Artificial photosynthesis and the splitting of water to generate hydrogen

It is no exaggeration to state that the energy crisis is the most serious challenge that we face today. Among the strategies to gain access to reliable, renewable energy, the use of solar energy has clearly emerged as the most viable option. A promising direction in this context is artificial photosynthesis. In this article, we briefly describe the essential features of artificial photosynthesis in comparison with natural photosynthesis and point out the modest success that we have had in splitting water to produce oxygen and hydrogen, specially the latter.

Geochemical behaviour of dissolved trace elements in a monsoon-dominated tropical river basin, Southwestern India

The study presents a 3-year time series data on dissolved trace elements and rare earth elements (REEs) in a monsoon-dominated river basin, the Nethravati River in tropical Southwestern India. The river basin lies on the metamorphic transition boundary which separates the Peninsular Gneiss and Southern Granulitic province belonging to Archean and Tertiary-Quaternary period (Western Dharwar Craton). The basin lithology is mainly composed of granite gneiss, charnockite and metasediment. This study highlights the importance of time series data for better estimation of metal fluxes and to understand the geochemical behaviour of metals in a river basin. The dissolved trace elements show seasonality in the river water metal concentrations forming two distinct groups of metals. First group is composed of heavy metals and minor elements that show higher concentrations during dry season and lesser concentrations during the monsoon season. Second group is composed of metals belonging to lanthanides and actinides with higher concentration in the monsoon and lower concentrations during the dry season. Although the metal concentration of both the groups appears to be controlled by the discharge, there are important biogeochemical processes affecting their concentration. This includes redox reactions (for Fe, Mn, As, Mo, Ba and Ce) and pH-mediated adsorption/desorption reactions (for Ni, Co, Cr, Cu and REEs). The abundance of Fe and Mn oxyhydroxides as a result of redox processes could be driving the geochemical redistribution of metals in the river water. There is a Ce anomaly (Ce/Ce*) at different time periods, both negative and positive, in case of dissolved phase, whereas there is positive anomaly in the particulate and bed sediments. The Ce anomaly correlates with the variations in the dissolved oxygen indicating the redistribution of Ce between particulate and dissolved phase under acidic to neutral pH and lower concentrations of dissolved organic carbon. Unlike other tropical and major world rivers, the effect of organic complexation on metal variability is negligible in the Nethravati River water.

Anisotropic merging and splitting of dipolar Bose-Einstein condensates

We study the merging and splitting of quasi-two-dimensional Bose-Einstein condensates with strong dipolar interactions. We observe that if the dipoles have a non-zero component in the plane of the condensate, the dynamics of merging or splitting along two orthogonal directions, parallel and perpendicular to the projection of dipoles on the plane of the condensate, are different. The anisotropic merging and splitting of the condensate is a manifestation of the anisotropy of the roton-like mode in the dipolar system. The difference in dynamics disappears if the dipoles are oriented at right angles to the plane of the condensate as in this case the Bogoliubov dispersion, despite having roton-like features, is isotropic.

Noteworthy performance of La1-xCaxMnO3 perovskites in generating H-2 and CO by the thermochemical splitting of H2O and CO2

Perovskite oxides of the composition La1-xCaxMnO3 ( LCM) have been investigated for the thermochemical splitting of H2O and CO2 to produce H-2 and CO, respectively. The study was carried out in comparison with La1-xSrxMnO3, CeO2 and other oxides. The LCM system exhibits superior characteristics in high-temperature evolution of oxygen, and in reducing CO2 to CO and H2O to H-2. The best results were obtained with La0.5Ca0.5MnO3 whose performance is noteworthy compared to that of other oxides including ceria. The orthorhombic structure of LCM seems to be a crucial factor.

A comparative study of a direct discretization and an operator-splitting solver for population balance systems

A direct discretization approach and an operator-splitting scheme are applied for the numerical simulation of a population balance system which models the synthesis of urea with a uni-variate population. The problem is formulated in axisymmetric form and the setup is chosen such that a steady state is reached. Both solvers are assessed with respect to the accuracy of the results, where experimental data are used for comparison, and the efficiency of the simulations. Depending on the goal of simulations, to track the evolution of the process accurately or to reach the steady state fast, recommendations for the choice of the solver are given. (C) 2015 Elsevier Ltd. All rights reserved.

Markov chain splitting methods in structural reliability integral estimation

Monte Carlo simulation methods involving splitting of Markov chains have been used in evaluation of multi-fold integrals in different application areas. We examine in this paper the performance of these methods in the context of evaluation of reliability integrals from the point of view of characterizing the sampling fluctuations. The methods discussed include the Au-Beck subset simulation, Holmes-Diaconis-Ross method, and generalized splitting algorithm. A few improvisations based on first order reliability method are suggested to select algorithmic parameters of the latter two methods. The bias and sampling variance of the alternative estimators are discussed. Also, an approximation to the sampling distribution of some of these estimators is obtained. Illustrative examples involving component and series system reliability analyses are presented with a view to bring out the relative merits of alternative methods. (C) 2015 Elsevier Ltd. All rights reserved.

