Kinetics of carbon monoxide oxidation with Sn(0.95)M(0.05)O(2-delta) (M = Cu, Fe, Mn, Co) catalysts

Base metal substituted Sn(0.95)M(0.05)O(2-delta) (M = Cu, Fe, Mn, Co) catalysts were synthesized by the solution combustion method and characterized by XRD, XPS, TEM and BET surface area analysis. The catalytic activities of these materials were investigated by performing CO oxidation. The rates and the apparent activation energies of the reaction for CO oxidation were determined for each catalyst. All the substituted catalysts showed high rates and lower activation energies for the oxidation of CO as compared to unsubstituted SnO(2). The rate was found to be much higher over copper substituted SnO(2) as compared to other studied catalysts. 100% CO conversion was obtained below 225 degrees C over this catalyst. A bifunctional reaction mechanism was developed that accounts for CO adsorption on base metal and support ions and O(2) dissociation on the oxide ion vacancy. The kinetic parameters were determined by fitting the model to the experimental data. The high rates of the CO oxidation reactions at low temperatures were rationalized by the high dissociative chemisorption of adsorbed O(2) over these catalysts.

Pt metal-CeO2 interaction: Direct observation of redox coupling between Pt-0/Pt2+/Pt4+ and Ce4+/Ce3+ states in Ce0.98Pt0.02O2-delta catalyst by a combined electrochemical and x-ray photoelectron spectroscopy study

Pt ions-CeO2 interaction in Ce1-xPtxO2-delta (x=0.02) has been studied for the first time by electrochemical method combined with x-ray diffraction and x-ray photoelectron spectroscopy. Working electrodes made of CeO2 and Ce0.98Pt0.02O2-delta mixed with 30% carbon are treated electrochemically between 0.0-1.2 V in potentiostatic (chronoamperometry) and potentiodynamic (cyclic voltametry) mode with reference to saturated calomel electrode. Reversible oxidation of Pt-0 to Pt2+ and Pt4+ state due to the applied positive potential is coupled to simultaneous reversible reduction of Ce4+ to Ce3+ state. CeO2 reduces to CeO2-y (y=0.35) after applying 1.2 V, which is not reversible; Ce0.98Pt0.02O2-delta reaches a steady state with Pt2+:Pt4+ in the ratio of 0.60:0.40 and Ce4+:Ce3+ in the ratio of 0.55:0.45 giving a composition Ce0.98Pt0.02O1.74 at 1.2 V, which is reversible. Composition of Pt ion substituted compound is reversible between Ce0.98Pt0.02O1.95 to Ce0.98Pt0.02O1.74 within the potential range of 0.0-1.2 V. Thus, Ce0.98Pt0.02O2-delta forms a stable electrode for oxidation of H2O to O-2 unlike CeO2. A linear relation between oxidation of Pt2+ to Pt4+ with simultaneous reduction in Ce4+ to Ce3+ is observed demonstrating Pt-CeO2 metal support interaction is due to reversible Pt-0/Pt2+/Pt4+ interaction with Ce4+/Ce3+ redox couple.

Pt2+ Dispersed in Ce0.83Ti0.15O2-delta: Significant Improvement in PROX Activity by Ti Substitution in CeO2 in Hydrogen Rich Stream

Pt2+ ion dispersed in CeO2, Ce1-xTixO2-delta and TiO2 have been tested for preferential oxidation of carbon monoxide (PROX) in hydrogen rich stream. It is found that Pt2+ substituted CeO2 and Ce(1-x)TixO(2-delta) in the form of solid solution Ce0.98Pt0.02O2-delta and Ce0.83Ti0.15Pt0.02O2-delta are highly CO selective low temperature PROX catalysts in hydrogen rich stream. Just 15% of Ti substitution in CeO2 improves the overall PROX activity.

Single-File Diffusion of Water Inside Narrow Carbon Nanorings

We use atomistic molecular dynamics (MD) simulations to study the diffusion of water molecules confined inside narrow (6,6) carbon nanorings. The water molecules form two oppositely polarized chains. It is shown that the effective interaction between these two chains is repulsive in nature. The computed mean-squared displacement (MSD) clearly shows a scaling with time <Delta theta(2)(t)> similar to t(1/2), which is consistent with single-file diffusion (SFD). The time up to which the water molecules undergo SFD is shown to be the lifetime of the water molecules inside these chains. Simulations of "uncharged" water molecules inside the nanoring show the formation of several water chains and yield SFD. These observations conclusively prove that the diffusion is Fickian when there is a single chain of water and SFD is observed only when two or more chains are present.

