Enhanced Raman Spectroscopy of Molecules Adsorbed on Carbon-Doped TiO2 Obtained from Titanium Carbide: A Visible-Light-Assisted Renewable Substrate

Titanium carbide (TiC) is an electrically conducting material with favorable electrochemical properties. In the present studies, carbon-doped TiO2 (C-TiO2) has been synthesized from TiC particles, as well as TiC films coated on stainless steel substrate via thermal annealing under various conditions. Several C-TiO2 substrates are synthesized by varying experimental, conditions and characterized by UV-visible spectroscopy, photoluminescence, X-ray diffraction and X-ray photoelectron spectroscopic techniques. C-TiO2 in the dry state (in powder form as well as in film form) is subsequently used as a substrate for enhancing Raman signals corresponding to 4-mercaptobenzoic acid and 4-nitrothiophenol by utilizing chemical enhancement based on charge-transfer interactions. Carbon, a nonmetal dopant in TiO2, improves the intensities of Raman signals, compared, to undoped TiO2. Significant dependence of Raman intensity on carbon doping is observed. Ameliorated performance obtained using C-TiO2 is attributed to the presence of surface defects that originate due to carbon as a dopant, which, in turn,, triggers charge transfer between TiO2 and analyte. The C-TiO2 substrates are subsequently regenerated for repetitive use by illuminating an analyte-adsorbed substrate with visible light for a period of 5 h.

Substrate integrated Lead-Carbon hybrid ultracapacitor with flooded, absorbent glass mat and silica-gel electrolyte configurations

Lead-Carbon hybrid ultracapacitors (Pb-C HUCs) with flooded, absorbent-glass-mat (AGM) and silica-gel sulphuric acid electrolyte configurations are developed and performance tested. Pb-C HUCs comprise substrate-integrated PbO2 (SI-PbO2) as positive electrodes and high surface-area carbon with graphite-sheet substrate as negative electrodes. The electrode and silica-gel electrolyte materials are characterized by XRD, XPS, SEM, TEM, Rheometry, BET surface area, and FTIR spectroscopy in conjunction with electrochemistry. Electrochemical performance of SI-PbO2 and carbon electrodes is studied using cyclic voltammetry with constant-current charge and discharge techniques by assembling symmetric electrical-double-layer capacitors and hybrid Pb-C HUCs with a dynamic Pb(porous)/PbSO4 reference electrode. The specific capacitance values for 2 V Pb-C HUCs are found to be 166 F/g, 102 F/g and 152 F/g with a faradaic efficiency of 98%, 92% and 88% for flooded, AGM and gel configurations, respectively.

Charge transport in functionalized multi-wall carbon nanotube-Nafion composite

The charge transport in sulfonated multi-wall carbon nanotube (sMWNT)-Nafion composite is reported. The scanning electron microscope images of the composite, at 1 and 10 wt % of sMWNT, show that the nanotubes are well dispersed in polymer matrix, with conductivity values of 0.005 and 3.2 S/cm, respectively; and the percolation threshold is nearly 0.42 wt. %. The exponent (∼0.25) of the temperature dependence of conductivity in both samples indicates Mott's variable range hopping (VRH) transport. The conductance in 1 wt. % sample increases by three orders of magnitude at high electric-fields, consistent with VRH model. The negative magnetoresistance in 10 wt. % sample is attributed to the forward interference scattering mechanism in VRH transport. The ac conductance in 1 wt. % sample is expressed by σ(ω)∝ωs, and the temperature dependence of s follows the correlated barrier hopping model.

Thermo-mechanical stability of a cellular assembly of carbon nanotubes in air

Carbon nanotubes (CNT) in bulk form offer outstanding structural and functional properties, and are shown to remain viscoelastic over a wide temperature range (77-1273 K) under inert conditions. We examine the quasi-static and dynamic compressive mechanical response of these cellular CNT materials in ambient air up to a temperature of 773 K. In uniaxial quasi-static compression, several displacement bursts are noted at large strains. These are results of the slippage and zipping of the CNT, and lead to significant mechanical energy absorption. Results of the dynamic mechanical analysis experiments show no degradation in storage modulus and loss coefficient for up to 20 h at 673 K. Hence, these stable cellular CNT structures can be utilized up to a maximum temperature of 673 K in air, which is much higher than the best polymers. (C) 2012 Elsevier Ltd. All rights reserved.

