Modeling current–voltage relationships of mixed conducting cathode materials for solid oxide fuel cells

In recent decades, high-temperature oxygen reduction reaction on mixed conducting cathodes were investigated intensively by many researchers. Computational approaches as well as electrochemical and spectroscopic studies have been made to elucidate the kinetics. Contribution of oxygen vacancy to the reaction rate was suggested in multiple reports, and plausible reaction pathways were proposed based on density functional theory (DFT) calculations. The picture of oxygen reduction reaction has become clearer in these years. However, there still is a discussion about a credible formula that represents the current–voltage relationships. Discrepancies are found among the reported data on the magnitude of the rate constant and on its dependencies on partial pressure and temperature. The difference is significant between a model electrode and a practical porous electrode. Comparison of the results suggests the existence of series reaction barriers, that is, the surface reaction and subsurface transport, which should be considered for consistent representation of the total electrode process.     

A novel polycondensation method for the synthesis of a two-faced β-1,4-glucan

Abstract  

The stereospecific synthesis of a chitosan derivative repeating 2-azido-3,6-di-O-benzyl-2-deoxy-β-d-glucopyranosyl-(1 → 4)-3,6-di-O-benzyl-2-deoxy-2-phthalimido-d-glucopyranose, which has two distinguishing faces, was achieved by polycondensation of the sole starting disaccharide, trichloroacetimidoyl 2-azido-3,6-di-O-benzyl-2-deoxy-β-d-glucopyranosyl-(1 → 4)-3,6-di-O-benzyl-2-deoxy-2-phthalimido-d-glucopyranoside in a short and efficient way.     

The N = 16 Spherical Shell Closure in 24O

The unbound excited states of the most neutron-rich dripline oxygen isotope, ²⁴O, have been investigated by using the ²⁴O(p,p′)²⁴O^* reaction at the beam energy of 62 MeV/nucleon in inverse kinematics. The first and second unbound excited states of ²⁴O have been observed at ${E_{\rm x}= 4.63_{-0.14}^{+0.30}}$  MeV and ${E_{\rm x}= 5.13_{-0.24}^{+0.19}}$  MeV (preliminary) along with the evidence for another higher lying state at around 7.3 MeV. The quadrupole deformation parameter ${\beta_{2^+}}$ was deduced to be ${0.15_{-0.03}^{+0.08}}$ (preliminary) for the first time. The systematics of the ${\beta_{2^+}}$ and the ${E_{\rm x}(2_1^+)}$ in the Z = 8 isotopes shows the N = 16 spherical shell closure in ²⁴O.     

Application of novel SIMS technique for imaging the active sites of oxygen reduction at the SOFC cathode/electrolyte interfaces

The oxygen reduction active sites were visualized around the O₂/SOFC cathode/electrolyte triple phase boundaries (TPB) by the¹⁶O/¹⁸O exchange techniques and secondary ion mass spectrometry (SIMS) analysis. The higher¹⁸O concentration is observed on the cathode top surfaces (La_0.9Sr_0.1MnO₃-mesh, Au-mesh, and Ag-porous), which suggested the promotion of oxygen adsorption and oxygen surface exchange at the cathode. The oxygen diffusion through the bulk of cathode occurred at the La_0.9Sr_0.1MnO₃-mesh and the Ag-porous cathodes, not at the Au-mesh cathode. On the YSZ surfaces after removing the cathode, the active sites for oxygen incorporation were analyzed by SIMS. The active sites for oxygen incorporation were at the La_0.9Sr_0.1MnO₃/YSZ interface as well as the TPB. On the other hand, the active sites for oxygen incorporation are limited to the TPB in the case of the Au-mesh removed YSZ surface. From the SIMS analysis, the expansion of the active sites for oxygen incorporation is less than a few μm from the TPB lines. Paper presented at the 8th EuroConference on Ionics, Carvoeiro, Algarve, Portugal, Sept. 16–22, 2001.     

Trifluoroacetaldehyde: A useful industrial bulk material for the synthesis of trifluoromethylated amino compounds

The synthesis of various trifluoromethylated amino compounds was studied using trifluoroacetaldehyde, an industrial bulk material, as a starting compound. One general application of trifluoroacetaldehyde is the preparation of trifluoroethylamino derivatives via reductive amination reaction. This synthesis includes the formation of the corresponding N,O-acetal intermediates followed by their reduction using NaBH₄ or 2-picoline borane complex, affording the target trifluoroethylamino compounds in moderate to good yields (47-87%).Another general application of trifluoroacetaldehyde is the synthesis of chiral α-substituted trifluoroethylamino compounds. In this synthesis, trifluoroacetaldehyde was first converted into the chiral trifluoromethyl tert-butyl sulfinimine, which was subjected to 1,2-nucleophilic addition reactions across its CN double bond. The addition of phenyllithium afforded α-(phenyl)trifluoroethylamino derivative in 83% yield and with 96% de. Allylation and Reformatsky reactions produced the corresponding α-substituted trifluoroethylamino derivatives in 82 and 58% yields and with 90 and 91% de, respectively.     

17O NMR chemical shifts versus structure relationships in oxiranes

Natural-abundance ¹⁷O NMR spectra have been measured for twenty one oxiranes. Their chemical shifts covering a 100 ppm range were interpreted in terms of the paramagnetic β- and diamagnetic γ-effects. In addition, through-space orbital interaction between the ethylenic π and the Walsh orbitals of the oxirane ring was suggested by a lowfield shift in norbornadiene $\text{exo}$-oxide.     

A new synthetic method for β-trimethylsilyl-α,β-unsaturated carbonyl compounds employing 1-methoxy-3-phenylthio-3-trimethylsilyl-1-propene

A new synthetic method for functionally substituted β-trimethylsilyl-α,β-unsaturated carbonyl compounds from 1-methoxy-3-phenylthio-3-trimethylsilyl-1-propene is described.     

3,3-Dimethoxypropylsulfonyl Group: A new versatile protecting and activating group for amine synthesis

3,3-Dimethoxypropylsulfonyl (Dimps) chloride was prepared and used as a new versatile sulfonating agent for ammonia, primary and secondary amines to afford corresponding Dimps-amides in excellent yields. The resulting N-nonsubstituted and N-monosubstituted Dimps-amides, activated amines, were alkylated satisfactorily under new Mitsunobu conditions. The Dimps group was removed by treatment in aqueous solution under acidic followed by basic conditions. Furthermore, epilachnene, the defensive droplets from the Mexican bean beetle, Epilachna varivestis, was synthesized utilizing this Dimps methodology in short steps.     

Raman studies of (Fe,V)3S4 solid solution

Raman scattering of Fe_xV_3-xS₄ with 0?x?2 has been studied. The observed spectra of V₃S₄, one of the end members of this solid solution, have been assigned to the Raman active lattice modes based on the C_2h³ space group symmetry. On the basis of the results obtained for V₃S₄, the nature of the metal-metal interactions and the site distributions of Fe atoms in (Fe, V)₃S₄ have been discussed.