Enhanced reducibility of Ce1-xTixO2 compared to that of CeO2 and higher redox catalytic activity of Ce1-x-yTixPtyO2-delta compared to that of Ce1-xPtxO2-delta

Nanocrystalline Ce1-xTixO2 (0 <= x <= 0.4) and Ce1-xTixPtyO2-delta (x = 0.15, gamma = 0.01, 0.02) solid solutions crystallizing in fluorite structure have been prepared by a single step solution combustion method. Temperature programmed reduction and XPS study of Ce1-xTixO2 (x = 0.0-04) show complete reduction of Ti4+ to Ti3+ and reduction of similar to 20% Ce4+ to Ce3+ state compared to 8% Ce4+ to Ce3+ in the case of pure CeO2 below 675 degrees C. The substitution of Ti ions in CeO2 enhances the reducibility of CeO2. Ce0.84Ti0.15Pt0.01O2-delta crystallizes in fluorite structure and Pt is ionically substituted with 2+ and 4+ oxidation states. The H/Pt atomic ratio at 30 degrees C over Ce0.84Ti0.15Pt0.01O2-delta is 5 and that over Ce0.99Pt0.01O2-delta is 4 against just 0.078 for 8 nm Pt metal particles. Carbon monoxide and hydrocarbon oxidation activity are much higher over Ce1-x-yTixPtyO2 (x = 0.15, 0.01, 0.02) compared to Ce1-xPtxO2 (x = 0.01, 0.02). Synergistic involvement of Pt2+/Pt degrees and Ti4+/Ti3+ redox couples in addition to Ce4+/Ce3+ due to the overlap of Pt(5d), Ti(3d), and Ce(4f) bands near E-F is shown to be responsible for improved redox property and higher catalytic activity.

Reactivity and catalytic activity of layered YBA2CU3O7-delta (123) type defect perovskites

The chemical modifications of structure, reactivity and catalytic properties of layered triple perovskite oxides, related to the YBa2Cu3O7-delta (123) system, have been briefly reviewed. These oxides form a versatile family of materials with wide-ranging chemical and physical properties. The multiple sites available for chemical doping, and the ability to reversibly intercalate oxygen at the defect sites have rendered these oxides important model systems in the area of oxide catalysis. An attempt has been made to comprehend the hitherto known catalytic reactions and correlate them to various factors like structure, oxygen diffusional limitations, different geometries adopted by various substituents, oxidative non-stoichiometry and activation energy for oxygen desorption. In particular, results on the enhanced catalytic activity of cobalt-substituted 123 oxide systems towards the selective catalytic oxidation of ammonia to nitric oxide and carbon monoxide to carbon dioxide are presented.

Diurnal variation of atmospheric CO2 concentration and delta C-13 in an urban atmosphere during winter-role of the Nocturnal Boundary Layer

The paper presents the importance of the Nocturnal Boundary Layer in driving the diurnal variability of the atmospheric CO2 mixing ratio and the carbon isotope ratio at ground level from an urban station in India. Our observations are the first of their kind from this region. The atmospheric CO2 mixing ratio and the carbon isotopic ratio were measured for both the morning (05:30-07:30 IST) and afternoon time (16:00-18:00 IST) air samples at 5 m above ground level in Bangalore city, Karnataka State (12 degrees 58' N, 77 degrees 38' E, masl = 920 m) for a 10 day period during the winter of 2008. We observed a change of similar to 7% the in CO2 mixing ratio between the morning and afternoon time air samples. A stable isotope analysis of CO2 from morning samples showed a depletion in the carbon isotope ratio by similar to 2 parts per thousand compared to the afternoon samples. Along with the ground-based measurement of air samples, data of radiosonde measurements were also obtained from the Indian Meteorological Department to identify the vertical atmospheric structure at different time in a day. We proposed the presence or absence of the NBL as a controlling factor for the observed variability in the mixing ratio as well as its isotopic composition. Here we used the Keeling model approach to find out the carbon isotope ratio for the local sources. The local sources have further been characterized as anthropogenic and biological respiration (in %) using a two-component mixing model. We also used a vertical mixing model based on the concept of the mixing of isotopically depleted (carbon isotope) ``polluted air'' (PA) with isotopically enriched ``free atmospheric air'' (FA) above. Using this modeling approach, the contribution of FA at ground level is being estimated for both the morning and afternoon time air samples.