Mixture solubilities of nitrobenzoic acid isomers in supercritical carbon dioxide

The ternary solubilities of solid isomers of nitrobenzoic acid (NBA) were experimentally determined at 308, 318 and 328K over a pressure range of 12-18 MPa in supercritical carbon dioxide (SCCO2). Compared to its binary solubility, the ternary solubilities of m-NBA increased at 308 K while it decreased at 328 K. However, the ternary solubilities of p-NBA increased at all temperatures and pressures except at 13 MPa and 328K. A new model was developed by applying solution model and activity coefficient model for the ternary solubilities of pharmaceutical and non-pharmaceutical solid mixtures in terms of temperature, density and cosolute composition. The model equation involves four temperature independent constraint-free parameters. The model equation correlates the ternary solubilities of seven pharmaceutical solid mixtures along with current data with an average AARD around 9.5% and sixteen non-pharmaceutical solid mixtures with 9% AARD. (C) 2012 Elsevier B.V. All rights reserved.

Electrical properties of buckled multiwalled carbon nanotube arrays in the diffusive regime

We report the geometrical effect of graded buckled multiwalled carbon nanotube arrays on the electrical transport properties in the diffusive regime, via successive breakdown caused by the Joule heating. This breakdown occurs in the straighter region. Empirical relations involving the current-carrying ability, resistance, breakdown power, threshold voltage, diameter and length of carbon nanotube arrays are discussed on the basis of an extensive set of experimental data along with justification. The experimental results are corroborated by the density functional tight-binding calculations of electronic band structure. The band gap decreases as buckleness increases leading to the enhancement in the current-carrying ability and elucidating the role of buckleness in carbon nanotubes. Copyright (c) EPLA, 2012

Climate response to changes in atmospheric carbon dioxide and solar irradiance on the time scale of days to weeks

Recent studies show that fast climate response on time scales of less than a month can have important implications for long-term climate change. In this study, we investigate climate response on the time scale of days to weeks to a step-function quadrupling of atmospheric CO2 and contrast this with the response to a 4% increase in solar irradiance. Our simulations show that significant climate effects occur within days of a stepwise increase in both atmospheric CO2 content and solar irradiance. Over ocean, increased atmospheric CO2 warms the lower troposphere more than the surface, increasing atmospheric stability, moistening the boundary layer, and suppressing evaporation and precipitation. In contrast, over ocean, increased solar irradiance warms the lower troposphere to a much lesser extent, causing a much smaller change in evaporation and precipitation. Over land, both increased CO2 and increased solar irradiance cause rapid surface warming that tends to increase both evaporation and precipitation. However, the physiological effect of increased atmospheric CO2 on plant stomata reduces plant transpiration, drying the boundary layer and decreasing precipitation. This effect does not occur with increased solar irradiance. Therefore, differences in climatic effects from CO2 versus solar forcing are manifested within days after the forcing is imposed.

Large scale synthesis of ultralong aligned buckled multiwalled carbon nanotubes by one-step pyrolysis

We report on the large scale synthesis of millimetre long buckled multiwalled carbon nanotubes by one-step pyrolysis. Current carrying capability of a highly buckled region is shown to be more as compared to a less buckled region.

