The electronic, chemical and electrocatalytic processes and intermediates on iron oxide surfaces during photoelectrochemical water splitting

We re-assess experimental soft X-ray absorption spectra of the oxygen K-shell which we recorded operando from iron oxide during photoelectrochemical water splitting in KOH electrolyte. In particular, we refer to recently reported transitional electron hole states which originate within the charge carrier depletion layer of the iron oxide and on the iron oxide surface. For the latter we find that an intermediate oxy-peroxo species is formed on the iron oxide with increasing bias potential, which disappears upon further polarization of the electrode, concomitantly with the evolution and disappearance of the aforementioned surface state. The oxygen spectra contain also the spectroscopic signatures of the electrolyte water, the position of which changes with increasing bias potential towards lower X-ray energies, revealing the breaking and formation of hydrogen bonds in the water during the experiment. Combined with potential dependent impedance spectroscopy data we are able to sketch the molecular structure of chemical intermediates and their charge carrier dynamics. (C) 2015 Elsevier B.V. All rights reserved.

Instrumentation and control of a two-stage 4-bed silica gel plus water adsorption cooling cum desalination system

This paper presents the instrumentation and control architecture for a laboratory based two-stage 4-bed silica gel + water adsorption system. The system consists of primarily two fluids: refrigerant (water vapour) and heat transfer fluid (water) flowing through various components. Heat input to the system is simulated using multiple heaters and ambient air is used as the heat sink. The laboratory setup incorporates a real time National Instruments (NI) controller to control several digital and analog valves, heaters, pumps and fans along with simultaneous data acquisition from various flow, pressure and temperature sensors. The paper also presents in detail the various automated and manual tasks required for successful operation of the system. Finally the system pressure and temperature dynamics are reported and its performance evaluated for various cycle times. (C) 2015 Elsevier Ltd. All rights reserved.

A dendrimer facilitates resonance energy transfer between hydrophobic aromatic guest molecules in water

A water soluble third generation poly(alkyl aryl ether) dendrimer was examined for its ability to solubilize hydrophobic polyaromatic molecules in water and facilitate non-radiative resonance energy transfer between them. One to two orders of magnitude higher aqueous solubilities of pyrene (PY), perylene (PE), acridine yellow (AY) and acridine orange (AO) were observed in presence of a defined concentration of the dendrimer. A reduction in the quantum yield of the donor PY* emission and a partial decrease in lifetime of the donor excited state revealed the occurrence of energy transfer from dendrimer solubilized excited PY to ground state PE molecules, both present within a dendrimer. The energy transfer efficiency was estimated to be similar to 61%. A cascade resonance energy transfer in a three component system, PY*-to-PE-to-AY and PY*-to-PE-to-AO, was demonstrated through incorporation of AY or AO in the two component PY-PE system. In the three-component system, excitation of PY resulted in emission from AY or AO via a cascade energy transfer process. Careful choice of dye molecules with good spectral overlap and the employment of dendrimer as the medium enabled us to expand absorption-emission wavelengths, from similar to 330 nm to similar to 600 nm in aqueous solution. (C) 2015 Elsevier B.V. All rights reserved.

Scaling analysis and numerical studies on water vapour adsorption in a columnar porous silica gel bed

This article presents a theoretical analysis of heat and mass transfer in a silica gel + water adsorption process using scaling principles. A two-dimensional columnar packed adsorber domain is chosen for the study, with side and bottom walls cooled and vapour inlet from the top. The adsorption process is initiated from the cold walls with a temperature jump of 15 K, whereas the water vapour supply is maintained at a constant inlet pressure of 1 kPa. The first part of the study is dedicated to deriving relevant scales for the adsorption process by an order of magnitude analysis of energy, continuity and momentum equations. In the latter part, the derived scales are compared with the outcome of numerical studies performed for various domain widths and aspect ratio of bed. A good correlation between scaling and simulation results is observed, thereby validating the scaling approach. (C) 2015 Elsevier Ltd. All rights reserved.

