Analysis of oxide and vanadate supports for catalytic hydrogen combustion: Kinetic and mechanistic investigations

Combustion synthesized oxide and vanadate compounds (CeO2, Fe2O3, CeVO4, and FeVO4) were tested for catalytic hydrogen combustion. The compounds were characterized by X-ray diffraction and X-ray photoelectron spectroscopy. All the four compounds showed good activity and stability for catalytic hydrogen combustion and more than 95% conversion was observed over all the compounds within 500 degrees C. The mechanisms for the reaction over the different classes of compounds (cerium-based and iron-based compounds) were proposed on the basis of spectroscopic observations. The main difference in the mechanisms was in the nature of adsorption of H2 over the sites. The elementary processes for the reaction were proposed, corresponding rate expressions were derived, and the rate parameters for the reaction were estimated using nonlinear regression. Langmuir-Hinshelwood and Eley-Rideal mechanisms were also tested for the reaction and the proposed mechanism was compared with these mechanisms. (c) 2011 American Institute of Chemical Engineers AIChE J, 2012

Transition metal oxide loaded MCM catalysts for photocatalytic degradation of dyes

Transition metal oxide (TiO2, Pe(2)O(3), CoO) loaded MCM-41 and MCM-48 were synthesized by a two-step surfactant-based process. Nanoporous, high surface area compounds were obtained after calcination of the compounds. The catalysts were characterized by SEM, XRD, XPS, UV-vis and BET surface area analysis. The catalysts showed high activity for the photocatalytic degradation of both anionic and cationic dyes. The degradation of the dyes was described using Langmuir-Hinshelwood kinetics and the associated rate parameters were determined.

Estimation of vapour pressure and partial pressure of subliming compounds by low-pressure thermogravimetry

A method for the estimation of vapour pressure and partial pressure of subliming compounds under reduced pressure, using rising temperature thermogravimetry, is described in this paper. The method is based on our recently developed procedure to estimate the vapour pressure from ambient pressure thermogravimetric data using Langmuir equation. Using benzoic acid as the calibration standard, vapour pressure temperature curves are calculated at 80, 160 and 1000 mbar for salicylic acid and vanadyl bis-2,4-pentanedionate, a precursor used for chemical vapour deposition of vanadium oxides. Using a modification of the Langmuir equation, the partial pressure of these materials at different total pressures is also determined as a function of temperature. Such data can be useful for the deposition of multi-metal oxide thin films or doped thin films by chemical vapour deposition (CVD).

Transition metal oxide loaded MCM catalysts for photocatalytic degradation of dyes

Transition metal oxide (TiO2, Pe(2)O(3), CoO) loaded MCM-41 and MCM-48 were synthesized by a two-step surfactant-based process. Nanoporous, high surface area compounds were obtained after calcination of the compounds. The catalysts were characterized by SEM, XRD, XPS, UV-vis and BET surface area analysis. The catalysts showed high activity for the photocatalytic degradation of both anionic and cationic dyes. The degradation of the dyes was described using Langmuir-Hinshelwood kinetics and the associated rate parameters were determined.

Ag@AgI, Core@Shell Structure in Agarose Matrix as Hybrid: Synthesis, Characterization, and Antimicrobial Activity

A novel in situ core@shell structure consisting of nanoparticles of Ag (Ag Nps) and AgI in agarose matrix (Ag@ AgI/agarose) has been synthesized as a hybrid, in order to have an efficient antibacterial agent for repetitive usage with no toxicity. The synthesized core@shell structure is very well characterized by XRD, UV-visible, photoluminescence, and TEM. A detailed antibacterial studies including repetitive cycles are carried out on Gram-negative Escherichia coli (E. coli) and Gram-positive Staphylococcus aureus (S. aureus) bacteria in saline water, both in dark and on exposure to visible light. The hybrid could be recycled for the antibacterial activity and is nontoxic toward human cervical cancer cells (HeLa cells). The water insoluble Ag@AgI in agarose matrix forms a good coating on quartz, having good mechanical strength. EPR and TEM studies are carried out on the Ag@AgI/agarose and the bacteria, respectively, to elucidate a possible mechanism for killing of the bacteria.

In Situ Electrochemical Polymerization at Air-Water Interface: Surface-Pressure-Induced, Graphene-Oxide-Assisted Preferential Orientation of Polyaniline

In situ electrochemical polymerization of aniline in a Langmuir trough under applied surface pressure assists in the preferential orientation of polyaniline (PANI) in planar polaronic structure. Exfoliated graphene oxide (EGO) spread on water surface is used to bring anilinium cations present in the subphase to air-water interface through electrostatic interactions. Subsequent electrochemical polymerization of aniline under applied surface pressure in the Schaefer mode results in EGO/PANT composite with PANT in planar polaronic form. The orientation of PANI is confirmed by electrochemical and Raman spectroscopic studies. This technique opens up possibilities of 2-D polymerization at the air-water interface. Electrochemical sensing of hydrogen peroxide is used to differentiate the activity of planar and coiled forms of PANI toward electrocatalytic reactions.

