Effect of functional groups on separating carbon dioxide from CO2/N-2 gas mixtures using edge functionalized graphene nanoribbons

Development of microporous adsorbents for separation and sequestration of carbon dioxide from flue gas streams is an area of active research. In this study, we assess the influence of specific functional groups on the adsorption selectivity of CO2/N-2 mixtures through Grand Canonical Monte Carlo (GCMC) simulations. Our model system consists of a bilayer graphene nanoribbon that has been edge functionalized with OH, NH2, NO2, CH3 and COOH. Ab initio Moller-Plesset (MP2) calculations with functionalized benzenes are used to obtain binding energies and optimized geometries for CO2 and N-2. This information is used to validate the choice classical forcefields in GCMC simulations. In addition to simulations of adsorption from binary mixtures of CO2 and N-2, the ideal adsorbed solution theory (IAST) is used to predict mixture isotherms. Our study reveals that functionalization always leads to an increase in the adsorption of both CO2 and N-2 with the highest for COOH. However, significant enhancement in the selectivity for CO2 is only seen with COOH functionalized nanoribbons. The COOH functionalization gives a 28% increase in selectivity compared to H terminated nanoribbons, whereas the improvement in the selectivity for other functional groups are much Enure modest. Our study suggests that specific functionalization with COOH groups can provide a material's design strategy to improve CO2 selectivity in microporous adsorbents. Synthesis of graphene nanoplatelets with edge functionalized COOH, which has the potential for large scale production, has recently been reported (Jeon el, al., 2012). (C) 2014 Elsevier Ltd. All rights reserved,

Reply to ``Comment on `Strongly magnetized cold degenerate electron gas: Mass-radius relation of the magnetized white dwarf'''

We show that the upper bound for the central magnetic field of a super-Chandrasekhar white dwarf calculated by Nityananda and Konar Phys. Rev. D 89, 103017 (2014)] and in the concerned comment, by the same authors, against our work U. Das and B. Mukhopadhyay, Phys. Rev. D 86, 042001 (2012)] is erroneous. This in turn strengthens the argument in favor of the stability of the recently proposed magnetized super-Chandrasekhar white dwarfs. We also point out several other numerical errors in their work. Overall we conclude that the arguments put forth by Nityananda and Konar are misleading.

Controlled synthesis of tunable nanoporous carbons for gas storage and supercapacitor application

A simple methodology has been developed for the synthesis of functional nanoporous carbon (NPC) materials using a metal-organic framework (IRMOF-3) that can act as a template for external carbon precursor (viz, sucrose) and also a self-sacrificing carbon source. The resultant graphitic NPC samples (abbreviated as NPC-0, NPC-150, NPC-300, NPC-500 and NPC-1000 based on sucrose loading) obtained through loading different amounts of sucrose exhibit tunable textural parameters. Among these, NPC-300 shows very high surface area (BET approximate to 3119 m(2)/g, Langmuir approximate to 4031 m(2)/g) with a large pore volume of 1.93 cm(3)/g. High degree of porosity coupled with polar surface functional groups, make NPC-300 remarkable candidate for the uptake of H-2 (2.54 wt% at 1 bar, and 5.1 wt% at 50 bar, 77 K) and CO2 (64 wt% at 1 bar, 195 K and 16.9 wt% at 30 bar, 298 K). As a working electrode in a supercapacitor cell, NPC-300 shows excellent reversible charge storage thus, demonstrating multifunctional usage of the carbon materials. (C) 2015 Elsevier Inc. All rights reserved.

