Structural and electronic properties of graphite layers grown on SiC(0 0 0 1)

Photoelectron spectroscopy, low-energy electron diffraction, and scanning probe microscopy were used to investigate the electronic and structural properties of graphite layers grown by solid state graphitization of SiC(0 0 0 1) surfaces. The process leads to well-ordered graphite layers which are rotated against the substrate lattice by 30°. On on-axis 6H-SiC(0 0 0 1) substrates we observe graphitic layers with up to several 100 nm wide terraces. ARUPS spectra of the graphite layers grown on on-axis 6H-SiC(0 0 0 1) surfaces are indicative of a well-developed band structure. For the graphite/n-type 6H-SiC(0 0 0 1) layer system we observe a Schottky barrier height of ?_B,n = 0.3 ± 0.1 eV. ARUPS spectra of graphite layers grown on 8° off-axis oriented 4H-SiC(0 0 0 1) show unique replicas which are explained by a carpet-like growth mode combined with a step bunching of the substrate.     

Solid-state Electrochemistry of Gadolinium Hexacyanoferrate Modified Electrode and Electrocatalytic Properties of Gadolinium Hexacyanoferrate

A new electroactive polynuclear inorganic compound of rare earth metal, gadolinium hexacyanoferrate (GdHCF), was prepared and characterized using the techniques of FTIR spectroscopy, thermogravimetric analysis (TG), UV-Vis spectrometry, X-ray photoelectron spectroscopy (XPS), ICP atomic emission spectroscopy, and EDX. The results of ICP atomic emission spectroscopy, EDX, and TGA indicated that the prepared GdHCF sample had a stoichiometry of NaGdFe(CN)₆·12H₂O (when GdHCF was prepared in NaCl solution). The FTIR spectrum of GdHCF showed that there were two types of water molecules in the structure of GdHCF: one was the interstitial water (5 H₂O), which resulted from the association of water due to H-bonding, and the other was water coordinated with Gd (7 H₂O). The results obtained using XPS showed that the oxidation state of Fe and Gd in the GdHCF sample was +2 and +3, respectively. GdHCF was immobilized on the surface of spectroscopically pure graphite (SG) electrode forming the GdHCF/SG electrode, and the solid-state electrochemistry of the resultant electrode was studied using cyclic voltammetry. The cyclic voltammetric results indicated that the GdHCF/SG electrode exhibited a pair of well-defined and stable redox peaks with the formal potential of E^0′=(197±3) mV. The effects of the concentration of the supporting electrolyte on the electrochemical characteristics of GdHCF were studied, and the results showed that the value of E^0′ increased linearly with the activity of the cationic ion of the supporting electrolyte (lga_Na⁺), with a slope of 54.1 mV, which may become a novel method for determining the activity of Na⁺ in solution. Further experimental results indicated that GdHCF had electrocatalytic activities toward the oxidation of dopamine (DA) and ascorbic acid (AA), and the electrocatalytic current increased linearly with the concentration of DA (or AA) in the range of 1.0–10.0 mmol·L^?1 (for DA) or 0.5–20.0 mmol·L^?1 (for AA).     

Selective quenching of tryptophanyl fluorescence in bovine serum albumin by the iodide ion

Modified Stern-Volmer equation is obeyed by bovine serum albumin (BSA)-iodide system showing selective quenching of tryptophanyl fluorescence of BSA. The fraction of accessible protein fluorescence is 0.56 and the effective Stern-Volmer constant is 290 M^-1 at pH 7.4 in 0.005 M phosphate buffer at 25°C. Collisional quenching is operative both in the BSA -I⁻¹ system and the model system, tryptophan-I⁻¹. It is supported by the observed relationship between the ratio of quenching rate constants (k _q ) and diffusion coefficients and alsok _q with bulk viscosity.     

Titanium nanocarbides: Synthesis and modeling

The present state of research on the production and modeling of nanostructures based on titanium carbide-a typical representative of an extensive class of carbides of d-and f-metals-is reviewed. Methods for the synthesis of various Ti-C nanostructures (molecular clusters, nanocrystallites, nanospheres, nanofibers, nanowires) are examined, and their morphology, atomic structure, and known physicochemical characteristics are described. Theoretical models of the atomic structure and properties of new types of nanostructures in the titanium-carbon system (endo-and exohedral titanofullerenes, “hybrid” structures based on carbon nanotubes, the so-called peapods, nanocables, and a number of others) and the prospects for their application as components of nanoceramics, hydrogen accumulators, materials for spintronics, etc. are discussed. __________ Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 43, No. 1, pp. 1–23, January–February, 2007.     

