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1. Membrane-supported metal organic framework based nanopacked bed for protection against toxic vapors and gases

   https://doi.org/https://doi.org/10.1016/j.seppur.2020.117406  

   Song, Yufeng ; Chau, John ; Sirkar, Kamalesh K. ; Peterson, Gregory W. ; Beuscher, Uwe ( July 2020 , Separation and purification technology)

   null (Ed.)

   Defense against small molecule toxic gases is an important aspect of protection against chemical and biological threat as well as chemical releases from industrial accidents. Current protective respirators/garments cannot effectively block small molecule toxic gases and vapors and retain moisture transmission capability without a heavy burden. Here, we developed a nanopacked bed of nanoparticles of UiO-66-NH₂ metal organic framework (MOF) by synthesizing them in the pores of microporous expanded polytetrafluoroethylene (ePTFE) membranes. The submicron scale size of membrane pores ensures a large surface area of MOF nanoparticles which can capture/adsorb and react with toxic gas molecules efficiently. It was demonstrated that the microporous ePTFE membrane with UiO-66-NH₂ MOF grown inside and around the membrane can defend against ammonia for a significant length of time while allowing passage of moisture and nitrogen. It was also demonstrated that the MOF-loaded ePTFE membrane could provide significant protection from Cl₂ intrusion as well as intrusion from 2-chloroethyl ethyl sulfide (CEES) (a simulant for sulfur mustard). Such MOF-filled membranes exhausted by NH₃ breakthrough experiments were regenerated conveniently by heating at 60 °C for one week under vacuum for further/repeated use; a single regenerated membrane could block NH₃ for 200–300 min. The moisture permeability of such a membrane/nanopacked bed was considerably above the breathability threshold value of 2000 g/m² -day. The results suggest that microporous membranes filled with reactive MOF nanoparticles could be designed as protective barriers against toxic gases/vapors, e.g., NH₃ and Cl₂ and yet be substantially permeable to H₂O and air. 

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2. Self‐Diffusion of a Chemical Warfare Agent Simulant and Water in Nafion by Pulsed Field Gradient NMR 

   https://doi.org/10.1002/cite.202300010  

   Trusty, Blake ; Fang, Junchuan ; Angelopoulos, Anastasios ; Vasenkov, Sergey ( July 2023 , Chemie Ingenieur Technik)

   Pulsed field gradient (PFG) NMR at high magnetic field was used to study microscopic diffusion of dimethyl methyl phosphonate (DMMP), a common chemical warfare agent (CWA) simulant, and water in Nafion membranes. PFG NMR measurements were performed for a broad range of molecular displacements. The self‐diffusivities were measured as a function of the DMMP concentration for several fixed water concentrations. The measured data suggest that DMMP and water diffuse in different regions of Nafion. While water mostly diffuses in hydrophilic regions of the membrane, viz. water channels, DMMP diffusion is mostly limited to interfacial perfluoroether regions between these water channels and the semi‐crystalline matrix.

    

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3. Etching and acidifying graphene oxide membranes to increase gas permeance while retaining molecular sieving ability

   https://doi.org/10.1002/aic.17022  

   Huang, Liang ; Jia, Weiguang ; Lin, Haiqing ( August 2020 , AIChE Journal)

   Graphene oxide (GO) nanosheets stacked in parallel with subnanometer channels can exhibit an excellent size‐sieving ability for membrane‐based gas separation. However, gas molecules have to diffuse through the tortuous nanochannels, leading to low permeability. Herein we demonstrate two versatile approaches to modify the GO (before membrane fabrication by vacuum‐filtration) to collectively increase gas permeability, etching using hydrogen peroxide to generate in‐plane nanopores and acidifying using hydrochloric acid. For example, a membrane prepared at a pH of 5.0 using the 4‐h‐etched GO (HGO‐4h) shows He permeability of 5.3 Barrer and He/CH₄selectivity of 800, which are 5 times and 1.5 times those of the GO membranes, respectively. Decreasing the pH from 5.0 to 2.0 for HGO‐4h enhances He permeability to 57 Barrer and He/CH₄selectivity to 1,800. The HGO‐4h prepared at the pH of 2.0 exhibits separation properties of H₂/CO₂, H₂/N₂, He/N₂, and He/CH₄surpassing their corresponding upper bounds.

