Amide Functionalized Microporous Organic Polymer (Am-MOP) for Selective CO2 Sorption and Catalysis

We report the design and synthesis of an amide functionalized microporous organic polymer (Am-MOP) prepared from trimesic acid and p-phenylenediamine using thionyl chloride as a reagent. Polar amide (CONH) functional groups act as a linking unit between the node and spacer and constitute the pore wall of the continuous polymeric network. The strong covalent bonds between the building blocks (trimesic acid and p-phenylenediamine) through amide bond linkages provide high thermal and chemical stability to Am-MOP. The presence of a highly polar pore surface allows selective CO2 uptake at 195 K over other gases such as N-2, Ar, and O-2. The CO2 molecule interacts with amide functional groups via Lewis acid base type interactions as demonstrated through DFT calculations. Furthermore, for the first time Am-MOP with basic functional groups has been exploited for the Knoevenagel condensation reaction between aldehydes and active methylene compounds. Availability of a large number of catalytic sites per volume and confined microporosity gives enhanced catalytic efficiency and high selectivity for small substrate molecules.

Comparison of CO2 and steam in transcritical Rankine cycles for concentrated solar power

High temperature, high pressure transcritical condensing CO2 cycle (TC-CO2) is compared with transcritical steam (TC-steam) cycle. Performance indicators such as thermal efficiency, volumetric flow rates and entropy generation are used to analyze the power cycle wherein, irreversibilities in turbo-machinery and heat exchangers are taken into account. Although, both cycles yield comparable thermal efficiencies under identical operating conditions, TC-CO2 plant is significantly compact compared to a TC-steam plant. Large specific volume of steam is responsible for a bulky system. It is also found that the performance of a TC-CO2 cycle is less sensitive to source temperature variations, which is an important requirement of a solar thermal system. In addition, issues like wet expansion in turbine and vacuum in condenser are absent in case of a TC-CO2 cycle. External heat addition to working fluid is assumed to take place through a heat transfer fluid (HTF) which receives heat from a solar receiver. A TC-CO2 system receives heat though a single HTF loop, whereas, for TC-steam cycle two HTF loops in series are proposed to avoid high temperature differential between the steam and HTF. (C) 2013 P. Garg. Published by Elsevier Ltd.

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,

Development of alloys with high strength at elevated temperatures by tuning the bimodal microstructure in the Al-Cu-Ni eutectic system

The development of high-strength aluminum alloys that can operate at 250 degrees C and beyond remains a challenge to the materials community. In this paper we report preliminary development of nanostructural Al-Cu-Ni ternary alloys containing alpha-Al, binary Al2Cu and ternary Al2Cu4Ni intermetallics. The alloys exhibits fracture strength of similar to 1 GPa with similar to 9% fracture strain at room temperature. At 300 degrees C, the alloy retains the high strength. The reasons for such significant mechanical properties are rationalized by unraveling the roles and response of various microstructural features. (C) 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Noteworthy performance of La1-xCaxMnO3 perovskites in generating H-2 and CO by the thermochemical splitting of H2O and CO2

Perovskite oxides of the composition La1-xCaxMnO3 ( LCM) have been investigated for the thermochemical splitting of H2O and CO2 to produce H-2 and CO, respectively. The study was carried out in comparison with La1-xSrxMnO3, CeO2 and other oxides. The LCM system exhibits superior characteristics in high-temperature evolution of oxygen, and in reducing CO2 to CO and H2O to H-2. The best results were obtained with La0.5Ca0.5MnO3 whose performance is noteworthy compared to that of other oxides including ceria. The orthorhombic structure of LCM seems to be a crucial factor.

