MOFwich: Sandwiched Metal-Organic Framework-Containing Mixed

Subscriber access provided by UNIVERSITY OF TOLEDO LIBRARIES

Letter

MOFwich: Sandwiched Metal-Organic Framework-Containing Mixed Matrix Composites for Chemical Warfare Agent Removal Gregory W. Peterson, Annie Xi Lu, Morgan G. Hall, Matthew A Browe, Trenton Tovar, and Thomas H. Epps, III ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.7b19365 • Publication Date (Web): 05 Feb 2018 Downloaded from http://pubs.acs.org on February 10, 2018

Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.

ACS Applied Materials & Interfaces is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.

Page 1 of 14 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Applied Materials & Interfaces

MOFwich: Sandwiched Metal-Organic Framework-Containing Mixed Matrix Composites for Chemical Warfare Agent Removal Gregory W. Peterson,[a,b]* Annie X. Lu,[d] Morgan G. Hall,[a] Matthew A. Browe,[a] Trenton Tovar,[a] and Thomas H. Epps, III[b,c]* a

Edgewood Chemical Biological Center, 8198 Blackhawk Road, BLDG 3549, Aberdeen Proving Ground, MD 21010 USA b Department of Materials Science and Engineering, University of Delaware, Newark, DE 19716 USA c Department of Chemical and Biomolecular Engineering, University of Delaware, Newark, DE 19716 USA d Defense Threat Reduction Agency, 8228 Scully Road, Aberdeen Proving Ground, MD 21010 USA *Corresponding author: Gregory W. Peterson, Email: [email protected]; Phone: (410) 436-9794; Thomas H. Epps, III, Email: [email protected]; Phone: (302) 831-0215

Abstract This work describes a new strategy for fabricating mixed matrix composites containing layered metal-organic framework (MOF)/polymer films as new functional barriers for chemical warfare agent protection. Through the use of mechanically robust polymers as the top and bottom encasing layers, a high MOF loading, high performance core layer can be sandwiched within. We term this multifunctional composite “MOFwich”. We found that the use of elastomeric encasing layers enabled core layer reformation after breakage, an important implication for composites and membranes alike.

The incorporation of MOFs into the core layer led to

enhanced removal of chemical warfare agents while simultaneously promoting moisture vapor 1 ACS Paragon Plus Environment

ACS Applied Materials & Interfaces 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

transport through the composite, showcasing the promise of these composites for protection applications.

Keywords: Mixed matrix composite, multilayers, metal-organic framework, chemical warfare agent, separations, block copolymer, elastomer

2 ACS Paragon Plus Environment

Page 2 of 14

Page 3 of 14 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Over the past decade, metal-organic frameworks (MOFs) have become a leading class of porous materials for applications in separations,1 air purification,2 catalysis,3 and sensing.4 The ability to tune functionality and pore structure of MOFs allows for unprecedented control at the nanoscale,5 which has translated to exciting new properties at the macroscale.6 The development of successful MOF-based technologies not only depends on scaling-related issues, but also the ability to incorporate these highly active assemblies into industry-relevant engineered constructs such as granules and membranes.7, 8

One example of a mature technology, which is most similar to our composites that are described below, is mixed matrix membranes (MMMs). MMMs have previously been prepared using zeolites,9 metal oxides,10 and carbons11 as active fillers for applications in filtration and separations. MMMs also have been fabricated containing MOFs and have demonstrated unique reactive capabilities.7, 12, 13 Generally speaking, however, MMMs have been limited to low MOF mass loadings, as higher loadings result in catastrophic defects and brittleness.7, 14 Furthermore, MMMs containing MOFs have been limited to single component systems13 and therefore lack versatility and multifunctionality. The combination of tailorable MOFs with tunable polymers, and especially block copolymers, enables the optimization of composite materials for specific applications.15 Traditional MMMs are generally fabricated using one of two techniques: (1) a filler particle (e.g., carbon, zeolite, MOF, etc.) is mixed with a polymer and cast as a freestanding film, or (2) a polymer or inorganic phase is used to grow the MOF as a secondary layer (i.e., templated growth).16 The former method permits the use of a broad range of MOFs and polymer substrates, as well as provides the ability to scale up MOFs before membrane formation. The latter allows less versatility for the type of MOF used, but generally results in more conformal membranes. Most recent MMM research incorporating MOFs has focused on carbon 3 ACS Paragon Plus Environment


dioxide (or other gas) separations and sequestration10, 13, 17, 18 with potential applicability to other areas.19,

20

To date, one application that has not been investigated using MMMs and similar

composites is the reactive removal of chemical warfare agents (CWAs).