Long way to go: how outflows from large galaxies propagate through the hot halo gas

Using hydrodynamic simulations, we study the mass-loss due to supernova-driven outflows from Milky Way type disc galaxies, paying particular attention to the effect of the extended hot halo gas. We find that the total mass-loss at inner radii scales roughly linearly with total mass of stars formed, and that the mass loading factor at the virial radius can be several times its value at inner radii because of the swept up hot halo gas. The temperature distribution of the outflowing material in the inner region (similar to 10 kpc) is bimodal in nature, peaking at 10(5) K and 10(6.5) K, responsible for optical and X-ray emission, respectively. The contribution of cold/warm gas with temperature <= 10(5.5) K to the outflow rate within 10 kpc is approximate to 0.3-0.5. The warm mass loading factor, eta(3e5) (T <= 3 x 10(5) K) is related to the mass loading factor at the virial radius (eta(v)) as eta(v) approximate to 25 eta(3e5) (SFR/M-circle dot yr(-1))(-0.15) for a baryon fraction of 0.1 and a starburst period of 50 Myr. We also discuss the effect of multiple bursts that are separated by both short and long periods. The outflow speed at the virial radius is close to the sound speed in the hot halo, less than or similar to 200 km s(-1). We identify two `sequences' of outflowing cold gas at small scales: a fast (approximate to 500 km s(-1)) sequence, driven by the unshocked free-wind; and a slow sequence (approximate to +/- 100 km s(-1)) at the conical interface of the superwind and the hot halo.

Studies on the effects of varying secondary gas properties in a low entrainment ratio supersonic ejector

A dilution cum purge ejector for application in fuel cells represents a domain of ejector operation involving low entrainment ratio with differing secondary and primary gas; which is hardly investigated and a cohesive design framework is not readily available. We comprehensively study a constant area ejector using analytical, experimental and numerical tools at low entrainment ratio (0.004-0.065) with Air, Helium and Argon as secondary gas while the primary gas is Air. For the first time, limits of operating parameters used in control volume method to design the ejector are found to be highly dependent on the secondary molecular weight. The entrainment ratio in the ejector (low for Helium and high for Argon) is affected by the molecular weight and the static pressure within the ejector (low for Air and high for Argon & Helium) by the gamma of the secondary gas. Sufficient suction pressure (0.3-0.55 bar) is generated by the ejector thereby preventing any backflow of secondary gas at all primary stagnation pressures (1.5, 2.2 and 3.1 bar). Numerical results agree well with experimental results. The ejector is shown to completely dilute and purge the secondary flow, meeting all key design requirements. (C) 2014 Elsevier Ltd. All rights reserved.

Calcium Permeable AMPA Receptor-Dependent Long Lasting Plasticity of Intrinsic Excitability in Fast Spiking Interneurons of the Dentate Gyrus Decreases Inhibition in the Granule Cell Layer

The local fast-spiking interneurons (FSINs) are considered to be crucial for the generation, maintenance, and modulation of neuronal network oscillations especially in the gamma frequency band. Gamma frequency oscillations have been associated with different aspects of behavior. But the prolonged effects of gamma frequency synaptic activity on the FSINs remain elusive. Using whole cell current clamp patch recordings, we observed a sustained decrease of intrinsic excitability in the FSINs of the dentate gyrus (DG) following repetitive stimulations of the mossy fibers at 30 Hz (gamma bursts). Surprisingly, the granule cells (GCs) did not express intrinsic plastic changes upon similar synaptic excitation of their apical dendritic inputs. Interestingly, pairing the gamma bursts with membrane hyperpolarization accentuated the plasticity in FSINs following the induction protocol, while the plasticity attenuated following gamma bursts paired with membrane depolarization. Paired pulse ratio measurement of the synaptic responses did not show significant changes during the experiments. However, the induction protocols were accompanied with postsynaptic calcium rise in FSINs. Interestingly, the maximum and the minimum increase occurred during gamma bursts with membrane hyperpolarization and depolarization respectively. Including a selective blocker of calcium-permeable AMPA receptors (CP-AMPARs) in the bath; significantly attenuated the calcium rise and blocked the membrane potential dependence of the calcium rise in the FSINs, suggesting their involvement in the observed phenomenon. Chelation of intracellular calcium, blocking HCN channel conductance or blocking CP-AMPARs during the experiment forbade the long lasting expression of the plasticity. Simultaneous dual patch recordings from FSINs and synaptically connected putative GCs confirmed the decreased inhibition in the GCs accompanying the decreased intrinsic excitability in the FSINs. Experimentally constrained network simulations using NEURON predicted increased spiking in the GC owing to decreased input resistance in the FSIN. We hypothesize that the selective plasticity in the FSINs induced by local network activity may serve to increase information throughput into the downstream hippocampal subfields besides providing neuroprotection to the FSINs. (c) 2014 Wiley Periodicals, Inc.

