Effect of the nature of a transition metal dopant in BaTiO3 perovskite on the catalytic reduction of nitrobenzene

In the present study, we have synthesized Fe, Co and Ni doped BaTiO3 catalyst by a wet chemical synthesis method using oxalic acid as a chelating agent. The concentration of the metal dopant varies from 0 to 5 mol% in the catalysts. The physical and chemical properties of doped BaTiO3 catalysts were studied using various analytical methods such as X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), BET surface area and Transmission electron microscopy (TEM). The acidic strength of the catalysts was measured using a n-butylamine potentiometric titration method. The bulk BaTiO3 catalyst exhibits a tetragonal phase with the P4mm space group. A structural transition from tetrahedral to cubic phase was observed for Fe, Co and Ni doped BaTiO3 catalysts with an increase in doped metal concentration from 1 to 5 mol%. The particle sizes of the catalysts were calculated from TEM images and are in the range of 30-80 nm. All the catalysts were tested for the catalytic reduction of nitrobenzene to azoxybenzene. The BaTiO3 catalyst was found to be highly active and less selective compared to the doped catalysts which are active and highly selective towards azoxybenzene. The increase in selectivity towards azoxybenzene is due to an increase in acidic strength and reduction ability of the doped metal. It was also observed that the nature of the metal dopant and their content at the B-site has an impact on the catalytic reduction of nitrobenzene. The Co doped BaTiO3 catalyst showed better activity with only 0.5 mol% doping than Fe and Ni doped BaTiO3 catalysts with maximum nitrobenzene conversion of 91% with 78% selectivity to azoxybenzene. An optimum Fe loading of 2.5 mol% in BaTiO3 is required to achieve 100% conversion with 93% selectivity whereas Ni with 5 mol% showed a conversion of 93% and a azoxybenzene selectivity of 84%.

Conformal perturbation theory and higher spin entanglement entropy on the torus

We study the free fermion theory in 1+1 dimensions deformed by chemical potentials for holomorphic, conserved currents at finite temperature and on a spatial circle. For a spin-three chemical potential mu, the deformation is related at high temperatures to a higher spin black hole in hs0] theory on AdS(3) spacetime. We calculate the order mu(2) corrections to the single interval Renyi and entanglement entropies on the torus using the bosonized formulation. A consistent result, satisfying all checks, emerges upon carefully accounting for both perturbative and winding mode contributions in the bosonized language. The order mu(2) corrections involve integrals that are finite but potentially sensitive to contact term singularities. We propose and apply a prescription for defining such integrals which matches the Hamiltonian picture and passes several non-trivial checks for both thermal corrections and the Renyi entropies at this order. The thermal corrections are given by a weight six quasi-modular form, whilst the Renyi entropies are controlled by quasi-elliptic functions of the interval length with modular weight six. We also point out the well known connection between the perturbative expansion of the partition function in powers of the spin-three chemical potential and the Gross-Taylor genus expansion of large-N Yang-Mills theory on the torus. We note the absence of winding mode contributions in this connection, which suggests qualitatively different entanglement entropies for the two systems.

Do carboximide-carboxylic acid combinations form co-crystals? The role of hydroxyl substitution on the formation of co-crystals and eutectics

Carboxylic acids, amides and imides are key organic systems which provide understanding of molecular recognition and binding phenomena important in biological and pharmaceutical settings. In this context, studies of their mutual interactions and compatibility through co-crystallization may pave the way for greater understanding and new applications of their combinations. Extensive co-crystallization studies are available for carboxylic acid/amide combinations, but only a few examples of carboxylic acid/imide co-crystals are currently observed in the literature. The non-formation of co-crystals for carboxylic acid/imide combinations has previously been rationalized, based on steric and computed stability factors. In the light of the growing awareness of eutectic mixtures as an alternative outcome in co-crystallization experiments, the nature of various benzoic acid/cyclic imide combinations is established in this paper. Since an additional functional group can provide sites for new intermolecular interactions and, potentially, promote supramolecular growth into a co-crystal, benzoic acids decorated with one or more hydroxyl groups have been systematically screened for co-crystallization with one unsaturated and two saturated cyclic imides. The facile formation of an abundant number of hydroxybenzoic acid/cyclic carboximide co-crystals is reported, including polymorphic and variable stoichiometry co-crystals. In the cases where co-crystals did not form, the combinations are shown invariably to result in eutectics. The presence or absence and geometric disposition of hydroxyl functionality on benzoic acid is thus found to drive the formation of co- crystals or eutectics for the studied carboxylic acid/imide combinations.

