Organically modified montmorillonite and chitosan–phosphotungstic acid complex nanocomposites as high performance membranes for fuel cell applications

Nanocomposite membranes based on polyelectrolyte complex (PEC) of chitosan/phosphotungstic acid (PWA) and different types of montmorillonite (MMT) were prepared as alternative membranes to Nafion for direct methanol fuel cell (DMFC) applications. Fourier transform infrared spectroscopy (FTIR) revealed an electrostatically fixed PWA within the PEC membranes, which avoids a decrease in proton conductivity at practical condition. Various amounts of pristine as well as organically modified MMT (OMMT) (MMT: Cloisite Na, OMMT: Cloisite 15A, and Cloisite 30B) were introduced to the PEC membranes to decrease in methanol permeability and, thus, enhance efficiency and power density of the cells. X-ray diffraction patterns of the nanocomposite membranes proved that MMT (or OMMT) layers were exfoliated in the membranes at loading weights of lower than 3 wt.%. Moreover, the proton conductivity and the methanol permeability as well as the water uptake behavior of the manufactured nanocomposite membranes were studied. According to the selectivity parameter, ratio of proton conductivity to methanol permeability, the PEC/2 wt.% MMT 30B was identified as the optimum composition. The DMFC performance tests were carried out at 70 °C and 5 M methanol feed and the optimum membrane showed higher maximum power density as well as acceptable durability compared to Nafion 117. The obtained results indicated that owing to the relatively high selectivity and power density, the optimum nanocomposite membrane could be considered as a promising polyelectrolyte membrane (PEM) for DMFC applications.     

MnSb/GaSb(001)界面半金属特性的第一性原理研究

利用密度泛函理论计算六角NiAs型和立方闪锌矿型MnSb的电子和电磁特性,研究闪锌矿MnSb与GaSb(001)界面,并采用广义渐变近似计算了交换-相关项．闪锌矿结构的MnSb具有半金属铁磁特性,单分子磁矩4μB,MnSb/GaSb(001)界面同样具有半金属特性．界面中Mn原子的磁矩减小,界面中Sb原子磁矩等于两个相应界面磁矩的平均值．另外计算了能带排列在异质结中价带偏移大约1.25 eV.     

Small Pd nanoparticles supported in large pores of mesocellular foam: an excellent catalyst for racemization of amines

Highly dispersed palladium nanoparticles (1–2 nm) supported in large‐pore mesocellular foam (MCF; 29 nm) were synthesized. The Pd‐nanocatalyst/MCF system was characterized by transmission electron microscopy (TEM), powder X‐ray diffraction (XRD) and X‐ray photoelectron spectroscopy (XPS). The performance of the Pd nanocatalyst obtained was examined for amine racemization. The Pd nanocatalyst showed higher activity and selectivity toward racemization of (S)‐1‐phenylethyl amine than any other amine racemization catalyst reported so far and it could be reused several times. Our data from TEM and XRD suggest a restructuring of the Pd nanocatalyst from amorphous to crystalline and an increase in Pd nanocatalyst size during the racemization reaction. This led to an unexpected increase of activity after the first use. The Pd nanocatalyst obtained can be integrated with other resolving processes of racemic organic compounds to increase the yield of chiral organic products.     

A hybrid legendre tau method for the solution of a class of nonlinear wave equations with nonlinear dissipative terms

This article presents a technique based on the hybrid Legendre tau‐finite difference method to solve the fourth order wave equation which arises in the elasto‐plastic‐microstructure models for longitudinal motion of an elasto‐plastic bar. Illustrative examples and numerical results obtained using new technique demonstrate that the proposed approach is efficient in treating longitudinal equation of ealsto‐plastic bar. © 2010 Wiley Periodicals, Inc. Numer Methods Partial Differential Eq 27: 1055–1071, 2011     

Stable silylenes with acyclic, cyclic, and unsaturated cyclic structures: Effects of heteroatoms and cyclopropyl α-substituents at DFT

