Microemulsions as Emerging Electrolytes: The Correlation of Structure to Electrochemical Response.

We describe the structural studies of microemulsions (µEs) prepared from water, toluene, butanol, and polysorbate 20 (PS20) that we recently used as electrolytes. Small-angle neutron scattering was used to monitor the development of the bicontinuous system as a function of the water-to-surfactant mass ratio on a constant oil-to-surfactant dilution line, revealing how the domain size, correlation length, amphiphilicity factor, and bending moduli change with composition. Kratky and Porod analyses are also employed, providing further structural detail of the scattering domains. We demonstrate that controlling the water-to-surfactant ratio with a constant oil-to-surfactant dilution affects the bicontinuous phase, reveals a sizeable compositional region with structural similarities, and provides insight into the correlation of structure to physical properties. Voltammetric results are presented to examine how the evolution of the bicontinuous structure formed in a µE prepared from water, toluene, butanol, and PS20 contributes to the electrochemical response. These findings, therefore, provide essential information that will guide the formulation of µEs as electrolytes for energy storage.

Dynamic Mixing Behaviors of Ionically Tethered Polymer Canopy of Nanoscale Hybrid Materials in Fluids of Varying Physical and Chemical Properties.

An emerging area of sustainable energy and environmental research is focused on the development of novel electrolytes that can increase the solubility of target species and improve subsequent reaction performance. Electrolytes with chemical and structural tunability have allowed for significant advancements in flow batteries and CO2 conversion integrated with CO2 capture. Liquid-like nanoparticle organic hybrid materials (NOHMs) are nanoscale fluids that are composed of inorganic nanocores and an ionically tethered polymeric canopy. NOHMs have been shown to exhibit enhanced conductivity making them promising for electrolyte applications, though they are often challenged by high viscosity in the neat state. In this study, a series of binary mixtures of NOHM-I-HPE with five different secondary fluids, water, chloroform, toluene, acetonitrile, and ethyl acetate, were prepared to reduce the fluid viscosity and investigate the effects of secondary fluid properties (e.g., hydrogen bonding ability, polarity, and molar volume) on their transport behaviors, including viscosity and diffusivity. Our results revealed that the molecular ratio of secondary fluid to the ether groups of Jeffamine M2070 (λSF) was able to describe the effect that secondary fluid has on transport properties. Our findings also suggest that in solution, the Jeffamine M2070 molecules exist in different nanoscale environments, where some are more strongly associated with the nanoparticle surface than others, and the conformation of the polymer canopy was dependent on the secondary fluid. This understanding of the polymer conformation in NOHMs can allow for the better design of an electrolyte capable of capturing and releasing small gaseous or ionic species.

Controlling Interfacial Dynamics: Covalent Bonding versus Physical Adsorption in Polymer Nanocomposites.

It is generally believed that the strength of the polymer-nanoparticle interaction controls the modification of near-interface segmental mobility in polymer nanocomposites (PNCs). However, little is known about the effect of covalent bonding on the segmental dynamics and glass transition of matrix-free polymer-grafted nanoparticles (PGNs), especially when compared to PNCs. In this article, we directly compare the static and dynamic properties of poly(2-vinylpyridine)/silica-based nanocomposites with polymer chains either physically adsorbed (PNCs) or covalently bonded (PGNs) to identical silica nanoparticles (RNP = 12.5 nm) for three different molecular weight (MW) systems. Interestingly, when the MW of the matrix is as low as 6 kg/mol (RNP/Rg = 5.4) or as high as 140 kg/mol (RNP/Rg= 1.13), both small-angle X-ray scattering and broadband dielectric spectroscopy show similar static and dynamic properties for PNCs and PGNs. However, for the intermediate MW of 18 kg/mol (RNP/Rg = 3.16), the difference between physical adsorption and covalent bonding can be clearly identified in the static and dynamic properties of the interfacial layer. We ascribe the differences in the interfacial properties of PNCs and PGNs to changes in chain stretching, as quantified by self-consistent field theory calculations. These results demonstrate that the dynamic suppression at the interface is affected by the chain stretching; that is, it depends on the anisotropy of the segmental conformations, more so than the strength of the interaction, which suggests that the interfacial dynamics can be effectively tuned by the degree of stretching-a parameter accessible from the MW or grafting density.

Understanding the Impact of Poly(ethylene oxide) on the Assembly of Lignin in Solution toward Improved Carbon Fiber Production.

Carbon fiber produced from lignin has recently become an industrial scalable product with applications ranging from thermal insulation to reinforcing automobile bodies. Previous research has shown that mixing 1-2 wt %, of poly(ethylene oxide) (PEO) with the lignin before fiber formation can enhance the properties of the final carbon fibers. The research reported here determines the impact of adding PEO to a lignin solution on its assembly, focusing on the role of the lignin structure on this assembly process. Results indicate the addition of PEO anisotropically directs the self-assembly of the hardwood and softwood lignin by lengthening the cylindrical building blocks that make up the larger global aggregates. On the other hand, results from an annual lignin exhibit a shapeless, more complex structure with a unique dependence on the PEO loading. These results are consistent with improved carbon fibers from solutions of lignin that include PEO, as the local ordering and directed assembly will inhibit the formation of defects during the carbon fiber fabrication process.

Accurate thermochemistry for transition metal complexes from first-principles calculations.

The "correlation consistent Composite Approach" or ccCA is an ab initio model chemistry based on the single reference MP2 level of theory. By adjusting the basis set and level of theory of the core valence additive correction, ccCA is capable of reliable thermochemical predictions of inorganic and organometallic transition metal-containing molecules, as well as achieving chemical accuracy on main group species, with a mean absolute deviation of 0.89 kcal mol(-1) against the 147 enthalpies of formation in the G2/97 test set. For a set of 52 complexes containing elements Sc-Zn, ranging in size from diatomics to Ni(PF(3))(4) and Fe(C(5)H(2))(2), ccCA on average predicts enthalpies of formation to within +/-3 kcal mol(-1) of the experimental result with a mean absolute deviation of 2.85 kcal mol(-1) and a root mean square deviation of 3.77 kcal mol(-1). The ccCA methodology is a significant step toward quantitative theoretical modeling of transition metal thermodynamics.