Recently, Cohen and coworkers utilized the underlying concept of MMMs to produce composites with significantly higher MOF loadings than traditional examples. These mixed matrix composites (MMCs) incorporated MOFs into single-layer freestanding films based on poly(vinylidene fluoride), (PVDF), as well as styrene/butadiene (SBS, SBR) copolymers.14, 20 In these cases, the main thrust was to investigate a new form factor for MOFs with a focus on high mass loadings. While the strategy was able to incorporate MOFs, the composites generally became fragile at appreciable MOF loadings.

Ideally, films should be developed that can accommodate high MOF loadings while maintaining structural stability. To overcome the above limitation, herein we present a method and several archetypes for preparing multifunctional composites using a high MOF-loaded, otherwise brittle, “active layer” sandwiched between low MOF-loaded flexible polymer “encasing layers” to stabilize the composite. Our method facilitates the tuning of functionality through the incorporation of multiple polymers, MOFs, and MOF loadings, with the novelty showcased through the ability to tune each parameter to meet specific application requirements. Such requirements include permeation and reaction rates, adsorption capacity, and moisture vapor transport rate (MVTR). As shown in Figure 1, a MOF/polymer film was cast using a draw-down coating method.20 Before the film completely dried, a second layer was drawn across the first layer. The solvent locally swelled or dissolved polymer chains, fusing the layers together, and the resulting layered structure could not be mechanically separated. This approach 4 ACS Paragon Plus Environment

Page 4 of 14

Page 5 of 14 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


was repeated any number of times using a broad range of compositions to create multilayered MMCs. For added robustness of composites, we focused primarily on rubbery (elastomeric) encasing polymers.

Fabricated composites were characterized using techniques including scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), powder X-ray diffraction (PXRD) and nitrogen adsorption. The performance of MMCs as barriers against CWAs and simulants was evaluated through permeation experiments, and the reactivity of various composites was monitored using

31

P magic angle spinning nuclear magnetic resonance (MAS

NMR) spectroscopy. MVTR measurements were conducted to determine the permeability of each membrane to moisture. Composites also were characterized for other applications, such as sensors, using gas adsorption isotherms and electrical impedance spectroscopy (EIS). Experimental details are provided in the supporting information.

Our multilayer approach was first demonstrated using a polystyrene-block-polyisoprene-blockpolystyrene (SIS) copolymer incorporating either HKUST-1 or UiO-66-NH2 MOFs in the encasing or active layers, with the middle (active layer) containing a higher MOF loading. SIS is a well-known elastomer that provides an excellent combination of strength and elasticity, and is readily processable. The two MOFs were chosen as they represent two of the most studied materials in the literature and also provide significant protection against toxic chemicals such as CWAs,21 ammonia,22 chlorine,23 and nitrogen dioxide.24 Furthermore, HKUST-1 and UiO-66NH2 are produced in sufficient quantities such that structure-activity-processing relationships can be readily studied at scales larger than typically available for most MOFs synthesized in subgram quantities.

These two initial systems are designated as SIS/UiO-66-NH2(20%) + 5 ACS Paragon Plus Environment


SIS/HKUST-1(67%) + SIS/UiO-66-NH2(20%), referred to as MOFwich 1 (M1), and SIS/HKUST-1(20%) + SIS/UiO-66-NH2(67%) + SIS/HKUST-1(20%) (M2). The details of these composites as well as a much wider array of configurations, chemistries, and constructs, are described in Table S1. The percentages represent the wt% MOF relative to polymer within each layer of the MOFwich. SEM and EDS images confirmed the delineation of each layer (Figure 2A, 2C, and S1) in the MMC. The low MOF-loaded outer layers formed protective borders around the high MOF- loaded layers, which otherwise cracked without the encasing layer.