Influence of a Counterion on the Ion Atmosphere of an Anion: A Molecular Dynamics Study of LiX and CsX (X = F-, Cl-, I-) in Methanol

We report molecular dynamics (MD) simulations to explore the influence of a counterion on the structure and dynamics of cationic and anionic solvation shells for various ions in methanol at 298 K. We show that the variation in ionic size of either the cation or the anion in an ion pair influences the solvation structure of the other ion as well as the diffusivity in an electrolyte solution of methanol. The extent of ionic association between the cation and its counteranion of different ionic sizes has been investigated by analyzing the radial distribution functions (RDFs) and the orientation of methanol molecules in the first solvation shell (FSS) of ions. It is shown that the methanol in the FSS of the anion as well the cation exhibit quite different radial and orientational structures as compared to methanol which lie in the FSS of either the anion or the cation but not both. We find that the coordination number (CN) of F-, Cr-, and I- ions decreases with increasing size of the anion which is contrary to the trend reported for the anions in H2O. The mean residence time (MRT) of methanol molecules in the FSS of ions has been calculated using the stable states picture (SSP) approach. It is seen that the ion-counterion interaction has a considerable influence on the MRT of methanol molecules in the FSS of ions. We also discuss the stability order of the ion-counterion using the potentials of mean force (PMFs) for ion pairs with ions of different sizes. The PMF plots reveal that the Li+-F- pair (small-small) is highly stable and the Li+-I- pair is least stable (small-large) in electrolyte solutions.

A Few Case Studies on the Correlation of Particle Network and Its Stability on the Ionic Conductivity of Solid-Liquid Composite Electrolytes

We discuss here the crucial role of the particle network and its stability on the long-range ion transport in solid liquid composite electrolytes. The solid liquid composite electrolytes chosen for the study here comprise nanometer sized silica (SiO2) particles having various surface chemical functionalities dispersed in nonaqueous lithium salt solutions, viz, lithium perchlorate (LiClO4) in two different polyethylene glycol based solvents. These systems constitute representative examples of an independent class of soft matter electrolytes known as ``soggy sand'' electrolytes, which have tremendous potential in diverse electrochemical devices. The oxide additive acts as a heterogeneous dopant creating free charge carriers and enhancing the local ion transport. For long-range transport, however, a stable spanning particle network is needed. Systematic experimental investigations here reveal that the spatial and time dependent characteristics of the particle network in the liquid solution are nontrivial. The network characteristics are predominantly determined by the chemical makeup of the electrolyte components and the chemical interactions between them. It is noteworthy that in this study the steady state macroscopic ionic conductivity and viscosity of the solid liquid composite electrolyte are observed to be greatly determined by the additive oxide surface chemical functionality, solvent chemical composition, and solvent dielectric constant.

Common effect of chemical and external pressures on the magnetic properties of RCoPO (R = La, Pr, Nd, Sm). II.

We investigate the direct correspondence between Co band ferromagnetism and structural parameters in the pnictide oxides RCoPO for different rare-earth ions (R = La, Pr, Nd, Sm) by means of muon-spin spectroscopy and ab initio calculations, complementing our results published previously G. Prando et al., Common effect of chemical and external pressures on the magnetic properties of RCoPO (R = La, Pr), Phys. Rev. B 87, 064401 (2013)]. We find that both the transition temperature to the ferromagnetic phase T-C and the volume of the crystallographic unit cell V are conveniently tuned by the R ionic radius and/or external pressure. We report a linear correlation between T-C and V and our ab initio calculations unambiguously demonstrate a full equivalence of chemical and external pressures. As such, we show that R ions influence the ferromagnetic phase only via the induced structural shrinkage without involving any active role from the electronic f degrees of freedom, which are only giving a sizable magnetic contribution at much lower temperatures.

