Abstract: Understanding the molecular-level mechanisms of phase transformation in solids is of fundamental interest for functional materials such as zeolites. Two-dimensional (2D) zeolites, when used as shape-selective catalysts, can offer improved access to the catalytically active sites and a shortened diffusion length in comparison with their 3D analogues. However, few materials are known to maintain both their intralayer microporosity and structure during calcination for organic structure-directing agent (SDA) removal. Herein we report that PST-9, a new 2D zeolite which has been synthesized via the multiple inorganic cation approach and fulfills the requirements for true layered zeolites, can be transformed into the small-pore zeolite EU-12 under its crystallization conditions through the single-layer folding process, but not through the traditional dissolution/recrystallization route. We also show that zeolite crystal growth pathway can differ according to the type of organic SDAs employed.

Abstract: In this work, we have fabricatedan aryl amino-substitutedgraphiticcarbon nitride (g-C3N4) catalyst with atomicallydispersed Mn capable of generating hydrogen peroxide (H2O2) directly from seawater. This new catalyst exhibitedexcellent reactivity, obtaining up to 2230 & mu;M H2O2 in 7 h from alkaline water and up to 1800 & mu;Mfrom seawater under identical conditions. More importantly, the catalystwas quickly recovered for subsequent reuse without appreciable lossin performance. Interestingly, unlike the usual two-electron oxygenreduction reaction pathway, the generation of H2O2 was through a less common two-electron water oxidation reaction(WOR) process in which both the direct and indirect WOR processesoccurred; namely, photoinduced h(+) directly oxidized H2O to H2O2 via a one-step 2e(-) WOR, and photoinduced h(+) first oxidized a hydroxide (OH-) ion to generate a hydroxy radical ((OH)-O-& BULL;), and H2O2 was formed indirectly by thecombination of two (OH)-O-& BULL;. We have characterized thematerial, at the catalytic sites, at the atomic level using electronparamagnetic resonance, X-ray absorption near edge structure, extendedX-ray absorption fine structure, high-resolution transmission electronmicroscopy, X-ray photoelectron spectroscopy, magic-angle spinningsolid-state NMR spectroscopy, and multiscale molecular modeling, combiningclassical reactive molecular dynamics simulations and quantum chemistrycalculations.

Abstract: Annular dark field TEM images exhibit a dominant mass-thickness contrast that can be quantified to extract single atom scattering cross sections. On top of this incoherent background, additional lattice fringes appear with a nonlinear information limit of 1.2 angstrom at 150 kV. The formation of these fringes is described by coherent nonlinear imaging theory and good agreement is found between experimental and simulated images. Calculations furthermore predict that the use of aberration corrected microscopes will improve the image quality dramatically. (c) 2005 Elsevier B.V. All rights reserved.

Abstract: The microstructure of (Bi,Pb)2Sr2Ca2Cu3Ox (Bi-2223) tapes has been investigated by means of transmission electron microscopy (TEM) and high-resolution TEM. The emphasis has been placed on: (1) an examination of the grain morphology and size, (2) grain and colony boundary angles, which are formed during the tape processing, (3) a study of the grain boundaries on an atomic scale, including intergrowth investigations. Tapes with different process parameters have been compared with respect to the microstructure. A fully processed tape has on the average 50% thicker Bi-2223 grains than a tape after the first annealing. The angles of c-axis tilt grain boundaries are on average 14° and 26° for the fully processed tape and the tape after the first annealing, respectively. The intergrowth content (15%) and distribution are similar in these two tapes.

Abstract: Metamorphic buffers (M-buffers) consisting of graded InAlAs or bulk InP were employed for the production of InP-based epiwafers on GaAs substrates by molecular-beam epitaxy. The graded InAlAs is the standard for production metamorphic high electron mobility transistors (M-HEMTs), while the bulk InP offers superior thermal properties for higher current density circuits. The surface morphology and crystal structure of the two M-buffers showed different relaxation mechanisms. The graded InAlAs gave a cross-hatched pattern with nearly full relaxation and very effective dislocation filtering, while the bulk InP had a uniform isotropic surface with dislocations propagating further up towards the active layers. Both types of M-buffers had atomic force microscopy root-mean-square roughness values around 2030 Å. The Hall transport properties of high electron mobility transistors (HEMTs) grown on the InAlAs M-buffer, and a baseline HEMT grown lattice matched on InP, both had room-temperature mobilities >10 000 cm2/V s, while the M-HEMT on the InP M-buffer showed a decrease to 9000 cm2/V  s. Similarly, the dc parameters of a double heterojunction bipolar transistor (DHBT) grown on the InAlAs M-buffer were much closer to the baseline heterojunction bipolar transistor than a DHBT grown on the InP M-buffer. A high breakdown voltage of 11.3 V was achieved on an M-DHBT with the InAlAs M-buffer. We speculate that the degradation in device characteristics on the InP M-buffer was related to the incomplete dislocation filtering.

