Statistical significance of episodes with general partial orders

Frequent episode discovery is one of the methods used for temporal pattern discovery in sequential data. An episode is a partially ordered set of nodes with each node associated with an event type. For more than a decade, algorithms existed for episode discovery only when the associated partial order is total (serial episode) or trivial (parallel episode). Recently, the literature has seen algorithms for discovering episodes with general partial orders. In frequent pattern mining, the threshold beyond which a pattern is inferred to be interesting is typically user-defined and arbitrary. One way of addressing this issue in the pattern mining literature has been based on the framework of statistical hypothesis testing. This paper presents a method of assessing statistical significance of episode patterns with general partial orders. A method is proposed to calculate thresholds, on the non-overlapped frequency, beyond which an episode pattern would be inferred to be statistically significant. The method is first explained for the case of injective episodes with general partial orders. An injective episode is one where event-types are not allowed to repeat. Later it is pointed out how the method can be extended to the class of all episodes. The significance threshold calculations for general partial order episodes proposed here also generalize the existing significance results for serial episodes. Through simulations studies, the usefulness of these statistical thresholds in pruning uninteresting patterns is illustrated. (C) 2014 Elsevier Inc. All rights reserved.

Oxygen-participated electrochemistry of new lithium-rich layered oxides Li3MRuO5 M = Mn, Fe)

We describe the synthesis, crystal structure and lithium deinsertion-insertion electrochemistry of two new lithium-rich layered oxides, Li3MRuO5 (M = Mn, Fe), related to rock salt based Li2MnO3 and LiCoO2. The Li3MnRuO5 oxide adopts a structure related to Li2MnO3 (C2/m) where Li and (Li0.2Mn0.4Ru0.4) layers alternate along the c-axis, while the Li3FeRuO5 oxide adopts a near-perfect LiCoO2 (R (3) over barm) structure where Li and (Li0.2Fe0.4Ru0.4) layers are stacked alternately. Magnetic measurements indicate for Li3MnRuO5 the presence of Mn3+ and low spin configuration for Ru4+ where the itinerant electrons occupy a pi*-band. The onset of a net maximum in the chi vs. T plot at 9.5 K and the negative value of the Weiss constant (theta) of -31.4 K indicate the presence of antiferromagnetic superexchange interactions according to different pathways. Lithium electrochemistry shows a similar behaviour for both oxides and related to the typical behaviour of Li-rich layered oxides where participation of oxide ions in the electrochemical processes is usually found. A long first charge process with capacities of 240 mA h g(-1) (2.3 Li per f.u.) and 144 mA h g(-1) (1.38 Li per f.u.) is observed for Li3MnRuO5 and Li3FeRuO5, respectively. An initial sloping region (OCV to ca. 4.1 V) is followed by a long plateau (ca. 4.3 V). Further discharge-charge cycling points to partial reversibility (ca. 160 mA h g(-1) and 45 mA h g(-1) for Mn and Fe, respectively). Nevertheless, just after a few cycles, cell failure is observed. X-ray photoelectron spectroscopy (XPS) characterisation of both pristine and electrochemically oxidized Li3MRuO5 reveals that in the Li3MnRuO5 oxide, Mn3+ and Ru4+ are partially oxidized to Mn4+ and Ru5+ in the sloping region at low voltage, while in the long plateau, O2- is also oxidized. Oxygen release likely occurs which may be the cause for failure of cells upon cycling. Interestingly, some other Li-rich layered oxides have been reported to cycle acceptably even with the participation of the O2- ligand in the reversible redox processes. In the Li3FeRuO5 oxide, the oxidation process appears to affect only Ru (4+ to 5+ in the sloping region) and O2- (plateau) while Fe seems to retain its 3+ state.