Diurnal and seasonal variation of mixing ratio and delta C-13 of air CO2 observed at an urban station Bangalore, India

We present here observations on diurnal and seasonal variation of mixing ratio and delta C-13 of air CO2, from an urban station-Bangalore (BLR), India, monitored between October 2008 and December 2011. On a diurnal scale, higher mixing ratio with depleted delta C-13 of air CO2 was found for the samples collected during early morning compared to the samples collected during late afternoon. On a seasonal scale, mixing ratio was found to be higher for dry summer months (April-May) and lower for southwest monsoon months (June-July). The maximum enrichment in delta C-13 of air CO2 (-8.04 +/- 0.02aEuro degrees) was seen in October, then delta C-13 started depleting and maximum depletion (-9.31 +/- 0.07aEuro degrees) was observed during dry summer months. Immediately after that an increasing trend in delta C-13 was monitored coincidental with the advancement of southwest monsoon months and maximum enrichment was seen again in October. Although a similar pattern in seasonal variation was observed for the three consecutive years, the dry summer months of 2011 captured distinctly lower amplitude in both the mixing ratio and delta C-13 of air CO2 compared to the dry summer months of 2009 and 2010. This was explained with reduced biomass burning and increased productivity associated with prominent La Nina condition. While compared with the observations from the nearest coastal and open ocean stations-Cabo de Rama (CRI) and Seychelles (SEY), BLR being located within an urban region captured higher amplitude of seasonal variation. The average delta C-13 value of the end member source CO2 was identified based on both diurnal and seasonal scale variation. The delta C-13 value of source CO2 (-24.9 +/- 3aEuro degrees) determined based on diurnal variation was found to differ drastically from the source value (-14.6 +/- 0.7aEuro degrees) identified based on seasonal scale variation. The source CO2 identified based on diurnal variation incorporated both early morning and late afternoon sample; whereas, the source CO2 identified based on seasonal variation included only afternoon samples. Thus, it is evident from the study that sampling timing is one of the important factors while characterizing the composition of end member source CO2 for a particular station. The difference in delta C-13 value of source CO2 obtained based on both diurnal and seasonal variation might be due to possible contribution from cement industry along with fossil fuel / biomass burning as predominant sources for the station along with differential meteorological conditions prevailed.

A trade-off between maxima in efficiency and specific work output of super- and trans-critical CO2 Brayton cycles

Several operational aspects for thermal power plants in general are non-intuitive and involve simultaneous optimization of a number of operational parameters. In the case of solar operated power plants, it is even more difficult due to varying heat source temperatures induced by variability in insolation levels. This paper introduces a quantitative methodology for load regulation of a CO2 based Brayton cycle power plant using the `thermal efficiency and specific work output' coordinate system. The analysis shows that a transcritical CO2 cycle offers more flexibility under part load performance than the supercritical cycle in case of non-solar power plants. However, for concentrated solar power, where efficiency is important, supercritical CO2 cycle fares better than transcritical CO2 cycle. A number of empirical equations relating heat source temperature, high side pressure with efficiency and specific work output are proposed which could assist in generating control algorithms. (C) 2015 Elsevier B.V. All rights reserved.

Economic tradeoffs in mitigation, due to different atmospheric lifetimes of CO2 and black carbon

Tradeoffs are examined between mitigating black carbon (BC) and carbon dioxide (CO2) for limiting peak global mean warming, using the following set of methods. A two-box climate model is used to simulate temperatures of the atmosphere and ocean for different rates of mitigation. Mitigation rates for BC and CO2 are characterized by respective timescales for e-folding reduction in emissions intensity of gross global product. There are respective emissions models that force the box model. Lastly there is a simple economics model, with cost of mitigation varying inversely with emission intensity. Constant mitigation timescale corresponds to mitigation at a constant annual rate, for example an e-folding timescale of 40 years corresponds to 2.5% reduction each year. Discounted present cost depends only on respective mitigation timescale and respective mitigation cost at present levels of emission intensity. Least-cost mitigation is posed as choosing respective e-folding timescales, to minimize total mitigation cost under a temperature constraint (e.g. within 2 degrees C above preindustrial). Peak warming is more sensitive to mitigation timescale for CO2 than for BC. Therefore rapid mitigation of CO2 emission intensity is essential to limiting peak warming, but simultaneous mitigation of BC can reduce total mitigation expenditure. (c) 2015 Elsevier B.V. All rights reserved.

