Electron field emission from sp (2)-induced insulating to metallic behaviour of amorphous carbon (a-C) films

The influence of concentration and size of sp (2) cluster on the transport properties and electron field emissions of amorphous carbon films have been investigated. The observed insulating to metallic behaviour from reduced activation energy derived from transport measurement and threshold field for electron emission of a-C films can be explained in terms of improvements in the connectivity between sp (2) clusters. The connectivity is resulted by the cluster concentration and size. The concentration and size of sp (2) content cluster is regulated by the coalescence of carbon globules into clusters, which evolves with deposition conditions.

Terahertz Time Domain Spectroscopy to Detect Low-Frequency Vibrations of Double-Walled Carbon Nanotubes

We have measured the frequency-dependent real index of refraction and extinction coefficient (and hence the complex dielectric function) of a free-standing double-walled carbon nanotube film of thickness 200 nm by using terahertz time domain spectroscopy in the frequency range 0.1 to 2.5 THz. The real index of refraction and extinction coefficient have very high values of approximately 52 and 35, respectively, at 0.1 THz, which decrease at higher frequencies. Two low-frequency phonon modes of the carbon nanotubes at 0.45 and 0.75 THz were clearly observed for the first time in the real and imaginary parts of the complex dielectric function along with a broad resonance centred at around 1.45 THz, the latter being similar to that in single-walled carbon nanotubes assigned to electronic excitations. Our experiments bring out a possible application of double-walled carbon nanotube films as a neutral density filter in the THz range.

Characterization, electrical percolation and magnetization studies of polystyrene/multiwall carbon nanotube composite films

Polystyrene/multiwall carbon nanotube composite films are prepared with loading up to 7 weight percent (wt%) of multiwall carbon nanotubes by solution processing and casting technique. In the formation of these composite films, iron filled carbon nanotubes with high aspect ratio (similar to 4000) were used. Scanning electron microscopy study shows that the nanotubes are uniformly dispersed within the polymer matrix. At high magnification, bending of carbon nanotubes is noticed which can be attributed to their elastic properties. The electrical conductivity measurements show that the percolation threshold is rather low at 0.21 wt%. Hysteresis loop measurements on the bulk multiwall carbon nanotube and composite samples are done at 10, 150 and 300 K and the coercivity values are found to be largest at all the temperatures, for 1 wt% composite sample. (C) 2010 Elsevier B.V. All rights reserved.

Mesoporous Carbon and Poly(3,4-ethylenedioxythiophene) Composite as Catalyst Support for Polymer Electrolyte Fuel Cells

In situ polymerization of 3,4-ethylenedioxythiophene with sol-gel-derived mesoporous carbon (MC) leading to a new composite and its subsequent impregnation with Pt nanoparticles for application in polymer electrolyte fuel cells (PEFCs) is reported. The composite exhibits good dispersion and utilization of platinum nanoparticles akin to other commonly used microporous carbon materials, such as carbon black. Pt-supported MC-poly(3,4-ethylenedioxythiophene) (PEDOT) composite also exhibits promising electrocatalytic activity toward oxygen reduction reaction, which is central to PEFCs. The PEFC with Pt-loaded MC-PEDOT support exhibits 75% of enhancement in its power density in relation to the PEFC with Pt-loaded pristine MC support while operating under identical conditions. It is conjectured that Pt-supported MC-PEDOT composite ameliorates PEFC performance/durability on repetitive potential cycling. (C) 2010 The Electrochemical Society. DOI: 10.1149/1.3486172] All rights reserved.

Study of stress Relief Patterns In Diamond-Like Carbon-Films

An optical microscopy study of stress relief patterns in diamondlike carbon films is presented. Interesting stress relief patterns are observed which include the well known sinusoidal type, branching pattern and string of beads pattern. The last one is shown to relieve stresses under marginal conditions. Two new stress relief patterns are noted in the present study. One of them is of a sinusoidal shape with two extra branches at every peak position. The distribution of different stress relief forms from the outer edge of the films towards the interior is markedly dependent on film thickness. Our new patterns support the approach in which the stress relief forms have been analysed earlier using the theory of plate buckling.