New uniform solid catalyst for the low-temperature oxidation of carbon monoxide: A triple-layered rare earth perovskite containing Co and Cu ions

Oxygen reactivity and catalytic activity of the cobalt-containing layered defect perovskites, YBa2Cu2CoO7+delta and LaBa2Cu2CoO7+delta, in comparison with LaBa2Cu3O7-delta have been investigated employing temperature-programmed desorption (TPD) and temperature-programmed surface reactions (TPSR) in the stoichiometric and catalytic mode using carbon monoxide as a probe molecule. TPD studies showed evidence for the presence of two distinct labile oxygen species, one at (0 0 1/2) sites and the other at (0 1/2 0) sites in LaBa2Cu2CoO7+delta against a single labile species at (0 1/2 0) in the case of two other oxides. The activation energies for the catalytic oxidation of carbon monoxide by oxygen over LaBa2Cu3O7-delta, YBa2Cu2CoO7+delta, and LaBa2Cu2CoO7+delta have been estimated to be 24.2, 15.9, and 13.6 kcal/mol, respectively. The reactivity and catalytic activity of the oxide systems have been interpreted in terms of the structural changes brought about by substituents, guided by a directing effect of the larger rare earth cation. TPSR profiles, structural analysis, and infrared spectroscopic investigations suggest that the oxygen present at (0 0 1/2) sites in the case of LaBa2Cu2CoO7+delta is accessible to catalytic oxidation of CO through a Mars-Van Krevelen pathway. Catalytic conversion of CO to CO2 over LaBa2Cu2CoO7+delta occurs at 200 degrees C. The enhanced reactivity is explained in terms of changes brought about in the coordination polyhedra around transition metals, enhanced basal plane oxygen diffusivity, and redox potentials of the different transition metal cations.

Ru(4+) ion in CeO(2) (Ce(0.95)Ru(0.05)O(2-delta)): A non-deactivating, non-platinum catalyst for water gas shift reaction

Hydrogen is a clean energy carrier and highest energy density fuel. Water gas shift (WGS) reaction is an important reaction to generate hydrogen from steam reforming of CO. A new WGS catalyst, Ce(1-x)Ru(x)O(2-delta) (0 <= x <= 0.1) was prepared by hydrothermal method using melamine as a complexing agent. The Catalyst does not require any pre-treatment. Among the several compositions prepared and tested, Ce(0.95)Ru(0.05)O(2-delta) (5% Ru(4+) ion substituted in CeO(2)) showed very high WGS activity in terms of high conversion rate (20.5 mu mol.g(-1).s(-1) at 275 degrees C) and low activation energy (12.1 kcal/mol). Over 99% conversion of CO to CO(2) by H(2)O is observed with 100% H(2) selectivity at >= 275 degrees C. In presence of externally fed CO(2) and H(2) also, complete conversion of CO to CO(2) was observed with 100% H(2) selectivity in the temperature range of 305-385 degrees C. Catalyst does not deactivate in long duration on/off WGS reaction cycle due to absence of surface carbon and carbonate formation and sintering of Ru. Due to highly acidic nature of Ru(4+) ion, surface carbonate formation is also inhibited. Sintering of noble metal (Ru) is avoided in this catalyst because Ru remains in Ru(4+) ionic state in the Ce(1-x)Ru(x)O(2-delta) catalyst.

Short- and long-term temporal variations in salinity and the oxygen, carbon and hydrogen isotopic compositions of the Hooghly Estuary water, India