Impact of lifetime control on the threshold of quantum dot lasers

Despite significant improvements in their properties as emitters, colloidal quantum dots have not had much success in emerging as suitable materials for laser applications. Gain in most colloidal systems is short lived, and needs to compete with biexcitonic decay. This has necessitated the use of short pulsed lasers to pump quantum dots to thresholds needed for amplified spontaneous emission or lasing. Continuous wave pumping of gain that is possible in some inorganic phosphors has therefore remained a very distant possibility for quantum dots. Here, we demonstrate that trilayer heterostructures could provide optimal conditions for demonstration of continuous wave lasing in colloidal materials. The design considerations for these materials are discussed in terms of a kinetic model. The electronic structure of the proposed dot architectures is modeled within effective mass theory.

Traveling waves in trimer granular lattice I: Bifurcation structure of traveling waves in the unit-cell model

Present paper is the first one in the series devoted to the dynamics of traveling waves emerging in the uncompressed, tri-atomic granular crystals. This work is primarily concerned with the dynamics of one-dimensional periodic granular trimer (tri-atomic) chains in the state of acoustic vacuum. Each unit cell consists of three spherical particles of different masses subject to periodic boundary conditions. Hertzian interaction law governs the mutual interaction of these particles. Under the assumption of zero pre-compression, this interaction is modeled as purely nonlinear, which means the absence of linear force component. The dynamics of such chains is governed by the two system parameters that scale the mass ratios between the particles of the unit cell. Such a system supports two different classes of periodic solutions namely the traveling and standing waves. The primary objective of the present study is the numerical analysis of the bifurcation structure of these solutions with emphasis on the dynamics of traveling waves. In fact, understanding of the bifurcation structure of the traveling wave solutions emerging in the unit-cell granular trimer is rather important and can shed light on the more complex nonlinear wave phenomena emerging in semi-infinite trimer chains. (c) 2016 Elsevier B.V. All rights reserved.

On the issues of resolving a low melting combination as a definite eutectic or an elusive cocrystal: A critical evaluation

Cocrystals and eutectics are different yet related crystalline multi-component adducts with diverse applications in pharmaceutical and materials fields. Recently, they were shown to be alternate products of cocrystallization experiments. Whereas a cocrystal shows distinct diffraction, spectroscopic and thermal signatures as compared to parent components, the hallmark of a eutectic is its low melting nature. However, in certain cases, there can be a problem when one resorts to design a cocrystal and assess its formation vis-A -vis a eutectic. In the absence of a gold standard method to make a cocrystal, it is often difficult to judge how exhaustive should the cocrystallization trials be to ensure the accomplishment of a desired/putative cocrystal. Further, a cocrystal can manifest with intermolecular interactions and/or crystal structure similar to that of its parent compounds such that the conventional diffraction and spectroscopic techniques will be of little help to conclusively infer the formation of cocrystal in the lack of single crystals. Such situations combined with low melting behavior of a combination brings the complication of resolving the combination as a cocrystal or eutectic since now both the adducts share common features. Based on the curious case of Caffeine-Benzoic acid combination, this study aims to unfold the intricate issues related to the design, formation and characterization of cocrystals and eutectics for a way forward. The utility of heteronuclear seeding methodology in establishing a given combination as a cocrystal-forming one or a eutectic-forming one in four known systems is appraised.

On the mechanism of void growth and the effect of straining mode in ductile materials

Finite element analysis is employed to investigate void growth embedded in elastic-plastic matrix material. Axisymmetric and plane stress conditions are considered. The simulation of void growth in a unit cell model is carried out over a wide range of triaxial tensile stressing or large plastic straining for various strain hardening materials to study the mechanism of void growth in ductile materials. Triaxial tension and large plastic strain encircling around the void are found to be of most importance for driving void growth. The straining mode of incremental loading which favors the necessary strain concentration around void for its growth can be characterized by the vanishing condition of a parameter called "the third invariant of generalized strain rate". Under this condition, it accentuates the internal strain concentration and the strain energy stored/dissipated within the material layer surrounding the void. Experimental results are cited to justify the effect of this loading parameter. (C) 2000 Elsevier Science Ltd. All rights reserved.