Figure 1. (A) Rubbery polymers with low MOF loadings were used to encase polymers with high MOF loadings (B), which are otherwise brittle. The strategy for fabricating the multi-layer MOFwich is shown in (C). 1 - An encasing layer using a MMC with low MOF loading first was cast and allowed to partially dry. 2 - A second MMC, generally a polymer with high MOF loading, was introduced, and the solvent annealed the new layer to the first layer, resulting in a distinct, but mechanically robust, interface. This process produced dual-layer composites. 3 - For additional layers, the same process was repeated by adding an additional encasing layer to produce a multi-layer MOFwich. (D) An encasing layer was drawn over an active layer. Multiple examples of two- and three-layer MOFwiches are shown in Figure S1. Encasing layers generally included SIS (i) and polystyrene-block-poly(ethylene-ran-butylene)-blockpolystyrene, SEBS (ii), while active layers included SIS and SEBS as well as poly(ethylene oxide), PEO (iii), poly(methyl methacrylate), PMMA (iv), polystyrene, PS (v), and PVDF (vi). Scale bar = 5 cm.


Page 6 of 14

Page 7 of 14 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


To exhibit the versatility of the method, a two-layer approach also was used to create a MOFwich consisting of high MOF-loaded SEBS. viscoelastic, and strong.

Like SIS, SEBS is easily processed,

The resulting composite, SEBS/HKUST-1(50%) + SEBS/UiO-66-

NH2(50%), is referred to as M3. M3 exhibited a well-defined two-layer structure as shown in Figures 2B and 2D. Nitrogen uptake data are shown in Figure S2, and surface area calculations are shown in Table S2. Many of the MOFwiches had considerable surface area unlike other composites with relatively low MOF percentages;14 however, all layered MMCs had significantly lower surface area in comparison to the pristine MOFs. The relatively low surface area is typical of MMCs, for which nitrogen is unable to penetrate deeply into the composites unless high MOF loadings are used.14 We note that our MOFwiches are not true MMMs as surface defects may increase nitrogen access to the MOF and govern permeation behavior; yet, it is possible to seal an active layer with high MOF loading with a low (40 h). Permeation data for mustard challenged to M3 and latex are shown in Figures S4-S5, respectively.

Beyond the barrier properties of the MOFwich in

comparison to latex, the M3 composite exhibited a MVTR (Table S3) of 16 g/m2/h – an order of magnitude higher than latex. These data suggest that not only do these MMC provide enhanced CWA protection in comparison to latex, but they also do so with the ability to provide evaporative cooling, reducing sweat and decreasing the thermal burden to users of potential protective equipment comprised of M3. Although the MVTR value was lower than fiber-based systems, it was significantly higher than current protective barrier equipment. The presence of defects within the film interface actually enhanced these effects, as the CWA had better access to active sites of the MOF, while moisture was more easily transmitted through the composite.

In addition to excellent barrier properties and high MVTR, M3 preferentially adsorbed carbon dioxide (CO2) in comparison to other gases such as methane (CH4), nitrogen (N2), and oxygen (O2), as shown in Figure 2F. The composite provided an ideal CO2/N2 selectivity of 18.9, a 50% increase over materials made from ZIF-8 and SEBS.17 Details of the calculations are provided in the SI. Further enhancements may be realized by optimizing the amount and type of MOF as well as the type of polymer(s) used within the MOFwich. The ability of M3 to sense toxic gases also was explored using EIS. After exposure to chlorine the impedance decreased by six orders of magnitude (Figure S6) stemming from the underlying reactivity of UiO-66-NH2 with chlorine.23

Next, we cast a bifunctional MOF/metal oxide composite comprised of UiO-66-NH2 and zirconium hydroxide [Zr(OH)4], M4, for the purpose of a dual-action G-series and V-series nerve agent barrier. UiO-66-NH2 was chosen because of its reactivity towards the G-series nerve 8 ACS Paragon Plus Environment

