Fascinating chemistry of metal clusters and carbon clusters (fullerenes)

Investigations of a variety of transition metal clusters by means of high-energy spectroscopies including BIS show the occurrence of a metal-insulator transition with decrease in the cluster size. The chemical reactivity of the clusters also varies significantly with the size. Among the many fascinating properties of the fullerenes C60 and C70, a noteworthy one is the interaction between metal clusters and fullerenes. Phase transitions of fullerenes involving orientational disorder and pressure-induced decrease in the band gap of C60 are other novel features of interest.

Nafion®-bound carbon electrodes containing transitionmetal phthalocyanines for oxygen reduction in solid-polymer-electrolyte fuel cells

Catalytic activities of some transition metal-phthalocyanine complexes towards electroreduction of molecular oxygen are examined on Nafion®-bound and bare porous carbon electrodes in 2.5 M H2SO4 electrolyte. It is found that these metal complexes exhibit better catalytic activities towards oxygen reduction with the Nafion®-bound electrodes.

CO2-fertilization and potential future terrestrial carbon uptake in India

There is huge knowledge gap in our understanding of many terrestrial carbon cycle processes. In this paper, we investigate the bounds on terrestrial carbon uptake over India that arises solely due to CO (2) -fertilization. For this purpose, we use a terrestrial carbon cycle model and consider two extreme scenarios: unlimited CO2-fertilization is allowed for the terrestrial vegetation with CO2 concentration level at 735 ppm in one case, and CO2-fertilization is capped at year 1975 levels for another simulation. Our simulations show that, under equilibrium conditions, modeled carbon stocks in natural potential vegetation increase by 17 Gt-C with unlimited fertilization for CO2 levels and climate change corresponding to the end of 21st century but they decline by 5.5 Gt-C if fertilization is limited at 1975 levels of CO2 concentration. The carbon stock changes are dominated by forests. The area covered by natural potential forests increases by about 36% in the unlimited fertilization case but decreases by 15% in the fertilization-capped case. Thus, the assumption regarding CO2-fertilization has the potential to alter the sign of terrestrial carbon uptake over India. Our model simulations also imply that the maximum potential terrestrial sequestration over India, under equilibrium conditions and best case scenario of unlimited CO2-fertilization, is only 18% of the 21st century SRES A2 scenarios emissions from India. The limited uptake potential of the natural potential vegetation suggests that reduction of CO2 emissions and afforestation programs should be top priorities.

Synergitic Promotion of Electrooxidation of Methanol of Carbon-Supported PT-SN Catalysts

Electrooxidation of methanol in sulphuric acid on carbon-supported electrodes containing Pt-Sn bimetal catalysts prepared by an in-situ route is reported, The catalysts have been characterized employing chemical analyses, XRD, and XANES data in conjunction with electrochemistry. This study suggests that the Sn content in Pt-Sn bimetals produces: (i) a charge transfer from Sn to Pt and (ii) an increase in the coverage of adsorbed methanolic residues with the Sn content. From the electrode-kinetics data, it is inferred that while the electrodes of (3:3) Pt-Sn/C catalyst involve a 2-electron rate-limiting step akin to Pt/C electrodes, it is shifted to only 1-electron on (3:2) Pt-Sn/C, (3:3) Pt-Sn/C, and (3:4) Pt-Sn/C electrodes.

Nano structured carbon nitrides prepared by chemical vapour deposition

Nanostructured carbon nitride films were prepared by pyrolysis assisted chemical vapour deposition(CVD). A two zone furnace with a temperature profile having a uniform temperature over a length of 20 cm length has been designed and developed. The precursor Azabenzimidazole was taken in a quartz tube and evaporated at 400 degrees C. The dense vapours enter the pyrolysis zone kept at a desired temperature and deposit on the quartz substrates. The FTIR spectrum of the prepared samples shows peaks at 1272 cm(-1) (C-N stretching) and 1600 cm(-1) (C=N) confirms the bonding of nitrogen with carbon. Raman D and G peaks, are observed at 1360 cm(-1) and 1576 cm(-1) respectively. XPS core level spectra of C 1s and N 1s show the formation of pi bonding between carbon and nitrogen atoms. The size of the nano crystals estimated from the SEM images and XRD is similar to 100 nm. In some regions of the sample a maximum of 57 atom % of nitrogen has been observed.