Analysis of Parameter Values in the van der Waals and Platteeuw Theory for Methane Hydrates Using Monte Carlo Molecular Simulations

The van der Waals and Platteuw (vdVVP) theory has been successfully used to model the thermodynamics of gas hydrates. However, earlier studies have shown that this could be due to the presence of a large number of adjustable parameters whose values are obtained through regression with experimental data. To test this assertion, we carry out a systematic and rigorous study of the performance of various models of vdWP theory that have been proposed over the years. The hydrate phase equilibrium data used for this study is obtained from Monte Carlo molecular simulations of methane hydrates. The parameters of the vdWP theory are regressed from this equilibrium data and compared with their true values obtained directly from simulations. This comparison reveals that (i) methane-water interactions beyond the first cage and methane-methane interactions make a significant contribution to the partition function and thus cannot be neglected, (ii) the rigorous Monte Carlo integration should be used to evaluate the Langmuir constant instead of the spherical smoothed cell approximation, (iii) the parameter values describing the methane-water interactions cannot be correctly regressed from the equilibrium data using the vdVVP theory in its present form, (iv) the regressed empty hydrate property values closely match their true values irrespective of the level of rigor in the theory, and (v) the flexibility of the water lattice forming the hydrate phase needs to be incorporated in the vdWP theory. Since methane is among the simplest of hydrate forming molecules, the conclusions from this study should also hold true for more complicated hydrate guest molecules.

Kinetics of adsorption of methylene blue and rhodamine 6G on acrylic acid-based superabsorbents

Superabsorbent polymers (SAPs) of acrylic acid, sodium acrylate, and acrylamide (AM), crosslinked with ethylene glycol dimethacrylate, were synthesized by inverse suspension polymerization. The equilibrium swelling capacities of the SAPs were determined and these decreased with increasing AM content. The adsorption of the two cationic dyes, methylene blue and rhodamine 6G, on the dry as well as equilibrium swollen SAPs was investigated. The amount of the dye adsorbed at equilibrium per unit weight of the SAPs and the rate constants of adsorption were determined. The amount of the dye adsorbed at equilibrium by the SAPs decreased with increasing mol % of AM in the SAPs. The amount of the dye adsorbed at equilibrium was almost equal for the dry and equilibrium swollen SAPs. However, the equilibrium swollen SAPs adsorbed dyes at a higher rate than the dry SAPs. The higher rate of adsorption was attributed to the availability of all the anionic groups present in the fully elongated conformation of the SAPs in the equilibrium swollen state. The effect of initial dye concentration on the adsorption was also investigated and the adsorption was described by Langmuir adsorption isotherms. (C) 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012

Dual functional performance of fiber Bragg gratings coated with metals using flash evaporation technique

Metallic and other type of coatings on fiber Bragg grating (FBG) sensors alter their sensitivity with thermal and mechanical stress while protecting the fragile optical fiber in harsh sensing surroundings. The behavior of the coated materials is unique in their response to thermal and mechanical stress depending on the thickness and the mode of coating. The thermal stress during the coating affects the temperature sensitivity of FBG sensors. We have explored the thermal response of FBGs coated with Al and Pb to an average thickness of 80 nm using flash evaporation technique where the FBG sensor is mounted in a region at room temperature in an evacuated chamber having a pressure of 10(6) Torr which will minimize any thermal stress during the coating process. The coating thickness is chosen in the nanometer region with the aim to study thermal behavior of nanocoatings and their effect on FBG sensitivity. The sensitivity of FBGs is evaluated from the wavelengths recorded using an optical sensing interrogator sm 130 (Micron Optics) from room temperature to 300 degrees C both during heating and cooling. It is observed that the sensitivity of the metal coated fibers is better than the reference FBG with no coating for the entire range of temperature. For a coating thickness of 80 nm, Al coated FBG is more sensitive than the one coated with Pb up to 170 degrees C and it reverses at higher temperatures. This point is identified as a reversible phase transition in Pb monolayers as the 2-dimensional aspects of the metal layers are dominant in the nanocoatings of Pb. On cooling, the phase transition reverses and the FBGs return to the original state and for repeated cycles of heating and cooling the same pattern is observed. Thus the FBG functions as a sensor of the phase transitions of the coatings also. (C) 2012 Elsevier Inc. All rights reserved.