Achieving Highly Efficient, Selective, and Stable CO2 Reduction on Nitrogen-Doped Carbon Nanotubes

The challenge in the electrosynthesis of fuels from CO2 is to achieve durable and active performance with cost-effective catalysts. Here, we report that carbon nanotubes (CNTs), doped with nitrogen to form resident electron-rich defects, can act as highly efficient and, more importantly, stable catalysts for the conversion of CO2 to CO. The unprecedented overpotential (-0.18 V) and selectivity (80%) observed on nitrogen-doped CNTs (NCNTs) are attributed to their unique features to facilitate the reaction, including (i) high electrical conductivity, (ii) preferable catalytic sites (pyridinic N defects), and (iii) low free energy for CO2 activation and high barrier for hydrogen evolution. Indeed, DFT calculations show a low free energy barrier for the potential-limiting step to form key intermediate COOH as well as strong binding energy of adsorbed CON and weak binding energy for the adsorbed CO. The highest selective site toward CO production is pyridinic N, and the NCNT-based electrodes exhibit no degradation over 10 h of continuous operation, suggesting the structural stability of the electrode.

Mycobacterium tuberculosis has diminished capacity to counteract redox stress induced by elevated levels of endogenous superoxide

Mycobacterium tuberculosis (Mtb) has evolved protective and detoxification mechanisms to maintain cytoplasmic redox balance in response to exogenous oxidative stress encountered inside host phagocytes. In contrast, little is known about the dynamic response of this pathogen to endogenous oxidative stress generated within Mtb. Using a noninvasive and specific biosensor of cytoplasmic redox state of Mtb, we for first time discovered a surprisingly high sensitivity of this pathogen to perturbation in redox homeostasis induced by elevated endogenous reactive oxygen species (ROS). We synthesized a series of hydroquinone-based small molecule ROS generators and found that ATD-3169 permeated mycobacteria to reliably enhance endogenous ROS including superoxide radicals. When Mtb strains including multidrug-resistant (MDR) and extensively drug-resistant (XDR) patient isolates were exposed to this compound, a dose-dependent, long-lasting, and irreversible oxidative shift in intramycobacterial redox potential was detected. Dynamic redox potential measurements revealed that Mtb had diminished capacity to restore cytoplasmic redox balance in comparison with Mycobacterium smegmatis (Msm), a fast growing nonpathogenic mycobacterial species. Accordingly, Mtb strains were extremely susceptible to inhibition by ATD-3169 but not Msm, suggesting a functional linkage between dynamic redox changes and survival. Microarray analysis showed major realignment of pathways involved in redox homeostasis, central metabolism, DNA repair, and cell wall lipid biosynthesis in response to ATD-3169, all consistent with enhanced endogenous ROS contributing to lethality induced by this compound. This work provides empirical evidence that the cytoplasmic redox poise of Mtb is uniquely sensitive to manipulation in steady-state endogenous ROS levels, thus revealing the importance of targeting intramycobacterial redox metabolism for controlling TB infection. (C) 2015 The Authors. Published by Elsevier Inc.

Al based ultra-fine eutectic with high room temperature plasticity and elevated temperature strength

