Tunable Metal-Free Imidazole-Benzimidazole Electrocatalysts for Oxygen Reduction in Aqueous Solutions.

A series of metal-free imidazole-benzimidazole catalysts (ImBenz-H, ImBenz-NO2 , ImBenz-OCH3 ) for oxygen reduction reaction (ORR) were prepared. We demonstrate that the electrocatalytic O2 reduction by ImBenz-NO2 with the electron-withdrawing group showed high selectivity toward H2 O with the number of electrons transferred (n=3.7) in a neutral aqueous solution. The highest ORR selectivity toward H2 O2 was achieved using ImBenz-H (n=2.4) in an alkaline solution. Electrochemical studies of reaction kinetics disclosed that the highest turnover frequencies were obtained from ImBenz-H in both neutral and alkaline aqueous solutions. The results prove that the ORR selectivity is tunable by modulating the substituent of the ImBenz catalysts. Furthermore, DFT calculations suggested that the ORR mechanism of ImBenz-H involves the electron transfer from imidazole-benzimidazole to O2 resulting in the formation of H2 O2 which supports the redox active properties of the catalysts ImBenz.

Selective Separation of Lithium, Magnesium and Calcium using 4-Phosphoryl Pyrazolones as pH-Regulated Receptors.

Ensuring continuous and sustainable lithium supply requires the development of highly efficient separation processes such as LLE (liquid-liquid extraction) for both primary sources and certain waste streams. In this work, 4-phosphoryl pyrazolones are used in an efficient pH-controlled stepwise separation of Li+ from Ca2+ , Mg2+ , Na+ and K+ . The factors affecting LLE process, such as the substitution pattern of the extractant, diluent/water distribution, co-ligand, pH, and speciation of the metal complexes involved, were systematically investigated. The maximum extraction efficiency of Li+ at pH 6.0 was 94 % when Mg2+ and Ca2+ were previously separated at pH<5.0, proving that the separation of these ions is possible by simply modulating the pH of the aqueous phase. Our study points a way to separation of lithium from acid brine or from spent lithium ion battery leaching solutions, which supports the future supply of lithium in a more environmentally friendly and sustainable manner.

Bis-BODIPY linked-triazole based on catechol core for selective dual detection of Ag+ and Hg2.

Herein, we introduced a new chemosensor, bis-BODIPY linked-triazole based on catechol (BODIPY-OO) prepared by bridging two units of BODIPY fluorophore/triazole binding group with a catechol unit. A solution of this compound displayed 4- and 2-fold enhancements in fluorescence intensity after adding a mole equivalent amount of Ag+ and Hg2+ ions in methanol media, respectively. 1H NMR titrations of BODIPY-OO with Ag+ and Hg2+ suggested that the triazole was involved in the recognition process. BODIPY-OO showed high sensitivity toward Ag+ and Hg2+ over other metal ions with detection limits of 0.45 µM and 1 µM, respectively. It can also distinguish Hg2+ from Ag+ by addition of an EDTA. This compound can therefore be employed as practical fluorescent probe for monitoring the presence of Ag+ and Hg2+ ions.

Iron oxide/cassava starch-supported Ziegler-Natta catalysts for in situ ethylene polymerization.

Iron oxide nanoparticles were used as supporters for in situ polymerization to produce polymer nanocomposites with well-dispersed fillers in polymer matrix. Iron oxide could be sustained as colloidal solutions by cassava starch to produce a good dispersion of iron oxide in the matrix. New supports based on iron oxide/cassava starch or cassava starch for Ziegler-Natta catalysts were utilized as heterogeneous supporters for partially hydrolyzed triethylaluminum. Then, TiCl4 was immobilized on the supports as catalysts for polymerization of ethylene. High-density polyethylene (HDPE) composites were obtained by the synthesized catalysts. A good dispersion of iron oxide/cassava starch particles was observed in the synthesized polymer matrix promoting to good mechanical properties of HDPE.