Rapid reduction of GO by hydrogen spill-over mechanism by in situ generated nanoparticles at room temperature and their catalytic performance towards 4-nitrophenol reduction and ethanol oxidation

Here, we report the clean and facile synthesis of Pt and Pd nanoparticles decorated on reduced graphene oxide (rGO) by the simultaneous reduction of graphene oxide (GO) and the metal ions in Mg/acid medium. As-generated Pt and Pd nanoparticles serve as a heterogeneous catalyst for the further reduction of the rGO by the hydrogen spill-over process. The C/O ratio is much higher as compared to the rGO obtained by the reduction of GO by only Mg/acid. Overall, the process is rapid, facile and green that does not require any toxic chemical agent or any rigorous chemical reactions. We perform the catalytic reduction of 4-nitophenol (4-NP) to 4-aminophenol (4-AP) at room temperature by Pd@rGO and Pt@rGO. The reduction is complete within 35 s for Pd@rGO and 60 s for Pt@rGO when 50 mu g of hybrid catalyst is used for 0.5 ml of 1 mM of 4-NP. In case of ethanol oxidation, the current density for Pd@rGO is comparable to commercial Pt/C but is doubled for Pt@rGO. Overall, both structures show highly stable catalytic activity compared to commercial Pt/C. (C) 2014 Elsevier B.V. All rights reserved.

Photochemical Deposition of Co-Ac Catalyst on ZnO Nanorods for Solar Water Oxidation

The preparation of ZnO nanorod films decorated with cobalt-acetate (CoAc) electrocatalyst and its activity for photoelectrolysis of water have been demonstrated. The photochemically prepared CoAc catalyst is chemically and morphologically similar to the electrochemically prepared CoAc catalyst. The on-set potential of oxygen evolution reaction is lower on CoAc-ZnO photoanode in relation to bare ZnO photoanode. There is a three to four fold increase in photooxidation current of OER due to the presence of CoAc co-catalyst on ZnO. Thus, the photochemically prepared CoAc on ZnO is an alternative and efficient co-catalyst for photoelectrochemical oxygen evolution reaction. The enhancement in photocatalytic activity of ZnO by the CoAc catalyst photochemically deposited from acetate buffer solution is significantly greater than the cobalt-phosphate (CoPi) co-catalyst deposited from phosphate buffer solution. (C) The Author(s) 2015. Published by ECS. All rights reserved.

Pt-Poisoning-Free Efficient CO Oxidation on Pt3Co Supported on MgO(100): An Ab Initio Study

Late-transition-metal-doped Pt clusters are prevalent in CO oxidation catalysis, as they exhibit better catalytic activity than pure Pt, while reducing the effective cost and poisoning However, completely eliminating the critical problem of Pt poisoning still poses a big challenge. Here, we report for the first time that, among the bimetallic clusters ((Pt3M where M = Co, Ni, and Cu)/MgO(100)), the CO adsorption site inverts for Pt3Co/MgO(100) from Pt to Co, due to the complete uptake of Pt d-states by lattice oxygen. While this resolves the problem of Pt poisoning, good reaction kinetics are predicted through low barriers for Langmuir-Hinshelwood and Mars van Krevelen (MvK) mechanisms of CO oxidation for Pt3Co/MgO(100) and Li-doped MgO(100), respectively. Li doping in MgO(100) compensates for the charge imbalance caused by a spontaneous oxygen vacancy formation. Pt-3 Co/Li-doped MgO(100) stands out as an exceptional CO oxidation catalyst, giving an MvK reaction barrier as low as 0.11 eV. We thereby propose a novel design strategy of d-band center inversion for CO oxidation catalysts with no Pt poisoning and excellent reaction kinetics.

