Density Functional Theory-Based Protocol to Calculate the Redox Potentials of First-row Transition Metal Complexes for Aqueous Redox Targeting Flow Batteries.

Transition metal complexes are a promising class of redox mediators for targeting redox flow batteries due to the tunability of their electrochemical potentials. However, reliable time-efficient tools for the prediction of their reduction potentials are needed. In this work, we establish a suitable density functional theory protocol for their prediction using an initial experimental data set of aqueous iron complexes with bidentate ligands. The approach is then cross-validated using different complexes found in the redox-flow literature. We find that the solvation model affects the prediction accuracy more than the functional or basis set. The smallest errors are obtained using the COSMO-RS solvation model (mean average error (MAE)=0.24 V). With implicit solvation models, a general deviation from experimental results is observed. For a set of similar ligands, they can be corrected using simple linear regression (MAE=0.051 V for the initial set of iron complexes).

Estimation of activity coefficients for aqueous organic redox flow batteries: Theoretical basis and equations.

The field of aqueous organic redox flow batteries (AORFBs) has been developing fast in recent years, and many chemistries are starting to emerge as serious contenders for grid-scale storage. The industrial development of these systems would greatly benefit from accurate physics-based models, allowing to optimize battery operation and design. Many authors in the field of flow battery modeling have brought evidence that the dilute solution hypothesis (the assumption that aqueous electrolytes behave ideally) does not hold for these systems and that calculating cell voltage or chemical potentials through concentrations rather than activities, while serviceable, may become insufficient when greater accuracy is required. This article aims to provide the theoretical basis for calculating activity coefficients of aqueous organic electrolytes used in AORFBs to provide tools to predict the concentrated behavior of aqueous electrolytes, thereby improving the accuracy of physics-based models for flow batteries.

Synthesis and antibacterial activity of catecholate-ciprofloxacin conjugates.

The development of an efficient route to obtain artificial siderophore-antibiotic conjugates active against Gram-negative bacteria is crucial. Herein, a practical access to triscatecholate enterobactin analogues linked to the ciprofloxacin along with their antibacterial evaluation are described. Two series of conjugates were obtained with and without a piperazine linker which is known to improve the pharmacokinetics profile of a drug. A monocatecholate-ciprofloxacin conjugate was also synthesized and evaluated. The antibacterial activities against Pseudomonas aeruginosa for some conjugates are related to the iron concentration in the culture medium and seem to depend on the bacterial iron uptake systems.

Formation of nanometric HT-LiCoO(2) by a precipitation and aging process in an alcoholic solution.

In this paper, we detailed the formation/evolution of precipitates in alcoholic media containing Co(II+) and Li(+) species, together with the evolution of the composition and structure/texture of the resulting solid phases during the aging process at controlled constant temperature. While the end product is found to be well-crystallized HT-LiCoO(2), its formation is shown to result from a two-step process enlisting the initial fast precipitation of ß-HCoO(2) and then its slow dissolution followed by recrystallization of the lithium-containing material. These results were obtained through combined X-ray diffraction, Raman and IR spectroscopy, elemental and oxidation-state analysis, and high-resolution transmission electron microscopy/selected-area electron diffraction observations. Depending on the cationic concentration, the size of the precipitated material can be controlled within the nanometric range. The electrochemical performances of these aged materials are slightly improved compared to those of the directly precipitated ones that we previously reported. The main limitation of these materials remains the presence of surface protons.

Synthesis of a manganese oxide nanocomposite through heteroepitaxy in aqueous medium.

A microporous manganese oxide nanocomposite is synthesized using heteroepitaxy in an aqueous medium at 95 degrees C.