A Single-Stage Water-Gas Shift Reaction over Highly Active and Stable Si- and Al-Substituted Pt/CeO2 Catalysts

Ce0.88Si0.1Pt0.02O2-d and Ce0.88Al0.1Pt0.02O2-d catalysts were synthesized by using a low-temperature sonochemical method and characterized by using XRD, TEM, XPS, FTIR, and BET surface analyzer. The catalytic activities of these compounds were investigated for the watergas shift reaction in the temperature range of 140-440 degrees C. The substitution of Si in Ce0.98Pt0.02O2-d increased the releasing capacity of lattice oxygen, whereas the substitution of Al decreased the reducibility of Ce0.98Pt0.02O2-d, as evidenced by hydrogen temperature-programmed reduction studies. However, both the catalysts showed a considerable improvement in terms of activity and stability compared to Ce0.98Pt0.02O2-d. The combined activity measurement and characterization results suggest that the increase in the oxygen vacancy, which acts as a dissociation center for water, is the primary reason for the improvement in the activity of modified Ce0.98Pt0.02O2-d. Both the catalysts are 100?% selective toward H2 production, and approximately 99?% conversion of CO to CO2 was observed at 260 and 270 degrees C for Ce0.88Si0.1Pt0.02O2-d and Ce0.88Al0.1Pt0.02O2-d, respectively. These catalysts do not deactivate during the daily startup/shutdown operations and are sustainable even after prolonged reaction. Notably, these catalysts do not require any pretreatment or activation during startup/shutdown operations.

Dual emissive borane-BODIPY dyads: molecular conformation control over electronic properties and fluorescence response towards fluoride ions

Facile synthesis of two new dimesitylboryl appended BODIPYs is reported. The two dyads have similar fluorescent chromophores but differ in their molecular conformations. They exhibit dual fluorescence, intramolecular energy transfer between boryl and BODIPY chromophores and different fluorescence responses (emission enhancement and quenching) upon fluoride binding.

Low temperature CO oxidation and water gas shift reaction over Pt/Pd substituted in Fe/TiO2 catalysts

We demonstrate the activity of Ti0.84Pt0.01Fe0.15O2-delta and Ti0.73Pd0.02Fe0.25O2-delta catalysts towards the CO oxidation and water gas shift (VMS) reaction. Both the catalysts were synthesized in the nano crystalline form by a low temperature sonochemical method and characterized by different techniques such as XRD, FT-Raman, TEM, FT-IR, XPS and BET surface analyzer. H-2-TPR results corroborate the intimate contact between noble metal and Fe ions in the both catalysts that facilitates the reducibility of the support. In the absence of feed CO2 and H-2, nearly 100% conversion of CO to CO2 with 100% H-2 selectivity was observed at 300 degrees C and 260 degrees C respectively, for Ti0.84Pt0.01Fe0.15O2-delta and Ti0.73Pd0.02Fe0.25O2-delta catalyst. However, the catalytic performance of Ti0.73Pd0.02Fe0.25O2-delta deteriorates in the presence of feed CO2 and H-2. The change in the support reducibility is the primary reason for the significant increase in the activity for CO oxidation and WGS reaction. The effect of Fe addition was more significant in Ti0.73Pd0.02Fe0.25O2-delta than Ti0.84Pt0.01Fe0.15O2-delta. Based on the spectroscopic evidences and surface phenomena, a hybrid reaction scheme utilizing both surface hydroxyl groups and the lattice oxygen was hypothesized over these catalysts for WGS reaction. The mechanisms based on the formate and redox pathway were used to fit the ldnetic data. The analysis of experimental data shows the redox mechanism is the dominant pathway over these catalysts. Copyright (C) 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

Modeling the effect of transmission errors on TCP controlled transfers over infrastructure 802.11 wireless LANs