The Hooghly River estuary provides a unique experimental site to understand the effect of monsoonal river discharge on freshwater and seawater mixing. Water samples collected bi-weekly for a duration of 17 months were analyzed for salinity, delta O-18,delta C-13(DIC), as well as delta D to investigate the differential mixing of freshwater and seawater. The differences in salinity and delta O-18 of samples collected during low and high tides on the same day are strongly correlated suggesting a well mixed water column at our sampling site. Low salinity and depleted delta O-18 during monsoon is consistent with increased river discharge as well as high rainfall. We identified different slopes in a delta O-18 versus salinity plot for the estuary water samples collected during monsoon and non-monsoon seasons. This is driven by composition of the freshwater source which is dominated by rainwater during monsoon and rivers during non-monsoon months. Selected delta D analyses of samples indicate that groundwater contributes significantly to the Hooghly Estuary during low rainfall times of the year. delta C-13(DIC) measured in the water recorded low values towards the end of monsoon indicating low productivity (i.e. increased organic respiration) while progressively increasing delta C-13(DIC) values from October till January as well as during some of the pre-monsoon months can be explained by increasing productivity. Very low delta C-13(DIC) (similar to-20%0) suggests involvement of carbon derived from anaerobic oxidation of organics and/or methane with potential contribution from increased anthropogenic water supply. An estimate of seawater incursion into the Hooghly Estuary at different times of the year is obtained by using salinity data in a two-component mixing model. Presence of seawater was found maximum (31-37%) during February till July and lowest (less than or equal to 6%) from September till November. We notice a temporal offset between Ganges River discharge farther upstream at Farakka and salinity variation at the Hooghly Estuary. We believe that this time lag is a result of the physical distance between Farakka and Kakdweep (our sampling location) and put constraints on the travel time of river water during early monsoon. (c) 2012 Published by Elsevier B.V.

An experimental set-up for carbon isotopic analysis of atmospheric CO2 and an example of ecosystem response during solar eclipse 2010

We present here, an experimental set-up developed for the first time in India for the determination of mixing ratio and carbon isotopic ratio of air-CO2. The set-up includes traps for collection and extraction of CO2 from air samples using cryogenic procedures, followed by the measurement of CO2 mixing ratio using an MKS Baratron gauge and analysis of isotopic ratios using the dual inlet peripheral of a high sensitivity isotope ratio mass spectrometer (IRMS) MAT 253. The internal reproducibility (precision) for the PC measurement is established based on repeat analyses of CO2 +/- 0.03 parts per thousand. The set-up is calibrated with international carbonate and air-CO2 standards. An in-house air-CO2 mixture, `OASIS AIRMIX' is prepared mixing CO2 from a high purity cylinder with O-2 and N-2 and an aliquot of this mixture is routinely analyzed together with the air samples. The external reproducibility for the measurement of the CO2 mixing ratio and carbon isotopic ratios are +/- 7 (n = 169) mu mol.mol(-1) and +/- 0.05 (n = 169) parts per thousand based on the mean of the difference between two aliquots of reference air mixture analyzed during daily operation carried out during November 2009-December 2011. The correction due to the isobaric interference of N2O on air-CO2 samples is determined separately by analyzing mixture of CO2 (of known isotopic composition) and N2O in varying proportions. A +0.2 parts per thousand correction in the delta C-13 value for a N2O concentration of 329 ppb is determined. As an application, we present results from an experiment conducted during solar eclipse of 2010. The isotopic ratio in CO2 and the carbon dioxide mixing ratio in the air samples collected during the event are different from neighbouring samples, suggesting the role of atmospheric inversion in trapping the emitted CO2 from the urban atmosphere during the eclipse.

Segmental relaxations and crystallization-induced phase separation in PVDF/PMMA blends in the presence of surface-functionalized multiwall carbon nanotubes

Crystallization-induced phase separation and segmental relaxations in poly(vinylidene fluoride)/poly(methyl methacrylate) (PVDF/PMMA) blends was systematically investigated by melt-rheology and broadband dielectric spectroscopy in the presence of multiwall carbon nanotubes (MWNTs). Different functionalized MWNTs (amine, -NH2; acid, -COOH) were incorporated in the blends by melt-mixing above the melting temperature of PVDF, where the blends are miscible, and the crystallization induced phase separation was probed in situ by shear rheology. Interestingly, only -NH2 functionalized MWNTs (a-MWNTs) aided in the formation of beta-phase (trans-trans) crystals in PVDF, whereas both the neat blends and the blends with -COOH functionalized MWNTs (c-MWNTs) showed only alpha-phase (trans-gauche-trans-gauche') crystals as inferred from wide-angle X-ray diffraction (WXRD) and Fourier transform infrared (FTIR). Furthermore, blends with only a-MWNTs facilitated in heterogeneous nucleation in the blends manifesting in an increase in the calorimetric crystallization temperature and hence, augmented the theologically determined crystallintion induced phase separation temperature. The dielectric relaxations associated with the crystalline phase of PVDF (alpha(c)) was completely absent in the blends with a-MWNTs in contrast to neat blends and the blends with c-MWNTs in the dielectric loss spectra. The relaxations in the blends investigated here appeared to follow Havriliak-Negami (HN) empirical equations, and, more interestingly, the dynamic heterogeneity in the system could be mapped by an extra relaxation at higher frequency at the crystallization-induced phase separation temperature. The mean relaxation time (tau(HN)) was evaluated and observed to be delayed in the presence of MWNTs in the blends, more prominently in the case of blends with a-MWNTs. The latter also showed a significant increase in the dielectric relaxation strength (Delta epsilon). Electron microscopy and selective etching was used to confirm the localization of MWNTs in the amorphous phases of the interspherulitic regions as observed from scanning electron microscopy (SEM). The evolved crystalline morphology, during crystallization-induced phase separation, was observed to have a strong influence on the charge transport processes in the blends. These observations were further supported by the specific interactions (like dipole induced dipole interaction) between a-MWNTs and PVDF, as inferred from FTIR, and the differences in the crystalline morphology as observed from WXRD and polarized optical microscopy (POM).

