@article{barton_jamir_davis_peterson_parsons_2021, title={Doubly Protective MOF-Photo-Fabrics: Facile Template-Free Synthesis of PCN-222-Textiles Enables Rapid Hydrolysis, Photo-Hydrolysis and Selective Oxidation of Multiple Chemical Warfare Agents and Simulants}, volume={27}, ISSN={["1521-3765"]}, url={https://doi.org/10.1002/chem.202003716}, DOI={10.1002/chem.202003716}, abstractNote={Attacks using chemical warfare agents (CWAs,) including organophosphate soman (GD) and thioether mustard gas (HD) threaten both innocent civilians and military personnel, spawning significant research into catalytically-active composite textiles and new wearable protective gear. In this work, we report the first metal-organic framework (MOF) fabric composite capable of both rapid catalytic hydrolysis and photo-oxidation of multiple chemical warfare agents (GD and HD) and their simulants. A simple template-free low-temperature synthesis yields new zirconium-porphyrin based nano-crystalline PCN-222 MOF-fabrics with adjustable MOF loading and robust mechanical adhesion on low-cost nonwoven polypropylene fibers. Importantly, we report the discovery of visible photo-activation of GD hydrolysis by a MOF-fabric, which is ascribed to oxidation at the active metal node site, significantly increasing the rate over that observed without illumination. Moreover, because the active MOF catalysts are uniformly displayed on the MOF-textile, the composite geometry enhances the kinetics of active agent photo-degradation relative to the same mass of MOF in common powder form. These results provide important new insights into the design of future materials and chemical systems to protect military, first-responders, and civilians upon exposure to complex chemical toxins.}, number={4}, journal={CHEMISTRY-A EUROPEAN JOURNAL}, publisher={Wiley}, author={Barton, Heather F. and Jamir, Jovenal D. and Davis, Alexandra K. and Peterson, Gregory W. and Parsons, Gregory N.}, year={2021}, month={Jan}, pages={1465–1472} }
 @misc{peterson_lee_barton_epps_parsons_2021, title={Fibre-based composites from the integration of metal-organic frameworks and polymers}, volume={6}, ISSN={["2058-8437"]}, url={https://doi.org/10.1038/s41578-021-00291-2}, DOI={10.1038/s41578-021-00291-2}, number={7}, journal={NATURE REVIEWS MATERIALS}, author={Peterson, Gregory W. and Lee, Dennis T. and Barton, Heather F. and Epps, Thomas H., III and Parsons, Gregory N.}, year={2021}, month={Jul}, pages={605–621} }
 @article{dai_pradeep_zhu_xie_barton_si_ding_yu_parsons_2021, title={Freestanding Metal Organic Framework-Based Multifunctional Membranes Fabricated via Pseudomorphic Replication toward Liquid- and Gas-Hazards Abatement}, volume={10}, ISSN={["2196-7350"]}, url={https://doi.org/10.1002/admi.202101178}, DOI={10.1002/admi.202101178}, abstractNote={Metal organic framework (MOF)‐based adsorptive membranes are attractive materials in high flux separation and/or in abatement of hazardous materials. However, fabrication of continuous MOF membrane with ultra‐high loading and anti‐solvent property is a challenging task. Here, the authors report a coordination replication synthetic approach via a morphological replacement procedure that employs pre‐shaped Al2O3 microfiltration membrane to produce freestanding MOF multifunctional membrane (FMMMs). The authors achieve precise control of crystal size, morphology, and orientation on the FMMMs. Moreover, the intrinsic porous structure inherited from Al2O3 pre‐fabricated membrane and newly introduced MOF active sites synergistically contribute to a great rejection (99%) of organic dyes from organic solvent with a permeability over 175 L m−2 h−1 bar−1. Furthermore, the as‐synthesized FMMMs enable heterogeneous HCHO catalytic oxidation and extremely rapid 2‐chloroethyl ethyl sulfide (CEES) detoxification. This work opens the way to design high‐performance FMMMs from pre‐shaped membranes for various applications.}, journal={ADVANCED MATERIALS INTERFACES}, publisher={Wiley}, author={Dai, Zijian and Pradeep, Shravan and Zhu, Jie and Xie, Wenyi and Barton, Heather F. and Si, Yang and Ding, Bin and Yu, Jianyong and Parsons, Gregory N.}, year={2021}, month={Oct} }