Page 8 of 14

Page 9 of 14 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


agent soman,21 while Zr(OH)4 is the fastest known solid catalyst for VX detoxification.27 The MOF and Zr(OH)4 were layered using SEBS at 50 wt% particle loading. The efficacy of M4 was evaluated by dropping neat liquid agents onto the composite and measuring degradation rates via 31P MAS NMR spectroscopy. NMR data along with optical and SEM images of M4 are shown in Figure 3 (A-C). The images exhibit clearly delineated layers of both MOF and metal oxide composites within the layered MMC. Both agents reacted on the substrate resulting in the formation of non-toxic products pinacolyl methylphosphonic acid21 and ethyl methylphosphonic acid27 for soman and VX, respectively, as determined by NMR (Figures S7-10). The calculated rate of disappearance of soman was 54 min while VX disappearance data showed two different regimes, one with a half-life of 71 min and a second one with a half-life of 158 min (Figure S10). Soman data were well described with a first-order kinetic model with a rate constant of 0.017 min-1. VX data initially conformed to first order kinetics with a rate constant of 0.012 min-1 and then deviated to a much slower 0.0029 min-1. The two regimes for VX removal are consistent with fast initial adsorption into the substrate followed by slower reaction within the pores of the sorbent.28 We anticipate faster rates will be achievable through optimization of both polymer and particle loading.



Figure 2. (A, B) SEM images and (C, D) EDS maps of M1 and M3, respectively. (E) 2-CEES permeation data through M3 and latex. The inset shows the total mass permeated through each material. (F) Adsorption isotherms of M3 for CO2, CH4, O2, and N2 showing loading (n) as a function of pressure. Scale bar = 100 µm in all images.

Additionally, we incorporated an assortment of polymers as the middle layer with a consistent 67 wt% HKUST-1 loading sandwiched between two SIS layers. Three resulting composites (M5-M7) incorporated PS, PEO, and PMMA, respectively. SEM images of the trilayer structure of each MMC are shown in Figure S11.

These MOFwiches demonstrated the potential

applicability towards hydrophobic/hydrophilic and brittle/flexible layered MMCs. Of particular interest was M7 – the sandwich structure could be folded without catastrophic failure of the inner PMMA active layer. When stretched, it exhibited local breakage; however, it readily reformed back to the original structure as shown in Figure 3 (D-E). This behavior has important implications for composites and membranes in general but is specifically applicable to CWA 10 ACS Paragon Plus Environment

Page 10 of 14

Page 11 of 14 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


protection. Indeed, even after cracking the material provided significant protection against 2CEES as shown in Figure S12.

An alternate polymer form factor in the form of PVDF

nanofibers also was placed within the layered matrix and is referred to as M9. This concept demonstrates the potential to utilize not only a wide range of polymers, but also, a wide range of polymeric structural forms. The MOFwich concept finally was taken to extreme loadings; M8 was fabricated with a layer of 80 wt% UiO-66-NH2 in SEBS and a protective layer of 20 wt% UiO-66-NH2 in SEBS, and the resulting layered composite had the highest surface area of all MMCs studied (226 m2/g, Table S2).

Figure 3. (A) Optical and (B) SEM images of M4. The layer with UiO-66-NH2 is yellow in (A) and the left layer in (B), and the Zr(OH)4 layer is white in (A) and the right layer in (B). Scale bar in (A) = 1 cm. Scale bar in (B) = 50 µm. (C) Temporal removal data for soman and VX as determined by 31P MAS NMR. Dotted lines represent first order kinetic models that capture the initial soman and VX degradation behavior. (D) The PMMA-based M7 composite was highly flexible; however, the PMMA layer of composite M7 broke when stretched (E) but reformed upon release (F). Scale bars in (D) – (F) = 1 cm.

In conclusion, we report on a new strategy for layering MOF/polymer films into hierarchical composites. The sandwich-like structures can be used for a variety of applications through tuning of the polymer, MOF type, MOF wt%, and layer order. Several composites exhibit 11 ACS Paragon Plus Environment


Page 12 of 14

impact resistant and reactive barrier properties to chemical warfare agents, making these materials applicable for a variety of protection applications. Moreover, the versatility of the MOFwich facilitates optimization of layered MMCs for more demanding applications. This feature is especially apparent with M3 and M4, in which the ability to provide a reactive barrier to CWAs while maintaining high MVTR values has led to the development of a breathable, yet protective, rubber. Further materials engineering for other applications is possible with the incorporation of the appropriate MOF and polymer combinations.

Acknowledgements The authors thank the Joint Science and Technology Office for Chemical Biological Defense (JSTO CBD) for funding under CB3934 and the U.S. Army for funding through ECBC’s Individual Laboratory Independent Research program (PE 0601101A 91A).

The opinions,

interpretations, conclusions, and recommendations are those of the authors and are not necessarily endorsed by the United States Government.

