Controllable surfactant-directed zeolitic-imidazolate-8 growth on swollen 2D zeolites

The authors would like to thank the European Research Council for funding opportunities under Advanced Grant No. 787073. The EPSRC Light Element Analysis Facility under Grant No. EP/T019298/1 and the EPSRC Strategic Equipment Resource under Grant No. EP/R023751/1 are gratefully acknowledged.To meet society’s need for more and more specialized materials, this work focuses on the preparation of porous metal–organic framework (MOF)–zeolite hybrid materials based on two 2D zeolites, namely, IPC-1P (Institute of Physical Chemistry - 1 Precursor) and the metal–organic framework ZIF-8 (Zeolitic Imidazolate Framework-8). Using the previously well-established assembly–disassembly–organization–reassembly method, the zeolite was (i) synthesized, (ii) hydrolyzed to a layered zeolite, (iii) the interlayer distance was increased using the swelling agent cetyltrimethylammonium chloride, and (iv) nanocrystals of ZIF-8 were grown stepwise on the zeolite surface but predominantly at the edges of the crystallites where the openings to the interlayer region are located. This selective MOF growth and attachment was facilitated by a combination of intercalation of the metal ions and the swelling agent between the zeolite layers. The influence of the solvent and the number of additional steps on the ZIF-8 growth on the zeolite was systematically investigated, and the synthesis protocol was successfully adapted to a further two-dimensional silicate RUB-18 (Ruhr-Universität Bochum - 18). This paves the way toward the controlled preparation of more MOF–zeolite hybrid materials, which might provide interesting properties for future applications.Publisher PDFPeer reviewe

Non-ohmic conduction in doped polyacetylene at low temperatures

The electrical conductivity of a iodine-doped polyacetylene is measured as a function of the electric field Escr at temperatures between 4K and 0.3K. We find that after an initial non-linear behavior sgr increases linearly with Escr in agreement with a theoretical description based on variable-range hopping conduction. The non-linear rise at low fields depends on the iodine concentration. In heavily doped samples the increase is small and varies as Escr2, whereas in less conductive samples a large change is observed at 0.3K which varies approximately as log Escr for fields from 1 V/m to 150 V/m

Mixed metal-organic framework mixed-matrix membranes : insights into simultaneous moisture-triggered and catalytic delivery of nitric oxide using cryo-scanning electron microscopy

Funding: This work was supported by the European Research Council grant ADOR (Advanced Grant 787073). The authors acknowledge the EPSRC Light Element Analysis Facility Grant (EP/T019298/1) and the EPSRC Strategic Equipment Resource Grant (EP/R023751/1).The fundamental chemical and structural diversity of metal–organic frameworks (MOFs) is vast, but there is a lack of industrial adoption of these extremely versatile compounds. To bridge the gap between basic research and industry, MOF powders must be formulated into more application-relevant shapes and/or composites. Successful incorporation of varying ratios of two different MOFs, CPO-27-Ni and CuBTTri, in a thin polymer film represents an important step toward the development of mixed MOF mixed-matrix membranes. To gain insight into the distribution of the two different MOFs in the polymer, we report their investigation by Cryo-scanning electron microscopy (Cryo-SEM) tomography, which minimizes surface charging and electron beam-induced damage. Because the MOFs are based on two different metal ions, Ni and Cu, the elemental maps of the MOF composite cross sections clearly identify the size and location of each MOF in the reconstructed 3D model. The tomography run was about six times faster than conventional focused ion beam (FIB)-SEM and the first insights to image segmentation combined with machine learning could be achieved. To verify that the MOF composites combined the benefits of rapid moisture-triggered release of nitric oxide (NO) from CPO-27-Ni with the continuous catalytic generation of NO from CuBTTri, we characterized their ability to deliver NO individually and simultaneously. These MOF composites show great promise to achieve optimal dual NO delivery in real-world medical applications.Publisher PDFPeer reviewe

Origin of the solid-state luminescence of MIL-53(Al) and its connection to the local crystalline structure

Metal-organic frameworks (MOFs) are extensively studied due to their unique surface properties, enabling many intriguing applications. Breathing MOFs, a subclass of MOFs, have gained recent interest for their ability to undergo structural changes based on factors like temperature, pressure, adsorbed molecules. Certain MOFs also exhibit remarkable optical properties useful for applications such as sensors, light-emitting diodes, and scintillators. The most promising MOFs possess high porosity, breathing properties, and photoluminescence activities, allowing for improved device responsiveness and selectivity. Understanding the relationship between crystal structures and photoluminescence properties is crucial in these cases. As studies on this topic are still very limited, we report for the first time an exhaustive study on the solid-state luminescence of the breathing MOF MIL-53(Al), that can stabilize in three different crystalline structures: open-pore, hydrated narrow-pore and closed-pore. We unveil a fascinating solid-state luminescence spectrum, comprising three partially overlapping bands, and elucidate the intricate electronic transitions within each band as well as their intimate correlation with the local crystalline structures. Our characterizations of spectroscopic properties and decay times provide a deeper understanding of the luminescent behaviour of MIL-53(Al) and demonstrate that is possible to identify present crystalline structures by optical measurements or to modify the optical properties inducing structural transitions for this type of materials. These insights could help to design next-generation, selective sensors or smart light emitting devices

In situ single-crystal X-ray diffraction studies of physisorption and chemisorption of SO2 within a metal-organic framework and its competitive adsorption with water

Funding: The authors are also grateful for financial assistancefrom the ERC under advanced grant 787073, the EPSRC for a studentship (EP/N509759/1) and support via the Collaborative Computational Projecton NMR Crystallography CCP-NC (EP/T02662/1), and the CRITICAT Centre for Doctoral Training (EP/L016419/1).Living on an increasingly polluted planet, the removal of toxic pollutants such as sulfur dioxide (SO2) from the troposphere and power station flue gas is becoming more and more important. The CPO-27/MOF-74 family of metal–organic frameworks (MOFs) with their high densities of open metal sites is well suited for the selective adsorption of gases that, like SO2, bind well to metals and have been extensively researched both practically and through computer simulations. However, until now, focus has centered upon the binding of SO2 to the open metal sites in this MOF (called chemisorption, where the adsorbent–adsorbate interaction is through a chemical bond). The possibility of physisorption (where the adsorbent–adsorbate interaction is only through weak intermolecular forces) has not been identified experimentally. This work presents an in situ single-crystal X-ray diffraction (scXRD) study that identifies discrete adsorption sites within Ni-MOF-74/Ni-CPO-27, where SO2 is both chemisorbed and physisorbed while also probing competitive adsorption of SO2 of these sites when water is present. Further features of this site have been confirmed by variable SO2 pressure scXRD studies, DFT calculations, and IR studies.Publisher PDFPeer reviewe

Feminist geographies of digital work

Feminist thought challenges essentialist and normative categorizations of ‘work’. Therefore, feminism provides a critical lens on ‘working space’ as a theoretical and empirical focus for digital geographies. Digital technologies extend and intensify working activity, rendering the boundaries of the workplace emergent. Such emergence heightens the ambivalence of working experience: the possibilities for affirmation and/or negation through work. A digital geography is put forward through feminist theorizations of the ambivalence of intimacy. The emergent properties of working with digital technologies create space through the intimacies of postwork places where bodies and machines feel the possibilities of being ‘at’ work

The global subject of precarity

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