Inclusion of ferrous phenanthroline in molybdenum disulfide

Ｉｎｔｅｒｃａｌａｔｉｏｎｃｈｅｍｉｓｔｒｙｏｆｌａｙｅｒｅｄｔｒａｎｓｉｔｉｏｎｍｅｔａｌｄｉｓｕｌｆｉｄｅｓｈａｓｂｅｅｎｅｘｔｅｎｓｉｖｅｌｙｓｔｕｄｉｅｄｉｎｔｈｅｐａｓｔｙｅａｒｓ[1].Ｉｔｈａｓｂｅｅｎｅｓｔａｂｌｉｓｈｅｄｔｈａｔｔｈｅｉｎｔｅｒｃａｌａｔｉｏｎｒｅａｃｔｉｏｎｄｅｐｅｎｄｓｓｔｒｏｎｇｌｙｏｎｅｌｅｃｔｒｏｎｉｃｓｔｒｕｃｔｕｒｅｏｆｔｈｅｔｒａｎｓｉｔｉｏｎｍｅｔａｌｄｉｓｕｌｆｉｄｅｓ.Ｆｏｒｉｎｓｔａｎｃｅ,ｖａｒｉｏｕｓｇｕｅｓｔｍｏｌｅｃｕｌｅｓｈａｖｅｂｅ…     

Sodium “stuffed” Ba2−xSrxFe4O8 ferrites: new cationic conductors

Sodium insertion in the tetrahedral layer structure of the ferrites Ba_2−xSr_xFe₄O₈ was performed by solid state reaction at 1220 K in air. Superstoichiometric oxides with the actual formula (Ba_2−xSr_x)_1−y/4Na_yFe₄O₈—y0.56; 0.60Ba/Sr1.67—were characterized by X-ray and neutron powder diffraction. The hexagonal unit-cell volume shows an increasing dependence on the sodium insertion when the Ba/Sr ratio reaches the largest values. The marked expansion of the c parameter is the likely signature of the location of the inserted sodium cations within the interlayer space. One-half of the sodium cations partly sits on the Sr(Ba) sites in octahedral coordination and the other half occupies extra octahedral and tetrahedral sites. ac conductivity measurements point to a cationic conductivity whose thermally activated regime—E_a 0.7 eV—evidenced from 570 K, is unsensitive to the sodium content. The bottleneck of the 2D sodium mobility regards the crossing of the oxygen triangular faces shared by the different polyhedra within the interlayer space.     

Syntheses and Crystal Structures of Two Metal Succinates Modified by Bipyridines

Two new metal succinates modified by rigid bipyridines, Cd(4, 4′‐bpy)(C₄H₄O₄)·1/4H₂O ( 1 ) and Cu(2, 2′‐bpy)(C₄H₄O₄)_0.5(NO₃)(H₂O) ( 2 ) (bpy = bipyridine), have been synthesized by hydrothermal reactions and structurally determined. Complex 1 crystallizes in the orthorhombic space group Cmca with the cell parameters a = 11.696(2), b = 15.554(2), c = 15.874(3) Å, α = β = γ = 90.00°, V = 2888(3) ų, Z = 8. Complex 2 crystallizes in the triclinic space group with a = 7.077(1), b = 9.838(2), c = 10.461(2) Å, α = 71.941(3)°, β = 73.078(3)°, γ = 74.502(3)°, V = 649.8(2) ų, Z = 2. In complex 1 , a 2‐D network was formed by Cd‐succinato bonding. The 2‐D networks are pillared by 4, 4′‐bpy ligands, forming a 3‐D grid framework. The 2‐fold interpenetration of the resulting 3‐D frameworks completes the molecular structure. In complex 2 , the Cu^II atom adopts a distorted octahedral in which the Cu^II atoms are bridged by two H₂O molecules into an infinite zigzag chain, [Cu₂(H₂O)₂(C₄H₄O₄)]_n. The neighboring chains are further linked by π‐π stacking interactions into a 2‐D network, and the interlayer hydrogen bonds lead to the final 3‐D crystal structure.     

On the two dimensional effective electron mass in quantum wells,inversion layers and NIPI superlattices of Kane type semiconductors in the presence of strong light waves: Simplified theory and relative comparison

An attempt is made to study the two dimensional (2D) effective electron mass (EEM) in quantum wells (Qws), inversion layers (ILs) and NIPI superlattices of Kane type semiconductors in the presence of strong external photoexcitation on the basis of a newly formulated electron dispersion laws within the framework of k.p. formalism. It has been found, taking InAs and InSb as examples, that the EEM in Qws, ILs and superlattices increases with increasing concentration, light intensity and wavelength of the incident light waves, respectively and the numerical magnitudes in each case is band structure dependent. The EEM in ILs is quantum number dependent exhibiting quantum jumps for specified values of the surface electric field and in NIPI superlattices; the same is the function of Fermi energy and the subband index characterizing such 2D structures. The appearance of the humps of the respective curves is due to the redistribution of the electrons among the quantized energy levels when the quantum numbers corresponding to the highest occupied level changes from one fixed value to the others. Although the EEM varies in various manners with all the variables as evident from all the curves, the rates of variations totally depend on the specific dispersion relation of the particular 2D structure. Under certain limiting conditions, all the results as derived in this paper get transformed into well known formulas of the EEM and the electron statistics in the absence of external photo-excitation and thus confirming the compatibility test. The results of this paper find three applications in the field of microstructures.     