G.W.P. thanks John Mahle for

conducting mustard permeation tests. G.W.P. and T.H.E. thank Kraton for providing the SEBS polymers and Kaleigh Reno for helpful discussions. T.H.E. acknowledges the Thomas & Kipp Gutshall Professorship at the University of Delaware for supporting this research effort.

Supporting Information Available: Mixed matrix composite formation procedures and associated exemplary MOFwiches, scanning electron microscopy and optical microscopy images, nitrogen isotherm data, additional permeation curves, nuclear magnetic resonance 12 ACS Paragon Plus Environment

Page 13 of 14 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


spectra, impedance data. This information is available free of charge via the Internet at http://pubs.acs.org.

References 1. 2. 3. 4. 5.

6.

7. 8. 9. 10.

11.

12. 13.

14. 15. 16. 17.

18. 19.

Li, J.-R.; Sculley, J.; Zhou, H.-C., Metal-Organic Frameworks for Separations. Chem. Rev. 2011, 112 (2), 869932. DeCoste, J. B.; Peterson, G. W., Metal-Organic Frameworks for Air Purification of Toxic Chemicals. Chem. Rev. 2014, 114 (11), 5695-5727. Lee, J.; Farha, O. K.; Roberts, J.; Scheidt, K. A.; Nguyen, S. T.; Hupp, J. T., Metal-Organic Framework Materials as Catalysts. Chem. Soc. Rev. 2009, 38 (5), 1450-1459. Cui, Y.; Yue, Y.; Qian, G.; Chen, B., Luminescent Functional Metal-Organic Frameworks. Chem. Rev. 2011, 112 (2), 1126-1162. Eddaoudi, M.; Kim, J.; Rosi, N.; Vodak, D.; Wachter, J.; O'Keeffe, M.; Yaghi, O. M., Systematic Design of Pore Size and Functionality in Isoreticular MOFs and Their Application in Methane Storage. Science 2002, 295 (5554), 469-472. Zhang, Y. Y.; Feng, X.; Li, H. W.; Chen, Y. F.; Zhao, J. S.; Wang, S.; Wang, L.; Wang, B., Photoinduced Postsynthetic Polymerization of a Metal-Organic Framework Toward a Flexible Stand-Alone Membrane. Angew. Chem. Int. Ed. 2015, 54 (14), 4259-4263. Zhang, Y. Y.; Feng, X.; Yuan, S.; Zhou, J. W.; Wang, B., Challenges and Recent Advances in MOF-Polymer Composite Membranes for Gas Separation. Inorg. Chem. Front. 2016, 3 (7), 896-909. Hendon, C. H.; Rieth, A. J.; Korzynski, M. D.; Dinca, M., Grand Challenges and Future Opportunities for Metal-Organic Frameworks. ACS Cent. Sci. 2017, 3 (6), 554-563. Pera-Titus, M., Porous Inorganic Membranes for CO2 Capture: Present and Prospects. Chem. Rev. 2014, 114 (2), 1413-1492. Nafisi, V.; Hagg, M. B., Development of Nanocomposite Membranes Containing Modified Si Nanoparticles in Pebax-2533 as a Block Copolymer and 6FDA-Durene Diamine as a Glassy Polymer. ACS Appl. Mater. Interfaces 2014, 6 (18), 15643-15652. Zhao, D.; Ren, J. Z.; Wang, Y.; Qiu, Y. T.; Li, H.; Hua, K. S.; Li, X. X.; Ji, J. M.; Deng, M. C., High CO2 Separation Performance of Pebax (R)/CNTs/GTA Mixed Matrix Membranes. J. Membr. Sci. 2017, 521, 104113. Kitao, T.; Zhang, Y. Y.; Kitagawa, S.; Wang, B.; Uemura, T., Hybridization of MOFs and Polymers. Chem. Soc. Rev. 2017, 46 (11), 3108-3133. Seoane, B.; Coronas, J.; Gascon, I.; Etxeberria Benavides, M.; Karvan, O.; Caro, J.; Kapteijn, F.; Gascon, J., Metal-Organic Framework Based Mixed Matrix Membranes: A Solution for Highly Efficient CO2 Capture? Chem. Soc. Rev. 2015, 44 (8), 2421-2454. Moreton, J. C.; Denny, M. S.; Cohen, S. M., High MOF Loading in Mixed-Matrix Membranes Utilizing Styrene/Butadiene Copolymers. Chem. Commun. 2016, 52 (100), 14376-14379. Epps, T. H., III; O'Reilly, R. K., Block Copolymers: Controlling Nanostructure to Generate Functional Materials - Synthesis, Characterization, and Engineering. Chem. Sci. 2016, 7 (3), 1674-1689. Denny Jr, M. S.; Moreton, J. C.; Benz, L.; Cohen, S. M., Metal-Organic Frameworks for Membrane-Based Separations. Nat. Rev. Mater. 2016, 1, 16078-16094. Chi, W. S.; Hwang, S.; Lee, S. J.; Park, S.; Bae, Y. S.; Ryu, D. Y.; Kim, J. H.; Kim, J., Mixed Matrix Membranes Consisting of SEBS Block Copolymers and Size-Controlled ZIF-8 Nanoparticles for CO2 Capture. J. Membr. Sci 2015, 495, 479-488. Kim, J.; Choi, J.; Kang, Y. S.; Won, J., Matrix Effect of Mixed-Matrix Membrane Containing CO2-Selective MOFs. J. Appl. Polym. Sci. 2016, 133 (1), 42853. Koros, W. J.; Zhang, C., Materials for Next-Generation Molecularly Selective Synthetic Membranes. Nat. Mater. 2017, 16 (3), 289-297.



