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.

Computational tools for mechanistic discrimination in the reductive and metathesis coupling reactions mediated by titanium(IV) isopropoxide

A theoretical study has been carried out at the B3LYP/LANL2DZ level to compare the reactivity of phenyl isocyanate and phenyl isothiocyanate towards titanium(IV) alkoxides. Isocyanates are shown to favour both mono insertion and double insertion reactions. Double insertion in a head-to-tail fashion is shown to be more exothermic than double insertion in a head-to-head fashion. The head-to-head double insertion leads to the metathesis product, a carbodiimide, after the extrusion of carbon dioxide. In the case of phenyl isothiocyanate, calculations favour the formation of only mono insertion products. Formation of a double insertion product is highly unfavourable. Further, these studies indicate that the reverse reaction involving the metathesis of N,N-'-diphenyl carbodiimide with carbon dioxide is likely to proceed more efficiently than the metathesis reaction with carbon disulphide. This is in excellent agreement with experimental results as metathesis with carbon disulphide fails to occur. In a second study, multilayer MM/QM calculations are carried out on intermediates generated from reduction of titanium(IV) alkoxides to investigate the effect of alkoxy bridging on the reactivity of multinuclear Ti species. Bimolecular coupling of imines initiated by Ti(III) species leads to a mixture of diastereomers and not diastereoselective coupling of the imine. However if the reaction is carried out by a trimeric biradical species, diastereoselective coupling of the imine is predicted. The presence of alkoxy bridges greatly favours the formation of the d,l (+/-) isomer, whereas the intermediate without alkoxy bridges favours the more stable meso isomer. As a bridged trimeric species, stabilized by bridging alkoxy groups, correctly explains the diastereoselective reaction, it is the most likely intermediate in the reaction.