Abstract: 1D CuO/ZnO nanocomposites were grown on Si(100) substrates by means of an original two-step synthetic strategy. ZnO nanorod (NR) arrays were initially deposited by plasma enhanced-chemical vapor deposition (PE-CVD) from an ArO2 atmosphere. Subsequently, tailored amounts of CuO were dispersed over zinc oxide matrices by radio frequency (RF)-sputtering of Cu from Ar plasmas, followed by thermal treatment in air. A thorough characterization of the obtained systems was carried out by X-ray photoelectron and X-ray excited-Auger electron spectroscopies (XPS and XE-AES), glancing incidence X-ray diffraction (GIXRD), field emission-scanning electron microscopy (FE-SEM), energy dispersive X-ray spectroscopy (EDXS), atomic force microscopy (AFM), transmission electron microscopy (TEM), electron diffraction (ED) and energy filtered-TEM (EF-TEM). Pure and highly oriented CuO/ZnO NR arrays, free from ternary ZnCuO phases and characterized by a copper(II) oxide content controllable as a function of the adopted RF-power, were successfully obtained. Interestingly, the structural relationships between the two oxides at the CuO/ZnO interface were found to depend on the overall CuO loading. The obtained nanocomposites displayed promising photocatalytic performances in H2 production by reforming of ethanolwater solutions under simulated solar illumination, paving the way to the sustainable conversion of solar light into chemical energy.

Abstract: A novel lithium zinc niobium oxide LiZnNb(4)O(11.5) (LZNO) has been found in the Nb-rich part of Li(2)O-ZnO-Nb(2)O(5) system. LZNO, with an original alpha-PbO(2) related structure, has been synthesized by the routine ceramic technique and characterized by X-ray diffraction and transmission electron microscopy (TEM). Reflections belonging to the LZNO phase, observed in X-ray powder diffraction (XRPD) and electron diffraction, have been indexed as monoclinic with unit cell parameters a=17.8358(9)angstrom, b=15.2924(7)angstrom, c=5.0363(3)angstrom and gamma=96.607(5)degrees or as alpha-PbO(2)-like with lattice constants a=4.72420(3)angstrom, b=5.72780(3)angstrom, c=5.03320(3)angstrom, gamma=90.048(16)degrees and modulation vector q=0.3a*+1.1b* indicating a commensurately modulated alpha-PbO(2) related structure. The monoclinic cell is a supercell related to the latter. Using synchrotron powder diffraction data, the structure has been solved and refined as a commensurate modulation (superspace group P112(1)/n(alpha beta 0)00) as well as a supercell (space group P2(1)/b). The superspace description allows us to consider the LZNO structure as a member of the proposed alpha-PbO(2)-Z (3 + 1)D structure type, which unifies both incommensurately and commensurately modulated structures. HRTEM reveals several types of defects in LZNO and structural models for these defects are proposed. Two new phases in Li(2)O-ZnO-Nb(2)O(5) system are predicted on the basis of this detailed HRTEM analysis. (C) 2009 Elsevier Inc. All rights reserved.

Abstract: The selective formation and stabilization of very small, naked metal particles inside the cavities of metal organic frameworks (MOFs) and the simultaneous realization of an even distribution of the particles throughout the crystalline MOF host matrix over a wide range of metal loading are challenging goals. MOFs reveal high specific surface areas, tunable pore sizes, and organic linkers, which are able to interact with guests. The chemically very robust zeolite imidazolate frameworks (ZIFs) are a subclass of MOFs. We chose the microporous sodalite-like ZIF-8 (Zn(MelM)(2); IM = imidazolate) and ZIF-90 (Zn(ICA)(2); ICA = imidazolate-2-carboxyaldehyde) as host matrices to influence the dispersion of imbedded gold nanoparticles (Au NPs). The metal loading was achieved via gas phase infiltration of [Au(CO)Cl] followed by a thermal hydrogenation step to form the Au NPs. Low-dose high-resolution transmission electron microscopy ((HR)TEM) and electron tomography reveal a homogeneous distribution of Au NPs throughout the ZIF matrix. The functional groups of ZIF-90 direct the anchoring of intermediate Au species and stabilize drastically smaller and quite monodisperse Au NPs in contrast to the parent not functionalized ZIF-8. The particles can be very small, match the cavity size and approach defined molecular clusters of magic numbers, i.e., Au(55), independently from the level of loading. Post-synthetic oxidation of the aldehyde groups to yield alkyl esters by the adjacent, catalytically active metal NPs is presented as a new concept of encapsulating nanoparticles inside MOFs and allows multiple steps of metal loadings without decomposition of the MOF.