High accuracy curve fits for chirality, length and diameter dependent initial modulus of single walled carbon nanotubes

Many previous studies regarding the estimation of mechanical properties of single walled carbon nanotubes (SWCNTs) report that, the modulus of SWCNTs is chirality, length and diameter dependent. Here, this dependence is quantitatively described in terms of high accuracy curve fit equations. These equations allow us to estimate the modulus of long SWCNTs (lengths of about 100-120 nm) if the value at the prescribed low lengths (lengths of about 5-10 nm) is known. This is supposed to save huge computational time and expense. Also, based on the observed length dependent behavior of SWCNT initial modulus, we predict that, SWCNT mechanical properties such as Young's modulus, secant modulus, maximum tensile strength, failure strength, maximum tensile strain and failure strain might also exhibit the length dependent behavior along with chirality and length dependence. (C) 2010 Elsevier B.V. All rights reserved.

Hydrogen Storage Capacity of Carbon-Foams: Grand Canonical Monte Carlo Simulations

Hydrogen storage in the three-dimensional carbon foams is analyzed using classical grand canonical Monte Carlo simulations. The calculated storage capacities of the foams meet the material-based DOE targets and are comparable to the capacities of a bundle of well-separated similar diameter open nanotubes. The pore sizes in the foams are optimized for the best hydrogen uptake. The capacity depends sensitively on the C-H-2 interaction potential, and therefore, the results are presented for its ``weak'' and ``strong'' choices, to offer the lower and upper bounds for the expected capacities. Furthermore, quantum effects on the effective C-H-2 as well as H-2-H-2 interaction potentials are considered. We find that the quantum effects noticeably change the adsorption properties of foams and must be accounted for even at room temperature.

Physics-Based Thermal Conductivity Model for Metallic Single-Walled Carbon Nanotube Interconnects

In this letter, a closed-form analytical model for temperature-dependent longitudinal diffusive lattice thermal conductivity (kappa) of a metallic single-walled carbon nanotube (SWCNT) has been addressed. Based on the Debye theory, the second-order three-phonon Umklapp, mass difference (MD), and boundary scatterings have been incorporated to formulate. in both low-and high-temperature regimes. It is proposed that. at low temperature (T) follows the T-3 law and is independent of the second-order three-phonon Umklapp and MD scatterings. The form factor due to MD scattering also plays a key role in the significant variation of. in addition to the SWCNT length. The present diameter-independent model of. agrees well with the available experimental data on suspended intrinsic metallic SWCNTs over a wide range of temperature and can be carried forward for electrothermal analyses of CNT-based interconnects.

Hybridization of carbon-glass epoxy composites: An approach to achieve low coefficient of thermal expansion at cryogenic temperatures

The paper is based on a study to develop carbon-glass epoxy hybrid composites with desirable thermal properties for applications at cryogenic temperatures. It analyzes the coefficient of thermal expansion of carbon-epoxy and glass-epoxy composite materials and compares it with the properties of carbon-glass epoxy hybrid composites in the temperature range 300 K to 125K. Urethane modified epoxy matrix system is used to make the composite specimens suitable for use even for temperatures as low as 20K. It is noted that the lay-up with 80% of carbon fibers in the total volume fraction of fibers oriented at 30 degrees and 20% of glass fibers oriented at 0 degrees yields near to zero coefficient of thermal expansion as the temperature is lowered from ambient to 125 K. (c) 2010 Elsevier Ltd. All rights reserved.

Metathesis of carbon dioxide and phenyl isocyanate catalysed by group(IV) metal alkoxides: An experimental and computational study

The insertion reactions of zirconium(IV) n-butoxide and titanium(IV) n-butoxide with a heterocumulene like carbodiimide, carbon dioxide or phenyl isocyanate are compared. Both give an intermediate which carries out metathesis at elevated temperatures by inserting a second heterocumulene in a head-to-head fashion. The intermediate metallacycle extrudes a new heterocumulene, different from the two that have inserted leading to metathesis. As the reaction is reversible, catalytic metathesis is feasible. In stoichiometric reactions heterocumulene insertion, metathesis and metathesis cum insertion products are observed. However, catalytic amounts of the metal alkoxide primarily led to metathesis products. It is shown that zirconium alkoxides promote catalytic metathesis (isocyanates, carbon dioxide) more efficiently than the corresponding titanium alkoxide. The difference in the metathetic activity of these alkoxides has been explained by a computational study using model complexes Ti(OMe)(4) (1bTi) and Zr(OMe)(4) (1bZr). The computation was carried out at the B3LYP/LANL2DZ level of theory.

