news in Soltion Chemsitry Community

 As the search for new battery chemistries with higher capacities and more stable supply chains expands, requiring increasingly complex electrolytes with multiple solvents and anions, it is becoming clear that understanding and controlling the working cation solvation structure is key to enabling improved stability and reversibility. In this work, we discover an emergent solvation behavior in multivalent electrolytes containing multiple anions, where bis(trifluoromethane sulfonyl) imide (TFSI−) anions that are fully dissociated in isolation form contact ion pairs with Zn2+ when combined with more strongly coordinating halides. This coordination modifies the electrochemical response, activating additional redox species as the halide association strength weakens (i.e., Cl− > Br− > I−) and systematically lowering overpotentials for metal deposition. This work suggests a completely new framework for electrolyte design in which anion chemistry can be used to tune both the bulk speciation and the interfacial solvation structure, enabling profound changes to the electrochemical behavior of the system. 

  Speciation is the key parameter in solution chemistry that describes the composition, concentration, and oxidation state of each chemical form of an element present in a sample. The speciation study of complex polyatomic ions has remained challenging because of the large number of factors affecting stability and the limited number of direct methods. To address these challenges, we developed the speciation atlas of 10 polyoxometalates commonly used in catalytic and biological applications in aqueous solutions, where the speciation atlas provides both a species distribution database and a predictive model for other polyoxometalates to be used. Compiled for six different polyoxometalate archetypes with three types of addenda ions based on 1309 nuclear magnetic resonance spectra under 54 different conditions, the atlas has revealed a previously unknown behavior of polyoxometalates that may account for their potency as biological agents and catalysts. The atlas is intended to promote the interdisciplinary use of metal oxides in various scientific fields. 

  Ion hydration in aqueous solutions plays a paramount role in many fields. Despite many studies on ion hydration, the nature of ion hydration is not consistently understood at the molecular level. Combining neutron scattering (NS), wide-angle X-ray scattering (WAXS), and molecular dynamics (MD), we quantify the ionic hydration degree (hydration ability) systematically for a series of alkali metal and halide ions based on static and dynamic hydration numbers. The former is based on the orientational correlation of water molecules bound to an ion derived from the positional information from NS and WAXS. The latter is defined as the mean number of water molecules remaining in the first coordination shell of an ion over a residence time of bound water molecules around the ion from MD. The static and dynamic hydration numbers distinguish hydration from coordination and quantify the ionic hydration degree, which provides a valuable reference for understanding various phenomena in nature.