Production of syngas from steam reforming and CO removal with water gas shift reaction over nanosized Zr0.95Ru0.05O2-delta solid solution

This study presents the synthesis, characterization, and kinetics of steam reforming of methane and water gas shift (WGS) reactions over highly active and coke resistant Zr0.93Ru0.05O2-delta. The catalyst showed high activity at low temperatures for both the reactions. For WGS reaction, 99% conversion of CO with 100% H-2 selectivity was observed below 290 degrees C. The detailed kinetic studies including influence of gas phase product species, effect of temperature and catalyst loading on the reaction rates have been investigated. For the reforming reaction, the rate of reaction is first order in CH4 concentration and independent of CO and H2O concentration. This indicates that the adsorptive dissociation of CH4 is the rate determining step. The catalyst also showed excellent coke resistance even under a stoichiometric steam/carbon ratio. A lack of CO methanation activity is an important finding of present study and this is attributed to the ionic nature of Ru species. The associative mechanism involving the surface formate as an intermediate was used to correlate experimental data. Copyright (C) 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

Pure shift NMR approach for fast and accurate extraction of heteronuclear couplings

The direct and accurate determination of heteronuclear ((n)J(HX), X = F-19, P-31) couplings from the one dimensional H-1-NMR spectrum is severely hampered due to the simultaneous presence of large numbers of (n)J(HH). The present study demonstrates the utility of the pure shift NMR approach for spectral simplification, and precise and direct measurement of heteronuclear couplings. As a consequence of refocusing of homonuclear couplings ((n)J(HH)) by the pure shift NMR, only heteronuclear couplings ((n)J(HX)) appear as simple multiplets at the resonance position of each chemically non-equivalent proton, enabling their direct measurement from the 1D-H-1 spectrum. The experiment is demonstrated on a number of molecules containing either F-19 or P-31, where (n)J(HF) and (n)J(HP) could be precisely measured in a straightforward manner. The distinct advantage of the experiment is demonstrated on molecules containing more than one fluorine atom, where most of the available NMR experiments fail or have restricted utility.

Design and analysis of integrated optic quadrature phase shift keying modulator

Quadrature phase shift keying (QPSK) is one of the most popular modulation schemes in coherent optical communication systems for data rates in excess of 40 Gbps because of its high spectral efficiency. This paper proposes a simple method of implementing a QPSK modulator in integrated optic (IO) domain. The QPSK modulator is realized using standard IO components, such as Y-branches and electro-optic modulators (EOMs). Design optimization of EOM is carried out considering the fabrication constraints, miniaturization aspects, and simplicity. Also, the interdependency between electrode length, operating voltage, and electrode gap of an EOM has been captured in the form of a family of curves. These plots enable designing of EOMs for custom requirements. An innovative approach has been adopted in demonstrating the operation of IO QPSK modulator in terms of phase data extracted from beam propagation model. The results obtained by this approach have been verified using the conventional interferometric approach. The operation of the proposed IO QPSK modulator is experimentally demonstrated. The design of IO QPSK modulator is taken up as a part of a broader scheme that aims at generation of QPSK modulated microwave signal based on optical heterodyning. (C) 2014 Society of Photo-Optical Instrumentation Engineers (SPIE)

Performance Analysis of Space-Shift Keying in Decode-and-Forward Multihop MIMO Networks

In this paper, space-shift keying (SSK) is considered for multihop multiple-input-multiple-output (MIMO) networks. In SSK, only one among n(s) = 2(m) available transmit antennas, chosen on the basis of m information bits, is activated during transmission. We consider two different systems of multihop co-operation, where each node has multiple antennas and employs SSK. In system I, a multihop diversity relaying scheme is considered. In system II, a multihop multibranch relaying scheme is considered. In both systems, we adopt decode-and-forward (DF) relaying, where each relay forwards the signal only when it correctly decodes. We analyze the end-to-end bit error rate (BER) and diversity order of both the systems with SSK. For binary SSK (n(s) = 2), our analytical BER expression is exact, and our numerical results show that the BERs evaluated through the analytical expression overlap with those obtained through Monte Carlo simulations. For nonbinary SSK (n(s) > 2), we derive an approximate BER expression, where the analytically evaluated BER results closely follow the simulated BER results. We show the comparison of the BERs of SSK and conventional phase-shift keying (PSK) and also show the instances where SSK outperforms PSK. We also present the diversity analyses for SSK in systems I and II, which predict the achievable diversity orders as a function of system parameters.

Negative hyperconjugation and red-, blue- or zero-shift in X-Z center dot center dot center dot Y complexes

A generalized explanation is provided for the existence of the red-and blue-shifting nature of X-Z bonds (Z = H, halogens, chalcogens, pnicogens, etc.) in X-Z center dot center dot center dot Y complexes based on computational studies on a selected set of weakly bonded complexes and analysis of existing literature data. The additional electrons and orbitals available on Z in comparison to H make for dramatic differences between the H-bond and the rest of the Z-bonds. The nature of the X-group and its influence on the X-Z bond length in the parent X-Z molecule largely controls the change in the X-Z bond length on X-Z center dot center dot center dot Y bond formation; the Y-group usually influences only the magnitude of the effects controlled by X. The major factors which control the X-Z bond length change are: (a) negative hyperconjugative donation of electron density from X-group to X-Z sigma* antibonding molecular orbital (ABMO) in the parent X-Z, (b) induced negative hyperconjugation from the lone pair of electrons on Z to the antibonding orbitals of the X-group, and (c) charge transfer (CT) from the Y-group to the X-Z sigma* orbital. The exchange repulsion from the Y-group that shifts partial electron density at the X-Z sigma* ABMO back to X leads to blue-shifting and the CT from the Y-group to the sigma* ABMO of X-Z leads to red-shifting. The balance between these two opposing forces decides red-, zero- or blue-shifting. A continuum of behaviour of X-Z bond length variation is inevitable in X-Z center dot center dot center dot Y complexes.

IMAGE DENOISING USING OPTIMALLY WEIGHTED BILATERAL FILTERS: A SURE AND FAST APPROACH

The bilateral filter is known to be quite effective in denoising images corrupted with small dosages of additive Gaussian noise. The denoising performance of the filter, however, is known to degrade quickly with the increase in noise level. Several adaptations of the filter have been proposed in the literature to address this shortcoming, but often at a substantial computational overhead. In this paper, we report a simple pre-processing step that can substantially improve the denoising performance of the bilateral filter, at almost no additional cost. The modified filter is designed to be robust at large noise levels, and often tends to perform poorly below a certain noise threshold. To get the best of the original and the modified filter, we propose to combine them in a weighted fashion, where the weights are chosen to minimize (a surrogate of) the oracle mean-squared-error (MSE). The optimally-weighted filter is thus guaranteed to perform better than either of the component filters in terms of the MSE, at all noise levels. We also provide a fast algorithm for the weighted filtering. Visual and quantitative denoising results on standard test images are reported which demonstrate that the improvement over the original filter is significant both visually and in terms of PSNR. Moreover, the denoising performance of the optimally-weighted bilateral filter is competitive with the computation-intensive non-local means filter.