Missing linker defects form carbonates. After combined 13CO2 adsorption + NMR experiments, new signals appeared in the 13C-MAS NMR 😮. Now, we have a cool new tool to identify and quantify defects in ZIFs and their melt quenched glasses!
Congratulations to Ayisha from the Team of @knebelalexander.bsky.social
On her paper out in Advanced Functional Materials! Nominally "non-porous" MIL-116(Ga) can be used for Helium Upgrading! Glad we could help! advanced.onlinelibrary.wiley.com/doi/10.1002/...
The membrane is an essential part in Zn/Br2 Redox Flow Batteries! In this collaboration with Sangaraju Shanmugams team from DGIST we demonstrate that Cationic COFs can be integrated into Nafion-Membranes allowing bi-ionic transport in RFBs! Now in Small!
onlinelibrary.wiley.com/doi/10.1002/...
Take a look at Albrechts work in @chemsci.bsky.social @royalsocietypublishing.org A series of electron deficient vinylene-linked COFs was prepared and used to host sulfur in cathodes for LiS 🔋 Financed by CRC-1415 @dfg.de pubs.rsc.org/en/content/a...
Tobias uncovered this behavior at the same time when we also discovered the reactivity of ZIF glasses towards CO2, previously published in Chemistry of Materials @acs.org pubs.acs.org/doi/full/10....
Beware of the defects in ZIFs and their glasses ⚠️ With @henkegroup.bsky.social
and the Brunner group @tudresden.bsky.social by NMR we observed that dangling linker imidazoles react with CO2 to form carbamates during adsorption studies - now in Chem. Mater. @acs.org !
pubs.acs.org/doi/10.1021/...
Now in Inorganic Chemistry @acs.org 📄! Collaboration with Nick and Liam from SSRL ⚠️ Treating of Mg(BH4)2 with liquid ammonia yields the hexammine (NH3)6Mg(BH4)2 whose structure was solved🔎 using radiation from SLAC. Congrats to the team NREL, @sandialabs.bsky.social ! pubs.acs.org/doi/10.1021/...
Now in @chemcomm.rsc.org - the Xenon induced phase transition in ZIF-4 uncovered by solid state NMR during 129Xe adsorption. Congratulations to Tobias from the Brunner group @tudresden.bsky.social and @henkegroup.bsky.social, @wenlong-xue.bsky.social !
pubs.rsc.org/en/content/a...
Square-triangle tilings could be an infinite topological playground for 2D COFs, but they require precise linker size matching to work. Here we present a system, where we see evidence of linker mixing and heteroepitaxy due to size matching.
New paper just out @jacs.acspublications.org In his 3rd first-author paper from his PhD, Wen-Long Xue shows that mechanochemical synthesis enables melting & glass formation of a Cd-based MOF, plus controlled nanocrystal growth to form MOF glass-ceramics. A great team effort!
doi.org/10.1021/jacs...
In situ 129Xe NMR spectroscopy reveals an unexpected, xenon adsorption-induced flexibility of ZIF-4. Beyond a certain threshold pressure, xenon induces a structural transition at low temperature. This...
Metal-organic frameworks (MOFs) are versatile materials with tunable properties and broad applications. Here, we report the first cadmium-based zeolitic imidazolate framework (ZIF) glass, prepared by melt-quenching sub-micrometer-sized Cd(im)2 particles (im– = imidazolate) obtained via mechanochemical synthesis. This route increases defect density and reduces crystallite domain size, lowering the melting temperature from 461 °C (for larger solution-synthesized microcrystals) to 455 °C, thereby mitigating thermal decomposition during melting. Crystalline Cd(im)2 adopts a two-fold interpenetrated diamondoid (dia-c) topology, assembled from tetrahedral Cd2+ centers and im– linkers. Rapid cooling of the Cd(im)2 melt yields a monolithic glass with a glass transition temperature (Tg) of 175 °C. Structural analysis confirms that short-range connectivity within individual networks is maintained, whereas interactions between the interpenetrated networks are disrupted in the glass. Upon reheating, partial recrystallization produces a single-component glass–ceramic with enhanced mechanical properties, an unprecedented behavior in melt-quenched ZIF glasses. Investigations of thermal parameters (cooling rates) and partial linker substitution reveal strategies for tuning the phase behavior of both glass and glass–ceramic. These findings extend ZIF glass systems to second-row transition metal ions and underscore mechanochemical synthesis as a tool for tailoring the thermal properties of MOFs. This dual-phase functionality, combining glassy and crystalline domains of identical composition within a single material, offers potential for applications in thermal energy storage, phase change memory, and optics.