Formation of Prestellar Cores via Non-Isothermal Gas Fragmentation

Sheet-like clouds are common in turbulent gas and perhaps form via collisions between turbulent gas flows. Having examined the evolution of an isothermal shocked slab in an earlier contribution, in this work we follow the evolution of a sheet-like cloud confined by (thermal) pressure and gas in it is allowed to cool. The extant purpose of this endeavour is to study the early phases of core-formation. The observed evolution of this cloud supports the conjecture that molecular clouds themselves are three-phase media (comprising viz. a stable cold and warm medium, and a third thermally unstable medium), though it appears, clouds may evolve in this manner irrespective of whether they are gravitationally bound. We report, this sheet fragments initially due to the growth of the thermal instability (TI) and some fragments are elongated, filament-like. Subsequently, relatively large fragments become gravitationally unstable and sub-fragment into smaller cores. The formation of cores appears to be a three stage process: first, growth of the TI leads to rapid fragmentation of the slab; second, relatively small fragments acquire mass via gas-accretion and/or merger and third, sufficiently massive fragments become susceptible to the gravitational instability and sub-fragment to form smaller cores. We investigate typical properties of clumps (and smaller cores) resulting from this fragmentation process. Findings of this work support the suggestion that the weak velocity field usually observed in dense clumps and smaller cores is likely seeded by the growth of dynamic instabilities. Simulations were performed using the smooth particle hydrodynamics algorithm.

Effect of Pt doping on the gas sensing properties of porous chromium oxide films through a kinetic response analysis approach

The effect of doping trace amounts of noblemetals (Pt) on the gas sensing properties of chromium oxide thin films, is studied. The sensors are fabricated by depositing chromium oxide films on a glass substrate using a modified spray pyrolysis technique and characterized using X-ray diffraction, scanning electron microscopy, transmission electron microscopy and X-ray photoelectron spectroscopy. The films are porous and nanocrystalline with an average crystallite size of similar to 30 nm. The typical p-type conductivity arises due to the presence of Cr vacancies, formed as a result of Cr non-stoichiometry, which is found to vary upon Pt doping. In order to analyze the effect of doping on the gas sensing properties, we have adopted a kinetic response analysis approach, which is based on Langmuir Adsorption isotherm (LA) theory. The sensor response is analyzed with equations obtained from LA theory and time constants as well as energies of adsorption-desorption are evaluated. It is seen that, Pt doping lowers the Schottky barrier height of the metal oxide semiconductor sensor from 222 meV to 172 meV. Subsequently the reduction in adsorption and desorption energies led to enhancement in sensor response and improvement in the kinetics of the sensor response i.e. the response time as well as recovery times of the sensor.

