Abstract: Defects on hollow silica spheres synthesized in a tetraethylorthosilicate-octylamine-HCl-H2O system were recorded by scanning microscope. Based on the results, influences of synthesis composition on the formation of these defects are discussed. It is evidenced that products prepared with different octylamine-to-tetraethylorthosilicate ratios may have surface depressions, cracks and non-hollow microspheres. However, by changing water and acid additions, these defects could be reduced or eliminated. Generally, samples synthesized with a large octylamine addition commonly exhibit surface depressions. A small octylamine or a large water addition benefits the formation of solid silica microspheres among the product. Acid, although is not indispensable for the formation of hollow spheres, helps to eliminate or reduce depressions on the hollow shells. It is explained that the added acid gives rise to a relative localized fast hydrolysis versus condensation, facilitating an easy mobility of hydrolyzed silica species, and consequently the shell surface is smoothened.

Abstract: Plasma-enhanced chemical vapor deposition, without a nickel-containing gaseous precursor, was used to synthesize continuous nickel (Ni) nanorods inside the hollow cavity of carbon nanofibers (CNFs), thus forming vertically aligned Ni/CNF core/shell structures. Scanning and transmission electron microscopic images indicate that the elongated Ni nanorods originate from the catalyst particles at the tips of the CNFs and that their formation is due to the effect of extrusion induced by the compressive force of the graphene layers during growth. Different from previous work, each vertically-aligned core/shell structure reported is totally isolated from its neighbors. Continuous Ni nanorods are found to separate into smaller ones with increasing growth time, which was ascribed to (i) the limited amount of Ni available in the tip of the CNF, (ii) the polycrystalline nature of the Ni nanorods and (iii) the combined effects of the compressive stresses on the side of the Ni nanorods and of the tensile stress along their axis.

Abstract: Elektronen bewegen sich im feldfreien Raum immer gleichförmig geradlinig, so steht es in den Lehrbüchern. Falsch, sagen wir. Elektronen lassen sich zu Tornados formen, die theoretisch Nanopartikel zerreißen können. In der Elektronenmikroskopie eingesetzt, versprechen sie neue Erkenntnisse in der Festkörperphysik.

Abstract: We investigated the structural stability of perovskite solar cells (PSCs) in n-i-p configuration comprising a rubidium-caesium-methylammonium-formamidinium (Rb-Cs-MA-FA) lead iodide/bromide perovskite absorber, interfaced with nanostructured ZnO-nanorod (NR) or mesostructured (MS) TiO2 electron transfer layers (ETL). An in-situ setup was established comprising synchrotron grazing incidence diffraction (GID) and Raman spectroscopy as a function of temperature under ambient and isothermal conditions; measurements of current-voltage (IV) characteristics and electron microscopic investigations were conducted discretely.The aging of the solar cells was performed at ambient conditions or at elevated temperatures directly in the in -situ measurement setup. The diffraction depth profiling results point to different degradation rates for different ETLs; moreover, electron microscopy and atomic force microscopy, as well as energy dispersive spectroscopy clarified surface conditions in terms of the extent of the degradation. Scanning transmission electron microscopy of lamellas, derived by dual beam microscopy, revealed that the origin of the degradation lay in the ETL/ absorber interface. For the case of the nanostructured zincite, the perovskite absorber contained many voids, leading to the conclusion that the investigated quadruple perovskite absorber showed limited compatibility with ZnO NR ETL due to a higher number of defects. Morphological defects promoted the absorber degradation and nullified the advantages initially achieved by nanostructuring. The exchange of the ZnO NR ETL with MS TiO2 improved the stability parameters of the absorber layer.

Abstract: Carbon nanotubes (CNTs) with a polygonal cross-section have been paid increasing attention since their three-dimensional structure is related to specific physical properties, which are found to be different in comparison to CNTs with a circular cross-section. Here, we report the existence of novel multi-walled CNTs yielding walls with a rounded-hexagonal configuration. This structure was directly confirmed for the first time by both cross-sectional transmission electron microscopy and electron tomography. The morphology of the Fe catalytic particle also exhibits hexagonal characteristics, and is proposed as the origin of the formation of the rounded-hexagonal walls of the CNT. This observation is of great importance with respect to the design of polygonal (such as pentagonal or hexagonal) cross-sectional CNTs. By controlling the morphology of the catalytic nanoparticles it will be possible to grow CNTs with desired electronic and mechanical properties.