Detection of sugar-lectin interactions by multivalent dendritic sugar functionalized single-walled carbon nanotubes

We show that single walled carbon nanotubes (SWNTs) decorated with sugar functionalized poly (propyl ether imine) (PETIM) dendrimer is a very sensitive platform to quantitatively detect carbohydrate recognizing proteins, namely, lectins. The changes in electrical conductivity of SWNT in field effect transistor device due to carbohydrate-protein interactions form the basis of present study. The mannose sugar attached PETIM dendrimers undergo charge-transfer interactions with the SWNTs. The changes in the conductance of the dendritic sugar functionalized SWNT after addition of lectins in varying concentrations were found to follow the Langmuir type isotherm, giving the concanavalin A (Con A)-mannose affinity constant to be 8.5 x 10(6) M-1. The increase in the device conductance observed after adding 10 nM of Con A is same as after adding 20 mu M of a non-specific lectin peanut agglutinin, showing the high specificity of the Con A-mannose interactions. The specificity of sugar-lectin interactions was characterized further by observing significant shifts in Raman modes of the SWNTs. (C) 2012 American Institute of Physics. http://dx.doi.org/10.1063/1.4739793]

Covalently Linked, Water-Dispersible, Cyciodextrin: Reduced-Graphene Oxide Sheets

Reduced-graphene oxide (rGO) sheets have been functionalized by covalently linking beta-cyclodextrin (beta CD) cavities to the sheets via an amide linkage. The functionalized beta-CD:rGO sheets, in contrast to rGO, are dispersible over a wide range of pH values (2-13). Zeta potential measurements indicate that there is more than one factor responsible for the dispersibility. We show here that planar aromatic molecules adsorbed on the rGO sheet as well as nonplanar molecules included in the tethered beta-CD cavities have their fluorescence effectively quenched by the beta-CD:rGO sheets. The beta-CD:rGO sheets combine the hydrophobicity associated with rGO along with the hydrophobicity of the cyclodextrin cavities in a single water-dispersible material.

Adsorption of anionic dyes on a reversibly swelling cationic superabsorbent polymer

A cationic monomer 2-(methacryloyloxy)ethyl]trimethylammonium chloride was polymerized using N,N'-methylenebisacrylamide as the crosslinker to obtain a cationic superabsorbent polymer (SAP). This SAP was characterized by Fourier transform-infrared spectroscopy, and the equilibrium swelling capacity was determined by swelling in water. The SAP was subjected to cyclic swelling/deswelling in water and NaCl solution. The conductivity of the swelling medium was monitored during the swelling/deswelling and was related to the swelling/deswelling characteristics of the SAP. The adsorption of five anionic dyes of different classes on the SAP was carried out and was found to follow the first-order kinetics. The Langmuir adsorption isotherms were found to fit the equilibrium adsorption data. The dye adsorption capacity of the SAP synthesized in this study was higher than that obtained for other hydrogels reported in the literature. (c) 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013

Retention characteristics of Cu2+, Pb2+, and Zn2+ from aqueous solutions by two types of low lime fly ashes

The technical feasibility of utilization of fly ash as a low-cost adsorbent for the removal of metals from water has been studied. For two types of fly ashes, the retention capacities of copper, lead, and zinc metal ions have been studied. Contact time, initial concentration, and pH have been varied and their effect on retention mechanism has been studied. The dominant mechanisms responsible for retention are found to be precipitation due to the presence of calcium hydroxide, and adsorption due to the presence of silica and alumina oxide surfaces in the fly ash. First-order kinetic plots have revealed that the rate constant increases with increase in the initial concentration and pH. Langmuir adsorption isotherms have been plotted to study the maximum adsorption capacities for metal ions considered under different conditions. X-ray diffraction studies revealed the formation of new peaks corresponding to respective metal ions precipitates under alkaline conditions.

Plasmonic tuning of photoluminescence from semiconducting quantum dot assemblies

We report tuning of photoluminescence enhancement and quenching from closed packed monolayers of cadmium selenide quantum dots doped with gold nanoparticles. Plasmon-mediated control of the emission intensity from the monolayers is achieved by varying the size and packing density of the quantum dots as well as the doping concentration of gold nanoparticles. We observe a unique packing density dependent crossover from enhancement to quenching and vice versa for fixed size of quantum dots and doping concentration of gold nanoparticles. We suggest that this behavior is indicative of a crossover from single particle to collective emission from quantum dots mediated by gold nanoparticles.

Micro-Raman and photoluminescence studies of self-assembled quantum well microtubes on GaAs substrate

The Semiconductor Quantum Well (QW) microtubes have been fabricated by strain-induced self assembling technique. Three types of multilayer structures have consisted of GaAs/InxGa1-xAs strained layers containing with various thickness of Monolayers of (GaAs/AlGaAs) QW were grown by Varian Gen II Molecular Beam Epitaxy (MBE) on the GaAs (100) substrate. The shape of the rolled up microtubes provide a clear idea about the formation of three dimensional micro- and nanostructures. Micro-Raman and photoluminescence (PL) studies were performed to the QW microtubes and as compared with their grown area on the GaAs substrate. The results of Raman spectra show the frequency shift of phonon modes measured in tube and compared with the grown area due to residual strain. The PL peaks of the microtube were red-shifted due to the strain effect and transition of bandgap from Type-II to Type-I. (C) 2013 Elsevier B.V. All rights reserved.