New Mixed-Valent Molybdenum Monophosphates with the KMo3P2O14 structure

New mixed valent molybdenum monophosphates AMo₃P₂O₁₄ have been synthesized for A = Ag, Rb, Na, Sr. The single crystal X-ray diffraction study of two of them (A = Ag, Sr) shows that they belong to the layer structure type KMo₃P₂O₁₄. Their structure consists of [Mo₃P₂O₁₄]_∞ layers involving MoO₆ octahedra and MoO₅ bipyramids, interleaved with A cations forming bicapped trigonal prisms AO₈. Bond valence calculations show a localisation of the Mo^V and Mo^VI species according to the formula A¹Mo^V_oct1Mo^VI_oct2Mo^VI_bipyP₂O₁₄ for A = Ag, Na and SrMo^V_oct1Mo^V_oct2Mo^VI_bipyP₂O₁₄. A comparison between the different Mo^V? Mo^VI phosphates is made.     

Crystal structure of the Molybdenum(V) Diphosphate KMoP2O8 isotypic with KNbP2O8

A new molybdenum(V) diphosphate KMoP₂O₈ has been isolated. The single crystal X-ray diffraction study of this phase has shown that it is isotypic with KNbP₂O₈. It crystallizes in the P2₁/n space group a = 5.0862(4), b = 11.720(1), c = 11.486(1) Å, β = 90.91(1)°. The structure of this phase is compared with those of other molybdenum(V) diphosphates. This tunnel structure is described in terms of [MP₂O₈]₈∞ ribbons running along ā, showing close relationships with the titanophosphate NaTiP₂O₇. The existence of one free apex for each MoO₆ octahedron and each P₂O₇ group, respectively, is emphasized, allowing a great flexibility of the structure.     

Octasubstituted metal-free phthalocyanine as core of phosphorus dendrimers: a probe for the properties of the internal structure

The synthesis of a new family of phosphorus dendrimers built from an octasubstituted metal-free phthalocyanine core is described up to generation 5. This core is used as a sensor and a probe for analyzing the properties of the internal structure and the influence of each structural part (core, branches, surface) upon the whole structure. UV-visible spectra show both a hyperchromic and bathochromic effect on the Q-bands with increasing generation, indicating that the chromophore is more isolated, and that the dendritic shell mimics a highly polar solvent. There is no evidence for aggregation, except for generation 0, showing again the isolation of the core. However, the dendritic shell is permeable to aqueous acids and bases, as demonstrated by the reversible splitting of the Q-band in an acidic medium (neutral form of the phthalocyanine) and the single Q-band in a basic medium (dianionic form), even for generation 4. The fluorescence quantum yield for the neutral form increases with increasing generation. The dianionic form of generation 0 is poorly fluorescent, whereas generations 3 and 4 (G3 and G4) exhibit better fluorescence. The cores of G3 and G4 are highly sensitive optical sensors for H3O+ and OH-. These experiments are carried out in THF/water mixtures, and the influence of water on the structure has been checked. The hydrodynamic radius of generation 4 is measured by NMR diffusion (pulse gradient spin-echo) experiments. R(H) varies from 35.4 A at 4 mol % of water to 32.5 A at 64 mol % of water in THF, indicating the hydrophobic nature of these dendrimers.     

An approach to control the spurious currents in a multiphase lattice Boltzmann method and to improve the implementation of initial condition

Multiphase lattice Boltzmann methods are known to generate spurious or parasitic currents at the fluid–fluid interfaces. This nonphysical phenomenon has to be avoided, or at least controlled, in order to achieve reliable solutions. In this article, a method to control these fictitious velocities via lattice refinement is proposed, which is based on interface thickness control for which both the spurious currents and the physical fluid–fluid interface thickness vanishes as the spatial resolution increases. It has been found that a proper interface thickness adjustment is required as the lattice refinement is applied, or an increase in spurious currents, instead of a reduction, can occur. By combining the new method with an appropriate multiphase flow initialization, the overall stability for high density O(1000) and viscosity O(100) ratios is greatly improved. Although this research has been conducted with a Rothman and Keller type lattice Boltzmann model, it is believed that other types of multiphase lattice Boltzmann models could benefit from the basic ideas underlying this research. Copyright © 2015 John Wiley & Sons, Ltd.     

Issue Information ‐ TOC

Numerical modeling of multiphase flow generally requires a special procedure at the solid wall in order to be consistent with Young's law for static contact angles. The standard approach in the lattice Boltzmann method, which consists of imposing fictive densities at the solid lattice sites, is shown to be deficient for this task. Indeed, fictive mass transfer along the boundary could happen and potentially spoil the numerical results. In particular, when the contact angle is less than 90 degrees, the deficiencies of the standard model are major. Various videos that demonstrate this behavior are provided (Supporting Information). A new approach is proposed and consists of directly imposing the contact angle at the boundaries in much the same way as Dirichlet boundary conditions are generally imposed. The proposed method is able to retrieve analytical solutions for static contact angles in the case of straight and curved boundaries even when variable density and viscosity ratios between the phases are considered. Although the proposed wetting boundary condition is shown to significantly improve the numerical results for one particular class of lattice Boltzmann model, it is believed that other lattice Boltzmann multiphase schemes could also benefit from the underlying ideas of the proposed method. The proposed algorithm is two‐dimensional, and the D2Q9 lattice is used. Copyright © 2016 John Wiley & Sons, Ltd.