Probing Changes in the Local Structure of Active Bimetallic Mn/Ru Oxides during Oxygen Evolution.

Identifying the active site of catalysts for the oxygen evolution reaction (OER) is critical for the design of electrode materials that will outperform the current, expensive state-of-the-art catalyst, RuO2. Previous work shows that mixed Mn/Ru oxides show comparable performances in the OER, while reducing reliance on this expensive and scarce Pt-group metal. Herein, X-ray photoelectron spectroscopy and X-ray absorption spectroscopy (XAS) are performed on mixed Mn/Ru oxide materials for the OER to understand structural and chemical changes at both metal sites during oxygen evolution. The results show that the Mn-content affects both the oxidation state and local coordination environment of Ru sites. Operando XAS experiments suggest that the presence of MnOx might be essential to achieve high activity likely by facilitating changes in the O-coordination sphere of Ru centers.

Charge-Transfer Complex of p-Aminodiphenylamine with Maleic Anhydride: Spectroscopic, Electrochemical, and Physical Properties.

A new charge-transfer complex and the amide formed by the interaction between the electron donor of the p-aminodiphenylamine and the electron acceptor of maleic anhydride are investigated by spectroscopic methods. The amidation reaction is caused by proton and charge transfer between the maleic anhydride and p-aminodiphenylamine molecules. The Benesi-Hildebrand equation is used to determine the formation constant, the molar extinction coefficient and the standard Gibbs free energy of the complex by using UV/Vis spectroscopy. To reveal the electronic and spectroscopic properties of these molecules, theoretical computations are performed on the structures of maleic anhydride, p-aminodiphenylamine and the conformers of their charge-transfer complex. The charge-transfer complex and amidation reaction mechanism are also confirmed by IR and NMR spectroscopy and HRMS. The nature of the maleic anhydride-p-aminodiphenylamine complex is characterized by cyclic voltammetry, thermogravimetric analysis, XRD and SEM. Solid microribbons of this complex show higher thermal stability than p-aminodiphenylamine.

The effect of synthesis media on the properties of substituted polyaniline/chitosan composites.

Substituted polyaniline/chitosan (sPANI/Ch) composites were chemically synthesized in H(2)SO(4) and CH(3)COOH synthesis media. Structural and physical properties of the composites were characterized by using FTIR, SEM, TGA, UV-vis, XRD techniques, and conductivity measurements. The effect of synthesis media on morphology, thermal stability, conductivity, and crystalline properties was investigated. Chemical interactions between substituted polyanilines and chitosan were explained using FTIR spectra results. The different morphological surfaces were observed in SEM images of the composites. The size of the substituted polyaniline/chitosan (sPANI/Ch) composites was in nanoscale, and the composites synthesized in acetic acid media showed smaller structures than those of H(2)SO(4) media and pure chitosan. It was interpreted from XRD results that the composites have amorphous structure and the PNEANI/Ch-CH(3)COOH composite has the highest crystallinity.