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1. Designing optimal core–shell MOFs for direct air capture

   https://doi.org/10.1039/D2NR03177A  

   Boone, Paul; He, Yiwen; Lieber, Austin R.; Steckel, Janice A.; Rosi, Nathaniel L.; Hornbostel, Katherine M.; Wilmer, Christopher E. (November 2022, Nanoscale)

   Metal–organic frameworks (MOFs), along with other novel adsorbents, are frequently proposed as candidate materials to selectively adsorb CO 2 for carbon capture processes. However, adsorbents designed to strongly bind CO 2 nearly always bind H 2 O strongly (sometimes even more so). Given that water is present in significant quantities in the inlet streams of most carbon capture processes, a method that avoids H 2 O competition for the CO 2 binding sites would be technologically valuable. In this paper, we consider a novel core–shell MOF design strategy, where a high-CO 2 -capacity MOF “core” is protected from competitive H 2 O-binding via a MOF “shell” that has very slow water diffusion. We consider a high-frequency adsorption/desorption cycle that regenerates the adsorbents before water can pass through the shell and enter the core. To identify optimal core–shell MOF pairs, we use a combination of experimental measurements, computational modeling, and multiphysics modeling. Our library of MOFs is created from two starting MOFs-UiO-66 and UiO-67-augmented with 30 possible functional group variations, yielding 1740 possible core–shell MOF pairs. After defining a performance score to rank these pairs, we identified 10 core–shell MOF candidates that significantly outperform any of the MOFs functioning alone. 

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2. Phosphorus-Functionalized Organic Linkers Promote Polysulfide Retention in MOF-Based Li–S Batteries

   https://doi.org/10.1021/acsaem.2c02925  

   Baumann, Avery E.; Anayah, Rasha I.; Thoi, V. Sara (November 2022, ACS Applied Energy Materials)

   Metal–organic frameworks (MOFs) have been an area of intense research for their high porosity and synthetic tunability, which afford them controllable physical and chemical properties for various applications. In this study, we demonstrate that functionalized MOFs can be used to mitigate the so-called polysulfide shuttle effect in lithium–sulfur batteries, a promising next-generation energy storage device. UiO-66-OH, a zirconium-based MOF with 2-hydroxyterephthalic acid, was functionalized with a phosphorus chloride species that was subsequently used to tether polysulfides. In addition, a molecular chlorophosphorane was synthesized as a model system to elucidate the chemical reactivity of the phosphorus moiety. The functionalized MOFs were then used as a cathode additive in coin cell batteries to inhibit the dissolution of polysulfides in solution. Through this work, we show that the functionalization of MOF with phosphorus enhances polysulfide redox and thereby capacity retention in Li–S batteries. While demonstrated here for polysulfide tethering in batteries, we envision this linker functionalization strategy could be more broadly utilized in separations, sensing, or catalysis applications. 

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3. Tailoring Hydrophobicity and Pore Environment in Physisorbents for Improved Carbon Dioxide Capture under High Humidity

   https://doi.org/10.1021/jacs.3c11671  

   Wang, Xiaoliang; Alzayer, Maytham; Shih, Arthur J; Bose, Saptasree; Xie, Haomiao; Vornholt, Simon M; Malliakas, Christos D; Alhashem, Hussain; Joodaki, Faramarz; Marzouk, Sammer; et al (February 2024, Journal of the American Chemical Society)

   CALF-20, a Zn-triazolate-based metal-organic framework (MOF), is one of the most promising adsorbent materials for CO2 capture. However, competitive adsorption of water severely limits its performance when the relative humidity (RH) exceeds 40%, limiting the potential implementation of CALF-20 in practical settings where CO2 is saturated with moisture, such as post-combustion flue gas. In this work, three newly designed MOFs related to CALF-20, denoted as NU-220, CALF-20M-w, and CALF-20M-e that feature hydrophobic methyl-triazolate linkers are presented. Inclusion of methyl groups in the linker is proposed as a strategy to improve CO2 uptake in the presence of water. Notably, both CALF-20M-w and CALF-20M-e retain over 20% of their initial CO2 capture efficiency at 70% RH – a threshold at which CALF-20 shows negligible CO2 uptake. Grand canonical Monte Carlo (GCMC) simulations reveal that the methyl group hinders water network formation in the pores of CALF-20M-w and CALF-20M-e and enhances their CO2 selectivity over N2 in the presence of high moisture content. Moreover, calculated radial distribution functions indicate that introducing the methyl group into the triazolate linker increases the distance between water molecules and Zn coordination bonds, offering insights into the origin of the enhanced moisture stability observed for CALF-20M-w and CALF-20M-e relative to CALF-20. Overall, this straightforward design strategy has afforded more robust sorbents that can potentially meet the challenge of effectively capturing CO2 in practical industrial applications. 

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4. Halogen bonding in UiO-66 frameworks promotes superior chemical warfare agent simulant degradation

   https://doi.org/10.1039/C9CC00642G  

   Kalaj, Mark; Momeni, Mohammad R.; Bentz, Kyle C.; Barcus, Kyle S.; Palomba, Joseph M.; Paesani, Francesco; Cohen, Seth M. (March 2019, Chemical Communications)

   Herein, a series of halogenated UiO-66 derivatives was synthesized and analyzed for the breakdown of the chemical warfare agent simulant dimethyl-4-nitrophenyl phosphate (DMNP) to analyze ligand effects. UiO-66-I degrades DMNP at a rate four times faster than the most active previously reported MOFs. MOF defects were quantified and ruled out as a cause for increased activity. Theoretical calculations suggest the enhanced activity of UiO-66-I originates from halogen bonding of the iodine atom to the phosphoester linkage allowing for more rapid hydrolysis of the P–O bond. 

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5. 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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