Structural and surface features of multiwall carbon nanotube

We present the direct evidence of defective and disorder places on the surface of multiwall carbon nanotube (MWCNT), visualizing the presence of amorphous carbon at those sites. These defective surfaces being higher in energy are the key features of functionalization with different materials. The interaction of the pi orbital electrons of different carbon atoms of adjacent layers is more at the bent portion, than that of regular portion of the CNT. Hence the tubular structure of the bent portion of nanotubes is spaced more than that of regular portion of the nanotubes, minimizing the stress. (C) 2011 Elsevier B.V. All rights reserved.

Dependence of the strength of interaction of carbon monoxide with transition metal clusters on the cluster size

The interaction of CO with Cu, Pd, and Ni at different coverages of the metals on solid substrates has been investigated by He II and core-level spectroscopies, after the nature of variation of the metal core-level binding energies with the coverage or the cluster size is established. The separation between the (1 pi + 5 sigma) and 4 sigma levels of CO increases with a decrease in the size of the metal clusters, accompanied by an increase in the desorption temperature. In the case of Cu, the intramolecular shakeup satellite of CO disappears on small clusters. More importantly, CO dissociates on small Ni clusters, clearly confirming that metal-CO interaction strength increases with a decrease in the cluster size.

Diamond-like carbon coating for optical windows

Hard, low stress diamond-like carbon films have been deposited by plasma assisted chemical vapour deposition technique, The various substrates include soft IR components like ZnS and ZnSe windows, Gaseous precursors such as propene, ethyl alcohol and acetone have been used to synthesize the films to study the nature of precursors in determining the film compatibility with the underlying component (substrate), The residual compressive stresses, the Young's modulus and the adhesion energy of the films have been estimated to be 10(10) dynes/cm(2), 10(10) N/m(2) and 1000 ergs/cm(2) respectively. To alleviate film failure, a study on the effects of additive gases such as hydrogen and the use of buffer layers such as ZrO2, has been undertaken, The diamond-like carbon films produced here are hard (5000 kg/mm(2)), specularly smooth in the wavelength region from 2.5 mu m to 20 mu m, with no microstructural features and have excellent adhesion on ZnS and ZnSe windows. The figure of merit of these films for aero-space applications has been evaluated by subjecting the film-buffer layer ZnS or ZnSe composite stack to wind, dust and rain erosion studies and by establishing the integrity of the specular IR transmittance of the stack upto 16 or 20 mu m as the case may be.

Double Aromaticity in the 3,5-Dehydrophenyl Cation and in Cyclo[6]carbon

The presence of two (4n+2)-electron conjugated systems in perpendicular planes results in considerable aromatic stabilization. Despite having two fewer hydrogens, the 6 pi e-2 sigma e 3,5-dehydrophenyl cation (C6H3+, 1) is 32.7 (CCSD(T)/6-31G**) and 35.2 kcal/mol (RMP4sdtq/6-3iG*//RMP2(fu)/6-31G*) more stable than the phenyl cation (evaluated by an isodesmic reaction involving benzene and m-dehydrobenzene (4)). Cation 1, the global C6H3+ minimum, is 11.7,24.2, 11.8, and 30.4 kcal/mol lower in energy than the 2,6- (11) and 3,4-dehydrophenyl (12) cations as well as the open-chain isomers 13 and 14 (RMP4sdtq/6-31G*//RMP2(fu)/6-31G* + ZPE(RMP2(fu)/6-31G*)). The stability of 1 is increased hyperconjugatively by 2,4,6-trisilyl substitution. The double aromaticity of 1 is indicated by the computed magnetic susceptibility exaltations (IGLO/II//RMP2(fu)/6-31G*) of -5.2, -6.8, -15, and -23.2 relative to 11, 12, 13, and 14, respectively. Thus, 1 fulfills the geometric, energetic, and magnetic criteria of aromaticity. The double aromaticity of the D-6h cyclo[6]carbon is apparent from the same criteria

Electrooxidation of methanol in sulfuric-acid electrolyte on platized-carbon electrodes with several functional-group characteristics

The effect of acid/base functional-groups associated with platinized-carbon electrodes on their catalytic activity toward electro-oxidation of methanol in sulfuric acid electrolyte at 60-degrees-C is studied. Platinized-carbon electrodes with sm amounts of functional groups exhibit higher catalytic activity compared to those with large concentrations of acidic/basic surface functionalities. The overpotential for methanol oxidation is minimum on electrodes of platinized carbons with pHzpc values between 6 and 7. An x-ray photoelectron spectroscopic study of various platinized carbons suggests that the acid/base surface functional-groups produce ample amounts of surface Pt-oxides and a consequent decrease in activity toward methanol oxidation.