C-H bond activation over metal oxides: A new insight into the dissociation kinetics from density functional theory

The C-H activation on metal oxides is a fundamental process in chemistry. In this paper, we report a density functional theory study on the process of the C-H activation of CH4 on Pd(111), Pt(111), Ru(0001), Tc(0001), Cu(111), PdO(001), PdO(110), and PdO(100). A linear relationship between the C-H activation barrier and the chemisorption in the dissociation final state on the metal surfaces is obtained, which is consistent with the work in the literature. However, the relationship is poor on the metal oxide surfaces. Instead, a strong linear correlation between the barrier and the lattice O-H bond strength is found on the oxides. The new linear relationship is analyzed and the physical origin is identified. (c) 2008 American Institute of Physics.

General insight into CO oxidation: A density functional theory study of the reaction mechanism on platinum oxides

CO oxidation on PtO2(110) has been studied using density functional theory calculations. Four possible reaction mechanisms were investigated and the most feasible one is the following: (i) the O at the bridge site of PtO2(110) reacts with CO on the coordinatively unsaturated site (CUS) with a negligible barrier; (ii) O-2 adsorbs on the bridge site and then interacts with CO on the CUS to form an OO-CO complex; (iii) the bond of O-OCO breaks to produce CO2 with a small barrier (0.01 eV). The CO oxidation mechanisms on metals and metal oxides are rationalized by a simple model: The O-surface bonding determines the reactivity on surfaces; it also determines whether the atomic or molecular mechanism is preferred. The reactivity on metal oxides is further found to be related to the 3rd ionization energy of the metal atom.

Microcolumn studies of dye adsorption onto manganese oxides modified diatomite

The method described here cannot fully replace the analysis of large columns by small test columns (microcolumns). The procedure, however, is suitable for speeding up the determination of adsorption parameters of dye onto the adsorbent and for speeding up the initial screening of a large adsorbent collection that can be tedious if a several adsorbents and adsorption conditions must be tested. The performance of methylene blue (MB), a basic dye, Cibacron reactive black (RB) and Cibacron reactive yellow (RY) was predicted in this way and the influence of initial dye concentration and other adsorption conditions on the adsorption behaviour were demonstrated.

Germanium on Sapphire By Wafer Bonding

This paper describes the creation of a germanium on sapphire platform, via wafer bonding technology, for system-on-a-chip applications. Similar thermal coefficients of expansion between germanium (5.8 x 10-6 K-1) and sapphire (5 x 10-6 K-1) make the bonding of germanium to sapphire a reality. Germanium directly bonded to sapphire results in microvoid generation during post bond annealing. Inclusion of an interface layer such as silicon dioxide layer by plasma enhanced chemical vapour deposition, prior to bonding, results in a microvoid free bond interface after annealing. Grinding and polishing of the subsequent germanium layer has been achieved leaving a thick germanium on sapphire (GeOS) substrate. Submicron GeOS layers have also been achieved with hydrogen/helium co-implantation and layer transfer. Circular geometry transistors exhibiting a field effect mobility of 890 cm2/V s have been fabricated onto the thick germanium on sapphire layer.

Germanium on sapphire

This paper explores the potential of germanium on sapphire (GeOS) wafers as a universal substrate for System on a Chip (SOC), mm wave integrated circuits (MMICs) and optical imagers. Ge has a lattice constant close to that of GaAs enabling epitaxial growth. Ge, GaAs and sapphire have relatively close temperature coefficients of expansion (TCE), enabling them to be combined without stress problems. Sapphire is transparent over the range 0.17 to 5.5 µm and has a very low loss tangent (a) for frequencies up to 72 GHz. Ge bonding to sapphire substrates has been investigated with regard to micro-voids and electrical quality of the Ge back interface. The advantages of a sapphire substrate for integrated inductors, coplanar waveguides and crosstalk suppression are also highlighted. MOS transistors have been fabricated on GeOS substrates, produced by the Smart-cut process, to illustrate the compatibility of the substrate with device processing. © 2008 World Scientific Publishing Company.