Abstract: Grains of K-feldspar are commonly seen as heterogeneous mixtures of mineral species and varieties with random microstructures. Most consider that observable features arise from incomplete re-equilibrations owing to slow kinetic and localized effects of aqueous fluids (catalyst), with geological environment and chemical impurities playing only a secondary role. Here, an alternative approach is explored by studying well-preserved regularities in the twin patterns of K-feldspars formed in the subsolidus stage from a historical perspective. Selected samples from granitic pegmatites were studied by polarized light optical microscopy (PLOM), electron-probe micro-analysis (EPMA), scanning (SEM) and transmission electron microscopy (TEM), cathodoluminescence imaging (CL), micro-Raman spectroscopy (MRS) and 31P nuclear magnetic resonance (NMR). We have found that the essential feature of this crystalline medium is the astounding capability to recrystallize in self-organized twin patterns. The mechanism involves coupling between short-range atomic motion, and long-range displacive correlations propagated as ideal and non-ideal Albite and Pericline orientations. We suggest a general evolutionary process to explain the development of macroscopic twin patterns in microcline, based on three twin generations as microtwins, macrotwins and cryptotwins. Evolutionary variants also were identified; they depend on both internal crystallochemical features and an external geological stimulus. We suggest a continuous monoclinictriclinic transformation for impure K-feldspar, whereas a discontinuous inversion occurs where the starting composition is close to the ideal chemical formula. Twin patterns can evolve by twin coarsening to single-orientation microcline if the system releases energy, or by twin fragmentation to finely twinned microcline if the system stores energy. Hence, K-feldspar is seen here as a very sensitive medium in which precious geological information is recorded in the form of twin patterns, and thus useful for general geological challenges.

Abstract: The study of shock metamorphism of olivine might help to constrain impact events in the history of meteorites. Although shock features in olivine are well known, so far, there are processes that are not yet completely understood. In shock veins, olivine clasts with a complex structure, with a ringwoodite rim and a dense network of lamellae of unidentified nature in the core, have been reported in the literature. A highly shocked (S5-6), L6 meteorite, Asuka 09584, which was recently collected in Antarctica by a Belgian-Japanese joint expedition, contains this type of shocked olivine clasts and has been, therefore, selected for detailed investigations of these features by transmission electron microscopy (TEM). Petrographic, geochemical, and crystallographic studies showed that the rim of these shocked clasts consists of an aggregate of nanocrystals of ringwoodite, with lower Mg/Fe ratio than the unshocked olivine. The clast's core consists of an aggregate of iso-oriented grains of olivine and wadsleyite, with higher Mg/Fe ratio than the unshocked olivine. This aggregate is crosscut by veinlets of nanocrystals of olivine, with extremely low Mg/Fe ratio. The formation of the ringwoodite rim is likely due to solid-state, diffusion-controlled, transformation from olivine under high-temperature conditions. The aggregate of iso-oriented olivine and wadsleyite crystals is interpreted to have formed also by a solid-state process, likely by coherent intracrystalline nucleation. Following the compression, shock release is believed to have caused opening of cracks and fractures in olivine and formation of olivine melt, which has lately crystallized under postshock equilibrium pressure conditions as olivine.

Abstract: The crystal structures of the three high-temperature polymorphs of K3AlF6 have been solved from neutron powder diffraction, synchrotron X-ray powder diffraction, and electron diffraction data. The β-phase (stable between 132 and 153 °C) and γ-phase (stable between 153 to 306 °C) can be described as unusually complex superstructures of the double-perovskite structure (K2KAlF6) which result from noncooperative tilting of the AlF6 octahedra. The β-phase is tetragonal, space group I4/m, with lattice parameters of a = 13.3862(5) Å and c = 8.5617(3) Å (at 143 °C) and Z = 10. In this phase, one-fifth of the AlF6 octahedra are rotated about the c-axis by 45° while the other four-fifths remain untilted. The large 45° rotations result in edge sharing between these AlF6 octahedra and the neighboring K-centered polyhedra, resulting in pentagonal bipyramidal coordination for four-fifths of the K+ ions that reside on the B-sites of the perovskite structure. The remaining one-fifth of the K+ ions on the B-sites retain octahedral coordination. The γ-phase is orthorhombic, space group Fddd, with lattice parameters of a = 36.1276(4) Å, b = 17.1133(2) Å, and c = 12.0562(1) Å (at 225 °C) and Z = 48. In the γ-phase, one-sixth of the AlF6 octahedra are randomly rotated about one of two directions by 45° while the other five-sixths remain essentially untilted. These rotations result in two-thirds of the K+ ions on the B-site obtaining 7-fold coordination while the other one-third remain in octahedral coordination. The δ-phase adopts the ideal cubic double-perovskite structure, space group Fmm, with a = 8.5943(1) Å at 400 °C. However, pair distribution function analysis shows that locally the δ-phase is quite different from its long-range average crystal structure. The AlF6 octahedra undergo large-amplitude rotations which are accompanied by off-center displacements of the K+ ions that occupy the 12-coordinate A-sites.

