Comparative X-ray photoelectron spectroscopic study on the desulfurization of thiophene by Raney Nickel and rapidly quenched skeletal nickel

The desulfurization of thiophene on Raney Ni and rapidly quenched skeletal Ni (RQ Ni) has been studied in ultrahigh vacuum (UHV) by X-ray photoelectron spectroscopy (XPS). The Raney Ni or RQ Ni can be approximated as a hydrogen-preadsorbed polycrystalline Ni-alumina composite. It is found that thiophene molecularly adsorbs on Raney Ni or RQ Ni at 103 K. At 173 K, thiophene on alumina is desorbed, while thiophene in direct contact with the metallic Ni in Raney Ni undergoes C-S bond scission, leading to carbonaceous species most probably in the metallocycle-like configuration and atomic sulfur. On RQ Ni, the temperature for thiophene dissociation is about 100 K higher than that on Raney Ni. The lower reactivity of RQ Ni toward thiophene is tentatively attributed to lattice expansion of Ni crystallites in RQ Ni due to rapid quenching. The existence of alumina and hydrogen may block the further cracking of the metallocycle-like species on Raney Ni and RQ Ni at higher temperatures, which has been the dominant reaction pathway on Ni single crystals. By 473 K, the C Is peak has disappeared, leaving nickel sulfide on the surface.

Resonant power conversion topologies for inductive charging of electrical vehicle batteries

This thesis is concerned with inductive charging of electric vehicle batteries. Rectified power form the 50/60 Hz utility feeds a dc-ac converter which delivers high-frequency ac power to the electric vehicle inductive coupling inlet. The inlet configuration has been defined by the Society of Automotive Engineers in Recommended Practice J-1773. This thesis studies converter topologies related to the series resonant converter. When coupled to the vehicle inlet, the frequency-controlled series-resonant converter results in a capacitively-filtered series-parallel LCLC (SP-LCLC) resonant converter topology with zero voltage switching and many other desirable features. A novel time-domain transformation analysis, termed Modal Analysis, is developed, using a state variable transformation, to analyze and characterize this multi-resonant fourth-orderconverter. Next, Fundamental Mode Approximation (FMA) Analysis, based on a voltage-source model of the load, and its novel extension, Rectifier-Compensated FMA (RCFMA) Analysis, are developed and applied to the SP-LCLC converter. The RCFMA Analysis is a simpler and more intuitive analysis than the Modal Analysis, and provides a relatively accurate closed-form solution for the converter behavior. Phase control of the SP-LCLC converter is investigated as a control option. FMA and RCFMA Analyses are used for detailed characterization. The analyses identify areas of operation, which are also validated experimentally, where it is advantageous to phase control the converter. A novel hybrid control scheme is proposed which integrates frequency and phase control and achieves reduced operating frequency range and improved partial-load efficiency. The phase-controlled SP-LCLC converter can also be configured with a parallel load and is an excellent option for the application. The resulting topology implements soft-switching over the entire load range and has high full-load and partial-load efficiencies. RCFMA Analysis is used to analyze and characterize the new converter topology, and good correlation is shown with experimental results. Finally, a novel single-stage power-factor-corrected ac-dc converter is introduced, which uses the current-source characteristic of the SP-LCLC topology to provide power factor correction over a wide output power range from zero to full load. This converter exhibits all the advantageous characteristics of its dc-dc counterpart, with a reduced parts count and cost. Simulation and experimental results verify the operation of the new converter.

Comparing impacts of new cropping systems on biodiversity in traditional rural China

This study selected six geographically-similar villages with traditional and alternative cultivation methods (two groups of three, one traditional and two alternatives) in two counties of Henan Province, China—a representative area of the Huang-huai-hai Plain representing traditional rural China. Soil heavy metal concentrations, floral and faunal biodiversity, and socio-economic data were recorded. Heavy metal concentrations of surface soils from three sites in each village were analysed using Inductively Coupled Plasma Mass Spectrometry (ICP-MS, chromium, nickel, copper, cadmium, and lead) and Atomic Absorption Spectrophotometer (AAS, zinc). The floral biodiversity of four land-use types was recorded following the Braun-Blanquet coverage-abundance method using 0.5×0.5m quadrats. The faunal biodiversity of two representative farmland plots was recorded using 0.3×0.3m quadrats at four 0.1m layers. The socio-economic data were recorded through face-to-face interviews of one hundred randomly selected households at each village. Results demonstrate different cultivation methods lead to different impact on above variables. Traditional cultivation led to lower heavy metal concentrations; both alternative managements were associated with massive agrochemical input causing heavy metal pollution in farmlands. Floral distribution was significantly affected by village factors. Diverse cultivation supported high floral biodiversity through multi-scale heterogeneous landscapes containing niches and habitats. Faunal distribution was also significantly affected by village factor nested within soil depth. Different faunal groups responded differently, with Acari being taxonomically diverse and Collembola high in densities. Increase in manual labour and crop number in villages using alternative cultivation may positively affect biodiversity. The results point to the conservation potential of diverse cultivation methods in traditional rural China and other regions under social and political reforms, where traditional agriculture is changing to unified, large-scale mechanized agriculture. This study serves as a baseline for conservation in small-holding agricultural areas of China, and points to the necessity of further studies at larger and longer scales.