Methane and carbon dioxide adsorption on edge-functionalized graphene: a comparative DFT study

With a view towards optimizing gas storage and separation in crystalline and disordered nanoporous carbon-based materials, we use ab initio density functional theory calculations to explore the effect of chemical functionalization on gas binding to exposed edges within model carbon nanostructures. We test the geometry, energetics, and charge distribution of in-plane and out-of-plane binding of CO2 and CH4 to model zigzag graphene nanoribbons edge-functionalized with COOH, OH, NH2, H2PO3, NO2, and CH3. Although different choices for the exchange-correlation functional lead to a spread of values for the binding energy, trends across the functional groups are largely preserved for each choice, as are the final orientations of the adsorbed gas molecules. We find binding of CO2 to exceed that of CH4 by roughly a factor of two. However, the two gases follow very similar trends with changes in the attached functional group, despite different molecular symmetries. Our results indicate that the presence of NH2, H2PO3, NO2, and COOH functional groups can significantly enhance gas binding, making the edges potentially viable binding sites in materials with high concentrations of edge carbons. To first order, in-plane binding strength correlates with the larger permanent and induced dipole moments on these groups. Implications for tailoring carbon structures for increased gas uptake and improved CO2/CH4 selectivity are discussed. (C) 2012 American Institute of Physics. http://dx.doi.org/10.1063/1.4736568]

Decentralised carbon footprint analysis for opting climate change mitigation strategies in India

Carbon footprint (CF) refers to the total amount of carbon dioxide and its equivalents emitted due to various anthropogenic activities. Carbon emission and sequestration inventories have been reviewed sector-wise for all federal states in India to identify the sectors and regions responsible for carbon imbalances. This would help in implementing appropriate climate change mitigation and management strategies at disaggregated levels. Major sectors of carbon emissions in India are through electricity generation, transport, domestic energy consumption, industries and agriculture. A majority of carbon storage occurs in forest biomass and soil. This paper focuses on the statewise carbon emissions (CO2. CO and CH4), using region specific emission factors and statewise carbon sequestration capacity. The estimate shows that CO2, CO and CH4 emissions from India are 965.9, 22.5 and 16.9 Tg per year, respectively. Electricity generation contributes 35.5% of total CO2 emission, which is followed by the contribution from transport. Vehicular transport exclusively contributes 25.5% of total emission. The analysis shows that Maharashtra emits higher CO2, followed by Andhra Pradesh, Uttar Pradesh, Gujarat, Tamil Nadu and West Bengal. The carbon status, which is the ratio of annual carbon storage against carbon emission, for each federal state is computed. This shows that small states and union territories (UT) like Arunachal Pradesh, Mizoram and Andaman and Nicobar Islands, where carbon sequestration is higher due to good vegetation cover, have carbon status > 1. Annually, 7.35% of total carbon emissions get stored either in forest biomass or soil, out of which 34% is in Arunachal Pradesh, Madhya Pradesh, Chhattisgarh and Orissa. (C) 2012 Elsevier Ltd. All rights reserved.

Mechanical and electrical contact resistance characteristics of a cellular assembly of carbon nanotubes

We employ nanoindentation coupled with electrical contact resistance measurements for simultaneous characterization of the electrical and mechanical behaviors of a cellular assembly of carbon nanotubes (CNTs). Experimental results reveal two different responses that correspond to relatively dense and porous regions of the cellular structure. Distinct nonlinear electron transport characteristics are observed, which mainly originate from diffusive conductance in the CNT structure. In the denser region, differential conductance shows asymmetric minima at lower bias, implying that conductivity mainly results from bulk tunneling. However, the porous regions show insignificant differential conduction as opposed to the denser region.

Structure of a carbon nanotube-dendrimer composite

Using all atomistic molecular dynamics (MD) simulations we report a microscopic picture of the carbon nanotube (6,5)-dendrimer complex for PAMAM dendrimers of generations 2 to 4. We study the compact wrapping conformations of the dendrimer onto the nanotube surface for all the three generations of PAMAM dendrimer. A high degree of wrapping for the non-protonated dendrimer is observed as compared to the protonated dendrimer. For comparison, we also study the interaction of another dendrimer, poly(propyl ether imine) (PETIM), with the nanotube. The results of the distance of closest approach as well as the number of close contacts between the nanotube and the dendrimer reveal that the PAMAM dendrimer interacts strongly as compared to the PETIM dendrimer. We also calculate the binding energy between the nanotube and the dendrimer using MM/PBSA methods and attribute the strong binding to the charge transfer between them. Dendrimer wrapping on the CNT will make it soluble and the dendrimer can act as an efficient dispersing agent for the nanotubes.