Experimental Investigation On The Slip Between Oil And Water In Horizontal Pipes

This work is devoted to study of the slip phenomenon between phases in water-oil two-phase flow in horizontal pipes. The emphasis is placed on the effects of input fluids flow rates, pipe diameter and viscosities of oil phase on the slip. Experiments were conducted to measure the holdup in two horizontal pipes with 0.05 m diameter and 0.025 m diameter, respectively, using two different viscosities of white oil and tap water as liquid phases. Results showed that the ratios of in situ oil to water velocity at the pipe of small diameter are higher than those at the pipe of big diameter when having same input flow rates. At low input water flow rate, there is a large deviation on the holdup between two flow systems with different oil viscosities and the deviation becomes gradually smaller with further increased input water flow rate. (C) 2008 Elsevier Inc. All rights reserved.

Shallow Water Model On Cubed-Sphere By Multi-Moment Finite Volume Method

A global numerical model for shallow water flows on the cubed-sphere grid is proposed in this paper. The model is constructed by using the constrained interpolation profile/multi-moment finite volume method (CIP/MM FVM). Two kinds of moments, i.e. the point value (PV) and the volume-integrated average (VIA) are defined and independently updated in the present model by different numerical formulations. The Lax-Friedrichs upwind splitting is used to update the PV moment in terms of a derivative Riemann problem, and a finite volume formulation derived by integrating the governing equations over each mesh element is used to predict the VIA moment. The cubed-sphere grid is applied to get around the polar singularity and to obtain uniform grid spacing for a spherical geometry. Highly localized reconstruction in CIP/MM FVM is well suited for the cubed-sphere grid, especially in dealing with the discontinuity in the coordinates between different patches. The mass conservation is completely achieved over the whole globe. The numerical model has been verified by Williamson's standard test set for shallow water equation model on sphere. The results reveal that the present model is competitive to most existing ones. (C) 2008 Elsevier Inc. All rights reserved.

Effect Of Water On Brittle Fracture Of Sio2 By Molecular Dynamics Study

The influence of water on the brittle behavior of beta-cristobalite is studied by means of molecular dynamics (MD) simulation With the TTAM potential. Crack extension of mode 1 type is observed as the crack opening is filled LIP With water. The critical stress intensity factor K-lc(MD) is used to characterize the crack extension of MD simulation. The surface energy of SiO2 covered with layers of water is calculated at temperature of 300 K. Based oil the Griffith fracture criterion, the critical stress intensity factor K-lc(Griffith) is calculated, and it is in good agreement with that of MD simulation. (C) 2008 Elsevier B.V. All rights reserved.

Deformation Of Pdms Membrane And Microcantilever By A Water Droplet: Comparison Between Mooney-Rivlin And Linear Elastic Constitutive Models

In this paper, we studied the role of vertical component Of Surface tension of a water droplet on the deformation of membranes and microcantilevers (MCLs) widely used in lab-on-a-chip and micro-and nano-electromechanical system (MEMS/NEMS). Firstly, a membrane made of a rubber-like material, poly(dimethylsiloxane) (PDMS), was considered. The deformation was investigated using the Mooney-Rivlin (MR) model and the linear elastic constitutive relation, respectively. By comparison between the numerical solutions with two different models, we found that the simple linear elastic model is accurate enough to describe such kind of problem, which would be quite convenient for engineering applications. Furthermore, based on small-deflection beam theory, the effect of a liquid droplet on the deflection of a MCL was also studied. The free-end deflection of the MCL was investigated by considering different cases like a cylindrical droplet, a spherical droplet centered on the MCL and a spherical droplet arbitrarily positioned on the MCL. Numerical simulations demonstrated that the deflection might not be neglected, and showed good agreement with our theoretical analyses. (C) 2008 Elsevier Inc. All rights reserved.

