Density functional theory study of the mechanism for the formation of glycidyl esters from triglyceride.

Glycidyl fatty acid esters (GEs) are by-products of edible oil refinement that have attracted attention globally due to concerns over their possible harmful effects on human health when consumed. It is thus important to improve our understanding of GE formation if we are to suppress GE production during edible oil refinement. In this paper, a first-principles density functional theory study of the formation mechanism of GEs was performed. Triglycerides undergo a self-condensation reaction between two adjacent ester groups to yield GEs and an anhydride as a by-product. This process is energetically unfavorable, having a relatively high activation energy of around 80 kcal/mol, which indicates that GE formation is intrinsically a high-temperature process. Both the thermodynamic and the kinetic energies of the reaction are insensitive to the size of the fatty chain substituents present. If water participates in the self-condensation, the activation barrier is notably decreased by 23.9 kcal/mol, indicating that GE production in the presence of high-temperature water vapor should be more kinetically favorable. Our results suggest that reducing the reaction temperature and avoiding the use of water should suppress GE production during edible oil refinement.

On the Mechanism of the Improved Operation Voltage of Rhombohedral Nickel Hexacyanoferrate as Cathodes for Sodium-Ion Batteries.

We reported a rhombohedral Na-rich nickel hexacyanoferrate (r-NiHCF) with high discharge voltage, which also possesses long cycle stability and excellent rate capability when serving as the cathode material of Na-ion batteries. First-principles calculations suggest that the high working voltage of r-NiHCF is correlated to the asymmetric residence of Na+ ions in the rhombohedral framework in parallel with the low charge density at the Fe2+ ions. In both aqueous and ether-based electrolytes, r-NiHCF exhibits higher voltage than that of cubic NiHCF. Rate and cycle experiments indicate that r-NiHCF delivers a specific capacity of 66.8 mAh g-1 at the current density of 80 mA g-1, which is approximate to the theoretical capacity of r-NiHCF. A capacity retention of 96% can be achieved after 200 cycles. The excellent stability of r-NiHCF can be assigned to the absence of rhombohedral-cubic phase transition and negligible volume variation during electrochemical redox, as proven by the ex situ XRD patterns at different depths of charge/discharge and the DFT calculations, respectively.

K-enriched WO3 nanobundles: high electrical conductivity and photocurrent with controlled polarity.

Potassium ions are successfully intercalated into WO3 nanobundles with the integrity of the pseudo-orthorhombic structure remaining intact. The nanobundles display a 5-fold increase in the electrical conductivity. It changes from a value of 10(-4) Sm(-1) for pure WO3 to 40 Sm(-1) upon potassium intercalation. The electrical conductivity also increases by ~200 times as temperature increases from 23 to 200 °C whereby analysis shows a thermal activation energy of ~1 eV. Density functional theory calculations show that K ions cause the reduction of the surrounding W atoms and lead to an increase in the electron population in the conduction band. Hence, the conductivity of the K-WO3 nanobundles is greatly enhanced. The calculated band structure also shows a gap of 1 eV that is consistent with the measured thermal activation energy. Upon illumination of focused laser beam, individual and isolated nanobundle displays significant photon induced current (9 nA) without external bias at low laser power (2 mW); the amplitude and polarity of photocurrent could be controlled by location of laser spot.