20. Denny, M. S., Jr.; Cohen, S. M., In Situ Modification of Metal-Organic Frameworks in Mixed-Matrix Membranes. Angew. Chem. Int. Ed. 2015, 54 (31), 9029-9032. 21. Peterson, G. W.; Moon, S.-Y.; Wagner, G. W.; Hall, M. G.; DeCoste, J. B.; Hupp, J. T.; Farha, O. K., Tailoring the Pore Size and Functionality of UiO-Type Metal-Organic Frameworks for Optimal Nerve Agent Destruction. Inorg. Chem. 2015, 54, 9684-9686. 22. Peterson, G. W.; Wagner, G. W.; Balboa, A.; Mahle, J.; Sewell, T.; Karwacki, C. J., Ammonia Vapor Removal by Cu3(BTC)2 and Its Characterization by MAS NMR. J. Phys. Chem. C 2009, 113 (31), 13906-13917. 23. DeCoste, J. B.; Browe, M. A.; Wagner, G. W.; Rossin, J. A.; Peterson, G. W., Removal of Chlorine Gas by an Amine Functionalized Metal-Organic Framework via Electrophilic Aromatic Substitution. Chem. Commun. 2015, 51 (62), 12474-12477. 24. Peterson, G. W.; Mahle, J. J.; DeCoste, J. B.; Gordon, W. O.; Rossin, J. A., Extraordinary NO2 Removal by the Metal-Organic Framework UiO-66-NH2. Angew. Chem., Int. Ed. 2016, 55 (21), 6235-6238. 25. Dubey, V.; Gupta, A. K.; Maiti, S. N., Mechanism of the Diffusion of Sulfur Mustard, a Chemical Warfare Agent, in Butyl and Nitrile Rubbers. J. Polym. Sci., Part B: Polym. Phys. 2002, 40 (17), 1821-1827. 26. Cmarik, G. E.; Kim, M.; Cohen, S. M.; Walton, K. S., Tuning the Adsorption Properties of UiO-66 via Ligand Functionalization. Langmuir 2012, 28 (44), 15606-15613. 27. Bandosz, T. J.; Laskoski, M.; Mahle, J.; Mogilevsky, G.; Peterson, G. W.; Rossin, J. A.; Wagner, G. W., Reactions of VX, GD, and HD with Zr(OH)(4): Near Instantaneous Decontamination of VX. J. Phys. Chem. C 2012, 116 (21), 11606-11614. 28. Wagner, G. W.; Koper, O. B.; Lucas, E.; Decker, S.; Klabunde, K. J., Reactions of VX, GD, and HD with Nanosize CaO: Autocatalytic Dehydrohalogenation of HD. J. Phys. Chem. B 2000, 104 (21), 5118-5123.

TOC Image


Page 14 of 14

MOFwich: Sandwiched Metal-Organic Framework-Containing Mixed

Recommend Documents