 @article{barton_davis_parsons_2020, title={The Effect of Surface Hydroxylation on MOF Formation on ALD Metal Oxides: MOF-525 on TiO2/Polypropylene for Catalytic Hydrolysis of Chemical Warfare Agent Simulants}, volume={12}, ISBN={1944-8252}, url={https://doi.org/10.1021/acsami.9b20910}, DOI={10.1021/acsami.9b20910}, abstractNote={Metal-organic framework (MOF) fibrous composites were synthesized in a variety of methods in attempt to incorporate the highly effective reactivity of MOFs into a more facile and applicable format. Recent advances have demonstrated incorporating a metal oxide nucleation surface or reactive layer promotes conformal, well-adhered MOF growth on substrates. These materials have demonstrated promising reactivity in capturing or degrading chemical warfare agents and simulants. Here, we examine the mechanisms for MOF nucleation from metal oxide thin films to explore why some metal oxide sources are better suited for one synthesis mechanism over another. We isolate metal oxide extent of hydroxylation as an indicative factor as to whether the film serves as a nucleation promoter or may be converted directly to the MOF thin films. MOF-525 growth on Al2O3, TiO2, and ZnO coated fibers is demonstrated to corroborate these findings and used to degrade chemical warfare agent simulant dimethyl-4-nitrophenyl phosphate.}, number={13}, journal={ACS APPLIED MATERIALS & INTERFACES}, publisher={American Chemical Society (ACS)}, author={Barton, Heather F. and Davis, Alexandra K. and Parsons, Gregory N.}, year={2020}, pages={14690–14701} }
 @article{pomerantz_anderson_dugan_hoffman_barton_lee_oldham_peterson_parsons_2019, title={Air, Water Vapor, and Aerosol Transport through Textiles with Surface Functional Coatings of Metal Oxides and Metal-Organic Frameworks}, volume={11}, ISSN={["1944-8252"]}, url={https://doi.org/10.1021/acsami.9b04091}, DOI={10.1021/acsami.9b04091}, abstractNote={Currently, air permeable chemical/biological (CB) protective garments are based on activated carbon technology, which reduces moisture vapor transport needed for evaporative cooling and has potential to absorb and concentrate toxic materials. Researchers are exploring classes of sorbent materials that can selectively accumulate and decompose target compounds for potential to enhance protective suits and allow for novel filtration devices. Here, the metal-organic frameworks (MOFs) UiO-66-NH2 and HKUST-1 have been identified as such materials. To better understand how MOFs can perform in future CB protective systems, atomic layer deposition (ALD) and solution deposition were used to modify nonwoven polypropylene and flame-resistant fabrics with HKUST-1 and UiO-66-NH2. Air permeation, water vapor transport, filtration efficiency, and chemical reactivity against chemical agent simulants were assessed in relation to ALD thickness and MOF crystal size. MOF deposition on substrates decreased both air and chemical permeation while increasing filtration efficiency and chemical sorption. Moisture vapor transport was not affected by MOF growth on substrates, which is promising when considering thermal properties of protective garments. Future work should continue to explore how MOF deposition onto fiber and textile substrates impacts transport properties and chemical absorbance.}, number={27}, journal={ACS APPLIED MATERIALS & INTERFACES}, publisher={American Chemical Society (ACS)}, author={Pomerantz, Natalie L. and Anderson, Erin E. and Dugan, Nicholas P. and Hoffman, Nicole F. and Barton, Heather F. and Lee, Dennis T. and Oldham, Christopher J. and Peterson, Gregory W. and Parsons, Gregory N.}, year={2019}, month={Jul}, pages={24683–24690} }