The effects of alkyl, amino, phosphino, oxy, and thio moieties on the stability, multiplicity and reactivity of α-cyclopropylsilylenes with acyclic, cyclic, and unsaturated cyclic structures are compared and contrasted at B3LYP/AUG-cc-pVTZ//B3LYP/6-31G∗ level. The simultaneous stabilizing effects of heteroatom and cyclopropyl α-substituents on the above silylenes create the following trend of singlet-triplet energy gaps (?E_S-T): amino ≈ oxy > thio > alkyl > phosphino. The ΔE_S-T values for all the above silylenes increase through cyclization, because cyclization stabilizes singlet states of all our α-heteroatom substitued silylenes while destabilizes their corresponding triplet states. The ΔE_S-T values for all the heteroatom substituted cyclic silylenes decrease upon unsaturation, due to the higher stabilization of triplet compared to the singlet state. Interestingly, isodesmic reactions showed the phosphino substituents stabilize the triplet more than the corresponding singlet states, not only in the unsaturated form but also in the acyclic and cyclic structures. This is in contrast to cyclopropyl which stabilizes singlet considerably more than the corresponding triplet states. The reactivity of the above silylenes is discussed in terms of nucleophilicity, and electrophilicity; showing phosphino- and aminocyclopropylsilylenes more nucleophilic than oxy- and thiocyclopropylsilylenes.     

The effect of cell orientations and environmental conditions on the performance of a passive DMFC single cell

A single cell passive air-breathing liquid feed direct methanol fuel cell (DMFC) is designed and fabricated. Furthermore, the effects of cell orientation and environmental conditions such as temperature and relative humidity on the performance of such passive DMFC are tested experimentally. The obtained results indicate that both environmental temperature and relative humidity have significant effects on the performance of fabricated fuel cell. The experimental data contained within this work shows that under lower relative humidity and higher temperature, the passive air-breathing direct methanol fuel cell has higher power output and better performance. According to experimental results, flooding has a vital role on the cell performance in various relative humidity and temperatures. The results also show that cell orientation has a strong effect on the performance of passive DMFC. The best power output and performance were achieved under vertical orientation.     

Highly dispersed palladium nanoparticles on mesocellular foam: an efficient and recyclable heterogeneous catalyst for alcohol oxidation

Palladium nanoparticles immobilized on amino-functionalized mesocellular foam constitute an efficient catalyst for the aerobic oxidation of primary and secondary alcohols to their corresponding carbonyl compounds in high to excellent yields. An exceptionally high TON of 365?000 was reached for the oxidation of 1-phenylethanol under solvent-free reaction conditions. The catalyst can be recycled many times with retained activity as shown by the identical rate curves of the first and fifth runs.     

Numerical solution of the Klein–Gordon equation via He’s variational iteration method

In this paper, we present the solution of the Klein--Gordon equation. Klein--Gordon equation is the relativistic version of the Schrödinger equation, which is used to describe spinless particles. The He’s variational iteration method (VIM) is implemented to give approximate and analytical solutions for this equation. The variational iteration method is based on the incorporation of a general Lagrange multiplier in the construction of correction functional for the equation. Application of variational iteration technique to this problem shows rapid convergence of the sequence constructed by this method to the exact solution. Moreover, this technique reduces the volume of calculations by avoiding discretization of the variables, linearization or small perturbations.     

Free-edge effects in a cylindrical sandwich panel with a flexible core and laminated composite face sheets

In the present study, the static response of cylindrical sandwich panels with a flexible core is investigated. The face sheets are considered as composite laminates with a cross-ply lay-up and the core as a flexible elastic medium. The flexibility of the low-strength core leads to high stress concentrations in terms of peeling stresses between the face sheets and the core at edges of the sandwich panel. To take into account the compressibility of the core and to determine the free-edge stresses of sandwich structures accurately, the Reddy layerwise theory (LWT) is used in this paper. The paper outlines the mathematical formulation, along with a numerical study, of a cylindrical sandwich panel with two simply supported and two free edges under a transverse load. The formulation includes the derivation of field equations along with boundary conditions. A Levy-type solution procedure is performed to determine the distributions of stresses and strains. In the numerical study, first a comparison is made with results from the commercial finite-element software ANSYS to verify the LWT results. Finally, a parametric study is conducted, and the effect caused by varying different parameters, such as the radii of curvature and the core to face sheet thickness ratio, on the results are investigated. The results obtained demonstrate a good agreement between LWT and FEM solutions and show increasing interlaminar stresses in the free edge of the sandwich panel     

Theoretical study of highly doped heterofullerenes evolved from the smallest fullerene cage

Structural Chemistry - The structural stabilities and electronic properties of C12X8 heterofullerenes where X = B, Al, Ga, C, Si, Ge, N, P, and As are probed at the...