Abstract: The problem of the epitaxial growth of the high temperature superconducting R1+xBa2xCu3O7δ (R = Y or rare earth except Ce and Tb) films has been addressed. Using in situ ultra high vacuum Scanning Tunneling Microscopy (UHV-STM) we have studied the role of cationic substitution and substrate mismatch on the growth mode of stoichiometric and Nd-rich Nd1+xBa2xCu3O7δ thin films. The results are compared to the growth of Y1Ba2Cu3O7δ, Dy1Ba2Cu3O7δ and Gd1Ba2Cu3O7δ epitaxial films. Two main phenomena are investigated: a) the first stage of the direct nucleation on the substrate and b) the crossover between 2D and 3D growth upon increasing the film thickness. At the first stage of the growth, pseudo-cubic perovskite (Re,Ba)CuO3 nuclei are formed. While they disappear after the growth of a few nm in stoichiometric films, they persist on the surface of Nd-rich films of up to 110 nm thickness. Stoichiometric R1+xBa2xCu3O7δ films exhibit a rough morphology with increasing thickness due to island growth mode, whereas Nd-rich films remain smooth and continue to grow layer by layer. It is proposed that linear defects (like anti-phase boundaries), which are formed due to the misalignment of growth fronts, are the source of screw dislocations in stoichiometric films. In Nd-rich films, linear defects are eliminated through the insertion of (Nd,Ba)CuO3 extra layers without introduction of any screw dislocations.

Abstract: The increasing need for precise determination of the atomic arrangement of non-periodic structures in materials design and the control of nanostructures explains the growing interest in quantitative transmission electron microscopy. The aim is to extract precise and accurate numbers for unknown structure parameters including atomic positions, chemical concentrations and atomic numbers. For this purpose, statistical parameter estimation theory has been shown to provide reliable results. In this theory, observations are considered purely as data planes, from which structure parameters have to be determined using a parametric model describing the images. As such, the positions of atom columns can be measured with a precision of the order of a few picometres, even though the resolution of the electron microscope is still one or two orders of magnitude larger. Moreover, small differences in average atomic number, which cannot be distinguished visually, can be quantified using high-angle annular dark-field scanning transmission electron microscopy images. In addition, this theory allows one to measure compositional changes at interfaces, to count atoms with single-atom sensitivity, and to reconstruct atomic structures in three dimensions. This feature article brings the reader up to date, summarizing the underlying theory and highlighting some of the recent applications of quantitative model-based transmisson electron microscopy.

Abstract: Porous metal oxides with nano-sized features attracted intensive interest in recent decades due to their high surface area which is essential for many applications, e.g. Li ion batteries, photocatalysts, fuel cells and dye-sensitized solar cells. Various approaches have so far been investigated to synthesize porous nanostructured metal oxides, including self-assembly and template-assisted synthesis. For the latter approach, forests of carbon nanotubes are considered as particularly promising templates, with respect to their one-dimensional nature and the resulting high surface area. In this work, we systematically investigate the formation of porous metal oxides (Al2O3, TiO2, V2O5 and ZnO) with different morphologies using atomic layer deposition on multi-walled carbon nanotubes followed by post-deposition calcination. X-ray diffraction, scanning electron microscopy accompanied by X-ray energy dispersive spectroscopy and transmission electron microscopy were used for the investigation of morphological and structural transitions at the micro- and nano-scale during the calcination process. The crystallization temperature and the surface coverage of the metal oxides and the oxidation temperature of the carbon nanotubes were found to produce significant influence on the final morphology.

Abstract: The size and lattice constant evolution of Pb nanoparticles (NPs) synthesized by high fluence implantation in crystalline Si have been studied with a variety of experimental techniques. Results obtained from small-angle x-ray scattering showed that the Pb NPs grow with increasing implantation fluence and annealing duration. The theory of NP growth kinetics can be applied to qualitatively explain the size evolution of the Pb NPs during the implantation and annealing processes. Moreover, the lattice constant of the Pb NPs was evaluated by conventional x-ray diffraction. The lattice dilatation was observed to decrease with increasing size of the Pb NPs. Such lattice constant tuning can be attributed to the pseudomorphism caused by the lattice mismatch between the Pb NPs and the Si matrix.

Abstract: Nano-sized nitrogen-doped carbon spheres are synthesized from two cheap, readily available and sustainable precursors: tannic acid and urea. In combination with a polymer structuring agent, nitrogen content, sphere size and the surface (up to 400 m(2)g(-1)) can be conveniently tuned by the precursor ratio, temperature and structuring agent content. Because the chosen precursors allow simple oven synthesis and avoid harsh conditions, this carbon nanosphere platform offers a more sustainable alternative to classical soots, for example, as printing pigments or conduction soots. The carbon spheres are demonstrated to be a promising as conductive carbon additive in anode materials for lithium ion batteries.

