Application of molecular models to electronic structure calculations of defects in oxide crystals. I. Parametrization of the modified INDO method

A modified calculation scheme of the INDO method is applied for calculating the electronic structure of perfect and imperfect oxide crystals. In order to obtain a flexible scheme permitting reliable calculation of both the electronic structure and the defect conformations, the INDO parameters for H, Li, Mg, Si, O are fitted directly to reproduce one-electron energies as well as the vicinity of the potential energy curve minima for a series of diatomic molecules and the electronic structure of MgO and -crystoballite form of SiO₂. The method is tested on the Li₂SiO₃ crystal calculated within the framework of the large unit cell model.     

Dynamics of low-coordinated surface atoms on gold nanocrystallites

The authors highlight the importance of transient configurations of atoms on the surface of nanocrystallites, and present methodologies for their investigation. A Monte Carlo method has been developed and is used to simulate the thermodynamic equilibrium of nanometer sized Au nanocrystallites, both free and supported on a MgO(100) surface. The authors find that appreciable numbers of atoms transiently occupy adatom positions on Au(111) facets, even at room temperature. This type of dynamically appearing site is usually neglected in relation to catalysis but may have a significant activity (for CO oxidation, for example). They also observe a complex solid-solid roughening transition which involves a variety of transient local atom configurations on the surface of nanocrystallites.     

Controlled manipulation of atoms in insulating surfaces with the virtual atomic force microscope

We predict how single oxygen ions can be manipulated on the MgO (100) surface and demonstrate the possibility of detecting a single-atom event using a noncontact atomic force microscope. The manipulation process is simulated explicitly in real time with a virtual dynamic atomic force microscope including the full response of the instrumentation and demonstrates a strong dependence on temperature. The proposed new atomistic mechanism and protocols for the controlled manipulation of single atoms and vacancies on insulating surfaces may be relevant for anchoring molecules and metal clusters at these surfaces and controlling their electronic properties.     

Relative energies of surface and defect states: ab initio calculations for the MgO (001) surface

We present the results of calculations of the energy levels of defects at the (001) surface of MgO relative to the top of the valence band and values of defect ionisation potentials and electron affinities. The calculations were made using an embedded cluster method in which a cluster of several tens of ions treated quantum mechanically is embedded in a finite array of polarisable and point ions modelling the crystalline potential and the classical polarisation of the host lattice. The calculated ionisation potential of the ideal surface, which fixes the position of the top of the valence band with respect to the vacuum level, is about 6.7 eV. This value is used as a reference for positioning the energy levels of three charge states of a surface anion vacancy, which are also calculated as ionisation energies with respect to the vacuum level. The surface and vacancy electron affinities are calculated using the same method. As a prototype low-coordinated surface site, we have considered a cube corner. Our calculations predict the splitting of the corner states from the top of the surface valence band by about 1.0 eV. Both unrelaxed and relaxed holes are strongly localised at the corner oxygen ion. The ionisation energies and electron affinities of the corner anion vacancy are calculated. The electrons in the F and F⁺ centres at the corner are shown to be significantly delocalised over surrounding Mg ions.     

Influence of Support Type and Metal Loading in Methane Decomposition over Iron Catalyst for Hydrogen Production

Natural gas resources, stimulate the method of catalytic methane decomposition. Hydrogen is a superb energy carrier and integral component of the present energy systems, while carbon nanotubes exhibit remarkable chemical and physical properties. The reaction was run at 700 °C in a fixed bed reactor. Catalyst calcination and reduction were done at 500 °C. MgO, TiO₂ and Al₂O₃ supported catalysts were prepared using a co‐precipitation method. Catalysts of different iron loadings were characterized with BET, TGA, XRD, H₂‐TPR and TEM. The catalyst characterization revealed the formation of multi‐walled nanotubes. Alternatively, time on stream tests of supported catalyst at 700 °C revealed the relative profiles of methane conversions increased as the %Fe loading was increased. Higher %Fe loadings decreased surface area of the catalyst. Iron catalyst supported with Al₂O₃ exhibited somewhat higher catalytic activity compared with MgO and TiO₂ supported catalysts when above 35% Fe loading was used. CH₄ conversion of 69% was obtained utilizing 60% Fe/Al₂O₃ catalyst. Alternatively, Fe/MgO catalysts gave the highest initial conversions when iron loading below 30% was employed. Indeed, catalysts with 15% Fe/MgO gave 63% conversion and good stability for 1 h time on stream. Inappropriateness of Fe/TiO₂ catalysts in the catalytic methane decomposition was observed.     