Two-Step Structure Phase Transition,Dielectric Anomalies,and Thermochromic Luminescence Behavior in a Direct Band Gap 2D Corrugated Layer Lead Chloride Hybrid of [(CH3)4N]4Pb3Cl10

A direct band gap 2D corrugated layer lead chloride hybrid, [(CH₃)₄N]₄Pb₃Cl₁₀ ( 1 ), shows analogous topology to the {Mg₃F₁₀⁴⁻}_∞ layer in Cs₄Mg₃F₁₀, and with the (CH₃)₄N⁺ cations locating in the inorganic layer voids and between the interlayers. Two reversible structural phase transitions occur in 1 at 225/210 K and 328/325 K upon heating/cooling, respectively. On going from the low- to intermediate-temperature phase, the space group changes from P2₁/c to Cmca, and the crystallographic axis perpendicular to the layers is doubled with the order–disorder transformation of (CH₃)₄N ⁺ cations between the interlayers. The intermediate- and high-temperature phases are isomorphic with similar cell parameters and packing structure; their main difference concerns the disorder degree of the (CH₃)₄N ⁺ cations between the interlayers. The two-step structural phase transitions lead to dielectric anomalies around the corresponding T_c. Interestingly, 1 shows multiband emission, originating from the recombination of exciton and emission of defects. Moreover, 1 exhibits divergent thermochromic luminescent features around the T_c on the intermediate to low temperature transition.     

Phase transition layers with boundary intersection for an inhomogeneous Allen–Cahn equation

We consider the nonlinear problem of inhomogeneous Allen–Cahn equation

${?}^2\mathrm{\Delta }u+V(y)u(1?u^2)=0\text{in}\mathrm{\Omega },\frac{?u}{?\nu }=0\text{on}?\mathrm{\Omega },$

where Ω is a bounded domain in ${\mathbb{R}}^2$ with smooth boundary, ? is a small positive parameter, ν denotes the unit outward normal of ?Ω, V is a positive smooth function on $\overline{\mathrm{\Omega }}$. Let Γ be a curve intersecting orthogonally with ?Ω at exactly two points and dividing Ω into two parts. Moreover, Γ satisfies stationary and non-degenerate conditions with respect to the functional ${\int }_{\mathrm{\Gamma }}{V}^{1/2}$. We can prove that there exists a solution $u_{?}$ such that: as $?\to 0$, $u_{?}$ approaches +1 in one part of Ω, while tends to ?1 in the other part, except a small neighborhood of Γ.     

“Confinement effects for nano-electrocatalysts for oxygen reduction reaction”

Oxygen reduction reaction (ORR) is one of the most technologically relevant reactions. It occurs at the interface of the electrocatalyst and electrolyte, where oxygen reacts with protons and electrons to produce water. Because the electrocatalyst is dispersed on a high surface area support, morphological confinement becomes critical, as it dictates proton and oxygen transport. Furthermore, confinement is induced by ionomer, ionic liquids (ILs), or molecular additives, and their impact on electrocatalyst reactivity and transport properties is currently not well understood. We present an overview of electrostatics and mass transport–induced confinement and zoom in into ILs and molecular additives and try to unravel how local confinement induced by them impacts ORR.     

A mixed hp FEM for the approximation of fourth‐order singularly perturbed problems on smooth domains

We consider fourth‐order singularly perturbed problems posed on smooth domains and the approximation of their solution by a mixed Finite Element Method on the so‐called Spectral Boundary Layer Mesh. We show that the method converges uniformly, with respect to the singular perturbation parameter, at an exponential rate when the error is measured in the energy norm. Numerical examples illustrate our theoretical findings.     

pH-Dependent Slipping and Exfoliation of Layered Covalent Organic Framework

Layered/two-dimensional covalent organic frameworks (2D COF) are crystalline porous materials composed of light elements linked by strong covalent bonds. Interlayer force is one of the main factors directing the formation of a stacked layer structure, which plays a vital role in the stability, crystallinity, and porosity of layered COFs. The as-developed new way to modulate the interlayer force of imine-linked 2D TAPB-PDA-COF (TAPB = 1,3,5-tris(4-aminophenyl)benzene, PDA = terephthaldehyde) by only adjusting the pH of the solution. At alkaline and neutral pH, the pore size of the COF decreases from 34 Å due to the turbostratic effect. Under highly acidic conditions (pH 1), TAPB-PDA-COF shows a faster and stronger turbostratic effect, thus causing the 2D structure to exfoliate. This yields bulk quantities of an exfoliated few/single-layer 2D COF, which was well dispersed and displayed a clear Tyndall effect (TE). Furthermore, nanopipette-based electrochemical testing also confirms the slipping of layers with increase towards acidic pH. A model of pH-dependent layer slipping of TAPB-PDA-COF was proposed. This controllable pH-dependent change in the layer structure may open a new door for potential applications in controlled gas adsorption/desorption and drug loading/releasing.     

Solvent-free deposition of hybrid halide perovskites onto thin films of copper iodide p-type conductor

1. Download : Download high-res image (151KB)
2. Download : Download full-size image