TiO2-RGO hybrid nanomaterials for enhanced water splitting reaction

The production of H-2 via photocatalytic water splitting reaction has attracted a great attention as a clean and renewable energy for next generation. Despite tremendous efforts, the present challenge for materials scientist is to develop highly active photo catalysts for splitting of water at low cost. This article reports the synthesis of TiO2-reduced graphene oxide hybrid nanomaterials through ionothermal method using functionalized ionic liquid for the enhanced hydrogen generation via water splitting reaction. The structural and morphological properties of the samples were investigated by XFtD, Raman spectroscopy, TG-DTA, UV-vis spectroscopy and TEM. A substantial increase of H-2 evolution was observed for TiO2-reduced graphene oxide hybrid nanomaterials. This is due to the high migration efficiency of photo-induced electrons and the inhibition of charge carrier recombination due to the electronic interaction between TiO2 and reduced graphene oxide. i.e, reduced graphene oxide acts as an electron-acceptor which effectively hinders the electron hole pair recombination of TiO2. Copyright (C) 2015, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

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.

Wild Ungulate Decision-Making and the Role of Tiny Refuges in Human-Dominated Landscapes

Wildlife conservation in human-dominated landscapes requires that we understand how animals, when making habitat-use decisions, obtain diverse and dynamically occurring resources while avoiding risks, induced by both natural predators and anthropogenic threats. Little is known about the underlying processes that enable wild animals to persist in densely populated human-dominated landscapes, particularly in developing countries. In a complex, semi-arid, fragmented, human-dominated agricultural landscape, we analyzed the habitat-use of blackbuck, a large herbivore endemic to the Indian sub-continent. We hypothesized that blackbuck would show flexible habitat-use behaviour and be risk averse when resource quality in the landscape is high, and less sensitive to risk otherwise. Overall, blackbuck appeared to be strongly influenced by human activity and they offset risks by using small protected patches (similar to 3 km(2)) when they could afford to do so. Blackbuck habitat use varied dynamically corresponding with seasonally-changing levels of resources and risks, with protected habitats registering maximum use. The findings show that human activities can strongly influence and perhaps limit ungulate habitat-use and behaviour, but spatial heterogeneity in risk, particularly the presence of refuges, can allow ungulates to persist in landscapes with high human and livestock densities.

Assessment of Microscale Test Methods of Peeling and Splitting along Surface of Thin-Film/Substrates

Peel test methods are assessed through being applied to a peeling analysis of the ductile film/ceramic substrate system. Through computing the fracture work of the system using the either beam bend model (BB model) or the general plane analysis model (GPA model), surprisingly, a big difference between both model results is found. Although the BB model can capture the plastic dissipation phenomenon for the ductile film case as the GPA model can, it is much sensitive to the choice of the peeling criterion parameters, and it overestimates the plastic bending effect unable to capture crack tip constraint plasticity. In view of the difficulty of measuring interfacial toughness using peel test method when film is the ductile material, a new test method, split test, is recommended and analyzed using the GPA model. The prediction is applied to a wedge-loaded experiment for Al-alloy double-cantilever beam in literature.

Diffusion dominated process for the crystal growth of a binary alloy

The pure diffusion process has been often used to study the crystal growth of a binary alloy in the microgravity environment. In the present paper, a geometric parameter, the ratio of the maximum deviation distance of curved solidification and melting interfaces from the plane to the radius of the crystal rod, was adopted as a small parameter, and the analytical solution was obtained based on the perturbation theory. The radial segregation of a diffusion dominated process was obtained for cases of arbitrary Peclet number in a region of finite extension with both a curved solidification interface and a curved melting interface. Two types of boundary conditions at the melting interface were analyzed. Some special cases such as infinite extension in the longitudinal direction and special range of Peclet number were reduced from the general solution and discussed in detail.

Viscosity-induced mode splitting and potential energy criterion for mode stability

This paper points out that viscosity can induce mode splitting in a uniform infinite cylinder of an incompressible fluid with self-gravitation, and that the potential energy criterion cannot be appropriate to all normal modes obtained, i.e., there will be stable modes with negative potential energy (<0). Therefore the condition >0 is not necessary, although sufficient, for the stability of a mode in an incompressible static fluid or magnetohydrodynamics (MHD) system, which is a correction of both Hare's [Philos. Mag. 8, 1305 (1959)] and Chandrasekhar's [Hydrodynamic and Hydromagnetic Stability (Oxford U.P., Oxford, 1961), p. 604] stability criterion for a mode. These results can also be extended to compressible systems with a polytropic exponent.

Splitting the fast and slow motions in molecular dynamics simulations based on the change of cold potential well bottom

Abstract. The atomic motion is coupled by the fast and slow components due to the high frequency vibration of atoms and the low frequency deformation of atomic lattice, respectively. A two-step approximate method was presented to determine the atomic slow motion. The first step is based on the change of the location of the cold potential well bottom and the second step is based on the average of the appropriate slow velocities of the surrounding atoms. The simple tensions of one-dimensional atoms and two-dimensional atoms were performed with the full molecular dynamics simulations. The conjugate gradient method was employed to determine the corresponding location of cold potential well bottom. Results show that our two-step approximate method is appropriate to determine the atomic slow motion under the low strain rate loading. This splitting method may be helpful to develop more efficient molecular modeling methods and simulations pertinent to realistic loading conditions of materials.

Abnormal phenomenon of ac Stark splitting in magneto-optical traps

We experimentally study the ac Stark splitting in D2 line of cold Rb-87 atoms. The frequency span between the Autler-Townes doublets is obviously larger than that derived from theoretical calculation. Two physical effects, which increase the effective Rabi frequency, contribute to the splitting broadening. First, atoms tend to distribute in strong lield places of a inhomogeneous red-detuned light field. Second, atoms reabsorb scattered light when they are huge in number and high in density.