@article{morgan_rivera_willis_peterson_mahle_mundy_parsons_2023, title={Factors and Limitations of Green, Rapid Metal-Organic Framework-Fabric Synthesis and Effects on Dual Chemical Warfare Agent Protection}, volume={7}, ISSN={["1520-5045"]}, url={https://doi.org/10.1021/acs.iecr.3c01282}, DOI={10.1021/acs.iecr.3c01282}, abstractNote={Metal–organic framework (MOF) fabric composites integrate important MOF chemistry with flexible, strong fabric substrates and are useful in many applications ranging from sensing, biomedical, and filtration to catalysis. Sorption-vapor synthesis (SVS) is a recently introduced method for MOF-fabric synthesis that allows high yields and rapid reactions and is scalable. However, little is known about the effects and limitations of process parameters on the final MOF-fabric properties and performance. This work investigates process parameter–MOF property–MOF performance relationships for UiO-66-NH2 fabric composites made using a rapid, benign SVS approach and is tested for toxic chemical vapor protection applications. Repeating SVS synthesis, ∼70 min per cycle, on the same fabric substrate led to an increase in MOF loading of 0.13 gMOF/gfiber per cycle and significant change in crystal morphology. It was determined that precursor concentrations >130 mM in the starting solution resulted in nonporous, amorphous MOF formation. The benign SVS method reported here achieved >95% heterogeneous MOF yield determined through scalability experiments. The MOF-fabrics were tested for organophosphate hydrolysis and permeation of both organophosphate and vesicant toxic vapors. It was found that the number of SVS cycles used to make a MOF-fabric significantly impacted performance, and despite having increased porous MOF loading, increasing over three SVS cycles led to reduced organophosphate hydrolysis rates and protection times. This work not only presents insights into the effect of synthesis process parameters on final MOF-fabric properties but also relates those changes to performance in dual toxic vapor protection applications.}, journal={INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH}, author={Morgan, Sarah E. E. and Rivera, Carwynn D. D. and Willis, Morgan L. L. and Peterson, Gregory W. W. and Mahle, John J. J. and Mundy, Laura and Parsons, Gregory N. N.}, year={2023}, month={Jul} }
 @article{morgan_willis_peterson_mahle_parsons_2022, title={Green MOF-Fabrics: Benign, Scalable Sorption-Vapor Synthesis of Catalytic Composites to Protect against Phosphorus-Based Toxins}, volume={10}, ISSN={["2168-0485"]}, url={https://doi.org/10.1021/acssuschemeng.1c07512}, DOI={10.1021/acssuschemeng.1c07512}, abstractNote={Metal–organic framework (MOF)-fabric composites are important for coupling wide-ranging MOF chemistry with portable, flexible substrates; however, synthesis methods reported to date rely on harmful solvents and typically use batch, solution-based processing. Here, using only ethanol, water, acetic acid, and γ-valerolactone solvents, we show facile synthesis of MOF-fabric composites using a scalable, sorption-vapor approach. UiO-66-NH2 was integrated onto spandex, polyethylene terephthalate, cotton, nyco, and polypropylene fabrics. MOF-fabrics made with green solvents had higher MOF loading, Brunauer–Emmett–Teller (BET) surface area, and superior performance for pesticide paraoxon-methyl hydrolysis than corresponding composites made with dimethylformamide (DMF). MOF loading, BET surface area, and performance increased with consecutive coatings of UiO-66-NH2. Process scalability was confirmed by coating 40 in.2 of fabric using only 20 mL of precursor solution, resulting in 76% total MOF heterogeneous yield. Moreover, spandex@UiO-66-NH2 composites made using benign methods outperformed those made with DMF in solid-state hydrolysis of the chemical warfare agent soman. Hong Kong University of Science and Technology (HKUST-1) and MOF-808 composites were also explored.}, number={8}, journal={ACS SUSTAINABLE CHEMISTRY & ENGINEERING}, publisher={American Chemical Society (ACS)}, author={Morgan, Sarah E. and Willis, Morgan L. and Peterson, Gregory W. and Mahle, John J. and Parsons, Gregory N.}, year={2022}, month={Feb}, pages={2699–2707} }
 @article{morgan_willis_dianat_peterson_mahle_parsons_2022, title={Toxin-Blocking Textiles: Rapid, Benign, Roll-to-Roll Production of Robust MOF-Fabric Composites for Organophosphate Separation and Hydrolysis}, volume={11}, ISSN={["1864-564X"]}, url={https://doi.org/10.1002/cssc.202201744}, DOI={10.1002/cssc.202201744}, abstractNote={Abstract Current approaches to create zirconium‐based metal–organic framework (MOF) fabric composites for catalysis, water purification, wound healing, gas sorption, and other applications often rely on toxic solvents, long reaction/post processing times, and batch methods hindering process scalability. Here, a novel mechanism was reported for rapid UiO‐66‐NH2 synthesis in common low‐boiling‐point solvents (water, ethanol, and acetic acid) and revealed acid–base chemistry promoting full linker dissolution and vapor‐based crystallization. The mechanism enabled scalable roll‐to‐roll production of mechanically resilient UiO‐66‐NH2 fabrics with superior chemical protective capability. Solvent choice and segregated spray delivery of organic linker and metal salt MOF precursor solutions allowed for rapid MOF nucleation on the fiber surface and decreased the energy and time needed for post‐processing, producing an activated composite in less than 165 min, far outpacing conventional MOF‐fabric synthesis approaches. The MOF‐fabric hydrolyzed and blocked permeation of the chemical warfare agent soman, outperforming the protection‐standard activated carbon cloth. This work presents both chemical insights into Zr‐MOF powder and fabric composite formation by a rapid, industrially relevant approach and demonstrates its practicality and affordability for high‐performing personal protective equipment.}, journal={CHEMSUSCHEM}, author={Morgan, Sarah E. E. and Willis, Morgan L. L. and Dianat, Golnaz and Peterson, Gregory W. W. and Mahle, John J. J. and Parsons, Gregory N. N.}, year={2022}, month={Nov} }