Characterization of surface-confined ionic liquid stationary phases: impact of cation and anion identity on retention

A series of surface-confined ionic liquid (SCIL) stationary phases for high-performance liquid chromatography were synthesized in-house. The synthesized phases were characterized by the linear solvation energy relationship (LSER) method to determine the effect of residual linking ligands and the role of the cation and the anion on retention. Statistical analysis was utilized to determine whether the system coefficients returned from multiple linear regression analysis of chromatographic retention data for a set of 28 neutral aromatic probe solutes were significantly different. Examination of the energetics of retention via κ−κ plots agrees with the results obtained from the LSER analysis. Residual linking ligands were determined to contribute reversed-phase-type retention character to the chromatographic system. Furthermore, retention on the SCIL phases was observed to be more profoundly affected by the identity of the anion than by that of the cation.     

Retention time prediction of compounds in Grob standard mixture for apolar capillary columns in temperature-programmed gas chromatography

This paper presents an extension of a previous investigation in which the behavior of nonpolar compounds in temperature-programmed gas chromatographic runs was predicted using thermodynamic (entropy and enthalpy) parameters derived from isothermal runs. In a similar manner, entropy and enthalpy parameters were determined for a Grob standard mixture of compounds with widely varying chemical characteristics. These parameters were used to predict the retention times and chromatographic behaviors of the compounds on four gas chromatography capillary columns: three that had phenyl-based stationary phases (with degrees of substitution of 0%, 5% and 50%) and one with (50%) cyanopropyl substitution. The predictions matched data empirically obtained from temperature-programmed chromatographic runs for all of the compounds extremely well, despite the wide variations in polarity of both the compounds and stationary phases. Thus, the results indicate that such simulations could greatly reduce the time and material costs of chromatographic optimizations.     

Poly(ethylene oxide)-bonded stationary phase for capillary ion chromatography

Methyl-capped poly(ethylene oxide) moieties were chemically bonded to silica gel using an amine-reactive modification reagent and evaluated as the stationary phase for ion chromatography. In this work, primary amino groups of an aminopropylsilica packing material were reacted with methyl-PEO₁₂-NHS ester (succinimidyl-{[N-methyl]-dodecaethyleneglycol} ester) in phosphate buffer (pH 7.0) at room temperature. The prepared poly(ethylene oxide)-bonded stationary was evaluated for the separation of inorganic anions, and the retention behavior of inorganic anions on the prepared stationary phase was examined. The elution order of the investigated anions was the same as that observed in common ion chromatography. Both cations and anions of the eluent affected the retention of the analyte anions. Ion exchange was involved for the retention of analyte anions, although the present stationary phase does not possess any discrete ion-exchange sites. The stationary phase was applied to the separation of trace anions contained in tap water and a rock salt.     

Retention mechanism of calcium ferrite and compositions of ash on selenium during chemical looping gasification

Selenium pollution by coal utilization is of increasing concern. Calcium-iron (Ca–Fe) oxygen carriers (OCs) and alkali metal ions have strong inhibitory effects on selenium, which can reduce the emissions of selenium vapor. The retention mechanisms of selenium by Fe₂O₃, CaFe₂O₄, Ca₂Fe₂O₅ and bottom ash are investigated during chemical looping gasification (CLG). Iron-based OC can oxidize H₂Se(g) to SeO₂(g); furthermore, lattice oxygen is released by Fe₂O₃, contributing to the formation of an Fe–O–Se structure to retain selenium and form selenite. Because calcium ferrite is poorly oxidizing, it cannot oxidize H₂Se(g), but the CaO produced when OCs are reduced can react with H₂Se(g) to form CaSe(s), and this process can be promoted by H₂S(g). The best retention rates reached 32.301% when Ca₂Fe₂O₅ was used. In the cyclic experiment, the selenium retention of the bottom ash gradually increases. Alkali metal ions in bottom ash are the main factor in retaining selenium. Ca²⁺ and Mg²⁺ do not easily vaporize due to their high melting points; therefore, their selenium retention is significantly better than that of K⁺ and Na⁺. This research provided a new idea for the removal of selenium by using OCs and bottom ash particles during CLG.     

Back Cover: Low-Cost,High-Strength Cellulose-based Quasi-Solid Polymer Electrolyte for Solid-State Lithium-Metal Batteries (Angew. Chem. Int. Ed. 25/2023)

Solid-state lithium-metal batteries are considered as the next generation of high-energy-density batteries. However, their solid electrolytes suffer from low ionic conductivity, poor interface performance, and high production costs, restricting their commercial application. Herein, a low-cost cellulose acetate-based quasi-solid composite polymer electrolyte (C-CLA QPE) was developed with a high Li⁺ transference number ( ) of 0.85 and excellent interface stability. The prepared LiFePO₄ (LFP)|C-CLA QPE|Li batteries exhibited excellent cycle performance with a capacity retention of 97.7 % after 1200 cycles at 1 C and 25 °C. The experimental results and Density Function Theory (DFT) simulation revealed that the partially esterified side groups in the CLA matrix contribute to the migration of Li⁺ and enhance electrochemical stability. This work provides a promising strategy for fabricating cost-effective, stable polymer electrolytes for solid-state lithium batteries.