Abstract: A new oxychloride Pb5Fe3TiO11Cl has been synthesized using the solid state method. Its crystal and magnetic structure was investigated in the 1.5550 K temperature range using electron diffraction, high angle annular dark field scanning transmission electron microscopy, atomic resolution energy dispersive X-ray spectroscopy, neutron and X-ray powder diffraction. At room temperature Pb5Fe3TiO11Cl crystallizes in the P4/mmm space group with the unit cell parameters a=3.91803(3) Å and c=19.3345(2) Å. Pb5Fe3TiO11Cl is a new n=4 member of the oxychloride perovskite-based homologous series An+1BnO3n−1Cl. The structure is built of truncated Pb3Fe3TiO11 quadruple perovskite blocks separated by CsCl-type Pb2Cl slabs. The perovskite blocks consist of two layers of (Fe,Ti)O6 octahedra sandwiched between two layers of (Fe,Ti)O5 square pyramids. The Ti4+ cations are preferentially located in the octahedral layers, however, the presence of a noticeable amount of Ti4+ in a five-fold coordination environment has been undoubtedly proven using neutron powder diffraction and atomic resolution compositional mapping. Pb5Fe3TiO11Cl is antiferromagnetically ordered below 450(10) K. The ordered Fe magnetic moments at 1.5 K are 4.06(4) μB and 3.86(5) μB on the octahedral and square-pyramidal sites, respectively.

Abstract: In this paper we analyse the gas phase production and loss pathways for several biomedically active species, i.e. N2(A), O, O3, O2(a), N, H, HO2, OH, NO, NO2, N2O5, H2O2, HNO2 and HNO3, in an argon plasma jet flowing into an open humid air atmosphere. For this purpose, we employ a zero-dimensional reaction kinetics model to mimic the typical experimental conditions by fitting several parameters to experimentally measured values. These include ambient air diffusion, the gas temperature profile and power deposition along the jet effluent. We focus in detail on how the pathways of the biomedically active species change as a function of the position in the effluent, i.e. inside the discharge device, active plasma jet effluent and afterglow region far from the nozzle. Moreover, we demonstrate how the reaction kinetics and species production are affected by different ambient air humidities, total deposited power into the plasma and gas temperature along the jet. It is shown that the dominant pathways can drastically change as a function of the distance from the nozzle exit or experimental conditions.

Abstract: Electron vortex beams have been predicted to enable atomic scale magnetic information measurement, via transfer of orbital angular momentum. Research so far has focused on developing production techniques and applications of these beams. However, methods to measure the outgoing orbital angular momentum distribution are also a crucial requirement towards this goal. Here, we use a method to obtain the orbital angular momentum decomposition of an electron beam, using a multipinhole interferometer. We demonstrate both its ability to accurately measure orbital angular momentum distribution, and its experimental limitations when used in a transmission electron microscope.

Abstract: Oriented attachment of synthetic semiconductor nanocrystals is emerging as a route for obtaining new semiconductors that can have Dirac-type electronic bands like graphene, but also strong spin-orbit coupling. The two-dimensional assembly geometry will require both atomic coherence and long-range periodicity of the superlattices. We show how the interfacial self-assembly and oriented attachment of nanocrystals results in two-dimensional (2D) metal chalcogenide semiconductors with a honeycomb superlattice. We present an extensive atomic and nanoscale characterization of these systems using direct imaging and wave scattering methods. The honeycomb superlattices are atomically coherent, and have an octahedral symmetry that is buckled; the nanocrystals occupy two parallel planes. Considerable necking and large-scale atomic motion occurred during the attachment process.

Abstract: Current-voltage analysis using different optical band pass filters has been performed on Cu2ZnSnSe4 and Cu2ZnSn(S, Se)(4) thin-film solar cells. When using red or orange light (i.e. wavelengths above 600 nm), a distortion appears in the I-V curve of the Cu2ZnSnSe4 solar cell, indicating an additional potential barrier to the current flow in the device for these conditions of illumination. This barrier is reduced when using a Cu2ZnSn(S, Se)(4) absorber. Numerical simulations demonstrate that the barrier visible under red light could be explained by a positive conduction band offset at the front interface coupled with compensating defects in the buffer layer.

Abstract: Gold-silica hybrids are appealing in different fields of applications like catalysis, sensorics, drug delivery, and biotechnology. In most cases, the morphology and distribution of the heterounits play significant roles in their functional behavior. Methods of synthesizing these hybrids, with variable ordering of the heterounits, are replete; however, a complete characterization in three dimensions could not be achieved yet. A simple route to the synthesis of Au-decorated SiO2 spheres is demonstrated and a study on the 3D ordering of the heterounits by scanning transmission electron microscopy (STEM) tomography is presentedat the final stage, intermediate stages of formation, and after heating the hybrid. The final hybrid evolves from a soft self-assembled structure of Au nanoparticles. The hybrid shows good thermal stability up to 400 degrees C, beyond which the Au particles start migrating inside the SiO2 matrix. This study provides an insight in the formation mechanism and thermal stability of the structures which are crucial factors for designing and applying such hybrids in fields of catalysis and biotechnology. As the method is general, it can be applied to make similar hybrids based on SiO2 by tuning the reaction chemistry as needed.