There have been several studies on the performance of TCP controlled transfers over an infrastructure IEEE 802.11 WLAN, assuming perfect channel conditions. In this paper, we develop an analytical model for the throughput of TCP controlled file transfers over the IEEE 802.11 DCF with different packet error probabilities for the stations, accounting for the effect of packet drops on the TCP window. Our analysis proceeds by combining two models: one is an extension of the usual TCP-over-DCF model for an infrastructure WLAN, where the throughput of a station depends on the probability that the head-of-the-line packet at the Access Point belongs to that station; the second is a model for the TCP window process for connections with different drop probabilities. Iterative calculations between these models yields the head-of-the-line probabilities, and then, performance measures such as the throughputs and packet failure probabilities can be derived. We find that, due to MAC layer retransmissions, packet losses are rare even with high channel error probabilities and the stations obtain fair throughputs even when some of them have packet error probabilities as high as 0.1 or 0.2. For some restricted settings we are also able to model tail-drop loss at the AP. Although involving many approximations, the model captures the system behavior quite accurately, as compared with simulations.

A nested linear codes approach to distributed function computation over subspaces

In this paper, we consider a distributed function computation setting, where there are m distributed but correlated sources X1,...,Xm and a receiver interested in computing an s-dimensional subspace generated by [X1,...,Xm]Γ for some (m × s) matrix Γ of rank s. We construct a scheme based on nested linear codes and characterize the achievable rates obtained using the scheme. The proposed nested-linear-code approach performs at least as well as the Slepian-Wolf scheme in terms of sum-rate performance for all subspaces and source distributions. In addition, for a large class of distributions and subspaces, the scheme improves upon the Slepian-Wolf approach. The nested-linear-code scheme may be viewed as uniting under a common framework, both the Korner-Marton approach of using a common linear encoder as well as the Slepian-Wolf approach of employing different encoders at each source. Along the way, we prove an interesting and fundamental structural result on the nature of subspaces of an m-dimensional vector space V with respect to a normalized measure of entropy. Here, each element in V corresponds to a distinct linear combination of a set {Xi}im=1 of m random variables whose joint probability distribution function is given.

A dynamic bandwidth allocation scheme for interactive multimedia applications over cellular networks

Cellular networks played key role in enabling high level of bandwidth for users by employing traditional methods such as guaranteed QoS based on application category at radio access stratum level for various classes of QoSs. Also, the newer multimode phones (e.g., phones that support LTE (Long Term Evolution standard), UMTS, GSM, WIFI all at once) are capable to use multiple access methods simulta- neously and can perform seamless handover among various supported technologies to remain connected. With various types of applications (including interactive ones) running on these devices, which in turn have different QoS requirements, this work discusses as how QoS (measured in terms of user level response time, delay, jitter and transmission rate) can be achieved for interactive applications using dynamic bandwidth allocation schemes over cellular networks. In this work, we propose a dynamic bandwidth allocation scheme for interactive multimedia applications with/without background load in the cellular networks. The system has been simulated for many application types running in parallel and it has been observed that if interactive applications are to be provided with decent response time, a periodic overhauling of policy at admission control has to be done by taking into account history, criticality of applications. The results demonstrate that interactive appli- cations can be provided with good service if policy database at admission control is reviewed dynamically.

Accelerating Reduction for Enabling Fast Multiplication over Large Binary Fields

In this paper we present a hardware-software hybrid technique for modular multiplication over large binary fields. The technique involves application of Karatsuba-Ofman algorithm for polynomial multiplication and a novel technique for reduction. The proposed reduction technique is based on the popular repeated multiplication technique and Barrett reduction. We propose a new design of a parallel polynomial multiplier that serves as a hardware accelerator for large field multiplications. We show that the proposed reduction technique, accelerated using the modified polynomial multiplier, achieves significantly higher performance compared to a purely software technique and other hybrid techniques. We also show that the hybrid accelerated approach to modular field multiplication is significantly faster than the Montgomery algorithm based integrated multiplication approach.

