A continuous flow process for the synthesis of a metal-organic framework using only water as the reaction medium and requiring only short residence times is described. This affords a new route to scale-up of materials incorporating many of the principles of green chemistry.The process is demonstrated by the synthesis MIL-53(Al) via continuous flow reaction requiring only 5-6 minutes with a space time yield of 1300 kg m -3 d -1 . We have demonstrated the synthesis of 500 g of MIL-53(Al) using this process, which can be scaled-up further by simply feeding further solutions of metal salt and ligand through the reactor. The product has a higher surface area and a better colour than a commercially produced sample of this MOF.In addition, a new and effective method for the extraction of terephthalic acid from within the pores of MIL-53(Al) using supercritical ethanol has been developed, representing a new methodology for activation and removal of substrates from porous hosts.___________________________________________________________________________

Structural characterisation of individual molecules by high‐resolution transmission electron microscopy (HRTEM) is fundamentally limited by the element and electron energy‐specific interactions of the material with the high energy electron beam. Here, the key mechanisms controlling the interactions between the e‐beam and C–H bonds, present in all organic molecules, are examined, and the low atomic weight of hydrogen—resulting in its facile atomic displacement by the e‐beam—is identified as the principal cause of the instability of individual organic molecules. It is demonstrated theoretically and proven experimentally that exchanging all hydrogen atoms within molecules with the deuterium isotope, and therefore doubling the atomic weight of the lightest atoms in the structure, leads to a more than two‐fold increase in the stability of organic molecules in the e‐beam. Substitution of H for D significantly reduces the amount of kinetic energy transferred from the e‐beam to the atom (main factor contributing to stability) and also increases the barrier for bond dissociation, primarily due to the changes in the zero‐point energy of the C–D vibration (minor factor). The extended lifetime of coronene‐d12, used as a model molecule, enables more precise analysis of the inter‐molecular spacing and more accurate measurement of the molecular orientations.

The microporous metal-organic framework {[Zn 2 (L)]•(H 2 O) 3 } • (H 4 L = 1,2,4,5-tetrakis(4-carboxyphenyl)benzene) has been synthesised using near-critical water (300 • C) as a cleaner alternative to toxic organic solvents. A single crystal X-ray structure determination confirms that the complex incorporates tetrahedral Zn(II) centres bridged through the carboxylate anions to form a binuclear building block, which extends into a one dimensional chain along the c axis. Four L 4ligands bind to each Zn(II) centre and cross-link the one dimensional chains along both a and b axes to afford a three dimensional network structure incorporating pores of ca. 4.3 A ˚in diameter. The complex shows high thermal stability up to 425 • C by gravimetric thermal analysis, and on desolvation, displays a high adsorption enthalpy of 11.0 kJ mol -1 for H 2 uptake at zero coverage, consistent with the narrow pore diameter for the framework.

The hydrothermal deposition of CrO(OH) from aqueous chromium(III) chloride, nitrate, and perchlorate, and of Cr3(SO4)2(OH)5•H2O and Cr(OH)SO4•2H2O(?) from aqueous chromium(III) sulfate, has been investigated. Aqueous chromium(III) is oxidized to chromium(VI) by 0.4 M perchloric acid above 225 °C, and by molecular oxygen above 250 °C. Aqueous chromium(III) can react at 300 °C with iron or steel, cobalt, and copper to produce FeCr2O4, CoCr2O4, and Cu2Cr2O4, respectively. CrO(OH) reacts with type 316 stainless steel at 440 °C in supercritical water of density 0.7 g cm−3 to yield (Fe,Ni)-Cr2O4, which is the "cubic Cr2O3" of Laubengayer and McCune. The spinels MCr2O4 (M = Mg, Mn, Fe, Co) can be made hydrothermally at ca. 300 °C from Cr(OH)3 and M(OH)2. This information is relevant to corrosion phenomena, and the possible hydrothermal origin of chromite deposits in serpentinized rocks.

NH2-MIL-53(Al) exhibited a considerable stronger affinity to water than MIL-53(Al). Thus, the hydrophobicity (shown by in situ FTIR) of the pores within MIL-53(Al) enhanced the CO2 adsorption.