Influence of CeO2 morphology on the catalytic activity of CeO2-Pt hybrids for CO oxidation

Ceria, because of its excellent redox behavior and oxygen storage capacity, is used as a catalyst for several technologically important reactions. In the present study, different morphologies of nano-CeO2 (rods, cubes, octahedra) were synthesized using the hydrothermal route. An ultrafast microwave-assisted method was used to efficiently attach Pt particles to the CeO2 polyhedra. These nanohybrids were tested as catalysts for the CO oxidation reaction. The CeO2/Pt catalyst with nanorods as the support was found to be the most active catalyst. XPS and IR spectroscopy measurements were carried out in order to obtain a mechanistic understanding and it was observed that the adsorbed carbonates with lower stability on the reactive planes of nanorods and cubes are the major contributor to this enhanced catalytic activity.

Scheduling for Fading Channels Under Partial Channel Information

We consider a scheduler for the downlink of a wireless channel when only partial channel-state information is available at the scheduler. We characterize the network stability region and provide two throughput-optimal scheduling policies. We also derive a deterministic bound on the mean packet delay in the network. Finally, we provide a throughput-optimal policy for the network under QoS constraints when real-time and rate-guaranteed data traffic may be present.

Burst error correction using partial fourier matrices and block sparse representation

There is a strong relation between sparse signal recovery and error control coding. It is known that burst errors are block sparse in nature. So, here we attempt to solve burst error correction problem using block sparse signal recovery methods. We construct partial Fourier based encoding and decoding matrices using results on difference sets. These constructions offer guaranteed and efficient error correction when used in conjunction with reconstruction algorithms which exploit block sparsity.

Experimental study of a small partial admission axial turbine with low aspect ratio blade

Experimental study of a small partial admission axial turbine with low aspect ratio blade has been done. Tests were also performed with full admission stator replacing the partial one for the same rotor to assess the losses occurring due to partial admission. Further tests were conducted with stator admission area split into two and three sectors to study the effects of multiple admission sectors. The method of Ainley and Mathieson with suitable correction for aspect ratio in secondary losses, as proposed by Kacker and Okapuu, gives a good estimate of the efficiency. Estimates of partial admission losses are made and compared with experimentally observed values. The Suter and Traupel correlations for partial admission losses yielded reasonably accurate estimates of efficiency even for small turbines though limited to the region of design u/c(is). Stenning's original concept of expansion losses in a single sector is extended to include multiple sectors of opening. The computed efficiency debit due to each additional sector opened is compared with test values. The agreement is observed to be good. This verified Stenning's original concept of expansion losses. When the expression developed on this extended concept is modified by a correction factor, the prediction of partial admission efficiencies is nearly as good as that of Suter and Traupel. Further, performance benefits accrue if the turbine is configured with increased aspect ratio at the expense of reduced partial admission.

Stable atmospheric methane in the 2000s: key-role of emissions from natural wetlands

Two atmospheric inversions (one fine-resolved and one process-discriminating) and a process-based model for land surface exchanges are brought together to analyse the variations of methane emissions from 1990 to 2009. A focus is put on the role of natural wetlands and on the years 2000-2006, a period of stable atmospheric concentrations. From 1990 to 2000, the top-down and bottom-up visions agree on the time-phasing of global total and wetland emission anomalies. The process-discriminating inversion indicates that wetlands dominate the time-variability of methane emissions (90% of the total variability). The contribution of tropical wetlands to the anomalies is found to be large, especially during the post-Pinatubo years (global negative anomalies with minima between -41 and -19 Tg yr(-1) in 1992) and during the alternate 1997-1998 El-Nino/1998-1999 La-Nina (maximal anomalies in tropical regions between +16 and +22 Tg yr(-1) for the inversions and anomalies due to tropical wetlands between +12 and +17 Tg yr(-1) for the process-based model). Between 2000 and 2006, during the stagnation of methane concentrations in the atmosphere, the top-down and bottom-up approaches agree on the fact that South America is the main region contributing to anomalies in natural wetland emissions, but they disagree on the sign and magnitude of the flux trend in the Amazon basin. A negative trend (-3.9 +/- 1.3 Tg yr(-1)) is inferred by the process-discriminating inversion whereas a positive trend (+1.3 +/- 0.3 Tg yr(-1)) is found by the process model. Although processed-based models have their own caveats and may not take into account all processes, the positive trend found by the B-U approach is considered more likely because it is a robust feature of the process-based model, consistent with analysed precipitations and the satellite-derived extent of inundated areas. On the contrary, the surface-data based inversions lack constraints for South America. This result suggests the need for a re-interpretation of the large increase found in anthropogenic methane inventories after 2000.