 @article{barton_davis_lee_parsons_2018, title={Solvothermal Synthesis of MIL-96 and UiO-66-NH2 on Atomic Layer Deposited Metal Oxide Coatings on Fiber Mats}, volume={6}, ISSN={["1940-087X"]}, DOI={10.3791/57734}, abstractNote={Metal-organic frameworks (MOFs), which contain reactive metal clusters and organic ligands allowing for large porosities and surface areas, have proven effective in gas adsorption, separations, and catalysis. MOFs are most commonly synthesized as bulk powder, requiring additional processes to adhere them to functional devices and fabrics that risk decreasing the powder porosity and adsorption capacity. Here, we demonstrate a method of first coating fabrics with metal oxide films using atomic layer deposition (ALD). This process creates conformal films of controllable thickness on each fiber, while providing a more reactive surface for MOF nucleation. By submerging the ALD coated fabric in solution during solvothermal MOF synthesis, the MOFs create a conformal, well-adhered coating on the fibers, resulting in a MOF-functionalized fabric, without additional adhesion materials that may block MOF pores and functional sites. Here we demonstrate two solvothermal synthesis methods. First, we form a MIL-96(Al) layer on polypropylene fibers using synthetic conditions that convert the metal oxide to MOF. Using initial inorganic films of varying thicknesses, diffusion of the organic linker into the inorganic allows us to control the extent of MOF loading on the fabric. Second, we perform a solvothermal synthesis of UiO-66-NH2 in which the MOF nucleates on the conformal metal oxide coating on polyamide-6 (PA-6) fibers, thereby producing a uniform and conformal thin film of MOF on the fabric. The resulting materials can be directly incorporated into filter devices or protective clothing and eliminate the maladroit qualities of loose powder.}, number={136}, journal={JOVE-JOURNAL OF VISUALIZED EXPERIMENTS}, author={Barton, Heather F. and Davis, Alexandra K. and Lee, Dennis T. and Parsons, Gregory N.}, year={2018}, month={Jun} }
 @article{daubert_wang_ovental_barton_rajagopalan_augustyn_parsons_2017, title={Intrinsic limitations of atomic layer deposition for pseudocapacitive metal oxides in porous electrochemical capacitor electrodes}, volume={5}, ISSN={["2050-7496"]}, url={https://doi.org/10.1039/C7TA02719B}, DOI={10.1039/c7ta02719b}, abstractNote={By comparing the pseudocapacitive performance of ALD V2O5 in micro-, meso-, and macro-porous carbon electrodes, we describe the fundamental limits to ALD in very fine pores for pseudocapacitive charge storage. Comparing experimental trends with an ALD coating model, we find that the thermal V2O5 ALD process using vanadium triisopropoxide (VTIP) and water is unable to deposit in pores where the pore diameter is below a critical diameter of 13 A. By adding the ALD V2O5 layer onto activated carbon electrodes, we find that the energy storage capacity could be increased by 144% for carbon with micropores and macropores, whereas for carbon black powder containing only macropores (i.e. a low surface area resulting in a relatively small starting capacity) the ALD coating increased the capacity more than 40-fold. To understand the ALD coating limits, the pores of the carbon electrodes were modeled as a series of connected tubes, and the volume of V2O5 deposited determined experimentally was compared to the calculated deposition limit. Pores below this critical diameter were sealed and decreased the accessible volume for V2O5 deposition by more than half, decreasing the maximum capacity. The effect of the pore sealing by the ALD process on the capacitive response of the activated carbon based electrodes was also studied. This work highlights the intrinsic capabilities and limitations of coating microporous materials using ALD.}, number={25}, journal={JOURNAL OF MATERIALS CHEMISTRY A}, publisher={Royal Society of Chemistry (RSC)}, author={Daubert, James S. and Wang, Ruocun and Ovental, Jennifer S. and Barton, Heather F. and Rajagopalan, Ramakrishnan and Augustyn, Veronica and Parsons, Gregory N.}, year={2017}, month={Jul}, pages={13086–13097} }