ADAPTATION OF MW LEVEL NATURAL GAS LEAN BURN ENGINE FOR PRODUCER GAS OPERATION A GRID CONNECTED POWER PLANT

Availability of producer gas engines at MW being limited necessitates to adapt engine from natural gas operation. The present work focus on the development of necessary kit for adapting a 12 cylinder lean burn turbo-charged natural gas engine rated at 900 kWe (Waukesha make VHP5904LTD) to operate on producer and set up an appropriate capacity biomass gasification system for grid linked power generation in Thailand. The overall plant configuration had fuel processing, drying, reactor, cooling and cleaning system, water treatment, engine generator and power evacuation. The overall project is designed for evacuation of 1.5 MWe power to the state grid and had 2 gasification system with the above configuration and 3 engines. Two gasification system each designed for about 1100 kg/hr of woody biomass was connected to the engine using a producer gas carburetor for the necessary Air to fuel ratio control. In the use of PG to fuel IC engines, it has been recognized that the engine response will differ as compared to the response with conventional fueled operation due to the differences in the thermo-physical properties of PG. On fuelling a conventional engine with PG, power de-rating can be expected due to the lower calorific value (LCV), lower adiabatic flame temperature (AFT) and the lower than unity product to reactant more ratio. Further the A/F ratio for producer gas is about 1/10th that of natural gas and requires a different carburetor for engine operation. The research involved in developing a carburetor for varying load conditions. The patented carburetor is based on area ratio control, consisting of a zero pressure regulator and a separate gas and air line along with a mixing zone. The 95 litre engine at 1000 rpm has an electrical efficiency of 33.5 % with a heat input of 2.62 MW. Each engine had two carburetors designed for producer gas flow each capable of handling about 1200 m3/hr in order to provide similar engine heat input at a lower conversion efficiency. Cold flow studies simulating the engine carburetion system results showed that the A/F was maintained in the range of 1.3 +/- 0.1 over the entire flow range. Initially, the gasification system was tested using woody biomass and the gas composition was found to be CO 15 +/- 1.5 % H-2 22 +/- 2% CH4 2.2 +/- 0.5 CO2 11.25 +/- 1.4 % and rest N-2, with the calorific value in the range of 5.0 MJ/kg. After initial trials on the engine to fine tune the control system and adjust various engine operating parameter a peak load of 800 kWe was achieved, while a stable operating conditions was found to be at 750 kWe which is nearly 85 % of the natural gas rating. The specific fuel consumption was found to be 0.9 kg of biomass per kWh.

Analyzing the kinetic response of tin oxide-carbon and tin oxide-CNT composites gas sensors for alcohols detection

Tin oxide nanoparticles are synthesized using solution combustion technique and tin oxide - carbon composite thick films are fabricated with amorphous carbon as well as carbon nanotubes (CNTs). The x-ray diffraction, Raman spectroscopy and porosity measurements show that the as-synthesized nanoparticles are having rutile phase with average crystallite size similar to 7 nm and similar to 95 m(2)/g surface area. The difference between morphologies of the carbon doped and CNT doped SnO2 thick films, are characterized using scanning electron microscopy and transmission electron microscopy. The adsorption-desorption kinetics and transient response curves are analyzed using Langmuir isotherm curve fittings and modeled using power law of semiconductor gas sensors. (C) 2015 Author(s).

Use of permeable reactive barrier to mitigate groundwater nitrate contamination from on-site sanitation

Nearly 50% of India's population depends on variants of pit-toilet systems for human waste disposal. Nitrate contamination of groundwater by pit-toilet leachate is a major environmental concern in the country as it sources a major proportion (50-80%) of potable water from aquifers. Therefore, minimizing nitrate contamination of groundwater due to leachate infiltration from pit-toilet systems is essential. Batch and column experiments demonstrated the capability of bentonite-enhanced sand (BES) specimens to reduce nitrate concentrations in synthetic solutions (initial NO3-N concentration = 22.7 mg/L, C/N = 3) by about 85-90% in 10 to 24 hour by a heterotrophic denitrification process. Based on the laboratory results, it is recommended that use of a BES-permeable reactive barrier layer at the base of pit-toilets will facilitate heterotrophic denitrification and mitigate nitrate contamination of the underlying aquifer.

