Abstract: We present a green, biological production route for silica-titania photocatalysts using diatom microalgae. Diatoms are single-celled, eukaryotic microalgae (2-2000 mu m) that self-assemble soluble silicon (Si(OH)(4)) into intricate silica cell walls, called frustules. These diatom frustules are formed under ambient conditions and consist of hydrated silica with specific 3D morphologies and micro-meso or macroporosity. A remarkable characteristic of diatoms is their ability to bioaccumulate soluble titanium from cell culture medium and incorporate them into their nanostructured silica cell wall. Controlled cultivation of the diatom Pinnularia sp. on soluble titanium in a batch process resulted in the biological immobilisation of titanium dioxide in the porous 3D architecture of the frustules. Six different titanium sources are tested. The silica-titania frustules were isolated by treating the harvested Pinnularia cells with nitric acid (65%) or by high temperature treatment. Thermal annealing converted the amorphous titania into crystalline titania. The produced silica-titania material is evaluated towards photocatalytic activity for acetaldehyde (C2H4O) abatement. Frustules cultivated with TiBaldH showed the highest photocatalytic performance. Comparison of the photocatalytic activity with P25 reveals that P25 has a 4 fold higher photocatalytic activity, but when photocatalytic activity is normalized for titania content, the frustules show double activity. Further material characterization (morphology, crystallinity, surface area and elemental distribution) of the TiBaldH silica-titania frustules provides additional insight into their structure-activity relationship. These natural biosilicatitania materials have excellent properties for photocatalytic purposes, including high surface area (108 m(2) g(-1)) and good porosity, and show reliable immobilization of TiO2 in the ordered structure of the diatom frustule.

Abstract: Although the search for new zeolites has traditionally been based on trial and error, more rational methods are now available. The theoretical concept of inverse transformation of a zeolite framework to generate a new structure by removal of a layer of framework atoms and contraction has for the first time been achieved experimentally. The reactivity of framework germanium atoms in strong mineral acid was exploited to selectively remove germanium-containing four-ring units from an UTL type germanosilicate zeolite. Annealing of the leached framework through calcination led to the new all-silica COK-14 zeolite with intersecting 12- and 10-membered ring channel systems. An intermediate stage of this inverse transformation with dislodged germanate four-rings still residing in the pores could be demonstrated. Inverse transformation involving elimination of germanium-containing structural units opens perspectives for the synthesis of many more zeolites.

Abstract: ITEM specimens of a LaAlO3/SrTiO3 multilayer are prepared by FIB with internal lift out. Using a Ga+1 beam of 5 kV, a final cleaning step yielding top, top-angle, side, and bottom-angle cleaning is performed. Different cleaning procedures, which can be easily implemented in a dual beam FIB system, are described and compared; all cleaning types produce thin lamellae, useful for HRTEM and HAADF-STEM work up to atomic resolution. However, the top cleaned lamellae are strongly affected by the curtain effect. Top-angle cleaned specimens show an amorphous layer of around 5 nm at the specimen surfaces, due to damage and redeposition. Furthermore, it is observed that the LaAlO3 layers are preferentially destroyed and transformed into amorphous material, during the thinning process.