Lowndes and Locke on the value of money

This paper was presented at the 11th Annual Conference of the European Society for the History of Economic Thought (ESHET).

The influence of some environmental variables on the apparent abundance of skipjack tuna, Katsuwonus pelamis, in the Eastern Pacific Ocean

ENGLISH: The abundance of skipjack larvae in the central and western Pacific approximately doubled for every 1°C increase in sea-surface temperature (SST) from 23°C to a maximum of about 29°C, and then usually decreased with further increases in SST. Skipjack larvae are scarce in the eastern Pacific Ocean (EPO), so most skipjack recruits and adults in this area are believed to have originated in the central and, possibly, the western Pacific. The catch per unit of effort (CPUE), in short tons per day's fishing, and the catch rate, in number of fish per day's fishing, are estimates of apparent abundance in a fishery. The logarithm of the annual CPUE for skipjack for international baitboats in the EPO for the 1934-1960 period was positively correlated with SST in the spawning area in the central Pacific 18 months earlier (r2 0.31), during the July-June period when most of the recruits in each cohort were presumed to have been spawned. Adequate data for other environmental variables were not available for testing with the baitboat data. The other environmental variables available and selected for testing for correlation with estimates of skipjack abundance for purse seiners for the 1961-1984 period and the reasons for their selection are as follows. 1)Wind-mixing index (WMI). The degree of mixing in the upper layers of the ocean is proportional to the cube of the wind speed, called WMI. The degree of mixing in the spawning areas of the central and the western Pacific may affect the concentration of organisms that skipjack larvae feed upon, thereby influencing their survival, and ultimately determining cohort strength and the number of recruits to the eastern Pacific fishery. 2) SST in the fishing areas at the time of fishing (SST). The CPUE for yellowfin tuna has been shown to be inversely related to SST in the fishing areas, and there are indications that skipjack CPUE is lower during EI Nino events when SST is higher than normal. 3) North-south SST gradient across the thermal front off the Gulf of Guayaquil. This is a measure of the degree of upwelling and nutrient enrichment of the upper waters south of the front and ultimately of the production of food for tunas. 4) Speed of the North Equatorial Countercurrent (NECC). Young skipjack may migrate from the central Pacific to the EPO in the eastward flowing NECC; if so, the number of recruits might be affected by variations in the speed of the current. The logarithm of the annual catch rate of skipjack recruits by international purse seiners in the EPO for the 1961-1984 period was positively correlated with SST in the spawning area of the central Pacific 18 months earlier (r2 = 0.21),and inversely correlated with WMI in the spawning area 18 months earlier (r2 0.46). The logarithm of CPUE for purse seiners in the area off the Gulf of Guayaquil was not correlated with SST in the spawning area 18 months earlier, but was inversely correlated with WMI in the spawning area 18 months earlier (r2 = 0.19), and inversely correlated with the north-south SST gradient in the fishing area at the time of fishing (r2 0.32). Neither of these estimates of apparent abundance from purse seiners were correlated with SST in the fishing areas, or with the speed of the NECC at earlier times. SPANISH: La abundancia de larvas de barrilete en el Pacífico central y occidental se multiplicó por dos, aproximadamente, por cada aumento de 1°Cen la temperatura de la superficie del mar (TSM) entre 23°C y un máximo de unos 29°C, y luego generalmente disminuyó con más aumentos en la TSM. Las larvas de barrilete son escasas en el Océano Pacífico oriental (OPO), y por lo tanto se cree que la mayoría de los reclutas y adultos en esta zona surgieron del Pacífico central, y posiblemente también del Pacífico occidental. La captura por unidad de esfuerzo (CPUE), en toneladas cortas por día de pesca, y la tasa de captura, en número de peces por día de pesca, son estimaciones de la abundancia aparente en una