Oxide reduction in NiO-containing solid solution systems during transmission electron microscopy

The effects of electron irradiation on NiO-containing solid solution systems are described. Partially hydrated NiO solid solutions, e. g. , NiO-MgO, undergo surface reduction to Ni metal after examination by TEM. This surface layer results in the formation of Moire interference patterns.

Chemical vapor deposited boron carbide : growth by a vapor-liquid-solid process

Detailed analytical electron microscope (AEM) studies of yellow whiskers produced by chemical vapor deposition (CVD)1 show that two basic types of whiskers are produced at low temperatures (between 1200°C and 1400°C) and low boron to carbon gas ratios. Both whisker types show planar microstructures such as twin planes and stacking faults oriented parallel to, or at a rhombohedral angle to, the growth direction. For both whisker types, the presence of droplet-like terminations containing both Si and Ni indicate that the growth process during CVD is via a vapor-liquid-solid (VLS) mechanism.

A hybrid smoothed finite element method (H-SFEM) to solid mechanics problems

In this paper, a hybrid smoothed finite element method (H-SFEM) is developed for solid mechanics problems by combining techniques of finite element method (FEM) and Node-based smoothed finite element method (NS-FEM) using a triangular mesh. A parameter is equipped into H-SFEM, and the strain field is further assumed to be the weighted average between compatible stains from FEM and smoothed strains from NS-FEM. We prove theoretically that the strain energy obtained from the H-SFEM solution lies in between those from the compatible FEM solution and the NS-FEM solution, which guarantees the convergence of H-SFEM. Intensive numerical studies are conducted to verify these theoretical results and show that (1) the upper and lower bound solutions can always be obtained by adjusting ; (2) there exists a preferable at which the H-SFEM can produce the ultrasonic accurate solution.

Effect of preparation method of palygorskite-supported Fe and Ni catalysts on catalytic cracking of biomass tar

In this study, the effect of catalyst preparation and additive precursors on the catalytic decomposition of biomass using palygorskite-supported Fe and Ni catalysts was investigated. The catalysts were characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). It is concluded that the most active additive precursor was Fe(NO3)3·9H2O. As for the catalyst preparation method, co-precipitation had superiority over incipient wetness impregnation at low Fe loadings.

A flexible solid-state pulsed power topology

Advances in solid-state switches and power electronics techniques have led to the development of compact, efficient and more reliable pulsed power systems. This paper proposes an efficient scheme that utilizes modular switch-capacitor units in obtaining high voltage levels with fast rise time (dv/dt) using low voltage solid-state switches. The proposed pulsed power supply has flexibility in terms of controlling energy and generating broad range of voltage levels. The energy flow can be controlled as the stored energy can be adjusted by a current source utilized at the first stage of the system. Desirable voltage level can be obtained by connecting adequate number of switch-capacitor units. Moreover, the proposed topology is load independent. Therefore it can easily supply wide range of applications especially the low impedance ones. The effectiveness of the proposed approach is verified by simulations

Nitrogen removal from natural gas using solid boron : A first-principles computational study

Selective separation of nitrogen (N2) from methane (CH4) is highly significant in natural gas purification, and it is very challenging to achieve this because of their nearly identical size (the molecular diameters of N2 and CH4 are 3.64 Å and 3.80 Å, respectively). Here we theoretically study the adsorption of N2 and CH4 on B12 cluster and solid boron surfaces a-B12 and c-B28. Our results show that these electron-deficiency boron materials have higher selectivity in adsorbing and capturing N2 than CH4, which provides very useful information for experimentally exploiting boron materials for natural gas purification.

A comparative study of different porous amorphous silica minerals supported TiO2 catalysts

Three porous amorphous silica minerals, including diatomite, opal and porous precipitated SiO2wereadopted to prepare supported TiO2catalysts by hydrolysis–deposition method. The prepared compoundmaterials were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Fouriertransform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM) and X-ray photo-electron spectroscopy (XPS). Through morphology and physical chemistry properties of the resultingTiO2/amorphous SiO2catalysts, it was proposed that the nature of silica supports could affect the particlesize and the crystal form of TiO2and then further influence the photocatalytic property of TiO2/amorphousSiO2catalysts. The catalytic properties of these porous amorphous silica supported photocatalysts(TiO2/SiO2) were investigated by UV-assisted degradation of Rhodamine B (RhB). Compared with pureTiO2(P25) and the other two TiO2/amorphous SiO2catalysts, TiO2/diatomite photocatalyst exhibits bet-ter catalytic performance at different calcined temperatures, the decoloration rate of which can be upto over 85% even at a relatively low calcined temperature. The TiO2/diatomite photocatalyst possessesmixed-phase TiO2with relatively smaller particles size, which might be responsible for higher photo-catalytic activity. Moreover, the stable and much inerter porous microstructure of diatomite could beanother key factor in improving its activity.