Implication of a sigma-Methane Complex en Route to Elimination of Methane from a Ruthenium Complex: An Experimental and Theoretical Investigation

The five-coordinated 16-electron complex Ru(Me)(dppe)(2)]OTf] (3) undergoes methane elimination at room temperature to afford the ortho-metalated species (dppe){(C6H5)(C6H4)PCH2CH2P(C6H5)(2)}Ru]OTf] (7). Methane elimination, monitored using NMR spectroscopy, revealed no intermediate throughout the reaction. The NOE between Ru-Me protons and ortho phenyl protons and an agostic interaction trans to the methyl group were found in complex 3 by NMR spectroscopy, which form the basis for three plausible pathways for methane elimination and ortho metalation: pathway I (through spatial interaction), pathway II (through oxidative addition and reductive elimination), and pathway III (through agostic interaction). Methane elimination from complex 3 via pathway I was discounted, since it involves interactions through space and not through bonds. Moreover, the calculated energy barrier for the pathway I transition state was quite high (71.3 kcal/mol), which also indicates that this pathway is very unlikely. Furthermore, no spectroscopic evidence for oxidatively added seven-coordinated Ru(IV) species was found and the computed energy barrier of the transition state for pathway II was moderately high (41.1 kcal/mol), which suggests that this cannot be the right pathway for methane elimination and ortho-metalation of complex 3. On the other hand, indirect evidence in the form of chemical reactions point to the most plausible pathway for methane elimination, pathway III, via the intermediacy of a sigma-CH4 complex that could not be found spectroscopically. DFT calculations at several levels on this pathway showed an initial low-barrier rearrangement through TS1 to a square-pyramidal intermediate wherein methyl and agostic C-H are cis to each other. Migration of hydrogen from agostic C-H and elimination of methane proceed through the transition state TS2, which retains a weak metal-H bonding through most parts of the reaction coordinate. Upon comparison of all three pathways, pathway III was found to be the most likely for methane elimination and ortho-metalation of complex 3.

Kinetics of CO oxidation on palladium using microkinetics coupled with reaction route analysis

A plausible microkinetic model has been proposed for the CO oxidation reaction catalysed by palladium (Pd) with the kinetic parameters obtained from the literature. A robust rate expression using the reaction route analysis has been developed for the presented microkinetic scheme and the obtained rate expressions have been validated against the experimental data presented in the literature. A wide range of experimental conditions ranging from single Pd crystals under ultra-high vacuum conditions and impregnated Pd used for fixed bed experiments under atmospheric pressure has been used to validate the reaction mechanism. (C) 2015 Elsevier Ltd. All rights reserved.

Pt-Doped and Pt-Supported La1-xSrxCoO3: Comparative Activity of Pt4+ and Pt-0 Toward the CO Poisoning Effect in Formic Acid and Methanol Electro-oxidation

Pt-supported La1-xSrxCoO3 and Pt-doped La1-xSrxCoO3 are synthesized using chemical reduction and solution combustion method, respectively. Chemical reduction is carried out using formaldehyde as a reducing agent giving Pt-supported La1-xSrxCoO3. Solution combustion method is used to prepare Pt-doped La1-xSrxCoO3. Detailed characterization using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Brunauer-Emmett-Teller (BET) surface area measurement, and transmission electron microscopy (TEM) is carried out to distinguish the Pt-supported and Pt-doped compounds in terms of their morphology and Pt oxidations states. TEM results indeed show the differences in their morphology. Further, electrochemical measurements are performed in neutral medium to differentiate their electrochemical activity. Cyclic voltammetry (CV) shows noticeable differences between Pt-supported La1-xSrxCoO3 and Pt-doped La1-xSrxCoO3. Importantly, our results show that Pt4+ in doped compound has poor to zero electrocatalytic activity toward formic acid and methanol electro-oxidation in comparison to Pt-0 in supported compound. This study shows that metallic Pt in zero oxidation state is a superior catalyst to Pt in +4 oxidation state.