Catalytic performance of highly dispersed Ni/TiO2 for dry and steam reforming of methane

The present study reports a sonochemical-assisted synthesis of a highly active and coke resistant Ni/TiO2 catalyst for dry and steam reforming of methane. The catalyst was characterized using XRD, TEM, XPS, BET analyzer and TGA/DTA techniques. The TEM analysis showed that Ni nanoparticles were uniformly dispersed on TiO2 surface with a narrow size distribution. The catalyst prepared via this approach exhibited excellent activity and stability for both the reactions compared to the reference catalyst prepared from the conventional wet impregnation method. For dry reforming, 86% CH4 conversion and 84% CO2 conversion was obtained at 700 degrees C. Nearly 92% CH4 conversion and 77% CO selectivity was observed under a H2O/CH4 ratio of 1.2 at 700 degrees C for the steam reforming reaction. In particular, the present catalyst is extremely active and resistant to coke formation for steam reforming at low steam/carbon ratios. There is no significant modification of Ni particles size and no coke deposition, even after a long term reaction, demonstrating its potential applicability as an industrial reformate for hydrogen production. The detailed kinetic studies have been presented for steam reforming and the mechanism involving Langmuir-Hinshelwood kinetics with adsorptive dissociation of CH4 as a rate determining step has been used to correlate the experimental data.

Zero-Sum Stochastic Games with Partial Information and Average Payoff

We consider a discrete time partially observable zero-sum stochastic game with average payoff criterion. We study the game using an equivalent completely observable game. We show that the game has a value and also we present a pair of optimal strategies for both the players.

Partial Integrated Guidance and Control of Interceptors for High-Speed Ballistic Targets

A new partial integrated guidance and control design approach is proposed in this paper, which combines the benefits of both integrated guidance and control as well as the conventional guidance and control design philosophies. The proposed technique essentially operates in a two-loop structure. In the outer loop, an optimal guidance problem is formulated considering the nonlinear six degrees-of-freedom equation of motion of the interceptor. From this loop, the required pitch and yaw rates are generated by solving a nonlinear suboptimal guidance formulation in a computationally efficient manner while simultaneously assuring roll stabilization. Next, the inner loop tracks these outer loop body rate commands. This manipulation of the six degrees-of-freedom dynamics in both loops preserves the inherent time scale separation property between the translational and rotational dynamics, while retaining the philosophy of integrated guidance and control design as well. Because of this, the tuning process is quite straightforward and nontedious as well. Extensive six degrees-of-freedom simulations studies have been carried out, considering three-dimensional engagement geometry, to demonstrate the effectiveness of the proposed new design approach engaging high-speed ballistic targets. A variety of comparison studies have also been carried out to demonstrate the effectiveness of the proposed approach.

A Modified Fluorimetric Method for Determination of Hydrogen Peroxide Using Homovanillic Acid Oxidation Principle

Hydrogen peroxide (H2O2) level in biological samples is used as an important index in various studies. Quantification of H2O2 level in tissue fractions in presence of H2O2 metabolizing enzymes may always provide an incorrect result. A modification is proposed for the spectrofluorimetric determination of H2O2 in homovanillic acid (HVA) oxidation method. The modification was included to precipitate biological samples with cold trichloroacetic acid (TCA, 5% w/v) followed by its neutralization with K2HPO4 before the fluorimetric estimation of H2O2 is performed. TCA was used to precipitate the protein portions contained in the tissue fractions. After employing the above modification, it was observed that H2O2 content in tissue samples was >= 2 fold higher than the content observed in unmodified method. Minimum 2 h incubation of samples in reaction mixture was required for completion of the reaction. The stability of the HVA dimer as reaction product was found to be > 12 h. The method was validated by using known concentrations of H2O2 and catalase enzyme that quenches H2O2 as substrate. This method can be used efficiently to determine more accurate tissue H2O2 level without using internal standard and multiple samples can be processed at a time with additional low cost reagents such as TCA and K2HPO4.

Cost-effective wear and oxidation resistant electrodeposited Ni-pumice coating

In the search for newer distributed phases that can be used in Ni-composite coatings, inexpensive and naturally available pumice has been identified as a potential candidate material. The composition of the pumice mineral as determined by Rietveld analysis shows the presence of corundum, quartz, mulllite, moganite and coesite phases. Pumice stone is crushed, ball-milled, dried and dispersed in a nickel sulfamate bath and Ni-pumice coatings are electrodeposited at different current densities and magnetic agitation speeds. Pumice particles are uniformly incorporated in the nickel matrix and Ni-pumice composite coatings with microhardness as high as 540 HK are obtained at the lowest applied current density. In the electrodeposited Ni-pumice coatings, the grain size of Ni increases with the applied current density. The overall intensity of texture development is slightly stronger for the Ni-pumice composite coating compared to plain Ni coating and the texture evolution is possibly not the strongest deciding factor for the enhanced properties of Ni-pumice coatings. The wear and oxidation resistances of Ni-pumice coating are commensurate with that of Ni-SiC coating electrodeposited under similar conditions. (C) 2014 Elsevier B.V. All rights reserved.

