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Synthetic System (synthetic + system)
Selected AbstractsZnO Hierarchical Micro/Nanoarchitectures: Solvothermal Synthesis and Structurally Enhanced Photocatalytic Performance,ADVANCED FUNCTIONAL MATERIALS, Issue 7 2008Fang Lu Abstract A novel ZnO hierarchical micro/nanoarchitecture is fabricated by a facile solvothermal approach in an aqueous solution of ethylenediamine (EDA). This complex architecture is of a core/shell structure, composed of dense nanosheet-built networks that stand on a hexagonal-pyramid-like microcrystal (core part). The ZnO hexagonal micropyramid has external surfaces that consist of a basal plane (000) and lateral planes {011}. The nanosheets are a uniform thickness of about 10,nm and have a single-crystal structure with sheet-planar surfaces as {20} planes. These nanosheets interlace and overlap each other with an angle of 60° or 120°, and assemble into a discernible net- or grid-like morphology (about 100,nm in grid-size) on the micropyramid, which shows a high specific surface area (185.6,m2,g,1). Such a ZnO micro/nanoarchitecture is new in the family of ZnO nanostructures. Its formation depends on the concentration of the EDA solution as well as on the type of zinc source. A two-step sequential growth model is proposed based on observations from a time-dependent morphology evolution process. Importantly, such structured ZnO has shown a strong structure-induced enhancement of photocatalytic performance and has exhibited a much better photocatalytic property and durability for the photodegradation of methyl orange than that of other nanostructured ZnO, such as the powders of nanoparticles, nanosheets, and nanoneedles. This is mainly attributed to its higher surface-to-volume ratio and stability against aggregation. This work not only gives insight into understanding the hierarchical growth behaviour of complex ZnO micro/nanoarchitectures in a solution-phase synthetic system, but also provides an efficient route to enhance the photocatalytic performance of ZnO, which could also be extended to other catalysts, such as the inherently excellent TiO2, if they are of the same hierarchical micro/nanoarchitecture with an open and porous nanostructured surface layer. [source] Cover Picture: Colloidal Synthesis of Hollow Cobalt Sulfide Nanocrystals (Adv. Funct.ADVANCED FUNCTIONAL MATERIALS, Issue 11 2006Mater. Abstract Hollow nanocrystals have been synthesized through a mechanism analogous to the Kirkendall Effect. When a cobalt nanocrystal reacts with sulfur in solution, the outward diffusion of cobalt atoms is faster than the inward diffusion of sulfur atoms through the sulfide shell. The dominating outward diffusion of cobalt cations produces vacancies that can condense into a single void in the center of the nanocrystal at high temperatures. This process provides a general route to the synthesis of hollow nanostructures of a large number of compounds and is described in the Full Paper by A.,P. Alivisatos and co-workers on p.,1389. Formation of cobalt sulfide hollow nanocrystals through a mechanism similar to the Kirkendall Effect has been investigated in detail. It is found that performing the reaction at >,120,°C leads to fast formation of a single void inside each shell, whereas at room temperature multiple voids are formed within each shell, which can be attributed to strongly temperature-dependent diffusivities for vacancies. The void formation process is dominated by outward diffusion of cobalt cations; still, the occurrence of significant inward transport of sulfur anions can be inferred as the final voids are smaller in diameter than the original cobalt nanocrystals. Comparison of volume distributions for initial and final nanostructures indicates excess apparent volume in shells, implying significant porosity and/or a defective structure. Indirect evidence for fracture of shells during growth at lower temperatures was observed in shell-size statistics and transmission electron microscopy images of as-grown shells. An idealized model of the diffusional process imposes two minimal requirements on material parameters for shell growth to be obtainable within a specific synthetic system. [source] Cover Picture: Functionalized Gold Nanoparticles Mimic Catalytic Activity of a Polysiloxane-Synthesizing Enzyme (Adv. Mater.ADVANCED MATERIALS, Issue 10 200510/2005) Abstract A system that acts as a biomimetic of the silica-synthesizing enzyme found in a marine sponge is reported by Morse and co-workers on p.,1234. Gold nanoparticles (GNPs) are functionalized with the same organic moieties that are found in the enzyme's catalytic