Aqueous Flow Reactor and Vapour-Assisted Synthesis of Aluminium Dicarboxylate Metal-Organic Frameworks with Tuneable Water Sorption Properties.

Energy-efficient indoors temperature and humidity control can be realised by using the reversible adsorption and desorption of water in porous materials. Stable microporous aluminium-based metal-organic frameworks (MOFs) present promising water sorption properties for this goal. The development of synthesis routes that make use of available and affordable building blocks and avoid the use of organic solvents is crucial to advance this field.

Control of Metal-Organic Framework Crystallization by Metastable Intermediate Pre-equilibrium Species.

There is an increasing amount of interest in metal-organic frameworks (MOFs) for a variety of applications, from gas sensing and separations to electronics and catalysis. However, the mechanisms by which they crystallize remain poorly understood. Herein, an important new insight into MOF formation is reported.

Probing the Evolution of Palladium Species in Pd@MOF Catalysts during the Heck Coupling Reaction: An Operando X-ray Absorption Spectroscopy Study.

The mechanism of the Heck C-C coupling reaction catalyzed by Pd@MOFs has been investigated using operando X-ray absorption spectroscopy (XAS) and powder X-ray diffraction (PXRD) combined with transmission electron microscopy (TEM) analysis and nuclear magnetic resonance (H NMR) kinetic studies. A custom-made reaction cell was used, allowing operando PXRD and XAS data collection using high-energy synchrotron radiation. By analyzing the XAS data in combination with ex situ studies, the evolution of the palladium species is followed from the as-synthesized to its deactivated form.

Green Synthesis of a New Al-MOF Based on the Aliphatic Linker Mesaconic Acid: Structure, Properties and In Situ Crystallisation Studies of Al-MIL-68-Mes.

A new aluminium metal-organic framework (MOF), based on the short aliphatic linker molecule mesaconic acid (H Mes; methylfumaric acid) is reported. Al-MIL-68-Mes with composition [Al(OH)(O C-C H -CO )]⋅n H O is obtained after short reaction times of 45 minutes under mild, aqueous synthesis conditions (95 °C). It exhibits a kagome-like framework structure with large hexagonal, and small trigonal channels (diameters of ≈6 and ≈2 Å, respectively) and a specific surface area of S ≈1040 m  g (V =0.

Green synthesis of a new layered aluminium citraconate: crystal structures, intercalation behaviour towards HO and in situ PXRD studies of its crystallisation.

A new Al-based layered MOF [Al(OH)(OC-CH-CO)]·nHO denoted as CAU-15-Cit was synthesised under mild aqueous conditions. It exhibits a layered structure incorporating infinite chains of edge-sharing AlO polyhedra being interconnected by citraconate anions to arrange into layers, which are stacked in an AAA fashion (citraconic acid = methylmaleic acid = HCit, HOC-CH-COH). The crystal structures of the hydrated and dehydrated MOF were determined ab initio from powder X-ray diffraction (PXRD) data.

Combined in- and ex situ studies of pyrazine adsorption into the aliphatic MOF Al-CAU-13: structures, dynamics and correlations.

The intercalation of different pyrazines (pyrazine, methylpyrazine, 2,5-dimethylpyrazine, 2,3-dimethylpyrazine, trimethylpyrazine and tetramethylpyrazine) into the trans-1,4-cyclohexanedicarboxylate (CDC) based Al-MOF [Al(OH)(CDC)], denoted as CAU-13, was investigated. The adsorption of the guest molecules into the flexible MOF was carried out from an aqueous solution or via vapour phase adsorption, starting with the hydrated narrow-pore form of the framework [Al(OH)(OC-CH-CO)]·HO (CAU-13-np). The obtained host-guest systems were characterised by thermogravimetry and vibrational spectroscopy and their crystal structures were elucidated using powder X-ray diffraction (PXRD) data.