Wireless scheduling with partial channel state information: large deviations and optimality

We consider a server serving a time-slotted queued system of multiple packet-based flows, where not more than one flow can be serviced in a single time slot. The flows have exogenous packet arrivals and time-varying service rates. At each time, the server can observe instantaneous service rates for only a subset of flows ( selected from a fixed collection of observable subsets) before scheduling a flow in the subset for service. We are interested in queue length aware scheduling to keep the queues short. The limited availability of instantaneous service rate information requires the scheduler to make a careful choice of which subset of service rates to sample. We develop scheduling algorithms that use only partial service rate information from subsets of channels, and that minimize the likelihood of queue overflow in the system. Specifically, we present a new joint subset-sampling and scheduling algorithm called Max-Exp that uses only the current queue lengths to pick a subset of flows, and subsequently schedules a flow using the Exponential rule. When the collection of observable subsets is disjoint, we show that Max-Exp achieves the best exponential decay rate, among all scheduling algorithms that base their decision on the current ( or any finite past history of) system state, of the tail of the longest queue. To accomplish this, we employ novel analytical techniques for studying the performance of scheduling algorithms using partial state, which may be of independent interest. These include new sample-path large deviations results for processes obtained by non-random, predictable sampling of sequences of independent and identically distributed random variables. A consequence of these results is that scheduling with partial state information yields a rate function significantly different from scheduling with full channel information. In the special case when the observable subsets are singleton flows, i.e., when there is effectively no a priori channel state information, Max-Exp reduces to simply serving the flow with the longest queue; thus, our results show that to always serve the longest queue in the absence of any channel state information is large deviations optimal.

Graphene oxide as an optimal candidate material for methane storage

Methane, the primary constituent of natural gas, binds too weakly to nanostructured carbons to meet the targets set for on-board vehicular storage to be viable. We show, using density functional theory calculations, that replacing graphene by graphene oxide increases the adsorption energy of methane by 50%. This enhancement is sufficient to achieve the optimal binding strength. In order to gain insight into the sources of this increased binding, that could also be used to formulate design principles for novel storage materials, we consider a sequence of model systems that progressively take us from graphene to graphene oxide. A careful analysis of the various contributions to the weak binding between the methane molecule and the graphene oxide shows that the enhancement has important contributions from London dispersion interactions as well as electrostatic interactions such as Debye interactions, aided by geometric curvature induced primarily by the presence of epoxy groups. (C) 2015 AIP Publishing LLC.

QUANTITATIVE OH PLANAR LASER INDUCED FLUORESCENCE DIAGNOSTICS OF SYNGAS AND METHANE COMBUSTION IN A CAVITY COMBUSTOR

The current work reports quantitative OH species concentration in the cavity of a trapped vortex combustor (TVC) in the context of mixing and flame stabilization studies using both syngas and methane fuels. Planar laser induced fluorescence (PLIF) measurements of OH radical obtained using a Nd: YAG pumped dye laser are quantified using a flat flame McKenna burner. The momentum flux ratio (MFR), defined as the ratio of the cavity fuel jet momentum to that of the guide vane air stream, is observed to be a key governing parameter. At high MFRs similar to 4.5, the flame front is observed to form at the interface of the fuel jet and the air jet stream. This is substantiated by velocity vector field measurements. For syngas, as the MFR is lowered to similar to 0.3, the fuel-air mixing increases and a flame front is formed at the bottom and downstream edge of the cavity where a stratified charge is present. This trend is observed for different velocities at similar equivalence ratios. In case of methane combustion in the cavity, where the MFRs employed are extremely low at similar to 0.01, a different mechanism is observed. A fuel-rich mixture is now observed at the center of the cavity and this mixture undergoes combustion. On further increase of the cavity equivalence ratio, the rich mixture exceeds the flammability limit and forms a thin reaction zone at the interface with air stream. As a consequence, a shear layer flame at the top of the cavity interface with the mainstream is also observed. The equivalence ratio in the cavity also determines the combustion characteristics in the case of fuel-air mixtures that are formed as a result of the mixing. Overall, flame stabilization mechanisms have been proposed, which account for the wide range of MFRs and premixing in the mainstream as well.