Mechanisms and chemistry of dye adsorption on manganese oxides-modified diatomite

The investigations into structural changes which occur during adsorbent modification and the adsorption mechanisms are essential for an effective design of adsorption systems. Manganese oxides were impregnated onto diatomite to form the type known as delta-birnessite. Initial investigations established the effectiveness of manganese oxides-modified diatomite (MOMD) to remove basic and reactive dyes from aqueous solution. The adsorption capacity of MOMD for methylene blue (MB), hydrolysed reactive black (RB) and hydrolysed reactive yellow (RY) was 320, 419, and 204 mg/g, respectively. Various analytical techniques were used to characterise the structure and the mechanisms of the dye adsorption process onto MOMD such as Fourier transform infrared (FTIR), X-ray diffraction (XRD) and atomic absorption spectrometry (A.A.). A small shift to higher values of the cl-spacing of dye/MOMD was observed indicating that a small amount of the dye molecules were intercalated in the MOMD structure and other molecules were adsorbed on the external surface of MOMD. Two mechanisms of dye adsorption onto MOMD were proposed; intercalation of the dye in the octahedral layers and adsorption of the dye on the MOMD external surface. Moreover, the results demonstrated that the MOMD structure was changed upon insertion of MB and RY with an obvious decrease in the intensity of the second main peak of the MOMD X-ray pattern. (C) 2009 Elsevier Ltd. All rights reserved.

Carboxyl-Functionalized Task-Specific Ionic Liquids for Solubilizing Metal Oxides

Imidazolium, pyridinium, pyrrolidinium, piperidinium, morpholinium, and quaternary ammonium bis(trifluoromethyl-sulfonyl)imide salts were functionalized with a carboxyl group. These ionic liquids are useful for the selective dissolution of metal oxides and hydroxides. Although these hydrophobic ionic liquids are immiscible with water at room temperature, several of them form a single phase with water at elevated temperatures. Phase separation occurs upon cooling. This thermomorphic behavior has been investigated by H-1 NMR, and it was found that it can be attributed to the temperature-dependent hydration and hydrogen-bond formation of the ionic liquid components. The crystal structures of four ionic liquids and five metal complexes have been determined.

Task-specific ionic liquid for solubilizing metal oxides

Protonated betaine bis(trifluoromethylsulfonyl) imide is an ionic liquid with the ability to dissolve large quantities of metal oxides. This metal-solubilizing power is selective. Soluble are oxides of the trivalent rare earths, uranium(VI) oxide, zinc(II) oxide, cadmium( II) oxide, mercury( II) oxide, nickel( II) oxide, copper(II) oxide, palladium(II) oxide, lead(II) oxide, manganese( II) oxide, and silver( I) oxide. Insoluble or very poorly soluble are iron(III), manganese(IV), and cobalt oxides, as well as aluminum oxide and silicon dioxide. The metals can be stripped from the ionic liquid by treatment of the ionic liquid with an acidic aqueous solution. After transfer of the metal ions to the aqueous phase, the ionic liquid can be recycled for reuse. Betainium bis( trifluoromethylsulfonyl) imide forms one phase with water at high temperatures, whereas phase separation occurs below 55.5 degrees C ( temperature switch behavior). The mixtures of the ionic liquid with water also show a pH-dependent phase behavior: two phases occur at low pH, whereas one phase is present under neutral or alkaline conditions. The structures, the energetics, and the charge distribution of the betaine cation and the bis( trifluoromethylsulfonyl) imide anion, as well as the cation-anion pairs, were studied by density functional theory calculations.

Germanium bonding to AI2O3

Germanium has been bonded to both single crystal Al2O 3 (sapphire) as well as fine grain Al2O3. A germanium to sapphire bonding energy of 3 J/m2 has been measured after a 200 °C bond anneal. Micro voids formed between the germanium/sapphire interface can be removed by employing an interfacial layer of silicon dioxide on either surface. Patterning the sapphire into a grid pattern prior to bonding creates an escape path for trapped gas or moisture allowing micro void free direct bonding to be achieved. Modifying the surface of the fine grain Al2O3 surface with a polycrystalline silicon deposition and polish creates a surface, having an rms roughness (measured over a 250© m2 area), of 1.5nm, suitable for bonding. Techniques employed in the germanium sapphire bonding can then be used in the bonding of fine grain A12O3 to germanium. © The Electrochemical Society.

Electrical characterization of ALD Al2O3 and HfO2 films on germanium

Al2O3 and HfO2 films were deposited on germanium substrates by atomic layer deposition (ALD) and analyzed by MOS capacitor electrical characterization. In-situ plasma nitridation performed prior to ALD was found to improve the stability of the interface. For Al 2O3/GeON/Ge capacitors, a 450°C anneal in nitrogen ambient reduced hysteresis and oxide fixed charge to 90 mV and 1012 cm-2 respectively, with low leakage current density. On the contrary, degradation was observed for un-nitrided Al2O3/Ge capacitors after 300 and 400°C post-metal anneals. HfO2/GeON/Ge capacitors benefitted from a 400°C densification anneal but exhibited degradation after post-metal anneals at temperatures greater than 300°C. This degradation is attributed to the influence of Al electrodes on the HfO 2 gate stack. HfO2 is considered to be a suitable material for the gate stack and Al2O3 for the buried dielectric in a GeOI structure. ©The Electrochemical Society.