Suspended core-shell Pt-PtOx nanostructure for ultrasensitive hydrogen gas sensor

High sensitivity gas sensors are typically realized using metal catalysts and nanostructured materials, utilizing non-conventional synthesis and processing techniques, incompatible with on-chip integration of sensor arrays. In this work, we report a new device architecture, suspended core-shell Pt-PtOx nanostructure that is fully CMOS-compatible. The device consists of a metal gate core, embedded within a partially suspended semiconductor shell with source and drain contacts in the anchored region. The reduced work function in suspended region, coupled with builtin electric field of metal-semiconductor junction, enables the modulation of drain current, due to room temperature Redox reactions on exposure to gas. The device architecture is validated using Pt-PtO2 suspended nanostructure for sensing H-2 down to 200 ppb under room temperature. By exploiting catalytic activity of PtO2, in conjunction with its p-type semiconducting behavior, we demonstrate about two orders of magnitude improvement in sensitivity and limit of detection, compared to the sensors reported in recent literature. Pt thin film, deposited on SiO2, is lithographically patterned and converted into suspended Pt-PtO2 sensor, in a single step isotropic SiO2 etching. An optimum design space for the sensor is elucidated with the initial Pt film thickness ranging between 10 nm and 30 nm, for low power (< 5 mu W), room temperature operation. (C) 2015 AIP Publishing LLC.

Multiobjective Optimization of Piezoelectric Bimorph Actuator with Rigid Extension

Production of high tip deflection in a piezoelectric bimorph laminar actuator by applying high voltage is limited by many physical constraints. Therefore, piezoelectric bimorph actuator with a rigid extension of non-piezoelectric material at its tip is used to increase the tip deflection of such an actuator. Research on this type of piezoelectric bending actuator is either limited to first order constitutive relations, which do not include non-linear behavior of piezoelectric element at high electric field, or limited to curve fitting techniques. Therefore, this paper considers high electric field, and analytically models tapered piezoelectric bimorph actuator with a rigid extension of non-piezoelectric material at its tip. The stiffness, capacitance, effective tip deflection, block force, output strain energy, output energy density, input electrical energy and energy efficiency of the actuator are calculated analytically. The paper also discusses the multi-objective optimization of this type of actuator subjected to the mechanical and electrical constraints.

Seismic response of reduced-scale modular block and rigid faced reinforced walls through shaking table tests

This paper focuses on understanding the seismic response of geosynthetic reinforced retaining walls through shaking table tests on models of modular block and rigid faced reinforced retaining walls. Reduced-scale models of retaining walls reinforced with geogrid layers were constructed in a laminar box mounted on a uniaxial shaking table and subjected to various levels of sinusoidal base shaking. Models were instrumented with ultrasonic displacement sensors, earth pressure sensors and accelerometers. Effects of backfill density, number of reinforcement layers and reinforcement type on the performance of rigid faced and modular block walls were studied through different series of model tests. Performances of the walls were assessed in terms of face deformations, crest settlement and acceleration amplification at different elevations and compared. Modular block walls performed better than the rigid faced walls for the same level of base shaking because of the additional support derived by stacking the blocks with an offset. Type and quantity of reinforcement has significant effect on the seismic performance of both the types of walls. Displacements are more sensitive to relative density of the backfill and decrease with increasing relative density, the effect being more pronounced in case of unreinforced walls compared to the reinforced ones. Acceleration amplifications are not affected by the wall facing and inclusion of reinforcement. (C) 2015 Elsevier Ltd. All rights reserved.

Reactive interlayer based ultra-low moisture permeable membranes for organic photovoltaic encapsulation

Reactive interlayers consisting of zero valent iron and copper nanoparticles have been successfully incorporated into Surlyn films to fabricate moisture barrier materials with reduced water vapor permeabilities. The reactive nanoparticles dispersed in stearic acid were employed as the interlayers due to their ability to react with moisture. The water vapor transmission rates through the fabricated barrier films with reactive iron and copper interlayers decreased by over 4 orders of magnitude when compared to neat Surlyn. The flexibility and transparency of the barrier films have been evaluated by tensile and UV-visible experiments. Moreover, the accelerated aging studies conducted in accordance with the ISOS-III protocol confirmed the increased lifetimes of the organic photovoltaic (OPV) devices encapsulated with these reactive barrier films.