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A new series of alkaline-earth-metal based coordination polymers were synthesized by using a pyrazine-2,5-dicarboxylic acid (2,5-H2pzdc) ligand under hydrothermal conditions. These compounds show a variety of structural topologies, reflecting the variable coordination geometries of the alkaline-earth ions as well as the key role of the metal precursor salts. Ca, Sr, and Ba give porous three-dimensional compounds, namely [Ca(2,5-pzdc)(H2O)2]·H2O (1), [Sr(2,5-pzdc)(H2O)4]·H2O (3), [Ba(2,5-pzdc)(H2O)4]·2H2O (4) and [Ba(2,5pzdc)(H2O)2] (5), that feature one-dimensional hydrophilic channels which are filled with water molecules. The Sr compound retains its structure when the lattice water molecules are removed, while the other compounds undergo a structural rearrangement. The hydrophilicity of the Sr compound combined with its high stability even in the absence of guest molecules are the key characteristics that determine its good water adsorption and proton conductivity properties.

We present a new coordination polymer, {[VO(pzdc)(H2O)2] H2O}n, built from vanadyl and pyrazine-2,5-dicarboxylate (pzdc) ions. It consists of a one-dimensional chain of vanadyl ions linked by pzdc ions. The carboxylate groups show monodentate coordination, while the pyrazine ring is present both in non-coordinated and coordinated modes. This novel structure is stabilized by an intricate network of hydrogen bonds. The material is highly robust, and thermally stable up to 400 K. It is also antiferromagnetic, with a maximum magnetic susceptibility at ca. 50 K. The orbital shape and population analysis by means of DFT analysis confirm the π-acceptor role of the aromatic nitrogen function of the ligand, while the oxygen-based moieties (carboxylates from pzdc, the aqua ligands and oxo from V=O group) behave as normal donors. Charting the density flow related with significant transitions computed by time-dependent DFT, we determined the ligand-to-metal charge transfer processes. The topology of the chain complex implies two different types of connecting bridges. Using Broken Symmetry DFT modelling gives evidence for two different exchange coupling mechanisms between the vanadyl ions along each of these two molecular bridges. One is strongly antiferromagnetic, practically reducing the chain to 'vanadyl dimers'. The other is almost uncoupled, due to the large distance between the vanadyl ions.

We report the synthesis and characterization of new V2O5/Al2O3-MgO catalysts and their application in oxidative dehydrogenation and epoxidation reactions. The materials were prepared by wet impregnation under excess acid conditions. Anchoring of the desired species on the support occurs via an exchange reaction between the vanadium complex and surface hydroxyl groups. The IR and UV-Vis spectra of these catalysts indicate the presence of monomeric vanadium species at 5 wt% V2O5 loading, along with small amounts of polymeric species at 5 and 10 wt% V2O5 loadings. Electron paramagnetic resonance (EPR) spectroscopy reveals the presence of ferromagnetic VO(2+) dimers following calcination at 773 K. The catalysts were then tested in two reactions, namely the gas phase oxidative dehydrogenation of n-butane under flow conditions at 773 K and the liquid phase epoxidation of limonene with H2O2. The dehydrogenation reaction gave butenes and 1,3-butadiene in moderate selectivity at 8-10% conversion. The epoxidation of limonene was less successful, giving 50-70% selectivity to the 1,2-epoxide at 10-20% conversion.

The performance of PbCrO(4) during reduction/oxidation cycles has been studied over the temperature range 673-873 K. During thermal treatment in an inert atmosphere, PbCrO(4) is stable up to 773 K. At higher temperatures, it decomposes rapidly and irreversibly to Pb(2)(CrO(4))O. Moreover, the redox cycling of Pb(2)(CrO(4))O is also irreversible at 873 K when the reduction semi-reaction is prolonged beyond 3 min. Taking a standard 2 min cyclic treatment, we demonstrate that the surface reduction/oxidation of Pb(2)(CrO(4))O is exothermic between 773-873 K. In contrast, the redox cycling of PbCrO(4) is endothermic at 673 K. These findings demonstrate for the first time the potential of Pb(2)(CrO(4))O as a solid oxygen reservoir for the oxidative dehydrogenation of alkanes; especially at T ≥ 773 K, where H(2) oxidation by Pb(2)(CrO(4))O is exothermic. Preliminary kinetic studies suggest that Pb(2)(CrO(4))O reduction and oxidation both proceed through a "3D diffusion of the reacting front" mechanism. Our results open up opportunities for developing energy-efficient oxidative dehydrogenation routes to commercially important olefins.

Ceria-based materials are promising solid "oxygen reservoirs" for propane oxidative dehydrogenation. The ceria lattice oxygen can selectively combust hydrogen from the dehydrogenation mixture at 550 degrees C. This shifts the dehydrogenation equilibrium to the desired products side, generates heat aiding the endothermic dehydrogenation, and simplifies product separation. The process is also safer, since it avoids mixing O(2) and H(2) at high temperatures. While ceria itself is unselective, its catalytic properties can be tuned by doping. We study the effects of dopant type, concentration and the crystallite size on the catalytic properties. Doping with Cr or Cu increases both the selectivity and activity of the ceria, albeit that propane combustion also increases linearly with the Cu-concentration. The Cu-doped catalysts give selectivities up to 95% and combust up to 8% of the hydrogen feed. The best results are obtained with Cr-doped ceria, with selectivities up to 98%, and combustion of up to 15% of the hydrogen feed. The Cr-doped catalysts are stable in the reductive gas feed, and no extra coke is formed when the catalyst is subjected to an extra 10 min in the dehydrogenation mixture, after the hydrogen combustion reaction has stopped. This robustness is essential for industrial dehydrogenation applications.

Copper-doped ceria catalysts feature in a variety of catalytic reactions. One important application is selective hydrogen combustion via oxygen exchange, which forms the basis of cyclic oxidative dehydrogenation. This paper describes the synthesis of monophasic (doped) and biphasic (supported) Cu-ceria catalysts, that are then characterized using a combination of temperature programmed reduction (TPR) and X-ray diffraction (XRD) methods. The catalysts are analyzed both as fresh samples and after redox cycling at 550-800 degrees C. TPR and XRD characterization clarify the role of the active sites on the catalyst surface and the copper-ceria interactions. Depending on the catalyst type, reduction occurs at approximately 110 degrees C, approximately 150 degrees C, or approximately 190 degrees C. The reduction at 110 degrees C is ascribed to highly dispersed copper species doped in the ceria lattice, and that at 190 degrees C to CuO crystallites supported on ceria. Remarkably, both types converge to the 150 degrees C feature after redox cycling. The reduction temperature of the doped catalyst increases after redox cycling, indicating that stable Cu clusters form at the surface. Conversely, the reduction temperature of the "supported" catalyst decreases after redox cycling, and the CuO crystallites disappear. With this knowledge, a copper-doped ceria catalyst is analyzed after application in selective hydrogen combustion (16 consecutive redox cycles at 550 degrees C). No CuO crystallites are observed, and the sample reduces at approximately 110 degrees C. This suggests that copper-doped ceria is the active oxygen exchange phase in selective hydrogen combustion.