Nonlinear X-wave formation and conical emission at different powers of a femtosecond laser pulse in water

Nonlinear X-wave formation at different pulse powers in water is simulated using the standard model of nonlinear Schrodinger equation (NLSE). It is shown that in near field X-shape originally emerges from the interplay between radial diffraction and optical Kerr effect. At relatively low power group-velocity dispersion (GVD) arrests the collapse and leads to pulse splitting on axis. With high enough power, multi-photon ionization (NIPI) and multi-photon absorption (MPA) play great importance in arresting the collapse. The tailing part of pulse is first defocused by MPI and then refocuses. Pulse splitting on axis is a manifestation of this process. Double X-wave forms when the split sub-pulses are self-focusing. In the far field, the character of the central X structure of conical emission (CE) is directly related to the single or double X-shape in the near field. (c) 2007 Elsevier B.V. All rights reserved.

Femtosecond laser-induced ZnSe nanowires on the surface of a ZnSe wafer in water

We present a simple route for ZnSe nanowire growth in the ablation crater on a ZnSe crystal surface. The crystal wafer, which was horizontally dipped in pure water, was irradiated by femtosecond laser pulses. No furnace, vacuum chamber or any metal catalyst were used in this experiment. The size of the nanowires is about 1-3 mu m long and 50-150 nm in diameter. The growth rate is 1-3 mu m/s, which is much higher than that achieved with molecular-beam epitaxy and chemical vapor deposition methods. Our discovery reveals a rapid and simple way to grow nanowires on designed micro-patterns, which may have potential applications in microscopic optoelectronics. (C) 2007 Elsevier Ltd. All rights reserved.

Effect of water content in sol on optical properties of hybrid sol-gel derived TiO2/SiO2/ormosil film

Sol-gel derived TiO2/SiO2/ormosil hybrid planar waveguides have been deposited on soda-lime glass slides and silicon substrates, films were heat treated at 150 degreesC for 2 h or dried at room temperature. Different amounts of water were added to sols to study their impacts on microstructures and optical properties of films. The samples were characterized by m-line spectroscopy, Fourier transform infrared spectroscopy (FT-IR), UV/VIS/NIR spectrophotometer (UV-vis), atomic force microscopy (AFM), thermal analysis instrument and scattering-detection method. The refractive index was found to have the largest value at the molar ratio H2O/OR = 1 in sol (OR means -OCH3, -OC2H5 and -OC4H9 in the sol), whereas the thickest film appears at H2O/OR = 1/2. The rms surface roughness of all the films is lower than 1.1 nm, and increases with the increase of water content in sol. Higher water content leads to higher attenuation of film. (C) 2004 Elsevier B.V. All rights reserved.

Near-complete transuranic waste incineration in a thorium fuelled pressurised water reactor

The production of long-lived transuranic (TRU) waste is a major disadvantage of fission-based nuclear power. Incineration, and virtual elimination, of waste stockpiles is possible in a thorium (Th) fuelled critical or subcritical fast reactor. Fuel cycles producing a net decrease in TRUs are possible in conventional pressurised water reactors (PWRs). However, minor actinides (MAs) have a detrimental effect on reactivity and stability, ultimately limiting the quality and quantity of waste that can be incinerated. In this paper, we propose using a thorium-retained-actinides fuel cycle in PWRs, where the reactor is fuelled with a mixture of thorium and TRU waste, and after discharge all actinides are reprocessed and returned to the reactor. To investigate the feasibility and performance of this fuel cycle an assembly-level analysis for a one-batch reloading strategy was completed over 125 years of operation using WIMS 9. This one-batch analysis was performed for simplicity, but allowed an indicative assessment of the performance of a four-batch fuel management strategy. The build-up of 233U in the reactor allowed continued reactive and stable operation, until all significant actinide populations had reached pseudo-equilibrium in the reactor. It was therefore possible to achieve near-complete transuranic waste incineration, even for fuels with significant MA content. The average incineration rate was initially around 330 kg per GW th year and tended towards 250 kg per GW th year over several decades: a performance comparable to that achieved in a fast reactor. Using multiple batch fuel management, competitive or improved end-of-cycle burn-up appears achievable. The void coefficient (VC), moderator temperature coefficient (MTC) and Doppler coefficient remained negative. The quantity of soluble boron required for a fixed fuel cycle length was comparable to that for enriched uranium fuel, and acceptable amounts can be added without causing a positive VC or MTC. This analysis is limited by the consideration of a single fuel assembly, and it will be necessary to perform a full core coupled neutronic-thermal-hydraulic analysis to determine if the design in its current form is feasible. In particular, the potential for positive VCs if the core is highly or locally voided is a cause for concern. However, these results provide a compelling case for further work on concept feasibility and fuel management, which is in progress. © 2011 Elsevier Ltd. All rights reserved.