 @article{tovar_zhao_nunn_barton_peterson_parsons_levan_2016, title={Diffusion of CO2 in Large Crystals of Cu-BTC MOF}, volume={138}, ISSN={["0002-7863"]}, url={http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcAuth=ORCID&SrcApp=OrcidOrg&DestLinkType=FullRecord&DestApp=WOS_CPL&KeyUT=WOS:000383410700007&KeyUID=WOS:000383410700007}, DOI={10.1021/jacs.6b05930}, abstractNote={Carbon dioxide adsorption in metal-organic frameworks has been widely studied for applications in carbon capture and sequestration. A critical component that has been largely overlooked is the measurement of diffusion rates. This paper describes a new reproducible procedure to synthesize millimeter-scale Cu-BTC single crystals using concentrated reactants and an acetic acid modulator. Microscopic images, X-ray diffraction patterns, Brunauer-Emmett-Teller surface areas, and thermogravimetric analysis results all confirm the high quality of these Cu-BTC single crystals. The large crystal size aids in the accurate measurement of micropore diffusion coefficients. Concentration-swing frequency response performed at varying gas-phase concentrations gives diffusion coefficients that show very little dependence on the loading up to pressures of 0.1 bar. The measured micropore diffusion coefficient for CO2 in Cu-BTC is 1.7 × 10(-9) m(2)/s.}, number={36}, journal={JOURNAL OF THE AMERICAN CHEMICAL SOCIETY}, author={Tovar, Trenton M. and Zhao, Junjie and Nunn, William T. and Barton, Heather F. and Peterson, Gregory W. and Parsons, Gregory N. and LeVan, M. Douglas}, year={2016}, month={Sep}, pages={11449–11452} }
 @article{zhao_lee_yaga_hall_barton_woodward_oldham_walls_peterson_parsons_2016, title={Ultra-Fast Degradation of Chemical Warfare Agents Using MOF-Nanofiber Kebabs}, volume={55}, ISSN={["1521-3773"]}, url={http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcAuth=ORCID&SrcApp=OrcidOrg&DestLinkType=FullRecord&DestApp=WOS_CPL&KeyUT=WOS:000385799200053&KeyUID=WOS:000385799200053}, DOI={10.1002/anie.201606656}, abstractNote={The threat associated with chemical warfare agents (CWAs) motivates the development of new materials to provide enhanced protection with a reduced burden. Metal-organic frame-works (MOFs) have recently been shown as highly effective catalysts for detoxifying CWAs, but challenges still remain for integrating MOFs into functional filter media and/or protective garments. Herein, we report a series of MOF-nanofiber kebab structures for fast degradation of CWAs. We found TiO2 coatings deposited via atomic layer deposition (ALD) onto polyamide-6 nanofibers enable the formation of conformal Zr-based MOF thin films including UiO-66, UiO-66-NH2 , and UiO-67. Cross-sectional TEM images show that these MOF crystals nucleate and grow directly on and around the nanofibers, with strong attachment to the substrates. These MOF-functionalized nanofibers exhibit excellent reactivity for detoxifying CWAs. The half-lives of a CWA simulant compound and nerve agent soman (GD) are as short as 7.3 min and 2.3 min, respectively. These results therefore provide the earliest report of MOF-nanofiber textile composites capable of ultra-fast degradation of CWAs.}, number={42}, journal={ANGEWANDTE CHEMIE-INTERNATIONAL EDITION}, author={Zhao, Junjie and Lee, Dennis T. and Yaga, Robert W. and Hall, Morgan G. and Barton, Heather F. and Woodward, Ian R. and Oldham, Christopher J. and Walls, Howard J. and Peterson, Gregory W. and Parsons, Gregory N.}, year={2016}, month={Oct}, pages={13224–13228} }