Blocking layer optimisation of poly(3-hexylthiopene)based solid state dye sensitized solar cells

The optimisation study of the fabrication of a compact TiO2 blocking layer (via Spray Pyrolysis Deposition) for poly (3-hexylthiopene) (P3HT) for Solid State Dye Sensitized Solar Cells (SDSCs) is reported. We used a novel spray TiO2 precursor solution composition obtained by adding acetylacetone to a conventional formulation (Diisopropoxytitanium bis (acetylacetonate) in ethanol). By Scanning Electron Microscopy a TiO2 layer with compact morphology and thickness of around 100 nmis shown. Through a Tafel plot analysis an enhancement of the device diode-like behaviour induced by the acetylacetone blocking layer respect to the conventional one is observed. Significantly, the device fabricatedwith the acetylacetone blocking layer shows an overall increment of the cell performance with respect to the cellwith the conventional one (DJsc/Jsc = +13.8%, DFF/FF = +39.7%, DPCE/PCE = +55.6%). A conversion efficiency optimumis found for 15 successive spray cycles where the diode-like behaviour of the acetylacetone blocking layer is more effective. Over three batches of cells (fabricated with P3HT and dye D35) an average conversion efficiency value of 3.9% (under a class A sun simulator with 1 sun A.M. 1.5 illumination conditions) was measured. From the best cell we fabricated a conversion efficiency value of 4.5% was extracted. This represents a significant increment with respect to previously reported values for P3HT/dye D35 based SDSCs.

Infrared study of the adsorption of NO, NO2 and CO on Rh/Al2O3 catalysts

Infrared spectra of NO, NO2 and CO adsorbed on Rh/Al2O3 have been recorded in order to identify the role of surface Rh-NO+ species in the reactions of NO and CO on Rh surfaces. Rh-NO+ was generated by thermally activated adsorption of NO, adsorption of NO on oxidised Rh or by adsorption of NO2. The latter also gave adsorbed nitrate on both Rh and the alumina support. In the presence of CO, Rh-NO+ acted as a precursor of the Rh(CO)(NO) mixed surface complex of CO and NO.

Infrared study of methyl formate and formaldehyde adsorption on reduced and oxidised silica-supported copper catalysts

Infrared spectra are reported of methyl formate and formaldehyde adsorbed at 300 K on silica, Cu/SiO2 reduced in hydrogen and Cu/SiO2 which had been oxidised by exposure to nitrous oxide after reduction. Silanol groups on silica form hydrogen bonds with carbonyl groups in weakly adsorbed methyl formate molecules. Methyl formate ligates via its carbonyl groups to Cu atoms in the surface of reduced copper. A low residual concentration of surface oxygen on copper promoted the slow reaction of ligated methyl formate to give a bridging formate species on copper and adsorbed methoxy groups. Methyl formate did not ligate to an oxidised copper surface but was rapidly chemisorbed to give unidentate formate and methoxy species. Formaldehyde slowly polymerises on silica to form trioxane and other oxymethylene species. The reaction is faster over Cu/SiO2 which, in the reduced state, also catalyses the formation of bridging formate anions adsorbed on copper. The reaction between formaldehyde and oxidised Cu/SiO2 leads to both unidentate and bidentate formate and adsorbed water.

Infrared study of the adsorption of formic acid on silica-supported copper and oxidised copper catalysts

Infrared spectra are reported of formic acid adsorbed at 300 K on a reduced copper catalyst (Cu/SiO2) and a copper surface which had been oxidised by exposure to nitrous oxide. Formic acid was weakly adsorbed on the silica support. Ligation of formic acid to the copper surface occurred only on the reduced catalyst. Dissociative adsorption resulted in the formation of unidentate formate on the oxidised catalyst. The presence of reduced copper metal instigated a rapid reorientation to a bidentate formate species.

