Nonlinear diffusion in two-dimensional ordered porous media based on a free volume theory.

A continuum nonlinear diffusion model is developed to describe molecular transport in ordered porous media. An existing generic van der Waals equation of state based free volume theory of binary diffusion coefficients is modified and introduced into the two-dimensional diffusion equation. The resulting diffusion equation is solved numerically with the alternating-direction fully implicit method under Neumann boundary conditions. Two types of pore structure symmetries are considered, hexagonal and cubic. The former is modeled as parallel channels while in case of the latter equal-sized channels are placed perpendicularly thus creating an interconnected network. First, general features of transport in both systems are explored, followed by the analysis of the impact of molecular properties on diffusion inside and out of the porous matrix. The influence of pore size on the diffusion-controlled release kinetics is assessed and the findings used to comment recent experimental studies of drug release profiles from ordered mesoporous silicates

Enhancing oxygen evolution functionality through anodization and nitridation of compositionally complex alloy

Compositionally complex materials (CCMs) have recently attracted great interest in electrocatalytic applications. To date, very few materials were systematically developed and tested due to the highly difficult preparation of high-surface-area CCMs. In this work, a surface of a compositionally complex FeCoNiCuZn alloy (CCA) was nitridated with subsequent anodization leading to morphological and compositional modifications. Notably, the electrochemical surface area and surface roughness as well as the electrocatalytic activity of the anodized material exhibit significant enhancement. Oxygen evolution reaction (OER) activity by the anodized CCN (CCN–AO) proceeds with remarkably small overpotential (233 mV) at 10 mA cm−2 in 1 M KOH. Experimental characterization indicates that the oxidation state of Co plays a critical role in the Fe–Co–Ni electrocatalyst. The developed approach and design strategy open up immense prospects in the preparation of a new, affordable, scalable and effective type of complex and high-performance electrocatalytic electrodes with tunable properties

Direct observation of active material concentration gradients and crystallinity breakdown in LiFePO4 electrodes during charge/discharge cycling of lithium batteries

The phase changes that occur during discharge of an electrode comprised of LiFePO4, carbon, and PTFE binder have been studied in lithium half cells by using X-ray diffraction measurements in reflection geometry. Differences in the state of charge between the front and the back of LiFePO4 electrodes have been visualized. By modifying the X-ray incident angle the depth of penetration of the X-ray beam into the electrode was altered, allowing for the examination of any concentration gradients that were present within the electrode. At high rates of discharge the electrode side facing the current collector underwent limited lithium insertion while the electrode as a whole underwent greater than 50% of discharge. This behavior is consistent with depletion at high rate of the lithium content of the electrolyte contained in the electrode pores. Increases in the diffraction peak widths indicated a breakdown of crystallinity within the active material during cycling even during the relatively short duration of these experiments, which can also be linked to cycling at high rate

Room-temperature single-phase Li insertion/extraction in nanoscale LixFePO4

Classical electrodes for Li-ion technology operate by either single-phase or two-phase Li insertion/de-insertion processes, with single-phase mechanisms presenting some intrinsic advantages with respect to various storage applications. We report the feasibility to drive the well-established two-phase room-temperature insertion process in LiFePO4 electrodes into a single-phase one by modifying the material's particle size and ion ordering. Electrodes made of LiFePO4 nanoparticles (40 nm) formed by a low-temperature precipitation process exhibit sloping voltage charge/discharge curves, characteristic of a single-phase behaviour. The presence of defects and cation vacancies, as deduced by chemical/physical analytical techniques, is crucial in accounting for our results. Whereas the interdependency of particle size, composition and structure complicate the theorists' attempts to model phase stability in nanoscale materials, it provides new opportunities for chemists and electrochemists because numerous electrode materials could exhibit a similar behaviour at the nanoscale once their syntheses have been correctly worked out

pH-based one pot synthesis of biocompatible olive shaped inorganic particles.

A novel, single-step, one-pot method for preparation of inorganic hollow particles is introduced. The concept is grounded on the classical theory of nucleation of growth and can be carried out entirely at room temperature. Starting from an appropriate solution, precipitation and selective dissolution of inorganic nanoparticles are triggered by continuous addition of a salt while carefully controlling the pH. The approach is demonstrated on the example of hollow calcium phosphate particles using calcium carbonate solid nanoparticles as a template. The proposed synthesis procedure is simple and cheap and can be extended to other biocompatible compounds. It also can be upgraded with an additional in situ ste