Buildup of aerosols over the Indian Region

Climate change has great significance globally in general and South Asia in particular. Here we have used data from a network of 35 aerosol observatories over the Indian region to generate the first time regional synthesis using primary data and estimate the aerosol trends. On an average, aerosol optical depth (AOD) was found increasing at a rate of 2.3% (of its value in 1985) per year and more rapidly (similar to 4%) during the last decade. If the trends continue so, AOD at several locations would nearly double and approach unity in the next few decades leading to an enhancement in aerosol-induced lower atmospheric warming by a factor of two. However, a regionally averaged scenario can be ascertained only in the coming years, when longer and denser data would become available. The regional and global climate implications of such trends in the forcing elements need to be better assessed using GCMs.

Performance evaluation of chemistry transport models over India

Using continuous and near-real time measurements of the mass concentrations of black carbon (BC) aerosols near the surface, for a period of 1 year (from January to December 2006) from a network of eight observatories spread over different environments of India, a space-time synthesis is generated. The strong seasonal variations observed, with a winter high and summer low, are attributed to the combined effects of changes in synoptic air mass types, modulated strongly by the atmospheric boundary layer dynamics. Spatial distribution shows much higher BC concentration over the Indo-Gangetic Plain (IGP) than the peninsular Indian stations. These were examined against the simulations using two chemical transport models, GOCART (Goddard Global Ozone Chemistry Aerosol Radiation and Transport) and CHIMERE for the first time over Indian region. Both the model simulations significantly deviated from the measurements at all the stations; more so during the winter and pre-monsoon seasons and over mega cities. However, the CHIMERE model simulations show better agreement compared with the measurements. Notwithstanding this, both the models captured the temporal variations; at seasonal and subseasonal timescales and the natural variabilities (intra-seasonal oscillations) fairly well, especially at the off-equatorial stations. It is hypothesized that an improvement in the atmospheric boundary layer (ABL) parameterization scheme for tropical environment might lead to better results with GOCART.

Probing the indefinite CP nature of the Higgs boson through decay distributions in the process e(+)e(-) -> t(t)over-bar Phi

The recently discovered scalar resonance at the Large Hadron Collider is now almost confirmed to be a Higgs boson, whose CP properties are yet to be established. At the International Linear Collider with and without polarized beams, it may be possible to probe these properties at high precision. In this work, we study the possibility of probing departures from the pure CP-even case, by using the decay distributions in the process e(+)e(-) -> t (t) over bar Phi, with Phi mainly decaying into a b (b) over bar pair. We have compared the case of a minimal extension of the Standard Model case (model I) with an additional pseudoscalar degree of freedom, with a more realistic case namely the CP-violating two-Higgs doublet model (model II) that permits a more general description of the couplings. We have considered the International Linear Collider with root s = 800 GeV and integrated luminosity of 300 fb(-1). Our main findings are that even in the case of small departures from the CP-even case, the decay distributions are sensitive to the presence of a CP-odd component in model II, while it is difficult to probe these departures in model I unless the pseudoscalar component is very large. Noting that the proposed degrees of beam polarization increase the statistics, the process demonstrates the effective role of beam polarization in studies beyond the Standard Model. Further, our study shows that an indefinite CP Higgs would be a sensitive laboratory to physics beyond the Standard Model.

DRIFTS studies on CO and NO adsorption and NO plus CO reaction over Pd2+-substituted CeO2 and Ce0.75Sn0.25O2 catalysts

