Binding of carbon dioxide and acetylene to free carboxylic acid sites in a metal-organic framework.

The functionalisation of organic linkers in metal-organic frameworks (MOFs) to improve gas uptake is well-documented. Although the positive role of free carboxylic acid sites in MOFs for binding gas molecules has been proposed in computational studies, relatively little experimental evidence has been reported in support of this. Primarily this is because of the inherent synthetic difficulty to prepare MOF materials bearing free, accessible -COOH moieties which would normally bind to metal ions within the framework structure.

Ultra-thin g-CN/MFM-300(Fe) heterojunctions for photocatalytic aerobic oxidation of benzylic carbon centers.

growth of the metal-organic framework material MFM-300(Fe) on an ultra-thin sheet of graphitic carbon nitride (g-CN) has been achieved exfoliation of bulk carbon nitride using supercritical CO. The resultant hybrid structure, CNNS/MFM-300(Fe), comprising carbon nitride nanosheets (CNNS) and MFM-300(Fe), shows excellent performance towards photocatalytic aerobic oxidation of benzylic C-H groups at room temperature under visible light. The catalytic activity is significantly improved compared to the parent g-CN, MFM-300(Fe) or physical mixtures of both.

Enhanced proton conductivity in a flexible metal-organic framework promoted by single-crystal-to-single-crystal transformation.

MFM-722(Pb)-DMA undergoes a single-crystal-to-single-crystal (SCSC) transformation to give MFM-722(Pb)-H2O via ligand substitution upon exposure to water vapour. In situ single crystal impedance spectroscopy reveals an increase in proton conductivity due to this structural transition, with MFM-722(Pb)-H2O showing a proton conductivity of 6.61 × 10-4 S cm-1 at 50 °C and 98% RH.

Locating the binding domains in a highly selective mixed matrix membrane via synchrotron IR microspectroscopy.

The binding domains within a mixed matrix membrane (MMM) that is selective for CO comprising MFM-300(Al) and the polymer 6FDA-Durene-DABA have been established via in situ synchrotron IR microspectroscopy. The MOF crystals are fully accessible and play a critical role in the binding of CO, creating a selective pathway to promote permeation of CO within and through the MMM. This study reveals directly the molecular mechanism for the overall enhanced performance of this MMM in terms of permeability, solubility and selectivity for CO.

Tailoring porosity and rotational dynamics in a series of octacarboxylate metal-organic frameworks.

Modulation and precise control of porosity of metal-organic frameworks (MOFs) is of critical importance to their materials function. Here we report modulation of porosity for a series of isoreticular octacarboxylate MOFs, denoted MFM-180 to MFM-185, via a strategy of selective elongation of metal-organic cages. Owing to the high ligand connectivity, these MOFs do not show interpenetration, and are robust structures that have permanent porosity.