Abstract: The double phosphate Ca9In(PO4)(7) was obtained by solid-state reaction and was studied by room and high-temperature Xray powder diffraction, electron diffraction, high-resolution electron microscopy, second-harmonic generation (SHG) technique, differential scanning calorimetry, dielectric and conductivity measurements. The beta-Ca9In(PO4)(7) room-temperature phase is related to the mineral whitlockite and is similar to beta-Ca-3(PO4)(2). It has space group R (3) over barc, with unit cell parameters: a = 10.4008(1) Angstrom, c = 37.272(1) Angstrom, Z = 6. The structure was refined by the Rietveld method (R-wp = 4.69, R-I = 1.81). A reversible first-order beta <----> beta' phase transition of the ferroelectric type with T-c = 902 K is revealed by SHG, differential scanning calorimetry and dielectric measurements. The centrosymmetric beta'-Ca9In(PO4)(7) (973 K) has space group R (3) over barc, a = 10.4611(2) Angstrom, c = 37.874 (1) Angstrom (R-wp = 4.27, R-I = 4.11). Compared to the low-temperature beta-Ca9In(PO4)(7) structure, beta'-Ca9In(PO4)(7) can be described as an orientational disordering of the P1O(4) tetrahedra together with a calcium disordering on the M3 site. (C) 2002 Elsevier Science (USA).

Abstract: Rational synthesis of nanowires via the vaporliquidsolid (VLS) mechanism with compositional and structural controls is vitally important for fabricating functional nanodevices from bottom up. Here, we show that branched indium tin oxide nanowires can be in situ seeded in vapor transport growth using tailored AuCu alloys as catalyst. Furthermore, we demonstrate that VLS synthesis gives unprecedented freedom to navigate the ternary InSnO phase diagram, and a rare and bulk-unstable cubic phase can be selectively stabilized in nanowires. The stabilized cubic fluorite phase possesses an unusual almost equimolar concentration of In and Sn, forming a defect-free epitaxial interface with the conventional bixbyite phase of tin-doped indium oxide that is the most employed transparent conducting oxide. This rational methodology of selecting phases and making abrupt axial heterojunctions in nanowires presents advantages over the conventional synthesis routes, promising novel composition-modulated nanomaterials.

Abstract: Monolithic nickel/carbon (Ni/C) composites were prepared from coal tar pitch-impregnated compressed expanded graphite pre-decorated with NiO particles (EGNiO) by pyrolysis at 550 °C and subsequent steam activation at 800 °C. The microstructural arrangement of the Ni-comprising nanoparticles in the composites was investigated using transmission electron microscopy. The specific surface area and porosity of the composites were analyzed by nitrogen adsorption. The catalytic activity of the composites was compared with the material obtained by the conventional H2 treatment of EGNiO using hydrocracking of 2,2,3-trimethylpentane as a model reaction.

Abstract: Ag/ZnO nanocomposites were developed by a plasma-assisted approach. The adopted strategy exploits the advantages of Plasma Enhanced-Chemical Vapor Deposition (PE-CVD) for the growth of columnar ZnO arrays on Si(100) and Al2O3 substrates, in synergy with the infiltration power of the Radio Frequency (RF)-sputtering technique for the subsequent dispersion of different amounts of Ag nanoparticles (NPs). The resulting composites, both as-prepared and after annealing in air, were thoroughly characterized with particular attention on their morphological organization, structure and composition. For the first time, the above systems have been used as catalysts in the production of hydrogen by photo-reforming of alcoholic solutions, yielding a stable H2 evolution even by the sole use of simulated solar radiation. In addition, Ag/ZnO nanocomposites presented an excellent response in the gas-phase detection of H2, opening attractive perspectives for advanced technological applications.