Ultra high performance liquid chromatography with mass spectrometry method for the simultaneous determination of phenolic constituents in honey from various floral sources using multiwalled carbon nanotubes as extraction sorbents

An ultra high performance liquid chromatography with mass spectrometry method has been developed for the simultaneous separation, identification and determination of 22 phenolic constituents in honey from various floral sources from Yemen. Solid‐phase extraction was used for extraction of the target phenolic constituents from honey samples, while multiwalled carbon nanotubes were used as solid‐phase adsorbent. The chromatographic separation of all phenolic constituents was performed on a BEH C₁₈ column using a linear gradient elution with a binary mobile phase mixture of aqueous 0.1% formic acid and methanol. The quantitation was carried out in selected ion reaction monitoring acquisition mode. The total amount of phenolic acids, flavonoids and other phenols in each analyzed honey was found in the range of 338–3312, 122–5482 and 2.4–1342 μg/100 g of honey, respectively. 4‐Hydroxybenzoic acid was found to be the major phenolic acid. The main detected flavonoid was chrysin, while cinnamic acid was found to be the major other phenol compound. The regeneration of solid phase adsorbent to be reused and recovery results confirm that the proposed method could be potentially used for the routine analysis of phenolic constituents in honey extract.     

Reactivity of (H)(e) color centers at the MgO surface: formation of O2 and N2 radical anions

We have considered the interaction of O₂ and N₂ molecules with electrons trapped at the surface of MgO by performing embedded cluster DFT calculations. Trapped electrons at the surface of MgO react instantaneously with O₂ and N₂ leading to the formation of the corresponding O₂⁻ and N₂⁻ molecular anions stabilized at specific surface sites. So far, the atomistic model for this process was based on the idea that the electrons are trapped at oxygen vacancies, the F_S⁺ centers. Recently, it has been shown that morphological sites at the MgO surface like a reverse corner, a step or a corner, can adsorb hydrogen and stabilize (H⁺)(e⁻) pairs giving rise to a new class of paramagnetic color centers. Here we show that these centers exhibit reactivity towards O₂ and N₂, which is fully consistent with the experimental observations, providing further support to the new model of electron traps at the MgO surface.     

Functionalized nanoparticles based solid‐phase membrane micro‐tip extraction and high‐performance liquid chromatography analyses of vitamin B complex in human plasma

Iron nanoparticles were prepared by a green method following functionalization using 1‐butyl‐3‐methylimidazolium bromide. 1‐Butyl‐3‐methylimidazole iron nanoparticles were characterized using FTIR spectroscopy, energy dispersive X‐ray fluorescence, X‐ray diffraction, scanning electron microscopy and transmission electron microscopy. The nanoparticles were used in solid‐phase membrane micro‐tip extraction to separate vitamin B complex from plasma before high‐performance liquid chromatography. The optimum conditions obtained were sorbent (15 mg), agitation time (30 min), pH (9.0), desorbing solvent [water (5 mL) + methanol (5 mL) + sodium hydroxide (0.1 N) + acetic acid (d = 1.05 kg/L, pH 5.5), desorbing volume (10 mL) and desorption time (30 min). The percentage recoveries of all the eight vitamin B complex were from 60 to 83%. A high‐performance liquid chromatography method was developed using a PhE column (250 × 4.6 mm, 5.0 μm) and water/acetonitrile (95:5, v/v; pH 4.0 with 0.1% formic acid) mobile phase. The flow rate was 1.0 mL/min with detection at 270 and 210 nm. The values of the capacity, separation and resolution factor were 0.57–39.47, 1.12–6.00 and 1.84–26.26, respectively. The developed sample preparation and chromatographic methods were fast, selective, inexpensive, economic and reproducible. The developed method can be applied for analyzing these drugs in biological and environmental matrices.     

Dipole-dipole interactions and the structure of self-assembled monolayers

The structure of self-assembled monolayers (SAMs) on the gold (111) surface is still a matter of debate despite a considerable experimental and theoretical effort. We address the problem from a new perspective, studying the influence of electrostatic interactions on the degree of disorder in COOH-terminated SAMs. We show that the HS(CH2)(n-1)COOH molecules carry two dipole moments associated with their head- and tail-groups. Depending on the coupling of these dipole moments along the molecules, the structure of the COOH-SAMs either resembles the structure of the corresponding alkanethiol monolayers (short molecules, strong dipole coupling) or shows a more complex behavior (long molecules, weak dipole coupling). In the latter case, the monolayer exhibits a crystalline-like order with respect to the hydrocarbon chains and a high degree of disorder with respect to the carboxylic head-groups. These results resolve the controversy of experimental data on the degree of order in COOH-monolayers with near-edge X-ray absorption fine structure spectroscopy (Himmel, H.-J.; Weiss, K.; J?ger, B.; Dannenberger, O.; Grunze, M.; W?ll, Ch. Langmuir 1997, 13, 4943), probing the tail-groups, showing that the monolayer is largely disordered, and the infrared data (Nuzzo, R. G.; Dubois, L. H.; Allara, D. L. J. Am. Chem. Soc. 1990, 112, 558) on the C-H stretching modes suggesting a crystalline-like order of the hydrocarbon chains.