Developments of aluminum alloys that can retain strength at and above 250 degrees C present a significant challenge. In this paper we report an ultrafine scale Al-Fe-Ni eutectic alloy with less than 3.5 aa transition metals that exhibits room temperature ultimate tensile strength of similar to 400 MPa with a tensile ductility of 6-8%. The yield stress under compression at 300 degrees C was found to be 150 MPa. We attribute it to the refinement of the microstructure that is achieved by suction casting in copper mold. The characterization using scanning and transmission electron microscopy (SEM and TEM) reveals an unique composite structure that contains the Al-Al3Ni rod eutectic with spacing of similar to 90 nm enveloped by a lamellar eutectic of Al-Al9FeNi (similar to 140 nm). Observation of subsurface deformation under Vickers indentation using bonded interface technique reveals the presence of extensive shear banding during deformation that is responsible for the origin of ductility. The dislocation configuration in Al-Al3Ni eutectic colony indicates accommodation of plasticity in alpha-Al with dislocation accumulation at the alpha-Al/Al3Ni interface boundaries. In contrast the dislocation activities in the intermetallic lamellae are limited and contain set of planner dislocations across the plates. We present a detailed analysis of the fracture surface to rationalize the origin of the high strength and ductility in this class of potentially promising cast alloy. (C) 2015 Elsevier B.V. All rights reserved.

Stable isotopic signature of Southern Ocean deep water CO2 ventilation

The link between atmospheric CO2 level and ventilation state of the deep ocean is poorly understood due to the lack of coherent observations on the partitioning of carbon between atmosphere and ocean. In this Southern Ocean study, we have classified the Southern Ocean into different zones based on its hydrological features and have binned the variability in latitudinal air-CO2 concentration and its isotopic ratios. Together with air-CO2, we analysed the surface water for the isotopic ratios in dissolved inorganic carbon (DIC). Using the binary mixing approach on the isotopic ratio of atmospheric CO2 and its concentration, we identified the delta C-13 value of source CO2. The isotopic composition of source CO2 was around -9.22 +/- 0.26 parts per thousand for the year 2011 and 2012, while a composition of -13.49 +/- 4.07 parts per thousand was registered for the year 2013. We used the delta C-13 of DIC to predict the CO2 composition in air under equilibrium and compared our estimates with actual observations. We suggest that the degeneration of the DIC in presence of warm water in the region was the factor responsible for adding the CO2 to the atmosphere above. The place of observation coincides with the zone of high wind speed which promotes the process of CO2 exsolution from sea water. (C) 2015 Elsevier Ltd. All rights reserved.

DESIGN OF AN EXPERIMENTAL TEST FACILITY FOR SUPERCRITICAL CO2 BRAYTON CYCLE

A supercritical CO2 test facility is currently being developed at Indian Institute of Science, Bangalore, India to analyze the performance of a closed loop Brayton cycle for concentrated solar power (CSP) generation. The loop has been designed for an external heat input of 20 kW a pressure range of 75-135 bar, flow rate of 11 kg/min, and a maximum cycle temperature of 525 degrees C. The operation of the loop and the various parametric tests planned to be performed are discussed in this paper The paper addresses various aspects of the loop design with emphasis on design of various components such as regenerator and expansion device. The regenerator design is critical due to sharp property variations in CO2 occurring during the heat exchange process between the hot and cold streams. Two types of heat exchanger configurations 1) tube-in-tube (TITHE) and 2) printed circuit heat exchanger (PCHE) are analyzed and compared. A PCHE is found to be similar to 5 times compact compared to a TITHE for identical heat transfer and pressure drops. The expansion device is being custom designed to achieve the desired pressure drop for a range of operating temperatures. It is found that capillary of 5.5 mm inner diameter and similar to 2 meter length is sufficient to achieve a pressure drop from 130 to 75 bar at a maximum cycle temperature of 525 degrees C.

ELEVATION OF HEAT REJECTION TEMPERATURE IN TRANSCRITICAL CONDENSING CYCLES USING CO2+PROPANE MIXTURES

In this paper, a detailed thermodynamic performance analysis of a transcritical condensing (TC) cycle is performed with pure CO2 and a blend of 48.5 % propane with 51.5 % CO2 as working fluids. A realistic thermodynamic model is used incorporating irreversibilities in turbo-machineries and heat exchangers. The Key finding is that the addition of propane elevates the heat rejection temperature, but does not impair any of the performance indicators. Such a fluid may be useful for power generation in concentrated solar power applications by using which a hike of up to 2 % can be realized in the thermal efficiency of a power plant.