    

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4. Structure and dynamics of lipid membranes interacting with antivirulence end-phosphorylated polyethylene glycol block copolymers

   https://doi.org/10.1039/C9SM01642B  

   Yu, Jing ; Mao, Jun ; Nagao, Michihiro ; Bu, Wei ; Lin, Binhua ; Hong, Kunlun ; Jiang, Zhang ; Liu, Yun ; Qian, Shuo ; Tirrell, Matthew ; et al ( January 2020 , Soft Matter)

   The structure and dynamics of lipid membranes in the presence of extracellular macromolecules are critical for cell membrane functions and many pharmaceutical applications. The pathogen virulence-suppressing end-phosphorylated polyethylene glycol (PEG) triblock copolymer ( Pi-ABAPEG ) markedly changes the interactions with lipid vesicle membranes and prevents PEG-induced vesicle phase separation in contrast to the unphosphorylated copolymer ( ABAPEG ). Pi-ABAPEG weakly absorbs on the surface of lipid vesicle membranes and slightly changes the structure of 1,2-dimyristoyl- sn-glycero -3-phosphocholine ( DMPC ) unilamellar vesicles at 37 °C, as evidenced by small angle neutron scattering. X-ray reflectivity measurements confirm the weak adsorption of Pi-ABAPEG on DMPC monolayer, resulting in a more compact DMPC monolayer structure. Neutron spin-echo results show that the adsorption of Pi-ABAPEG on DMPC vesicle membranes increases the membrane bending modulus κ . 

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5. Carbon Molecular Sieve-derived POC/Mixed-Matrix Membranes for Gas Separation

   kowey, Isha ; Rownaghi, Ali ( May 2023 , North American Membrane Society 2023)

   Membrane-based separations offer the potential for the lowest energy demand requirements of all separation options. Among all nanoporous membranes, the carbon molecular sieves (CMS), metal-organic frameworks (MOFs), and mixed-matrix membranes (MMMs) with angstrom level molecular discrimination properties makes them appealing for separating a wide spectrum of gas-pairs. Here we present results of gas selectivity and diffusion of different gases (C2H6, C2H4, C3H8, C3H6, H2, N2, CO2, and CH4) in porous organic cages (POCs) incorporated into fluorinated copolyimides polymers (FCPs). The FCPs were synthesized by the iridization reaction of fluorinated dianhydrides, nonfluorinated dianhydride, and nonfluorinated diamine. Asymmetric hollow fiber membranes formed by the dry-jet/wet-quench spinning process. Once fresh FCP fibers were synthesized, they were crosslinked with POCs, vacuum dried at 90 °C. We investigated the uptake, gas selectivity and diffusion of different gases (C2H6, C2H4, C3H8, C3H6, H2, N2, CO2, and CH4) over synthesized POC-mixed matrixed membranes (POC-MMM) at 25 °C and pressures up to 1 bar. At 1 bar and 25 °C, C2H6, C2H4, C3H8, C3H6 adsorption capacities reached to 42.61, 2.56, 2.77 and 2.65 mmol/g over POC-MMM, respectively, while CO2, CH4, CO, N2 and H2 adsorption capacities of 1.48, 0.84, 0.33, 0.11, and 0.068 mmol/g, respectively. Furthermore, stable CMS membrane were formed by pyrolysis of POC-MMMs under an inert argon atmosphere at 1 atm. To test the gas transport properties of CMS-derived POC/MMM, a lab-scale hollow fiber module with two-five fibers was constructed. The results of longer-term operation of synthesized CMS membrane that was continuously operated for 264 h (10 days) with an equimolar binary H2/CO2, CH4/CO2 and C3H6/C3H8 feed at 25°C and 1 bar feed pressure. The modification yielded promising results in the reduction of physical aging of CMS membranes. 

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