Platinum‐Promoted Ga/Al2O3 as Highly Active,Selective, and Stable Catalyst for the Dehydrogenation of Propane

A novel catalyst material for the selective dehydrogenation of propane is presented. The catalyst consists of 1000 ppm Pt, 3 wt % Ga, and 0.25 wt % K supported on alumina. We observed a synergy between Ga and Pt, resulting in a highly active and stable catalyst. Additionally, we propose a bifunctional active phase, in which coordinately unsaturated Ga³⁺ species are the active species and where Pt functions as a promoter.     

Elastomers by atactic linkage of α-olefins using soluble Ziegler catalysts

With bis (cyclopentadienyl) zirconiumIV-compounds and methylalumoxane as soluble Ziegler catalyst propylene can be polymerized to pure atactic polypropylene with molecular weights up to 600 000. The copolymerization of ethylene and propylene or butene gives elastomers with different properties. The butene units are distributed at random in the polyethylene chain as carried out by ¹³C NMR measurements. The regiospecifity of the catalyst leads exclusively to the formation of head-to-tail enchainments. Using ethylene together with propylene and diolefins, EPDM rubber is formed. Glass transition temperatures of -60 to -50 °C could be observed.     

New Pathways in Plastics Recycling

The catalytic degradation of polyethylene to short-chain hydrocarbons is possible with zirconium hydride compounds (see picture), and represents the first step in the reversal of Ziegler - Natta polymerization. Thus, even in the case of polyolefins the important target of plastics recycling, the recovery of reusable monomers from polymer waste, may be achieved.     

Estimation of isotropic nuclear magnetic shieldings in the CCSD(T) and MP2 complete basis set limit using affordable correlation calculations

A linear correlation between isotropic nuclear magnetic shielding constants for seven model molecules (CH₂O, H₂O, HF, F₂, HCN, SiH₄ and H₂S) calculated with 37 methods (34 density functionals, RHF, MP2 and CCSD(T)), with affordable pcS‐2 basis set and corresponding complete basis set results, estimated from calculations with the family of polarization‐consistent pcS‐n basis sets is reported. This dependence was also supported by inspection of profiles of deviation between CBS estimated nuclear shieldings and shieldings obtained with the significantly smaller basis sets pcS‐2 and aug‐cc‐pVTZ‐J for the selected set of 37 calculation methods. It was possible to formulate a practical approach of estimating the values of isotropic nuclear magnetic shielding constants at the CCSD(T)/CBS and MP2/CBS levels from affordable CCSD(T)/pcS‐2, MP2/pcS‐2 and DFT/CBS calculations with pcS‐n basis sets. The proposed method leads to a fairly accurate estimation of nuclear magnetic shieldings and considerable saving of computational efforts. Copyright © 2013 John Wiley & Sons, Ltd.     

Aspect-ratio dependent oscillatory thermocapillary convection in the floating half zone

The dependency of the critical Marangoni number on the geometrical aspect ratio of the floating half zone is essential to predict the onset of oscillatory thermocapillary convection.The experimental studies in the microgravity conditions on floating half zones of several centimeters in diameter have predicted that the critical Marangoni number increases with the increasing aspect ratio,and the terrestrial experimental studies have predicted the contradictory conclusion for floating half zones of several mil...     

Non-Gravitational Effects with Density-Matching in Evaluating the Influence of Sedimentation on Colloidal Coagulation

The method of density matching between the solid and liquid phases is often adopted to effectively eliminate the effect of sedimentation of suspensions in studies on dynamic behaviour of a colloidal system. However, the associated changes in the solvent composition may bring side effects to the properties investigated and therefore might lead to a faulty conclusion if the relevant correction is not made. To illustrate the importance of this side effect, we present an example of the sedimentation influence on the coagulation rate of suspensions of 2μm （diameter） polystyrene. The liquid mixtures, in the proper proportions of water （H2O）, deuterium oxide （D2O） and methanol （MeOH） as the liquid phase, density-matched and unmatched experiments are performed. Besides the influence of viscosity, the presence of methanol in solvent media, used to enhance the sedimentation effect, causes significant changes （reduction） in rapid coagulation rates compared to that in pure water. Without the relevant corrections for those non-gravitational factors it seems that gravitational sedimentation would retard the coagulation. The magnitude of the contribution from the non-gravitational factor is quantitatively determined, making the relevant correction possible. After necessary the influence of the sedimentation on coagulation rates at corrections for all factors, our experiments show that the initial stage of the coagulation is not observable.     

The competing roles of topology and spin density in the magnetic behavior of spin-delocalized radicals: Donor–acceptor annelated nitronyl nitroxides

The effects of acceptor–donor interactions in thienyl substituted benzimidazole-nitronyl nitroxides (TBNN) on the absorption spectroscopy, spin density distribution, magnetic behavior, and crystallographic packing were explored through spectroscopy, computation, and characterization of structure and magnetic properties in the crystalline phase. The electronic spectra of the radicals exhibit a strong broad absorption in the NIR (λ_max ～ 1000 nm) that exhibits solvatochromism consistent with charge transfer between the thienyl (donor) and benzonitronyl nitroxide (acceptor) dyads. Computational analysis allowed assignment of the transition as a HOMO–SOMO transition (TD-DFT UB3LYP/6-31G7). The TBNN radicals form highly disordered slipped π-stacks in the solid state that give rise to antiferromagnetic interactions consistent with 1D chain interactions. The magnetic behavior was well-fit to a Bonner–Fisher model to give exchange parameters of J = ?2 to ?10 cm^?1 depending on substitution. The weak exchange parameters are attributed to the degree of solid-state disorder, and the observed properties can be rationalized by the effects of substitution on the electronic structure and topology of the radicals.