Diruthenium(III) compounds, Ru2O(O2CAr)2(MeCN)4(PPh3)2(ClO4)2.cntdot.H2O and Ru2O(O2CAr)4(PPh3)2, with an (Ru2(.mu.-O)(.mu.-O2CAr)22+) core as model systems for the diiron centers in hemerythrin

Diruthenium(II1) compounds, Ru20(02CAr)2(MeCN)4(PPh3)2(C104)(z1~) Hazn0d R U ~ O ( O ~ C A ~ ) ~(2() P(PA~r ~= )P~h,C6H4-p-OMe), were prepared by reacting R U ~ C I ( O ~ CaAnd~ P)P~h 3 in MeCN and characterized by analytical and spectral data. The molecular structures of 1 with Ar = Ph and of 2 with Ar = C&p-OMe were determined by X-ray crystallography. Crystal data for Ru~~(~~CP~)~(M~CN),(PP~(~la)):~ m(oCnIoc~lin,ic), n~/~cH, ~a O= 27.722 (3) A, b = 10.793 (2) A, c = 23.445 ( 2 )A , fi = 124.18 (l)', V = 5803 A3, and 2 = 4. Cr stal data for Ru~O(O~CC~H~-~-O(M2b~): )o~rth(orPhoPm~bi~c, )Pn~n a, a = 22.767 (5) A, b = 22.084 (7) A, c = 12.904 (3) 1, V = 6488 AS; and 2 = 4. Both 1 and 2 have an (Ruz0(02CAr)z2t1 core that is analogous to the diiron core present in the oxidized form of the nonheme respiratory protein hemerythrin. The Ru-Ru distances of 3.237 (1) and 3.199 ( I ) A observed in 1 and 2, respectively, are similar to the M-M distances known in other model systems. The essentially diamagnetic nature of 1 and 2 is due to the presence of two strongly interacting t22 Ru"' centers. The intense colors of 1 (blue) and 2 (purple) are due to the charge-transfer transition involving an ( R ~ ~ ( f i - 0m)o~ie~ty.) The presence of labile MeCN and carboxylato ancillary ligands in I and 2, respectively, makes these systems reactive toward amine and heterocyclic bases.

Carbon-13 NMR studies of lipid mobilization pattern in germinating groundnut (Arachis hypogaea L.) seeds

The products of lipid mobilization in groundnut (Arachis hypogaea L.) seeds as a function of time immediately after imbibition are monitored by 13C NMR. Different parts of the embryonic axis, namely,the radicle, hypocotyl, and plumule, exhibit characteristic time dependent 13C NMR spectra observed at 24-h intervals after imbibition. The various stages in the transformation of storage lipids present in different parts of the embryonic axis are clearly demonstrated. The transformaton of storage lipids is completed first in the radicle followed by the hypocotyl and finally the plumule. A mechanism of the transformation of the storage lipids is discussed.

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.

Coordination-Driven Self-Assembly of M3L2 Trigonal Cages from Preorganized Metalloligands Incorporating Octahedral Metal Centers and Fluorescent Detection of Nitroaromatics

The design and preparation of novel M3L2 trigonal cages via the coordination-driven self-assembly of preorganized metalloligands containing octahedral aluminum(III), gallium(III), or ruthenium(II) centers is described. When tritopic or dinuclear linear metalloligands and appropriate complementary subunits are employed, M3L2 trigonal-bipyramidal and trigonal-prismatic cages are self-assembled under mild conditions. These three-dimensional cages were characterized with multinuclear NMR spectroscopy (H-1 and P-31) and high-resolution electrospray ionization mass spectrometry. The structure of one such trigonal-prismatic cage, self-assembled from an arene ruthenium metalloligand, was confirmed via single-crystal X-ray crystallography. The fluorescent nature of these prisms, due to the presence of their electron-rich ethynyl functionalities, prompted photophysical studies, which revealed that electron-deficient nitroaromatics are effective quenchers of the cages' emission. Excited-state charge transfer from the prisms to the nitroaromatic substrates can be used as the basis for the development of selective and discriminatory turn-off fluorescent sensors for nitroaromatics.