Simplest Prussian-blue deposition from ferric ferricyanide solution by a reducing Ag spot put onto an ITO substrate

Prussian-blue (PB) film for electro-chromism can be electro-deposited on to an electrode (usually tin-doped indium oxide/glass) either directly from a PB colloid or from ferric ferricyanide in a two-electrode electro-chemical cell by applying a reductive potential. Alternatively, a “sacrificial” electron-producing silver flag electrode in the solution, when connected to the PB-receiving electrode, can effect the required reductive deposition. A silver spot, here innovatively applied as silver paint directly onto the deposition electrode, produces PB film on immersion in the iron(III)(III) solution, obviating the separate counter-electrode method.     

Chemical Inhomogeneity,Short‐Range Order,and Magnetism in the LiNiO2‐NiO Solid Solution

NiO:Li is an early exemplar for which hole‐doping of a correlated insulator gives rise to rich and varied magnetic behavior. It is also an important system from the viewpoint of p‐type transparent conducting oxides, and is representative of a large class of materials that have been used in lithium ion batteries, since the end‐member compound, LiNiO₂, belongs to the class of layered cathode materials. Despite the deceptive structural and compositional simplicity of this system, a complete understanding of its complex magnetic properties has remained elusive. Here a comprehensive investigation of the solid solution Li_xNi_2?xO₂, examining samples of precise stoichiometry using a combination of high‐resolution synchrotron X‐ray powder diffraction and SQUID magnetometry, is provided. The focus is on the interesting region between 0.40<x<1.00 in which the magnetic ordering temperature changes drastically with composition. The magnetism evolves from strong G‐type antiferromagnetism of x=0.40 with T_N=327 K to robust uncompensated magnetic order at T_N=240 K when x is close to 0.7, and to glassy A‐type antiferromagnetism of x=1.00 at T_N=9 K. This study demonstrates this magnetic behavior is linked to the Li–Ni chemical order that develops from short‐ to long‐range. The interfaces between ordered domains give rise to magnetic exchange bias, which manifests as a shift in the magnetization‐field loop for samples with nanoscale coherence lengths (0.54<x<0.66).     

Shape Selectivity by Guest‐Driven Restructuring of a Porous Material

A flexible metal‐organic framework selectively sorbs para‐ (pX) over meta‐xylene (mX) by synergic restructuring around pX coupled with generation of unused void space upon mX loading. The nature of the structural change suggests more generally that flexible structures which are initially mismatched in terms of fit and capacity to the preferred guest are strong candidates for effective molecular separations.     

Sponge‐Like Behaviour in Isoreticular Cu(Gly‐His‐X) Peptide‐Based Porous Materials

We report two isoreticular 3D peptide‐based porous frameworks formed by coordination of the tripeptides Gly‐L ‐His‐Gly and Gly‐L ‐His‐L ‐Lys to Cu^II which display sponge‐like behaviour. These porous materials undergo structural collapse upon evacuation that can be reversed by exposure to water vapour, which permits recovery of the original open channel structure. This is further confirmed by sorption studies that reveal that both solids exhibit selective sorption of H₂O while CO₂ adsorption does not result in recovery of the original structures. We also show how the pendant aliphatic amine chains, present in the framework from the introduction of the lysine amino acid in the peptidic backbone, can be post‐synthetically modified to produce urea‐functionalised networks by following methodologies typically used for metal–organic frameworks built from more rigid “classical” linkers.     

Intermolecular overlap geometry gives two classes of fulleride superconductor: electronic structure of 38 K Tc Cs3C60

Superconductivity emerges for the A15 polymorph of the fulleride Cs3C60 upon compression to a pressure of approximately 4 kbar. Using density functional theory we study the bonding in the A15 phase as a function of unit cell volume comparing it to that in the fcc polymorph. We find that, despite its smaller packing density, the bcc-derived A15 phase has both a substantially wider bandwidth for the partially occupied t1u band and a higher density of states at the Fermi level. This result can be traced to the striking differences in the nature of the interanion Tc--the two sphere packings (body centered versus face centered) observed experimentally produce two electronically distinct classes of fulleride superconductors.     

Verification of a model to predict the influence of particle inertia and gravity on a decaying turbulent particle-laden flow

In an earlier publication some of the authors presented a theoretical model for the calculation of the influence of particle inertia and gravity on the turbulence in a stationary particle-laden flow. In the present publication the model is extended for application to a decaying suspension. Also a comparison is given between predictions made with the model and experimental data (own data and data reported in the literature) on a decaying turbulent flow with particles in a water tunnel or in a wind tunnel. For most of the experiments a prediction with reasonable accuracy and an interpretation is possible by means of the model.