Sequential adsorption of CO and NO as well as equimolar NO + CO reaction with variation of temperature over Pd2+ ion-substituted CeO2 and Ce0.75Sn0.25O2 supports has been studied by DRIFTS technique. The results are compared with 2 at.% Pd/Al2O3 containing Pd-0. Both linear and bridging Pd-0-CO bands are observed over 2 at.% Pd/Al2O3. But, band positions are shifted to higher frequencies in Ce0.98Pd0.02O2-delta and Ce0.73Sn0.25Pd0.02O2-delta catalysts that could be associated with Pd delta+-CO species. In contrast, a Pd2+-CO band at 2160 cm(-1) is observed upon CO adsorption over Ce0.98Pd0.02O2-delta and Ce0.73Sn0.25Pd0.02O2-delta catalysts pre-adsorbed with NO and a Pd+-CO band at 2120 cm(-1) is slowly developed on Ce(0.73)Srl(0.25)Pd(0.02)O(2-delta) over time. An intense linear Pd-0-NO band at 1750 cm(-1) found upon NO exposure to CO pre-adsorbed 2 at.% Pd/Al2O3 indicates molecular adsorption of NO. On the other hand, a weak Pd2+-NO band at 1850 cm(-1) is noticed after NO exposure to Ce0.98Pd0.02O2-delta catalyst pre-adsorbed with CO indicating dissociative adsorption of NO which is crucial for NO reduction. Pd-0-NO band is initially formed over CO pre-adsorbed Ce0.73Sn0.25Pd0.02O2-delta which is red-shifted over time along with formation of Pd2+-NO band. Several intense bands related to nitrates and nitrites are observed after exposure of NO to fresh as well as CO pre-adsorbed Ce0.98Pd0.02O2-delta and Ce0.73Sn0.25Pd0.02O2-delta catalysts. Ramping the temperature in a DRIFTS cell upon NO and CO adsorption shows the formation of N2O and NCO surface species, and N2O-formation temperature is comparable with the reaction done in a reactor.

Large scale features and assessment of spatial scale correspondence between TMPA and IMD rainfall datasets over Indian landmass

Daily rainfall datasets of 10 years (1998-2007) of Tropical Rainfall Measuring Mission (TRMM) Multi-satellite Precipitation Analysis (TMPA) version 6 and India Meteorological Department (IMD) gridded rain gauge have been compared over the Indian landmass, both in large and small spatial scales. On the larger spatial scale, the pattern correlation between the two datasets on daily scales during individual years of the study period is ranging from 0.4 to 0.7. The correlation improved significantly (similar to 0.9) when the study was confined to specific wet and dry spells each of about 5-8 days. Wavelet analysis of intraseasonal oscillations (ISO) of the southwest monsoon rainfall show the percentage contribution of the major two modes (30-50 days and 10-20 days), to be ranging respectively between similar to 30-40% and 5-10% for the various years. Analysis of inter-annual variability shows the satellite data to be underestimating seasonal rainfall by similar to 110 mm during southwest monsoon and overestimating by similar to 150 mm during northeast monsoon season. At high spatio-temporal scales, viz., 1 degrees x1 degrees grid, TMPA data do not correspond to ground truth. We have proposed here a new analysis procedure to assess the minimum spatial scale at which the two datasets are compatible with each other. This has been done by studying the contribution to total seasonal rainfall from different rainfall rate windows (at 1 mm intervals) on different spatial scales (at daily time scale). The compatibility spatial scale is seen to be beyond 5 degrees x5 degrees average spatial scale over the Indian landmass. This will help to decide the usability of TMPA products, if averaged at appropriate spatial scales, for specific process studies, e.g., cloud scale, meso scale or synoptic scale.

Unsteady separation and vortex shedding from a laminar separation bubble over a bluff body

Boundary layers are subject to favorable and adverse pressure gradients because of both the temporal and spatial components of the pressure gradient. The adverse pressure gradient may cause the flow to separate. In a closed loop unsteady tunnel we have studied the initiation of separation in unsteady flow past a constriction (bluff body) in a channel. We have proposed two important scalings for the time when boundary layer separates. One is based on the local pressure gradient and the other is a convective time scale based on boundary layer parameters. The flow visualization using a dye injection technique shows the flow structure past the body. Nondimensional shedding frequency (Strouhal number) is calculated based on boundary layer and momentum thicknesses. Strouhal number based on the momentum thickness shows a close agreement with that for flat plate and circular cylinder.