Scanning Electrochemical Microscopy Meets Optical Microscopy: Probing the Local Paths of Charge Transfer Operando in Booster-Microparticles for Flow Batteries.

Understanding the oxidation/reduction dynamics of secondary microparticles formed from agglomerated nanoscale primary particles is crucial for advancing electrochemical energy storage technologies. In this study, the behavior of individual copper hexacyanoferrate (CuHCF) microparticles is explored at both global and local scales combining scanning electrochemical microscopy (SECM), for electrochemical interrogation of a single, but global-scale microparticle, and optical microscopy monitoring to obtain a higher resolution dynamic image of the local electrochemistry within the same particle. Chronoamperometric experiments unveil a multistep oxidation/reduction process with varying dynamics. On the one hand, the global SECM analysis enables quantifying the charge transfer as well as its dynamics at the single microparticle level during the oxidation/reduction cycles by a redox mediator in solution. These conditions allow mimicking the charge storage processes in these particles when they are used as solid boosters in redox flow batteries. On the other hand, optical imaging with sub-particle resolution allows the mapping of local conversion rates and state-of-charge within individual CuHCF particles. These maps reveal that regions of different material loadings exhibit varying charge storage capacities and conversion rates. The findings highlight the significance of porous nanostructures and provide valuable insights for designing more efficient energy storage materials.

Effective and Apparent Diffusion Coefficients of Chloride Ions and Chloride Binding Kinetics Parameters in Mortars: Non-Stationary Diffusion-Reaction Model and the Inverse Problem.

A non-equilibrium diffusion-reaction model is proposed to describe chloride transport and binding in cementitious materials. A numerical solution for this non-linear transport with reaction problem is obtained using the finite element method. The effective chloride diffusion coefficients and parameters of the chloride binding are determined using the inverse method based on a diffusion-reaction model and experimentally measured chloride concentrations. The investigations are performed for two significantly different cements: ordinary Portland and blast furnace cements. The results are compared with the classical diffusion model and appropriate apparent diffusion coefficients. The role of chloride binding, with respect to the different binding isotherms applied, in the overall transport of chlorides is discussed, along with the applicability of the two models. The proposed work allows the determination of important parameters that influence the longevity of concrete structures. The developed methodology can be extended to include more ions, electrostatic interactions, and activity coefficients for even more accurate estimation of the longevity.

Precipitation of Inorganic Salts in Mitochondrial Matrix.

In the mitochondrial matrix there are insoluble, osmotically inactive complexes that maintain constant pH and calcium concentration. In the present paper we examine the properties of insoluble calcium and magnesium salts, namely phosphates, carbonates and polyphosphates which might play this role. We find that non-stoichiometric, magnesium-rich carbonated apatite, with very low crystallinity, precipitates in the matrix under physiological conditions. Precipitated salt acts as pH buffer, and hence can contribute in maintaining ATP production in ischemic conditions, delaying irreversible damages to heart and brain cells after stroke.

Sensitivity and Selectivity of Ion-Selective Electrodes Interpreted Using the Nernst-Planck-Poisson Model.

The Nernst-Planck-Poisson model is used for modeling the sensitivity and selectivity of ion-selective electrodes (ISEs) with plastic membranes. Two pivotal parameters characterizing ISE response are in focus: sensitivity and selectivity. An interpretation of sensitivity, which considers the concurrent influence of anions and cations on the ISE slope, is presented. The interpretation of selectivity shows the validity and limits of approaches hitherto taken to measure the true (unbiased) selectivity coefficient. The validity of more idealized interpretations by the diffusion-layer model is conceived.

Neutral-carrier ion-selective electrodes assessed by the Nernst-Planck-Poisson model.

Ion-selective electrodes (ISEs) containing neutral ionophores are used in clinical, industrial, and environmental analysis. The wide range of applications requires deep theoretical description. This work concentrates on the development of the general approach to the description of electro-diffusion processes, namely, Nernst-Planck-Poisson (NPP) model to allow the description of the time-dependent responses in the case of complexation reactions occurring in the ion-selective membranes. The impact of the chemical reaction on the calibration curves and apparent selectivity of ISE is discussed. Results obtained using NPP model with time-dependent reaction are compared with those obtained with the Phase Boundary Model (PBM), as well as with the previous solutions of NPP model, using the infinite reaction rates and constant ligand concentration assumption. The validity of these assumptions is investigated and the limitations of PBM in the description of neutral-carrier ISE are discussed.