Fabrication and characterization of doped and porous silicon nanowires as anodes for lithium ion batteries

By using Si(100) with different dopant type (n++-type (As) or p-type (B)), it is shown how metal-assisted chemically (MAC) etched silicon nanowires (Si NWs) can form with rough outer surfaces around a solid NW core for p-type NWs, and a unique, defined mesoporous structure for highly doped n-type NWs. High resolution electron microscopy techniques were used to define the characteristic roughening and mesoporous structure within the NWs and how such structures can form due to a judicious choice of carrier concentration and dopant type. Control of roughness and internal mesoporosity is demonstrated during the formation of Si NWs from highly doped n-type Si(100) during electroless etching through a systematic investigation of etching parameters (etching time, AgNO3 concentration, %HF and temperature). Raman scattering measurements of the transverse optical phonon confirm quantum size effects and phonon scattering in mesoporous wires associated with the etching condition, including quantum confinement effects for the nanocrystallites of Si comprising the internal structure of the mesoporous NWs. Laser power heating of NWs confirms phonon confinement and scattering from internal mesoporosity causing reduced thermal conductivity. The Li+ insertion and extraction characteristics at n-type and p-type Si(100) electrodes with different carrier density and doping type are investigated by cyclic voltammetry and constant current measurements. The insertion and extraction potentials are demonstrated to vary with cycling and the occurrence of an activation effect is shown in n-type electrodes where the charge capacity and voltammetric currents are found to be much higher than p-type electrodes. X-ray photo-electron spectroscopy (XPS) and Raman scattering demonstrate that highly doped n-type Si(100) retains Li as a silicide and converts to an amorphous phase as a two-step phase conversion process. The findings show the succinct dependence of Li insertion and extraction processes for uniformly doped Si(100) single crystals and how the doping type and its effect on the semiconductor-solution interface dominate Li insertion and extraction, composition, crystallinity changes and charge capacity. The effect of dopant, doping density and porosity of MAC etched Si NWs are investigated. The CV response is shown to change in area (current density) with increasing NW length and in profile shape with a changing porosity of the Si NWs. The CV response also changes with scan rate indicative of a transition from intercalation or alloying reactions, to pseudocapactive charge storage at higher scan rates and for p-type NWs. SEM and TEM show a change in structure of the NWs after Li insertion and extraction due to expansion and contraction of the Si NWs. Galvanostatic measurements show the cycling behavior and the Coulombic efficiency of the Si NWs in comparison to their bulk counterparts.

Formation and characterisation of ordered porous vanadium oxide inverse opal materials for Li-ion batteries

This thesis presents several routes towards achieving artificial opal templates by colloidal self-assembly of polystyrene (PS) or poly(methyl methacrylate) (PMMA) spheres and the use of these template for the fabrication of V2O5 inverse opals as cathode materials for lithium ion battery applications. First, through the manipulation of different experimental factors, several methods of affecting or directing opal growth towards realizing different structures, improving order and/or achieving faster formation on a variety of substrates are presented. The addition of the surfactant sodium dodecyl sulphate (SDS) at a concentration above the critical micelle concentration for SDS to a 5 wt% solution of PMMA spheres before dip-coating is presented as a method of achieving ordered 2D PhC monolayers on hydrophobic Au-coated silicon substrates at fast and slow rates of withdrawal. The effect that the degree of hydrophilicity of glass substrates has on the ordering of PMMA spheres is next investigated for a slow rate of withdrawal under noise agitation. Heating of the colloidal solution is also presented as a means of affecting order and thickness of opal deposits formed using fast rate dip coating. E-beam patterned substrates are shown as a means of altering the thermodynamically favoured FCC ordering of polystyrene spheres (PS) when dip coated at slow rate. Facile routes toward the synthesis of ordered V2O5 inverse opals are presented with direct infiltration of polymer sphere templates using liquid precursor. The use of different opal templates, both 2D and 3D partially ordered templates, is compared and the composition and arrangement of the subsequent IO structures post infiltration and calcination for various procedures is characterised. V2O5 IOs are also synthesised by electrodeposition from an aqueous VOSO4 solution at constant voltage. Electrochemical characterisation of these structures as cathode material for Li-ion batteries is assessed in a half cell arrangement for samples deposited on stainless steel foil substrates. Improved rate capabilities are demonstrated for these materials over bulk V2O5, with the improvement attributed to the shorter Li ion diffusion distances and increased electrolyte infiltration provided by the IO structure.

