Widespread access to greener energy is required in order to mitigate the effects of climate change. A significant barrier to cleaner natural gas usage lies in the safety/efficiency limitations of storage technology. Despite highly porous metal-organic frameworks (MOFs) demonstrating record-breaking gas-storage capacities, their conventionally powdered morphology renders them non-viable. Traditional powder shaping utilising high pressure or chemical binders collapses porosity or creates low-density structures with reduced volumetric adsorption capacity. Here, we report the engineering of one of the most stable MOFs, Zr-UiO-66, without applying pressure or binders. The process yields centimetre-sized monoliths, displaying high microporosity and bulk density. We report the inclusion of variable, narrow mesopore volumes to the monoliths’ macrostructure and use this to optimise the pore-size distribution for gas uptake. The optimised mixed meso/microporous monoliths demonstrate Type II adsorption isotherms to achieve benchmark volumetric working capacities for methane and carbon dioxide. This represents a critical advance in the design of air-stable, conformed MOFs for commercial gas storage.

Metal-organic frameworks (MOFs) have been evaluated as potential nanocarriers for intra-ocular incorporation of brimonidine tartrate to treat chronic glaucoma. Experimental results show that UiO-67 and MIL-100 (Fe) exhibit the highest loading capacity with values up to 50-60 wt.%, while the performance is quite limited for MOFs with narrow cavities (below 0.8 nm, e.g. UiO-66 and HKUST-1). The large loading capacity in UiO-67 is accompanied by an irreversible structural amorphization in aqueous and physiological media that promotes extended release kinetics above 12 days. Compared to the traditional drawbacks associated with the sudden release of the commercial drugs (e.g., ALPHAGAN), these results anticipate UiO-67 as a potential nanocarrier for drug delivery in intra-ocular therapeutics. These promising results are further supported by cytotoxicity tests using retinal photoreceptor cells (661W). Toxicity of these structures (including the metal nodes and organic ligands) for retinal cells is rather low for all samples evaluated, except for HKUST-1.

Novel MOF-based polymer nanocomposite films were successfully prepared using Zrbased UiO-67 as a metal-organic framework (MOF) and polyurethane (PU) as a polymeric matrix. Synchrotron X-ray powder diffraction (SXRPD) analysis confirms the improved stability of the UiO-67 embedded nanocrystals and scanning electron microscopy images confirm their homogeneous distribution (average crystal size ~ 100-200 nm) within the 50-µm thick film. Accessibility to the inner porous structure of the embedded MOFs was completely suppressed for N2 at cryogenic temperatures.However, ethylene adsorption measurements at 25ºC confirm that at least 45% of the MOF crystals are fully accessible for gas phase adsorption of non-polar molecules.Although this partial blockage limits the adsorption performance of the embedded MOFs for ocular drugs (e.g., brimonidine tartrate) compared to the pure MOF, an almost 60-fold improvement in the adsorption capacity was observed for PU matrix after incorporation of the UiO-67 nanocrystals. UiO-67@PU nanocomposite exhibits a prolonged release of brimonidine (up to 14 days were quantified). Finally, the combined use of SXRPD, thermogravimetric analysis (TGA) and FTIR analysis confirmed the presence of the drug in the nanocomposite film, the stability of the MOF framework and the drug upon loading, and the presence of brimonidine in an amorphous phase once adsorbed. These results open the gate towards the application of these polymeric nanocomposite films for drug delivery in optical therapeutics, either as a component of contact lens, in the composition of lacrimal stoppers (e.g., punctal plugs) or in sub-tenon inserts.

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The pufferfish effect in ZIF-4: synchrotron X-ray powder diffraction studies under operando conditions confirm that ZIF-4 experiences a breathing phenomenon above ∼30 kPa associated with a large expansion in the unit cell volume (∼8–9%). The presence of an expanded-pore (N2) ZIF-4 structure is predicted by molecular simulations.

TThe rapid increase in the concentrations of atmospheric carbon dioxide is one of the most pressing problems facing our planet. This challenge has motivated the development of different strategies not...

Oxygen-enriched boron carbonitrides -known as boron carbon oxinitrides, BCNOshave exhibited remarkable properties with numerous works reporting on their performance as phosphors and some few ones as H 2 -adsorbents. However, the study of BCNOs capability for CO 2 uptaking has yet to be achieved. Herein, we have designed a simple process for preparation of freestanding three-dimensional (3D) BCNO structures via pyrolysis of supramolecular gels formed by H-bonding of melamine, boric acid and glucose. The 3D porous materials obtained by pyrolysis of supramolecular gels containing glucose exhibited a seaweed-like 3D structure formed by BCNO nanocrystals embedded within a carbonaceous matrix with a certain content of amorphous hydrogenated carbon. The particularly narrow porosities exhibited by these samples proved effective for CO 2 adsorption with uptakes of up to ca. 2 mmol/g at 25 °C. More interestingly, those samples prepared with high concentration of glucose behaved as molecular sieves and exhibited an excellent performance for CO 2 -CH 4 separation, especially at low pressures with k H values of up to 1.04•10 3 . M A N U S C R I P T A C C E P T E D ACCEPTED MANUSCRIPT 29 Ma, R.; Bando, Y.; Sato, T.; Kurashima, K. Growth, Morphology, and Structure of Boron Nitride Nanotubes, Chem. Mater. 2001, 13, 2965−2971 30 Zhang, X.; Lu, Z.; Lin, J.; Li, L.; Fan, Y.; Hu, L.; Xu, X.; Meng, F.; Zhao, J.; Tang, C. Luminescence properties of BCNO phosphor prepared by a green and simple method, Mater. Lett. 2013, 194, 72-75 31 Estroff, L. A.; Hamilton, A. D. Water Gelation by Small Organic Molecules, Chem. Rev. 2004, 104, 1201-1217 32 Zhang, S.; Dokko, K.; Watanabe, M. Carbon materialization of ionic liquids: from solvents to materials, Mater. Horiz. 2015, 2, 168-197

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