Abstract: Zeolitic growth is often absent or occurs in separate phases when synthetic strategies based on the combination of zeolite templates and mesopore templating agents are applied. In this work, zeolitic growth and mesopore formation have been investigated at different temperatures by applying a one-pot templating approach, based on a TS-1 zeolite synthesis whereby part of the microtemplate (tetrapropylammonium hydroxide, TPAOH) is replaced by a mesotemplate (hexadecyltrimethylammonium bromide, CTMABr). Moreover, the synthesis duration and the molar ratio of the microtemplate/mesotemplate have also been studied. The different syntheses clearly show the inherent competitive mechanism between zeolitic growth and mesopore formation. These insights have led to the conclusion that by following a one-pot templating strategy with standard, nonexotic commercial templates, i.e. CTMABr and TPAOH, it is not possible to develop a true hierarchical mesoporous zeolite, meaning a mesoporous siliceous material with highly crystalline zeolitic walls. The resultant materials are instead combined zeolitic/mesoporous composite structures with, however, highly tuneable and controllable porosity characteristics.

Abstract: Faraday rotation has been used to investigate a series of polymer films doped with magnetic iron oxide nanoparticles. The films have been prepared by spin-coating and melt-processing. In each case, upon varying the angle of optical incidence on the films, an in-plane magnetic anisotropy is observed. The effect of such an anisotropy on the Faraday rotation as a function of the angle of optical incidence is verified by comparison with magnetically poled films. These results demonstrate that care should be taken upon analyzing the magnetic behavior of such films on account of the sample preparation techniques themselves being able to affect the magnetization.

Abstract: The crystalline and defect structure of epitaxial hexagonal RExMnyO3 (RE = Er, Dy) films with varying cationic composition was investigated by X-ray diffraction and transmission electron microscopy. The films are composed of a strained layer at the interface with the substrate and of a relaxed layer on top of it. The critical thickness is of 10 to 25 nm. For Mn-rich films (or RE deficient), an off-stoichiometric composition maintaining the hexagonal LuMnO3-type structure is stabilized over a large range of the RE/Mn ratio (0.72−1.00), with no Mn-rich secondary phases observed. A linear dependence of the out-of-plane lattice parameter with RE/Mn is observed in this range. Out-of-phase boundary (OPB) extended defects are observed in all films and exhibit a local change in stoichiometry. Such a large solubility limit in the RE deficient region points toward the formation of vacancies on the RE site (RExMnO3−δ, with 0.72 ≤ x < 1), a phenomenon that is encountered in perovskite manganites such as LaxMnO3−δ (x < 1) and that may strongly impact the physical properties of hexagonal manganites.

Abstract: The Zn-carboxylate-based porous coordination polymer MOF-5 [Zn4O(bdc)3] and the metal oxide loaded materials ZnO@MOF-5 and TiO2@MOF-5 were loaded in a second step with the precursor [ClAuCO] to yield intermediate materials denoted as [ClAuCO]@MOF-5, [ClAuCO]/ZnO@MOF-5 and [ClAuCO]/TiO2@MOF-5. These composites were decomposed to Au@MOF-5, Au/ZnO@MOF-5 and Au/TiO2@MOF-5 under hydrogen at 100 °C. The nanoparticle-loaded hybrid materials were characterised by powder X-ray diffraction (PXRD), IR spectroscopy, X-ray photoelectron spectroscopy (XPS) and N2 sorption measurements, which reveal an intact MOF-5 structure that maintains a high specific surface area. For Au@MOF-5, crystalline Au nanoparticles were distributed over the MOF matrix in a homogeneous fashion with a size of ca. 13 nm, evidenced by high resolution transmission electron microscopy. In the case of Au/ZnO@MOF-5, the Au and metal oxide particles of a few nm in size were coexistent in a given volume of the MOF-5 matrix and were not separated in different crystalline MOF particles. For the TiO2 loaded materials the oxide is preferentially located near the outer surface of the MOF particles, leading to an increase of larger exterior Au particles in comparison to very small interior Au particles as observed for the other materials. Au@MOF-5, Au/ZnO@MOF-5 and Au/TiO2@MOF-5 were tested in liquid-phase oxidation of alcohols. Preliminary results show a high activity for the Au loaded materials in this reaction. This observation is attributed to the microstructure of the composites with very small Au particles distributed homogeneously over the MOF matrix.