Increasing Stability of Lithium-Ion Batteries with Ordered Graphene Silicon Negative Electrodes

Currently, lackluster battery capability is restricting the widespread integration of Smart Grids, limiting the long-term feasibility of alternative, green energy conversion technologies. Silicon nanoparticles have great conductivity for applications in rechargeable batteries, but have degradation issues due to changes in volume during lithiation/delithiation cycles. To combat this, we use electrochemical deposition to uniformly space silicon particles on graphene sheets to create a more stable structure. We found the process of electrochemical deposition degraded the graphene binding in the electrode material, severely reducing charge capacity. But, the usage of mechanically mixing silicon particles with grapheme yielded batteries better than those that are commercially available.

Cyclic voltammetry and spectroelectrochemical study of nickel and cobalt diphenyltetraazaannulene complexes

The absorption spectra. cyclic voltammetry and spectroelectrochemistry of [Ni(II)DPTAA] and [Co(II)DPTAA] (DPTAA = 6,13-diphenyldibenzo[b,i][1,4,8,11] tetraaza[14]annulene) complexes in DMF are reported in detail. The ligand oxidation is observed for [Ni(II)DPTAA] at +0.70 V vs. SCE whereas Ni2(+/+) occurs at - 1.60 V. For [Co(II)DPTAA], a ligand oxidation redox couple is seen at +0.56 V while the Co2+/+ and Co2+/3+ redox couples appear at -1.21 and +0.24 V, respectively. All observed redox couples are assigned to reversible one-electron processes on account of peak separations and scan-rate dependency. These processes were further investigated by spectroelectrochemistry for [Co(II)DPTAA]. For [Co(II)DPTAA], axial ligation of pyridine was found to shift the Co2+/3+ redox couple more negative. while the ligand oxidation was shifted to more positive potentials. From a spectrophotometric titration of [Co(II)DPTAA] with pyridine an equilibrium constant, K-f, was determined for the binding of pyridine to [Co(II)DPTAA]. This was found to be 10.2 dm(3) mol(-1), slightly lower than that of [Co(II)TAA], indicating the influence of the phenyl groups. From this value and shifts in the Co2+/3+ redox couple upon ligation, an equilibrium constant for the binding of pyridine to [Co(III)DPTAA], K'(f), was found to be 5.06 x 10(6) dm(3) mol(-1). (c) 2007 Elsevier B.V. All rights reserved.

Hormesis - Stimulation Of Colony Growth In Campanularia-Flexuosa (Hydrozoa) By Copper Cadmium And Other Toxicants

It is shown experimentally that subinhibitory concentrations of a number of toxic, or other agents that are typically inhibitory (copper, cadmium, tributyl tin fluoride, reduced salinity), may stimulate the growth of colonies of the hydroid Campanularia flexuosa, exhibiting a phenomenon known as hormesis. It is suggested that the stimulation of growth is not due to the specific properties of the different toxicants, but to an adaptive response of the hydroid to the inhibitory effect that they have in common. Growth is regulated by a control mechanism and it is proposed that the increased growth is a consequence of overcorrections to low levels of an inhibitory challenge. Examination of the toxicological literature shows that hormesis is a more common occurrence that is generally supposed, and it is suggested that the explanation given here might apply in other cases of hormesis.

Simulating The Impact Of Technological-Change On Dissolved Cadmium Distribution In The Severn Estuary

An estuarine model is described which computes the dispersive and advective properties of the Severn Estuary. It was calibrated and validated using 50 measured salinity distributions and then used to predict the magnitude and sitings of the major inputs of dissolved cadmium levels throughout the estuary. The results provided an impetus for implementing tighter controls on effluents and for improving estimates of cadmium discharges from industrial sources. The model has also been used to investigate the sensitivity of the estuarine system to changes in dispersion; by considering large reductions in the dispersion coefficients it is hoped that the results might be indicative of the environmental consequences following the construction of a tidal power generating scheme.