Multiwalled-carbon-nanotube-induced miscibility in near-critical PS/PVME blends: assessment through concentration fluctuations and segmental relaxation

The effects of multiwalled carbon nanotubes (MWNTs) on the concentration fluctuations, interfacial driven elasticity, phase morphology, and local segmental dynamics of chains for near-critical compositions of polystyrene/poly(vinyl to methyl ether) (PS/PVME) blends were systematically investigated using dynamic shear rheology and dielectric spectroscopy. The contribution of the correlation length (xi) of the concentration fluctuations to the evolving stresses was monitored in situ to probe the different stages of demixing in the blends. The classical upturn in the dynamic moduli was taken as the rheological demixing temperature (T-rheo), which was also observed to be in close agreement with those obtained using concentration fluctuation variance, <(delta phi)(2)>, versus temperature curves. Further, Fredrickson and Larson's approach involving the mean-field approximation and the double-reptation self-concentration (DRSC) model was employed to evaluate the spinodal decomposition temperature (T-s). Interestingly, the values of both T-rheo and T-s shifted upward in the blends in the presence of MWNTs, manifesting in molecular-level miscibility. These phenomenal changes were further observed to be a function of the concentration of MWNTs. The evolution of morphology as a function of temperature was studied using polarized optical microscopy (POM). It was observed that PVME, which evolved as an interconnected network during the early stages of demixing, coarsened into a matrix-droplet morphology in the late stages. The preferential wetting of PVME onto MWNTs as a result of physicochemical interactions retained the interconnected network of PVME for longer time scales, as supported by POM and atomic force microscopy (AFM) images. Microscopic heterogeneity in macroscopically miscible systems was studied by dielectric relaxation spectroscopy. The slowing of segmental relaxations in PVME was observed in the presence of both ``frozen'' PS and MWNTs interestingly at temperatures much below the calorimetric glass transition temperature (T-g). This phenomenon was observed to be local rather than global and was addressed by monitoring the evolution of the relaxation spectra near and above the demixing temperature.

Impact of heavy metals on bacterial communities from mangrove soils of the Mahanadi Delta (India)

This study aimed to assess soil nutrient status and heavy metal content and their impact on the predominant soil bacterial communities of mangroves of the Mahanadi Delta. Mangrove soil of the Mahanadi Delta is slightly acidic and the levels of soil nutrients such as carbon, nitrogen, phosphorous and potash vary with season and site. The seasonal average concentrations (g/g) of various heavy metals were in the range: 14810-63370 (Fe), 2.8-32.6 (Cu), 13.4-55.7 (Ni), 1.8-7.9 (Cd), 16.6-54.7 (Pb), 24.4-132.5 (Zn) and 13.3-48.2 (Co). Among the different heavy metals analysed, Co, Cu and Cd were above their permissible limits, as prescribed by Indian Standards (Co=17g/g, Cu=30 g/g, Cd=3-6 g/g), indicating pollution in the mangrove soil. A viable plate count revealed the presence of different groups of bacteria in the mangrove soil, i.e. heterotrophs, free-living N-2 fixers, nitrifyers, denitrifyers, phosphate solubilisers, cellulose degraders and sulfur oxidisers. Principal component analysis performed using multivariate statistical methods showed a positive relationship between soil nutrients and microbial load. Whereas metal content such as Cu, Co and Ni showed a negative impact on some of the studied soil bacteria.

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.