Abstract: Based on a facile one-pot templating synthesis, using a TS-1 zeolite recipe whereby part of the zeolite structure directing agent is replaced by a mesopore templating agent, a trimodal material is formed. The resulting meso-TSM material combines mesoporosity (Ti-MCM-41) with zeolitic features (TS-1) and a unique sheet-like morphology with uniform macroporous voids (macroholes). Moreover, the macrohole formation, mesoporosity and zeolitic properties of the meso-TSM material can be controlled in a straightforward way by adjusting the length of the hydrothermal treatment. This newly developed material may imply great potential for catalytic redox applications and diffusion limitated processes because of its highly tunable character in all three dimensions (micro-, meso- and macroporous scale).

Abstract: Porous titanosilicate beads with a diameter of 0.51.5 mm (TiSil-HPB-60) were synthesized from a preformed titanosilicate solution with a porous anion-exchange resin as template. The bead format of this material enables its straightforward separation from the reaction mixture in its application as a liquid-phase heterogeneous catalyst. The material displays hierarchical porosity (micro/mesopores) and incipient TS-1 structure building units. The titanium species are predominantly located in tetrahedral framework positions. TiSil-HPB-60 is a highly active catalyst for the epoxidation of cyclohexene with t-butyl hydroperoxide (TBHP) and aqueous H2O2. With both oxidants, TiSil-HPB-60 gave higher epoxide yields than Ti-MCM-41 and TS-1. The improved catalytic performance of TiSil-HPB-60 is mainly ascribed to the large mesopores favoring the diffusion of reagents and products to and from the titanium active sites. The epoxide yield and selectivity could be further improved by silylation of the titanosilicate beads. Importantly, TiSil-HPB-60 is a stable catalyst immune to titanium leaching, and can be easily recovered and reused in successive catalytic cycles without significant loss of activity. Moreover, TiSil-HPB-60 is active and selective in the epoxidation of a wide range of bulky alkenes.

Abstract: An interface modification of (LaCa)MnO3-BaTiO3 superlattices was found to massively influence magnetic and magnetotransport properties. Moreover it determines the crystal structure of the manganite layers, changing it from orthorhombic (Pnma) for the conventional superlattice (cSL), to rhombohedral (R3̅ c) for the modified one (mSL). While the cSL shows extremely nonlinear ac transport, the mSL is an electrically homogeneous material. The observations go beyond an oversimplified picture of dead interface layers and evidence the importance of electronic correlations at perovskite interfaces.

Abstract: Pd particles supported on SnO2 and GeO2 have been structurally investigated by X-ray diffraction, (High-Resolution) transmission and scanning electron microscopy after different reductive treatments to monitor the eventual formation of bimetallic phases and catalytically tested in methanol dehydrogenation/ reforming. For both oxides this included a thin film sample with well-defined Pd particles and a powder catalyst prepared by incipient wetness impregnation. The hexagonal and the tetragonal polymorph were studied for powder GeO2. Pd2Ge formation was observed on all GeO2-supported catalysts, strongly depending on the specific sample used. Reduction of the thin film at 573K resulted in full transformation into the bimetallic state. The partial solubility of hexagonal GeO2 in water and its thermal structural instability yielded Pd2Ge formation at 473 K, at the cost of a structurally inhomogeneous support and Ge metal formation at higher reduction temperatures. Pd on tetragonal GeO2 entered a state of strong metalsupport interaction after reduction at 573673 K, resulting in coalescing Pd2Ge particles on a sintered and re-crystallized support, apparently partially covering the bimetallic particles and decreasing the catalytic activity. Pd2Ge on amorphous thin film and hexagonal GeO2 converted methanol primarily via dehydrogenation to CO and H2. At 573 K, formation of Pd2Sn and also PdSn occurred on the Pd/SnO2 thin film. Pd3Sn2 (and to some extent Pd2Sn) were predominantly obtained on the respective powder catalyst. Strong deactivation with increasing reduction temperature was observed, likely not based on the classical strong metalsupport interaction effect, but rather on a combination of missing active structural ensembles on Sn-enriched bimetallic phases and the formation of metallic -Sn. Correlations to Pd and its bimetallics supported on ZnO, Ga2O3 and In2O3 were also discussed.