Selective CO₂ capture in metal-organic frameworks with azine-functionalized pores generated by mechanosynthesis

Two new three-dimensional porous Zn(II)-based metal-organic frameworks, containing azine-functionalized pores, have been readily and quickly isolated via mechanosynthesis, by using a nonlinear dicarboxylate and linear N-donor ligands. The use of nonfunctionalized and methyl-functionalized N-donor ligands has led to the formation of frameworks with different topologies and metal-ligand connectivities and therefore different pore sizes and accessible volumes. Despite this, both metal-organic frameworks (MOFs) possess comparable BET surface areas and CO₂ uptakes at 273 and 298 K at 1 bar. The network with narrow and interconnected pores in three dimensions shows greater affinity for CO compared to the network with one-dimensional and relatively large pores-attributable to the more effective interactions with the azine groups

A robust binary supramolecular organic framework (SOF) with high CO2 adsorption and selectivity

A robust binary hydrogen-bonded supramolecular organic framework (SOF-7) has been synthesized by solvothermal reaction of 1,4-bis-(4-(3,5-dicyano-2,6 dipyridyl)dihydropyridyl)benzene (1) and 5,5’-bis-(azanediyl)-oxalyl-diisophthalic acid (2). Single crystal X-ray diffraction analysis shows that SOF-7 comprises 2 and 1,4-bis-(4-(3,5-dicyano-2,6-dipyridyl)pyridyl)benzene (3), the latter formed in situ from the oxidative dehydrogenation of 1. SOF-7 shows a three-dimensional four-fold interpenetrat-ed structure with complementary O−H···N hydrogen bonds to form channels that are decorated with cyano- and amide-groups. SOF-7 exhibits excellent thermal stability and sol-vent and moisture durability, as well as permanent porosity. The activated desolvated material SOF-7a shows high CO2 sorption capacity and selectivity compared with other po-rous organic materials assembled solely through hydrogen bonding

A spray-drying strategy for synthesis of nanoscale metal-organic frameworks and their assembly into hollow superstructures

Metal-organic frameworks (MOFs) are among the most attractive porous materials known today. Their miniaturization to the nanoscale-into nanoMOFs-is expected to serve myriad applications from drug delivery to membranes, to open up novel avenues to more traditional storage and catalysis applications, and to enable the creation of sophisticated superstructures. Here, we report the use of spray-drying as a versatile methodology to assemble nanoMOFs, yielding spherical hollow superstructures with diameters smaller than 5 μm. This strategy conceptually mimics the emulsions used by chemists to confine the synthesis of materials, but does not require secondary immiscible solvents or surfactants. We demonstrate that the resulting spherical, hollow superstructures can be processed into stable colloids, whose disassembly by sonication affords discrete, homogeneous nanoMOFs. This spray-drying strategy enables the construction of multicomponent MOF superstructures, and the encapsulation of guest species within these superstructures. We anticipate that this will provide new routes to capsules, reactors and composite materials. © 2013 Macmillan Publishers Limited. All rights reserved.I.I. and M.C.S. thank MICINN and ICN for a Ramón y Cajal grant and a research contract, respectively. A.C. thanks the Generalitat de Catalunya for a FI fellowship.Peer Reviewe

The Essential Work of Fracture (EWF) method – Analyzing the Post-Yielding Fracture Mechanics of polymers

The Post-Yielding Fracture Mechanics describe the fracture behaviour of pre-cracked films and thin sheets that show yielding phenomenon at the crack tip during fracture. The Essential Work of Fracture method (EWF) has been used for this type of fracture characterization, determining two parameters: the specific work of fracture, we related with the real fracture process area, and the specific non-essential work of fracture, wp that corresponds with the work done in the outer region of the crack tip. The EWF technique has been successfully employed especially with polymers, allowing the study of the influence of many variables in fracture properties, unavailable using other techniques such us KIC or JIC determination. In this work, the fundamentals of the technique and examples of application are reviewed, presenting a brief summary of the most relevant contributions of our group to the EWF method

Layered transition metal carboxylates: synthesis, structural aspects and observation of multi-step magnetic transition through phase diagram

Two new layered transition metal carboxylate frameworks, [Co-3(L)(2)(H2O)(6)]center dot 2H(2)O (1) and [Ni-3(L)(2)(H2O)(6)]center dot 2H(2)O (2) (L = tartronate anion or hydroxymalonic acid), have been synthesized and characterized by X-ray single crystal analysis. Both compounds have similar 2D structures. In both compounds there are two types of metal centers where one center is doubly bridged by the alkoxy oxygen atoms through mu(2)-O bridging to form a 1D infinite chain parallel to the crystallographic b-axis with the corners shared between the metal polyhedra. Magnetic susceptibility measurements revealed the existence of antiferromagnetic short range correlations between Co(Ni) intra-chain metal centers (with exchange constants J(Co) = -22.6 and J(Ni) = -35.4 K). At low temperatures, long range order is observed in both compounds at Neel temperatures of 11 (for 1) and 16 (for 2) K, revealing that other exchange interactions, rather than the intra-chain ones, play a role in these systems. Whereas compound 1 has an antiferromagnetic ground state, compound 2 exhibits a ferromagnetic component, probably due to spin canting. Isothermal magnetization data unveiled a rich phase diagram with three metamagnetic phase transitions below 8 K in compound 1