site. Interaction between the nucleophilic (OH-terminated) and hydrogen-bonding (imidazole-terminated) GNPs, as shown on the cover, is required for the hydrolysis of a silicon alkoxide precursor and subsequent polycondensation to form silica at a low temperature and near-neutral pH. Replacement of either of the required functional groups by a non-reactive methyl group abolishes catalysis in this synthetic system, as it does in the biological enzyme. Cover art provided by Peter Allen. [source] Minerals as Model Compounds for Cu/ZnO Catalyst Precursors: Structural and Thermal Properties and IR Spectra of Mineral and Synthetic (Zincian) Malachite, Rosasite and Aurichalcite and a Catalyst Precursor MixtureEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 10 2009Malte Behrens Abstract The Cu/ZnO system is a model for Cu/ZnO/Al2O3 catalysts, which are employed industrially for the synthesis of methanol. These catalysts are usually prepared from mixed basic carbonate precursors. A complex phase mixture, with constituents structurally related to the minerals rosasite andaurichalcite, is present at the industrially applied composition (Cu/Zn , 70:30). Using minerals and phase-pure synthetic samples as references, a comprehensive characterisation of such a phase mixture, including the determination of the individual compositions of the different phases, has been attempted by complementary analytical laboratory techniques (XRD, TGA, IR). The results are critically discussed in light of the complexity of the system. A thermally very stable carbonate species , well-known for mixed synthetic systems , is also detected for the mineral reference samples. Significant amounts of amorphous phases are found to be present in the synthetic zincian malachite sample but not in synthetic aurichalcite or the catalyst precursor. A simplified explanation for the shift of the characteristic 20 reflection of the malachite structure as a function of Zn incorporation based on the varying average Jahn,Teller distortion of the MO6 octahedra is proposed. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] The Stereostructure of Porphyra-334: An Experimental and Calculational NMR Investigation.HELVETICA CHIMICA ACTA, Issue 3 2007Evidence for an Efficient, Proton Sponge' Abstract The mycosporine-like amino acid (MAA) porphyra-334 (1) is subjected to extensive 1H- and 13C-NMR analysis as well as to density-functional-theory (DFT) calculations. All 1H- and 13C-NMR signals of 1 are assigned, as well as the resonances of prochiral proton pairs. This is achieved by 500-MHz standard COSY, HMQC, and HMBC experiments, as well as by one-dimensional (DPFGSE-NOE) and two-dimensional (NOESY) NOE experiments. Diffusion measurements (DOSY) confirm that 1 is monomeric in D2O solution. DFT Calculations yield 13C-NMR chemical shifts which are in good agreement for species 6 which is the imino N-protonated form of 1. An exceptionally high proton affinity of 265.7,kcal/mol is calculated for 1, indicating that 1 may behave as a very powerful ,proton sponge' of comparable strength as synthetic systems studied so far. Predictions of 13C-NMR chemical shifts by the ,NMRPredict' software are in agreement with the DFT data. The absolute configuration at the ring stereogenic center of 1 is concluded to be (S) from NOE data as well as from similarities with the absolute configuration (S) found in mycosporine-glycine 16. This supports the assumption that 1 is biochemically derived from 3,3- O -didehydroquinic acid (17). The data obtained question the results recently published by a different research group claiming that the configuration at the imino moiety of 1 is (Z), rather than (E) as established by the here presented study. [source] New Templating Strategies with Salen Scaffolds (Salen=N,N,-Bis(salicylidene)ethylenediamine Dianion)CHEMISTRY - A EUROPEAN JOURNAL, Issue 34 2008Arjan Abstract Templated approaches towards selective organic synthesis is a common feature in nature in which nucleic acid templated synthesis plays a crucial role in various fundamental biological processes. The key feature that allows control over the amazing selectivity found in natural processes is evidently the effective molarity of the reaction partners that is mediated by the macromolecular templation event. An ongoing challenge within many chemical sciences is to exploit similar templating principles and make use of synthetic systems that are designed for specific chemical conversions. Here, we describe the recent developments that involve (metallo)salen scaffolds that are used for diverse templating events (salen=N,N,-bis(salicylidene)ethylenediamine dianion). [source] | |||||||||||||