The performance of closed reactor grade plutonium-thorium fuel cycles in reduced-moderation pressurised water reactors

The production of long-lived transuranic (TRU) waste is a major disadvantage of fission-based nuclear power. Previous work has indicated that TRU waste can be virtually eliminated in a pressurised water reactor (PWR) fuelled with a mixture of thorium and TRU waste, when all actinides are returned to the reactor after reprocessing. However, the optimal configuration for a fuel assembly operating this fuel cycle is likely to differ from the current configuration. In this paper, the differences in performance obtained in a reduced-moderation PWR operating this fuel cycle were investigated using WIMS. The chosen configuration allowed an increase of at least 20% in attainable burn-up for a given TRU enrichment. This will be especially important if the practical limit on TRU enrichment is low. The moderator reactivity coefficients limit the enrichment possible in the reactor, and this limit is particularly severe if a negative void coefficient is required for a fully voided core. Several strategies have been identified to mitigate this. Specifically, the control system should be designed to avoid a detrimental effect on moderator reactivity coefficients. The economic viability of this concept is likely to be dependent on the achievable thermal-hydraulic operating conditions. © 2012 Elsevier Ltd. All rights reserved.

Light water breeding with nitride fuel

This scoping study proposes using mixed nitride fuel in Pu-based high conversion LWR designs in order to increase the breeding ratio. The higher density fuel reduces the hydrogen-to-heavy metal ratio in the reactor which results in a harder spectrum in which breeding is more effective. A Resource-renewable Boiling Water Reactor (RBWR) assembly was modeled in MCNP to demonstrate this effect in a typical high conversion LWR design. It was determined that changing the fuel from (U,TRU)O2 to (U,TRU)N in the assembly can increase its fissile inventory ratio (fissile Pu mass divided by initial fissile Pu mass) from 1.04 to up to 1.17. © 2011 Elsevier Ltd. All rights reserved.

Mechanism study on the frequent variations of cell-bound microcystins in cyanobacterial blooms in Lake Taihu: Implications for water quality monitoring and assessments

Although Microcystis-based toxins have been intensively studied, previous studies using laboratory cultures of Microcystis strains are difficult to explain the phenomenon that microcystin concentrations and toxin variants in natural blooms differ widely and frequently within a short-term period. The present study was designed to unravel the mechanisms for the frequent variations of intracellular toxins related to the differences in cyanobacterial colonies during bloom seasons in Lake Taihu, China. Monitoring of Microcystis colonies during warm seasons indicated that the variations in microcystins in both concentrations and toxin species were associated with the frequent alteration of Microcystis colonies in Lake Taihu. High concentration of microcystins in the blooms was always associated with two Microcystis colonies, Microcystis flos-aquae and Microcystis aeruginosa, whereas when Microcystis wesenbergii was the dominant colonial type, the toxin production of the blooms was low. Additionally, environmental factors such as temperature and nutrition were also shown to have an effect on the toxin production of the blooms, and may also potentially influence the Microcystis species present. The results of the present study provides insight into a new consideration for quick water quality monitoring, assessment and risk alert in cyanobacterium- and toxin-contaminated freshwaters, which will be beneficial not only for water agencies but also for public health. (C) 2009 Elsevier Ltd. All rights reserved.