A Durable Graphitic-Carbon Support for Pt and Pt3Co Cathode Catalysts in Polymer Electrolyte Fuel Cells

The high efficiency of fuel-cell-powered electric vehicles makes them a potentially viable option for future transportation. Polymer Electrolyte Fuel Cells (PEFCs) are most promising among various fuel cells for electric traction due to their quick start-up and low-temperature operation. In recent years, the performance of PEFCs has reached the acceptable level both for automotive and stationary applications and efforts are now being expended in increasing their durability, which remains a major concern in their commercialization. To make PEFCs meet automotive targets an understanding of the factors affecting the stability of carbon support and platinum catalyst is critical. Alloying platinum (Pt) with first-row transition metals such as cobalt (Co) is reported to facilitate both higher degree of crystallinity and enhanced activity in relation to pristine Pt. But a major challenge for the application of Pt-transition metal alloys in PEFCs is to improve the stability of these binary catalysts. Dissolution of the non-precious metal in the acidic environment could alleviate the activity of the catalysts and hence cell performance. The use of graphitic carbon as cathode-catalyst support enhances the long-term stability of Pt and its alloys in relation to non-graphitic carbon as the former exhibits higher resistance to carbon corrosion in relation to the latter in PEFC cathodes during accelerated-stress test (AST). Changes in electrochemical surface area (ESA), cell performance and charge-transfer resistance are monitored during AST through cyclic voltammetry, cell polarization and impedance measurements, respectively. Studies on catalytic electrodes with X-ray diffraction, Raman spectroscopy and transmission electron microscopy reflect that graphitic carbon-support resists carbon corrosion and helps mitigating aggregation of Pt and Pt3Co catalyst particles. (C) 2012 The Electrochemical Society. DOI: 10.1149/2.051301jes] All rights reserved.

Translocation and encapsulation of siRNA inside carbon nanotubes

We report spontaneous translocation of small interfering RNA (siRNA) inside carbon nanotubes (CNTs) of various diameters and chirality using all atom molecular dynamics simulations with explicit solvent. We use umbrella sampling method to calculate the free energy landscape of the siRNA entry and translocation event. Free energy profiles show that siRNA gains free energy while translocating inside CNT, and barrier for siRNA exit from CNT ranges from 40 to 110 kcal/mol depending on CNT chirality and salt concentration. The translocation time tau decreases with the increase of CNT diameter with a critical diameter of 24 angstrom for the translocation. In contrast, double strand DNA of the same sequence does not translocate inside CNT due to large free energy barrier for the translocation. This study helps in understanding the nucleic acid transport through nanopores at microscopic level and may help designing carbon nanotube based sensor for siRNA. (C) 2013 American Institute of Physics. http://dx.doi.org/10.1063/1.4773302]

A 12 V Substrate-Integrated PbO2-Activated Carbon Asymmetric Hybrid Ultracapacitor with Silica-Gel-Based Inorganic-Polymer Electrolyte

A 12 V Substrate-Integrated PbO2-Activated Carbon hybrid ultracapacitor (SI-PbO2-AC HUCs) with silica-gel sulfuric acid electrolyte is developed and performance tested. The performance of the silica-gel based hybrid ultracapacitor is compared with flooded and AGM-based HUCs. These HUCs comprise substrate-integrated PbO2 (SI-PbO2) as positive electrodes and high surface-area activated carbon with dense graphite-sheet substrate as negative electrodes. 12 V SI-PbO2-AC HUCs with flooded, AGM and gel electrolytes are found to have capacitance values of 308 F, 184 F, and 269 F at C-rate and can be pulse charged and discharged for 100,000 cycles with only a nominal decrease in their capacitance values. The best performance is exhibited by gel-electrolyte HUCs.