Toward high-performance nanostructured thermoelectric materials: The progress of bottom-up solution chemistry approaches

Significant research effort has recently gone into the synthesis of thermoelectric nanomaterials through different chemical approaches since nanomaterials chemistry became a promising strategy for improving thermoelectric performance. Different thermoelectric nanocrystals, especially PbTe, Bi2Te3 and CoSb3, with various compositions and morphologies have been successfully prepared by solvo/hydrothermal, electrochemical, and ligand-based synthesis methods. Such nanoscale materials show not only substantial reduction in thermal conductivity due to increased phonon scattering at nanoscale grain boundaries and lower densities of phonon states but possibly also an enhancement in thermopower due to electronic quantum size effects. More recently, the notoriously low power factors of thermoelectric nanomaterials prepared by wet chemistry have been significantly improved by using an increasingly cross-disciplinary approach towards the bottom-up synthesis that combines expertise from chemistry, physics, and materials engineering. In this review, we discuss the recent progress and current challenges of preparing thermoelectric nanomaterials with solution-based chemistry approaches

Evolution of microscopic heterogeneity and dynamics in choline chloride-based deep eutectic solvents

Deep eutectic solvents (DESs) are an emerging class of non-aqueous solvents that are potentially scalable, easy to prepare and functionalize for many applications ranging from biomass processing to energy storage technologies. Predictive understanding of the fundamental correlations between local structure and macroscopic properties is needed to exploit the large design space and tunability of DESs for specific applications. Here, we employ a range of computational and experimental techniques that span length-scales from molecular to macroscopic and timescales from picoseconds to seconds to study the evolution of structure and dynamics in model DESs, namely Glyceline and Ethaline, starting from the parent compounds. We show that systematic addition of choline chloride leads to microscopic heterogeneities that alter the primary structural relaxation in glycerol and ethyleneglycol and result in new dynamic modes that are strongly correlated to the macroscopic properties of the DES formed

Cadmium and/or copper excess induce interdependent metal accumulation, DNA methylation, induction of metal chelators and antioxidant defences in the seagrass Zostera marina

Publisher’s embargo period: Embargo set on 01.03.2019 by SR (TIS)

NIRT: Active nanoparticles in nanostructured materials enabling advances in renewable energy and environmental remediation

Issued as final reportUniversity of Alabam

Entropy–Enthalpy Compensation in Electron-Transfer Processes

Solvent reorganization energies, free energies, and entropies are obtained for photoexcitation of three molecules that exhibit strong solvatochromism [Nile red, 5-(dimethylamino)-5′-nitro-2,2-bisthiophene, and Reichardt’s dye B30] by measuring their optical absorption spectra at temperatures between 150 and 300 K in solvents with a range of polarities. Energies, free energies, and entropies of solvent reorganization are also obtained from computer simulations of three intramolecular electron-transfer reactions (charge separation and recombination in Zn–porphyrin–quinone cyclophane and charge transfer in a bis-biphenylandrostane radical anion). Entropy–enthalpy compensation in the solvent reorganization free energy for photoexcitation or electron transfer is found to be essentially complete (having nearly equal and opposite contributions from entropic and enthalpic effects) for all of the processes with solvent reorganization energies less than about 0.1 eV. Compensation becomes less complete as the reorganization energy becomes larger. A semiclassical treatment of the solvent reorganization entropy can rationalize these results

Hydrodynamic voltammetry of Fe2+/3+ in aqueous deep eutectic solvents towards redox flow batteries

Deep eutectic solvents (DESs) have recently attracted much attention as potential green electrolyte solvents for redox flow batteries. DESs are considered not only as environmentally sustainable but also economically attractive electrolytes because they can be resourced from biological feedstock (alcohols, urea, choline) and are earth-abundant and of low toxicity. Despite these advantages, DESs still have limitations in important aspects such as reactant and ion transport, which is inhibited due to hydrogen-bonding-induced viscosity. Thus, improving the transport properties of redox species in DESs is essential. In addition, we explore the quantitative addition of water to ethaline (a 1:2 choline chloride: ethylene glycol mixture) in order to understand its influence on the kinetics and mass transport properties of DESs. In this work, we show that DESs can be made more fluid and less dense, while avoiding most of the electrochemical instabilities of water. Herein, we investigate the effects of gradually increasing amounts of water to the redox system of Fe2+/3+in ethaline. Our study shows that systematic addition of water leads to a three-fold increase in ionic conductivity and decrease in viscosity that enhances the mass transport and kinetics of DES-based electrolytes while still maintaining an electrochemical window of approximately 1.90 V. The use of environmentally benign electrolyte components together with the observed increase in conductivity will result in a more efficient redox flow battery (RFB) that operates at higher power density without relying on harmful solvents and fossil fuel-based processes