Structural Aspects of P2-Type Na0.67Mn0.6Ni0.2Li0.2O2 (MNL) Stabilization by Lithium Defects as a Cathode Material for Sodium-Ion Batteries

A known strategy for improving the properties of layered oxide electrodes in sodium-ion batteries is the partial substitution of transition metals by Li. Herein, the role of Li as a defect and its impact on sodium storage in P2-Na_0.67Mn_0.6Ni_0.2Li_0.2O₂ is discussed. In tandem with electrochemical studies, the electronic and atomic structure are studied using solid-state NMR, operando XRD, and density functional theory (DFT). For the as-synthesized material, Li is located in comparable amounts within the sodium and the transition metal oxide (TMO) layers. Desodiation leads to a redistribution of Li ions within the crystal lattice. During charging, Li ions from the Na layer first migrate to the TMO layer before reversing their course at low Na contents. There is little change in the lattice parameters during charging/discharging, indicating stabilization of the P2 structure. This leads to a solid-solution type storage mechanism (sloping voltage profile) and hence excellent cycle life with a capacity of 110 mAh g^-1 after 100 cycles. In contrast, the Li-free compositions Na_0.67Mn_0.6Ni_0.4O₂ and Na_0.67Mn_0.8Ni_0.2O₂ show phase transitions and a stair-case voltage profile. The capacity is found to originate from mainly Ni³⁺/Ni⁴⁺ and O^2-/O^2-δ redox processes by DFT, although a small contribution from Mn⁴⁺/Mn⁵⁺ to the capacity cannot be excluded.     

Chemoenzymatic Asymmetric Synthesis of Pyridine-Based α-Fluorinated Secondary Alcohols

Fluoro-substituted and heteroaromatic compounds are valuable intermediates for a variety of applications in pharma- and agrochemistry and synthetic chemistry. This study investigates the chemoenzymatic preparation of chiral alcohols bearing a heteroaromatic ring with an increasing degree of fluorination in α-position. Starting from readily available picoline derivatives prochiral α-halogenated acyl moieties were introduced with excellent selectivity and 64–95 % yield. The formed carbonyl group was subsequently reduced to the corresponding alcohols using the alcohol dehydrogenase from Lactobacillus kefir, yielding an enantiomeric excess of 95–>99 % and up to 98 % yield.     

Towards type-selective carbon nanotube growth at low substrate temperature via photo-thermal chemical vapour deposition

Carbon nanotubes have been intensively researched for electronic applications, driven by their excellent electronic properties, where the goals are control and reproducibility of growth, semiconducting/metallic type selectivity and maintaining high quality of carbon nanotubes, in a process that is temperature-compatible with the electronics. Photo-thermal chemical vapour deposition can achieve these goals and, through a thorough investigation of the parameter space, we achieve very high nanotube-quality and growth rates, and produce a phase-diagram that reveals distinct regions for growing semiconducting and metallic single-walled nanotubes, as well as multi-walled. Correlation with the carbon-catalyst phase diagram allows for the development of a novel growth model. We propose that the temperature-gradient induces carbon diffusivity-gradient across the catalyst to yield the high growth rate. This is attributed to the increase of α-iron of catalyst. The growth control demonstrated here allows for integration of the nanotube growth process by photo-thermal deposition into mainstream electronics manufacture.     

Structural properties of phosphorous-doped polycrystalline silicon

The structural properties and hydrogen bonding of undoped and phosphorous doped polycrystalline silicon produced by step-by-step laser dehydrogenation and crystallization technique were investigated using Raman spectroscopy and hydrogen effusion measurements. At low laser fluences, E_L, a two-layer system is created. This is accompanied by the change in hydrogen bonding. The intensity of the Si–H vibration mode at 2000 decreases faster than the one at 2100 cm⁻¹. This is even more pronounced in phosphorous-doped specimens. The laser crystallization results in an increase of the hydrogen binding energy by approximately 0.2–0.3 eV compared to the amorphous starting materials.     

High surface area submicrometer-sized β-SiC particles grown by shape memory synthesis method

A high surface area and non-microporous submicrometer-sized β-SiC material was successfully obtained according to the Shape Memory Synthesis (SMS) method. The attack by SiO vapors of a nanodiamond preform with sp³-bound carbon, at 1200–1300 °C under dynamic vacuum, formed β-SiC nanoparticles by carboreduction of the SiO vapors. These β-SiC nanoparticles had a mean size distribution centered at 10 nm and a specific surface area of 140 m²/g. The high carbon to carbide conversion obtained and the location of the remaining unreacted carbon in the core of the β-SiC nanoparticles allowed a direct use of the material as a catalyst support without any stabilizing post-synthesis oxidative treatment. The material showed dispersive properties and a good resistance towards oxidation, due to the presence of a thick and partially oxidized protecting amorphous coating, preventing from the extensive oxidation of SiC into silica.     

Formation of GaAsP interface layers monitored by reflectance anisotropy spectroscopy

Reflectance anisotropy spectroscopy (RAS) has been used to study As-by-P exchange during metalorganic vapor phase epitaxy. The study focuses on the processes occurring during switching from GaAs to GaInP, especially the effect of purging PH₃ over a GaAs surface. GaAsP/GaAs superlattices of different periodicity were grown and the P-content was determined by high-resolution x-ray diffraction and correlated to the RAS spectra. From the temperature dependence of the P-content, an activation energy of 0.56 eV was estimated for the incorporation mechanism. In addition to the insights into the processes at mixed group-V heterointerfaces, our study demonstrates the reproducibility of RAS transients that thus can be used for process monitoring.     

Investigation of Ni/4H-SiC diodes as radiation detectors with low doped n-type 4H-SiC epilayers

The development of SiC minimum ionising particle (MIP) detectors imposes severe constrains in the electronic quality and the thickness of the material due to the relatively high value of the energy required to produce an electron–hole pair in this material by MIP against the value for Si. In this work, particle detectors were made using semiconductor epitaxial undoped n-type 4H-SiC as the detection medium. The thickness of the epilayer is on the order of 40 μm and the detectors are realised by the formation of a nickel silicide on the silicon surface of the epitaxial layer (Schottky contact) and of the ohmic contact on the back side of 4H-SiC substrate. The low doping concentration (6×10¹³ cm⁻³) of the epilayer allows the detector to be totally depleted at relatively low reverse voltages (100 V). We present experimental data on the charge collection properties by using 5.486 MeV -particles impinging on the Schottky contact. A 100% charge collection efficiency (CCE) is demonstrated for reverse voltages higher than the one needed to have a depletion region equal to the -particle extrapolated range in SiC. The diffusion contribution of the minority change carriers to CCE is pointed out. By comparing measured CCE values to the outcomes of drift–diffusion simulation, values are inferred for the hole lifetime within the neutral region of the charge carrier generation layer.     

Ammoxidation of methylaromatics over vanadium phosphate catalysts II. Catalyst formation, active sites and reaction mechanism

The interactions of VOHPO₄· 0.5H₂O and (VO)₂P₂O₇ with the ammoxidation feed and the single components such as ammonia, oxygen, water and component mixtures were studied in detail using XRD and temperature-programmed reaction spectroscopy. The aim of this work was to improve the knowledge of the formation of the active phases or active sites of the catalysts from their precursors under the condition of the ammoxidation reaction. Similar catalytic properties of various applied VPO materials were discussed in terms of the presence of similar structure elements (domains of adjacent edge-sharing VO₆ octahedra-units and P-O-NH₄ groups).