Abstract: We report the synthesis of colloidal CsPbX3-Pb4S3Br2 (X = Cl, Br, I) nanocrystal heterostructures, providing an example of a sharp and atomically resolved epitaxial interface between a metal halide perovskite and a non-perovskite lattice. The CsPbBr3-Pb4S3Br2 nanocrystals are prepared by a two-step direct synthesis using preformed subnanometer CsPbBr3 clusters. Density functional theory calculations indicate the creation of a quasi-type II alignment at the heterointerface as well as the formation of localized trap states, promoting ultrafast separation of photogenerated excitons and carrier trapping, as confirmed by spectroscopic experiments. Postsynthesis reaction with either Cl- or I- ions delivers the corresponding CsPbCI3-Pb4S3Br2 and CsPbI3-Pb4S3Br2 heterostructures, thus enabling anion exchange only in the perovskite domain. An increased structural rigidity is conferred to the perovskite lattice when it is interfaced with the chalcohalide lattice. This is attested by the improved stability of the metastable gamma phase (or “black” phase) of CsPbI3 in the CsPbI3-Pb4S3Br2 heterostructure.

Abstract: Good’s buffers can act both as nucleating and shape- directing agents during the synthesis of anisotropic gold nanostars (AuNS). Although different Good’s buffers can produce AuNS shapes with branches that are oriented along specific crystallographic directions, the mechanism is not fully understood. This paper reports how an analysis of the intermediate structures during AuNS synthesis from HEPES, EPPS, and MOPS Good’s buffers can provide insight into the formation of seedless AuNS. Electron tomography of AuNS structures quenched at early times (minutes) was used to characterize the morphology of the incipient seeds, and later times were used to construct the growth maps. Through this approach, we identified how the crystallinity and shape of the first structures synthesized with different Good’s buffers determine the final AuNS morphologies.

Abstract: Transmission electron microscopy is used to evaluate different deposition techniques, which optimize the microstructure and physical properties of superconducting thin films. High-resolution electron microscopy proves that the use of an YBa2Cu2Ox buffer layer can avoid a variable interface configuration in YBa2Cu3O7-delta thin films grown on SrTiO3. The growth can also be controlled at an atomic level by, using sub-unit cell layer epitaxy, which results in films with high quality and few structural defects. Epitaxial strain in Sr0.85La0.15CuO2 infinite layer thin films influences the critical temperature of these films, as well as the microstructure. Compressive stress is released by a modulated or a twinned microstructure, which eliminates superconductivity. On the other hand, also tensile strain seems to lower the critical temperature of the infinite layer.

Abstract: <script type='text/javascript'>document.write(unpmarked('By depositing ceria on the surface of yttrium stabilized zirconia (YSZ) nanocrystals and further activation under high-temperature reducing conditions, a 13% mol. CeO2/YSZ catalyst structured as subnanometer thick, pyrochlore-type, ceria-zirconia islands has been prepared. This nanostructured catalyst depicts not only high oxygen storage capacity (OSC) values but, more importantly, an outstandingly stable redox response upon oxidation and reduction treatments at very high temperatures, above 1000 degrees C. This behavior largely improves that observed on conventional ceria-zirconia solid solutions, not only of the same composition but also of those with much higher molar cerium contents. Advanced scanning transmission electron microscopy (STEM-XEDS) studies have revealed as key not only to detect the actual state of the lanthanide in this novel nanocatalyst but also to rationalize its unusual resistance to redox deactivation at very high temperatures. In particular, high-resolution X-ray dispersive energy studies have revealed the presence of unique bilayer ceria islands on top of the surface of YSZ nanocrystals, which remain at surface positions upon oxidation and reduction treatments up to 1000 degrees C. Diffusion of ceria into the bulk of these crystallites upon oxidation at 1100 degrees C irreversibly deteriorates both the reducibility and OSC of this nanostructured catalyst.'));

Abstract: The implementation of plasmonic nanoparticles in vivo remains hindered by important limitations such as biocompatibility, solubility in biological fluids, and physiological stability. A general and versatile protocol is presented, based on seeded emulsion polymerization, for the controlled encapsulation of gold and silver nanoparticles. This procedure enables the encapsulation of single nanoparticles as well as nanoparticle clusters inside a protecting polymer shell. Specifically, the efficient coating of nanoparticles of both metals is demonstrated, with final dimensions ranging between 50 and 200 nm, i.e., sizes of interest for bio-applications. Such hybrid nanocomposites display extraordinary stability in high ionic strength and oxidizing environments, along with high cellular uptake, and low cytotoxicity. Overall, the prepared nanostructures are promising candidates for plasmonic applications under biologically relevant conditions.