Abstract: Octahedral-shaped perovskite PbTiO3 nanocrystals (PT OCT) with well-defined {111} facets exposed have been successfully synthesized via a facile hydrothermal method by using LiNO3 as an ion surfactant. The Li-O bond on the surface of PT OCT nanocrystals is essential to the stability of such nanocrystals and also results in a dramatic high visible-light photocatalytic activity.

Abstract: The concept of protecting groups, widely used in organic chemistry, has been applied for the synthesis of Au-silica Janus stars, in which gold branches protrude from one half of Au-silica Janus spheres. This configuration opens up new possibilities to apply the plasmonic properties of gold nanostars, as well as a variety of chemical functionalizations on the silica component.

Abstract: As part of a mitigation and adaptation approach to increasing carbon dioxide atmospheric concentrations, we report superior performance of various metal-nitrogen-doped carbon catalysts, synthesized using an easily up-scalable method, for the electrochemical reduction to carbon monoxide and/or formate at industrially relevant current densities up to 200 mAcm−2. Altering the embedded transition metal (i.e. Sn, Co, Fe, Mn and Ni) allowed to tune the selectivity towards the desired product. Mn-N-C and Fe-N-C performance was compromised by its high CO* binding energy, while Co-N-C catalyzed preferentially the HER. Ni-N-C and Sn-N-C revealed to be promising electrocatalysts, the latter being evaluated for the first time in a flow reactor. A productivity of 589 L CO m-2 h-1 at -1.39 VRHE with Ni-N-C and 751 g HCOO- m-2 h-1 at -1.47 VRHE with Sn-N-C was achieved with no signs of degradation detected after 24 h of operation at industrially relevant current densities (100 mAcm−2). Stable operation at 200 mAcm−2 led to turnover frequencies for the production of carbon products of up to 5176 h-1. These enhanced productivities, in combination with high stability, constitute an essential step towards the scalability and ultimately towards the economical valorization of CO2 electrolyzers using metal-containing nitrogen-doped catalysts.

Abstract: With the aim of an improved understanding of the metal-complexation properties of alicyclic β-amino acid stereoisomers, and their peptides, the complex equilibria and modes of coordination with copper(II) of l-phenylalanine (F) derivatives of cis/trans-2-aminocyclohexanecarboxylic acid (c/tACHC), i.e. the dipeptides F-c/tACHC and c/tACHC-F, were investigated by a combination of CW and pulsed EPR methods. For the interpretation of the experimental data, DFT quantum-chemical calculations were carried out. Simulation of a pH-dependent series of room-temperature CW-EPR spectra revealed the presence of EPR-active complexes ([Cu(aqua)]2+, [CuL]+, [CuLH1], [CuLH2]−, and [CuL2H1]−), and an EPR-inactive species ([Cu2L2H3]−) in aqueous solutions for all studied cases. [CuLH]2+ was included in the equilibrium model for the c/tACHC-Fcopper(II) systems, and [CuL2], together with two coordination isomers of [CuL2H1]−, were also identified in the F-tACHCcopper(II) system. Comparison of the complexation properties of the diastereomeric ligand pair F-(1S,2R)-ACHC and F-(1R,2S)-ACHC did not reveal significant differences. Considerably lower formation constants were obtained for the trans than for the cis isomers for both the F-c/tACHC and the c/tACHC-F pairs in the case of [CuLH1] involving tridentate coordination by the amino, the deprotonated peptide, and the carboxylate groups. A detailed structural analysis by pulsed EPR methods and DFT calculations indicated that there was no significant destabilization for the complexes of the trans isomers. The lower stability of their complexes was explained by the limitation that only the conformer with donor groups in equatorialequatorial ring positions can bind to copper(II), whereas both equatorial-axial conformers of the cis isomers are capable of binding. From a consideration of the proton couplings obtained with X-band 1H HYSCORE, 2H exchange experiments, and DFT, the thermodynamically most stable cyclohexane ring conformer was assigned for all four [CuLH1] complexes. For the F-cACHC case, the conformer did not match the most stable conformer of the free ligand.

Abstract: The precipitation of a disordered FCC surface structure after low angle Ga+ ion irradiation during focused ion beam thinning of a B2 Cu-Zn-Al alloy with e/a=1.48 is reported. Conventional as well as high-resolution transmission electron microscopy techniques reveal FCC layers on both sides of the thinned sample. The occurrence of this structure is attributed to disordering and dezincification of the alloy resulting from the sputtering process during the irradiation. Changes in crystallographic sample orientation with respect to the incoming ion beam do not have a significant effect on the appearance of the FCC surface structure.