Energy based approach for the evaluation of damage under partial slip and gross sliding condition

Three possible contact conditions may prevail at a contact interface depending on the magnitude of normal and tangential loads, that is, stick condition, partial slip condition or gross sliding condition. Numerical techniques have been used to evaluate the stress field under partial slip and gross sliding condition. Cattaneo and Mindlin approach has been adapted to model partial slip condition. Shear strain energy density and normalized strain energy release rate have been evaluated at the surface and in the subsurface region. It is apparent from the present study that the shear strain energy density gives a fair prediction for the nucleation of damage, whereas the propagation of the crack is controlled by normalized strain energy release rate. Further, it has been observed that the intensity of damage strongly depends on coefficient of friction and contact conditions prevailing at the contact interface. (C) 2014 Elsevier B.V. All rights reserved.

Evaluating methane storage targets: from powder samples to onboard storage systems

The development of a viable adsorbed natural gas onboard fuel system involves synthesizing materials that meet specific storage target requirements. We assess the impact on natural gas storage due to intermediate processes involved in taking a laboratory powder sample to an onboard packed or adsorbent bed module. We illustrate that reporting the V/V (volume of gas/volume of container) capacities based on powder adsorption data without accounting for losses due to pelletization and bed porosity, grossly overestimates the working storage capacity for a given material. Using data typically found for adsorbent materials that are carbon and MOF based materials, we show that in order to meet the Department of Energy targets of 180 V/V (equivalent STP) loading at 3.5 MPa and 298 K at the onboard packed bed level, the volumetric capacity of the pelletized sample should be at least 245 V/V and the corresponding gravimetric loading varies from 0.175 to 0.38 kg/kg for pellet densities ranging from 461.5 to 1,000 . With recent revision of the DOE target to 263 V/V at the onboard packed bed level, the volumetric loadings for the pelletized sample should be about 373 V/V.

Calculation of three-phase methane-ethane binary clathrate hydrate phase equilibrium from Monte Carlo molecular simulations

Methane and ethane are the simplest hydrocarbon molecules that can form clathrate hydrates. Previous studies have reported methods for calculating the three-phase equilibrium using Monte Carlo simulation methods in systems with a single component in the gas phase. Here we extend those methods to a binary gas mixture of methane and ethane. Methane-ethane system is an interesting one in that the pure components form sII clathrate hydrate whereas a binary mixture of the two can form the sII clathrate. The phase equilibria computed from Monte Carlo simulations show a good agreement with experimental data and are also able to predict the sI-sII structural transition in the clathrate hydrate. This is attributed to the quality of the TIP4P/Ice and TRaPPE models used in the simulations. (C) 2014 Elsevier B.V. All rights reserved.

Formation Flying with Nonlinear Partial Integrated Guidance and Control

Using the dynamic inversion philosophy, a nonlinear partial integrated guidance and control approach is presented in this paper for formation flying. It is based on the evolving philosophy of integrated guidance and control. However, it also retains the advantages of the conventional guidance then control philosophy by retaining the timescale separation between translational and rotational dynamics explicitly. Simulation studies demonstrate that the proposed technique is effective in bringing the vehicles into formation quickly and maintaining the formation.

Effect of metal oxidation state on FRET: a Cu(I) silent but selectively Cu(II) responsive fluorescent reporter and its bioimaging applications

Copper(II) and copper(I) complexes of a newly designed and crystallographically characterized Schiff base (HL) derived from rhodamine hydrazide and cinnamaldehyde were isolated in pure form formulated as Cu(L)(NO3)] (L-Cu) (1) and Cu(HL)(CH3CN)(H2O)]ClO4 (HL-Cu) (2), and characterized by physicochemical and spectroscopic tools. Interestingly, complex 1 but not 2 offers red fluorescence in solution state, and eventually HL behaves as a Cu(II) ions selective FRET based fluorosensor in HEPES buffer (1 mM, acetonitrile-water: 1/5, v/v) at 25 degrees C at biological pH with almost no interference of other competitive ions. The dependency of the FRET process on the +2 oxidation state of copper has been nicely supported by exhaustive experimental studies comprising electronic, fluorimetric, NMR titration, and theoretical calculations. The sensing ability of HL has been evaluated by the LOD value towards Cu(II) ions (83.7 nM) and short responsive time (5-10 s). Even the discrimination of copper(I) and copper(II) has also been done using only UV-Vis spectroscopic study. The efficacy of this bio-friendly probe has been determined by employing HL to detect the intercellular distribution of Cu(II) ions in HeLa cells by developing image under fluorescence microscope.