Carbide precipitates in solution-quenched PH13-8 Mo stainless steel: A small-angle neutron scattering investigation

This paper deals with the small-angle neutron scattering (SANS) investigation on solution-quenched PH13-8 Mo stainless steel. From the nature of the variation of the functionality of the profiles for varying specimen thickness and also from the transmission electron microscopy (TEM), it has been established that the small-angle scattering signal predominantly originates from the block-like metallic carbide precipitates in the specimen. The contribution due to double Bragg reflection is not significant in the present case. The single scattering profile has been extracted from the experimental profiles corresponding to different values of specimen thickness. In order to avoid complexity and non-uniqueness of the multi-parameter minimization for randomly oriented polydisperse block-like precipitate model, the data have been analyzed assuming randomly oriented polydisperse cylindrical particle model with a locked aspect ratio.     

Interpretation of initial stage of 3C-SiC growth on Si(1 0 0) using dimethylsilane

The initial stage of cubic silicon carbide (3C-SiC) growth on a Si(0 0 1) surface using dimethylsilane (DMS) as a source gas was observed using scanning tunneling microscopy (STM) and reflection high-energy electron diffraction (RHEED). It was found that the dimer vacancies initially existing on the Si(0 0 1)-(2 × 1) surface were repaired by the Si atoms in DMS molecules, during the formation of the c(4 × 4) surface. From the STM measurement, nucleation of SiC was found to start when the Si surface was covered with the c(4 × 4) structure but before the appearance of SiC spots in the RHEED pattern. The growth mechanism of SiC islands was also discussed based on the results of RHEED, STM and temperature-programmed desorption (TPD).     

Microstructure Evolution in Laser RS Co-base Metastable Alloy

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Indium(I) iodide as a radical initiator: intramolecular cyclization of functionalized bromo-alkynes to substituted tetrahydrofurans

Aryl substituted α-carbonyl bromo-alkynes undergo facile cyclizations to the corresponding substituted 4-methylene-tetrahydrofurans using indium(I) iodide in acetonitrile under sonication in high yields. The reaction is predicted to proceed via a radical process initiated by InI and a plausible radical pathway is suggested.     

Flame Temperature Effect on the Structure of SiC Nanoparticles Grown by Laser Pyrolysis

Small SiC nanoparticles (10 nm diameter) have been grown in a flow reactor by CO₂ laser pyrolysis from a C₂H₂ and SiH₄ mixture. The laser radiation is strongly absorbed by SiH₄ vibration. The energy is transferred to the reactive medium and leads to the dissociation of molecules and the subsequent growth of the nanoparticles. The reaction happens with a flame. The purpose of the experiments reported in this paper is to limit the size of the growing particles to the nanometric scale for which specific properties are expected to appear. Therefore the effects of experimental parameters on the structure and chemical composition of nanoparticles have been investigated. For a given reactive mixture and gas velocity, the flame temperature is governed by the laser power. In this study, the temperature was varied from 875°C to 1100°C. The chemical analysis of the products indicate that their composition is a function of the temperature. For the same C/Si atomic ratio in the gaseous phase, the C/Si ratio in the powder increases from 0.7 at 875°C up to 1.02 at 1100°C, indicating a growth mechanism limited by C₂H₂ dissociation. As expected, X-ray diffraction has shown an improved crystallisation with increasing temperature. Transmission electron microscopy observations have revealed the formation of 10 nm grains for all values of laser power (or flame temperature). These grains appear amorphous at low temperature, whereas they contain an increasing number of nanocrystals (2 nm diameter) when the temperature increases. These results pave the way to a better control of the structure and chemical composition of laser synthesised SiC nanoparticles in the 10 nm range.     

Oxidative Coupling of Thiols to Disulfides with Ti(IV) in the Presence of NaI under Air Atmosphere

Ti(IV) as TiCl₃(O₃SCF₃) and TiO(O₂CCF₃)₂ are used as efficient catalysts for oxidative coupling of aliphatic, aromatic and heteroaromatic thiols to their disulfides in the presence of NaI under air atmosphere.