Abstract: The ground state of colloidal magnetic particles in a modulated channel are investigated as a function of the tilt angle of an applied magnetic field. The particles are confined by a parabolic potential in the transversal direction while in the axial direction a periodic substrate potential is present. By using Monte Carlo simulations, we construct a phase diagram for the different crystal structures as a function of the magnetic field orientation, strength of the modulated potential, and the commensurability factor of the system. Interestingly, we found first-and second-order phase transitions between different crystal structures, which can be manipulated by the orientation of the external magnetic field. A reentrant behavior is found between two-and four-chain configurations, with continuous second-order transitions. Novel configurations are found consisting of frozen solitons of defects. By changing the orientation and/or strength of the magnetic field and/or the strength and periodicity of the substrate potential, the system transits through different phases.

Abstract: Efforts to replace noble-metal catalysts by low-cost alternatives are of constant interest. The organometallic, non-aqueous wet-chemical synthesis of various hitherto unknown nanocrystalline Ni/Ga intermetallic materials and the use of NiGa for the selective semihydrogenation of alkynes to alkenes are reported. Thermal co-hydrogenolysis of the all-hydrocarbon precursors [Ni(COD)(2)] (COD = 1,5-cyclooctadiene) and GaCp* (Cp* = pentamethylcyclopentadienyl) in high-boiling organic solvents mesitylene and n-decane in molar ratios of 1 : 1, 2 : 3 and 3 : 1 yields the nano-crystalline powder materials of the over-all compositions NiGa, Ni2Ga3 and Ni3Ga, respectively. Microwave induced co-pyrolysis of the same precursors without additional hydrogen in the ionic liquid [BMIm][BF4] (BMIm = 1-butyl-3-methyl-imidazolium) selectively yields the intermetallic phases NiGa and Ni3Ga from the respective 1 : 1 and 3 : 1 molar ratios of the precursors. The obtained materials are characterized by transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDX), IR, powder X-ray diffraction (PXRD) and atomic absorption spectroscopy (AAS). The single-source precursor [Ni(GaCp*)(PMe3)(3)] with a fixed Ni : Ga stoichiometry of 1 : 1 was employed as well. In comparison with the co-hydrogenolytic dual precursor source approach it turned out to be less practical due to inefficient nickel incorporation caused by the parasitic formation of stable [Ni(PMe3)(4)]. The use of ionic liquid [BMIm][BF4] as a non-conventional solvent to control the reaction and stabilize the nanoparticles proved to be particularly advantageous and stable colloids of the nanoalloys NiGa and Ni3Ga were obtained. A phase-selective Ni/Ga colloid synthesis in conventional solvents and in the presence of surfactants such as hexadecylamine (HDA) was not feasible due to the undesired reactivity of HDA with GaCp* leading to inefficient gallium incorporation. Recyclable NiGa nanoparticles selectively semihydrogenate 1-octyne and diphenylacetylene (tolan) to 1-octene and diphenylethylene, respectively, with a yield of about 90% and selectivities of up to 94 and 87%. Ni-NPs yield alkanes with a selectivity of 97 or 78%, respectively, under the same conditions.

Abstract: The synthesis of a new class of fluorescent carbon nanomaterials, carbon-dot-decorated nanodiamonds (CDD-ND), is reported. These CDD-NDs are produced by specific acid treatment of detonation soot, forming tiny rounded sp2 carbon species (carbon dots), 12 atomic layers thick and 12 nm in size, covalently attached to the surface of the detonation diamond nanoparticles. A combination of nanodiamonds bonded with a graphitic phase as a starting material and the application of graphite intercalated acids for oxidation of the graphitic carbon is necessary for the successful production of CDD-ND. The CDD-ND photoluminescence (PL) is stable, 20 times more intense than the intrinsic PL of well-purified NDs and can be tailored by changing the oxidation process parameters. Carbon-dot-decorated DNDs are shown to be excellent probes for bioimaging applications and inexpensive additives for PL nanocomposites.

Abstract: Computer simulations based on the particle-in-cell/Monte Carlo collision method are performed to study the plasma characteristics and especially the transition in electron heating mechanisms in a hybrid direct current (dc)/dual-frequency (DF) capacitively coupled CF 4 discharge. When applying a superposed dc voltage, the plasma density first increases, then decreases, and finally increases again, which is in good agreement with experiments. This trend can be explained by the transition between the four main heating modes, i.e., DF coupling, dc and DF coupling, dc source dominant heating, and secondary electron dominant heating.

Abstract: We present the post-modification of a gallium based Metal Organic Framework, COMOC-4, with a Mo-complex. The resulting Mo@COMOC-4 was characterized by means of N2 sorption, XRPD, DRIFT, TGA, XRF, XPS and TEM analysis. The results demonstrate that even at high Mo-complex loadings on the framework, no aggregation or any Mo or Mo oxide species are formed. Moreover, the Mo@COMOC-4 was evaluated as a catalyst in the epoxidation of cyclohexene, cyclooctene and cyclododecene employing TBHP in decane as oxidant. The post-modified COMOC-4 exhibits a very high selectivity toward the epoxide (up to 100%). Regenerability and stability tests have been carried out demonstrating that the catalyst can be recycled without leaching of Mo or loss of crystallinity.