Abstract: Three different perovskite-related phases were isolated in the SrGa(1-x)Sc(x)O(2.5) system: Sr(2)GaScO(5), Sr(10)Ga(6)Sc(4)O(25), and SrGa(0.75)Sc(0.25)O(2.5), Sr(2)GaScO(5) (x = 0.5) crystallizes in a brownrnillerite-type structure [space group (S.G.) Icmm, a = 5.91048(5) angstrom, b = 15.1594(1) angstrom, and c = 5.70926(4) angstrom] with complete ordering of Sc(3+) and Ga(3+) over octahedral and tetrahedral positions, respectively. The crystal structure of Sr(10)Ga(6)Sc(4)O(25) (x = 0.4) was determined by the Monte Carlo method and refined using a combination of X-ray, neutron, and electron diffraction data [S.G. I4(1)/a, a = 17.517(1) angstrom, c = 32.830(3) angstrom]. It represents a novel type of ordering of the B cations and oxygen vacancies in perovskites. The crystal structure of Sr(10)Ga(6)Sc(4)O(25) can be described as a stacking of eight perovskite layers along the c axis ...[-(Sc/Ga)O(1.6)-SrO(0.8)-(Sc/Ga)O(1.8)-SrO(0.8)-](2 center dot center dot center dot) Similar to Sr(2)GaScO(5), this structure features a complete ordering of the Sc(3+) and Ga(3+) cations over octahedral and tetrahedral positions, respectively, within each layer. A specific feature of the crystal structure of Sr(10)Ga(6)Sc(4)O(25) is that one-third of the tetrahedra have one vertex not connected with other Sc/Ga cations. Further partial replacement of Sc(3+) by Ga(3+) leads to the formation of the cubic perovskite phase SrGa(0.75)Sc(0.25)O(2.5) (x = 0.25) with a = 3.9817(4) angstrom. This compound incorporates water molecules in the structure forming SrGa(0.75)Sc(0.25)O(2.5)center dot xH(2)O hydrate, which exhibits a proton conductivity of similar to 2.0 x 10(-6) S/cm at 673 K.

Abstract: This work focuses on the use of tailored copper oxide nanoarchitectures as multi-functional materials for the sustainable production of hydrogen and its on-line detection. An innovative copper(II) precursor, Cu(hfa)2TMEDA, was adopted in the CVD of CuxO (x=1,2) nanosystems under both O2 and O2+H2O atmospheres on Si(100) and Al2O3 substrates. A multi-technique characterization indicates that both the phase composition (from Cu2O to CuO) and morphology (from continuous films to entangled quasi-1D nanosystems) can be tailored by varying the growth temperature and reaction atmosphere. The obtained CuxO nanodeposits are active in the photocatalytic H2 production from aqueous solutions under UV-Vis irradiation and display interesting gas sensing performances towards hydrogen detection even at moderate temperatures.

Abstract: A model for superstructure ordering in the <<chain>> layers of Ga (Co) substituted YBCO intergrowths with general formula (REO2)NSr2MCu2O5 (M = Co, Ga; n = 1, 2, ...) is proposed. By Ga or Co substitution for Cu, the structure of the <<chain>> layer changes : instead of the CuO4 planar squares, the chains consist of MO4 tetrahedra (M = Ga, Co) running along the [110] perovskite direction. The existing model for the Ga substituted <<123>> implies that all the chains are the same. Our new model is based on the results of Electron diffraction and High-resolution electron microscopy investigations. The model reveals the occurrence of two types of chains as a consequence of <<opposite>> ordering between neighbouring tetrahedra. The comer linked tetrahedra in each chain appear as alternatingly rotated in opposite sense, and a chain itself, as being displaced with respect to the underlying structure in one of two senses ; either forth (right) or back (left) along the chain direction. The regular alternation of chains of opposite type doubles the periodicity within a layer and induces the possibility for intrinsic disorder in the chain layer stacking sequence. The planar superstructure and a staggered stacking of the tetrahedral chain layers is found irrespective of the rest of the intergrowth structure. Superstructure ordering in the case of Co substitution is more perfect than for the Ga substitution.

Abstract: As a size- and shape-selective catalyst, zeolites are widely used in petroleum and fine-chemicals processing. However, their small micropores severely hinder molecular diffusion and are sensitive to coke formation. Hierarchically porous zeolite single crystals with fully interconnected, ordered, and tunable multimodal porosity at macro-, meso-, and microlength scale, like in leaves, offer the ideal solution. However, their synthesis remains highly challenging. Here, we report a versatile confined zeolite crystallization process to achieve these superior properties. Such zeolite single crystals lead to significantly improved mass transport properties by shortening the diffusion length while maintaining shape-selective properties, endowing them with a high efficiency of zeolite crystals, enhanced catalytic activities and lifetime, highly reduced coke formation, and reduced deactivation rate in bulky-molecule reactions and methanol-to-olefins process. Their industrial utilization can lead to the design of innovative and intensified reactors and processes with highly enhanced efficiency and minimum energy consumption.