.org/10.1039/D0FD00103A	journal	January 2021
Functionalized flexible MOFs as fillers in mixed matrix membranes for highly selective separation of CO2 from CH4 at elevated pressures Zornoza, Beatriz; Martinez-Joaristi, Alberto; Serra-Crespo, Pablo Chemical Communications, Vol. 47, Issue 33 https://doi.org/10.1039/c1cc13431k	journal	January 2011
Interaction of Polymer with Discotic Clay Particles Lal, Jyotsana; Auvray, Loic Molecular Crystals and Liquid Crystals Science and Technology. Section A. Molecular Crystals and Liquid Crystals, Vol. 356, Issue 1 https://doi.org/10.1080/10587250108023729	journal	February 2001
Models for the Permeability of Filled Polymer Systems Nielsen, Lawrence E. Journal of Macromolecular Science: Part A - Chemistry, Vol. 1, Issue 5 https://doi.org/10.1080/10601326708053745	journal	August 1967
Interaction of polymer with clays Lal, J.; Auvray, L. Journal of Applied Crystallography, Vol. 33, Issue 3 https://doi.org/10.1107/S0021889899013308	journal	June 2000
The Nature of Laponite: Pure Hectorite or a Mixture of Different Trioctahedral Phases? Christidis, George; Aldana, Carlos; Chryssikos, Georgios Minerals, Vol. 8, Issue 8 https://doi.org/10.3390/min8080314	journal	July 2018
Mixed matrix membranes for gas separation with special nanoporous fillers Zornoza, Beatriz; Gorgojo, Patricia; Casado, Clara Desalination and Water Treatment, Vol. 27, Issue 1-3 https://doi.org/10.5004/dwt.2011.2045	journal	March 2011

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36 MATERIALS SCIENCE
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chemical warfare agent
membrane
metal-organic framework
permeation

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