Infrared study of CO adsorption on reduced and oxidised silica-supported copper catalysts

FTIR spectra are reported of CO adsorbed on silica-supported copper catalysts prepared from copper(II) acetate monohydrate. Fully oxidised catalyst gave bands due to CO on CuO, isolated Cu2+ cations on silica and anion vacancy sites in CuO. The highly dispersed CuO aggregated on reduction to metal particles which gave bands due to adsorbed CO characteristic of both low-index exposed planes and stepped sites on high-index planes. Partial surface oxidation with N2O or H2O generated Cu+ adsorption sites which were slowly reduced to Cu° by CO at 300 K. Surface carbonate initially formed from CO was also slowly depleted with time with the generation of CO2. The results are consistent with adsorbed carbonate being an intermediate in the water-gas shift reaction of H2O and CO to H2 and CO2.

Infrared study of the adsorption of methanol on oxidised and reduced Cu/SiO2 catalysts

Infrared spectra are reported of methanol adsorbed at 295 K on reduced Cu/SiO2 and on Cu/SiO2 which had been preoxidised by exposure to excess nitrous oxide. Methanol was chemisorbed on reduced Cu/SiO2 to give methoxy species on both silica and copper, gave a trace of formate on copper via reaction with residual surface oxygen, and was weakly adsorbed at SiOH sites on the silica support. Heating the adsorbed species at 393 K led to the loss of methoxy groups on copper and the concomitant formation of a bidentate surface formate. Heating reduced Cu/SiO2 in methanol at 538 K initially gave both gaseous and adsorbed (on Cu) methyl formate which subsequently decomposed to CO and hydrogen. The reactions of methanol with oxidised Cu/SiO2 were similar to those for the reduced catalyst although surface oxygen promoted the formation of surface methoxy groups on copper. Subsequent heating at 393 K led first to unidentate formate before the appearance of bidentate formate.

An in situ high pressure FT-IR study of CO2/H2 interactions with model ZnO/SiO2, Cu/SiO2 and Cu/ZnO/SiO2 methanol synthesis catalysts

In situ FT-IR spectroscopy allows the methanol synthesis reaction to be investigated under actual industrial conditions of 503 K and 10 MPa. On Cu/SiO2 catalyst formate species were initially formed which were subsequently hydrogenated to methanol. During the reaction a steady state concentration of formate species persisted on the copper. Additionally, a small quantity of gaseous methane was produced. In contrast, the reaction of CO2 and H2 on ZnO/SiO2 catalyst only resulted in the formation of zinc formate species: no methanol was detected. The interaction of CO2 and H2 with Cu/ZnO/SiO2 catalyst gave formate species on both copper and zinc oxide. Methanol was again formed by the hydrogenation of copper formate species. Steady-state concentrations of copper formate existed under actual industrial reaction conditions, and copper formate is the pivotal intermediate for methanol synthesis. Collation of these results with previous data on copper-based methanol synthesis catalysts allowed the formulation of a reaction mechanism

Evidence for the adsorption of molecules at special sites located at copper/zinc oxide interfaces. Part 2. -- A fourier-transform infrared spectroscopy study of methanol adsorption on reduced and oxidised Cu/ZnO/SiO2 catalysts

FTIR spectra are reported of methanol adsorbed at 295 K on ZnO/SiO 2, on reduced Cu/ZnO/SiO2 and on Cu/ZnO/SiO2 which had been preoxidised by exposure to nitrous oxide. Methanol on ZnO/SiO2 gave methoxy species on ZnO and SiO, in addition to both strongly and weakly physisorbed methanol on SiO2. The corresponding adsorption of methanol on reduced Cu/ZnO/SiO2 also gave methoxy species on Cu and a small amount of bridging formate. Reaction of methanol with a reoxidised Cu/ZnO/SiO2 catalyst resulted in an enhanced quantity of methoxy species on Cu. Heating adsorbed species on Cu/ZnO/SiO2 at 393 K led to the loss of methoxy groups on Cu and the concomitant formation of formate species on both ZnO and Cu. The comparable reaction on a reoxidised Cu/ZnO/SiO2 catalyst gave an increased amount of formate species on ZnO and this correlated with an increased quantity of methoxy groups lost from Cu. An explanation is given in terms of adsorption of formate and formaldehyde species at special sites located at the copper/zinc oxide interface.