pesquería. El logaritmo de la CPUE anual de barrilete lograda por barcos de carnada en el OPO en el período 1934-1960 se correlacionó positivamente con la TSM en la zona de desove en el Pacífico central de 18 meses antes (r2 = 0.31), durante el período de junio-julio en el cual se cree que nació la mayoría de los reclutas en cada cohorte. No se dispuso de datos suficientes sobre otras variables ambientales para comprobarlos con los datos de los barcos de carnada. Las demás variables ambientales disponibles y seleccionadas para someterlas a pruebas de correlación con las estimaciones de la abundancia del barrilete de barcos cerqueros en el período 1961-1984, y las razones por su selección, son las siguientes: 1) Indice de mezcla por el viento (IMV). El grado de mezcla en las capas superiores del océano es proporcional al cubo de la velocidad del viento, llamado IMV. Es posible que el grado de mezcla en las zonas de desove del Pacífico central y occidental afecte la concentración de los organismos que alimentan a las larvas del barrilete, afectando así la supervivencia de éstas, y finalmente determinando el tamaño de las cohortes y el número de reclutas a la pesquería del OPO. 2) TSM en la zona de pesca al realizarse la pesca (TSM). Se ha mostrado que la relación de la CPUE del atún aleta amarilla a la TSM en la zona de pesca es inversa, y existen indicaciones que la CPUE de barrilete es inferior durante eventos del Niño, cuando las TSM son superiores a lo normal. 3) Gradiente norte-sur de las TSM a través del frente térmico frente al Golfo de Guayaquil. Esto es una medida del grado de afloramiento y enriquecimiento nutritivo del nivel superior de las aguas al sur de dicho frente, y finalmente de la producción de alimento para los atunes. 4) La velocidad de la Contracorriente Ecuatorial del Norte (CCEN). Es posible que los bariletes juveniles migren del Pacífico central al Pacífico oriental en la CCEN, que fluye hacia el este; de ser así, es posible que la cantidad de reclutas se vea afectada por variaciones en la velocidad de la corriente. El logaritmo de la tasa anual de captura de reclutas de barrilete por cerqueros de varias banderas en el OPO en el período 1961-1964 estuvo correlacionado de forma positiva con las TSM en la zona de desove del Pacífico central de 18meses antes (r2 0.21),y de forma inversa con el IMV de la zona de desove de 18 meses antes (r2 0.46). El logaritmo de la CPUE de los cerqueros en la zona frente al Golfo de Guayaquil no estuvo correlacionado con las TSM en la zona de desove de 18 meses antes, pero sí estuvo correlacionado de forma inversa con el IMV en la zona de desove de 18 meses antes (r2 0.19),y con el gradiente norte-sur de las TSM en la zona de pesca al realizarse la pesca (r2 0.32). Ninguna de estas estimaciones de abundancia aparente provenientes de barcos cerqueros estuvo correlacionada con las TSM en las zonas de pesca o con la velocidad de la CCEN en épocas anteriores. (PDF contains 140 pages.)

The effects of brood stock size on the economy of catfish (Clarias anguillaris) fry production using the hormone induced natural breeding technique

89 ripe female brooders of the catfish, Clarias anguillaris (Body wt. Range 150g-1, 200g) were induced to spawn by hormone (Ovaprim) induced natural spawning technique over a period of 10 weeks. Matching ripe males were used for pairing the females at the ratio of two males to a female. Six ranges of brood stock body weights were considered as follows; <200g; 200g-399g; 400g-599g; 600-799g; 800g-999g; > 1000g and the number of fry produced by each female brooder was scored/recorded against the corresponding body weight range. The number of fry per unit quantity of hormone and the cost of production a fry based on the current price of Ovaprim (hormon) were determined so as to ascertain most economic size range. The best and most economic size range was between 400g-599g body weight with about 20,000 fry per ml of hormone and N0.028 per fry, while the females above 1000g gave the poorest results of 9,519 fry per ml of hormone and N0.059 per fry. For optimum production of Clarias anguillaris fry and maximum return on investment female brooders of body weights ranging between 400g-599g are recommended for hormone induced natural breeding exercises