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While used in minor proportion respect to other components in cathode formulations, binders play a crucial role in lithium batteries cathode. This is particularly true in Li-O2 batteries which represent a very harsh environment mainly because of the formation, upon cycling, of very aggressive superoxide radicals. In such batteries, the use of catalyst in the cathode formulation is quite usual to help oxygen reduction reaction and oxygen evolution reaction (ORR and OER) to proceed rapidly and reversibly. However, the slightest binder degradation upon cycling can hinder the catalyst effects dramatically, modifying them to act on other reactions associated with the generated side-products, thus deteriorating cell performances and preventing researchers from drawing the right conclusions about catalytic properties of new materials. In this work, the influence of different catalysts in the degradation of the PVDF binder, on the performance of Li-O2 batteries, was investigated. The results obtained were compared with the ones of cathodes prepared with the same catalysts but Li-Nafion binder instead (already reported as stable), to further demonstrate that the choice of binder must be strongly linked to the nature of the catalyst. The catalysts employed for this study were α-MnO2, and commercial Co3O4, and Co phthalocyanines (CoPc).

In this work, a cationic porphyrin, ascribed as [Ttolyl(P-(C6H5)3)4]4+, where Ttolyl = 5,10,15,20 tetrakistolylporphyrin, was electrostatically assembled with CdTe quantum dots capped with glutathione (GSH) of diameter ~3.28 nm via a layer-by-layer methodology. This multilayer assembly was evaluated as a biocompatible interface with synergic effects for calf thymus double-stranded DNA (CT DNA) immobilization, considering that the hybrid assembly contains a cationic porphyrin with a high binding constant for CT DNA, and quantum dots with polypeptide as a capping agent. The multilayer assembly, ascribed as ITO/{[Ttolyl(P-(C6H5)3)4]4+/CdTe} n (n = 1–5), was characterized by UV-Vis spectroscopy, cyclic voltammetry, and electrochemical impedance spectroscopy (EIS). The last technique was explored in order to check the adsorption of CT DNA onto the multilayer porphyrin/quantum dot assembly. The difference in electron transfer resistance (ΔR ct) obtained after CT DNA incubations showed the best result for a specific multilayer assembly, n = 3. {[Ttolyl(P-(C6H5)3)4]4+/CdTe}3 showed a good correlation of ΔR ct with the logarithmic concentration of CT DNA, in the range 1.0 × 10−10 to 1.0 × 10−6 M with a limit of detection (LOD) of 1.5 × 10−12 M. Conversely, when the {[Ttolyl(P-(C6H5)3)4]4+/CdTe}3 system was incubated with calf thymus single-stranded DNA and salmon testes DNA, no significant difference in ΔR ct was observed. We conclude that the newly described {[Ttolyl(P-(C6H5)3)4]4+/CdTe} n system is a choice method for the impedimetric determination of CT DNA.

In this work, the modification of a glassy carbon electrode with tetraruthenated porphyrins electrostatically assembled onto a Nafion film, previously adsorbed on the electrode surface, is reported. This modified electrode was characterized by scanning electron microscopy–energy-dispersive X-ray, Raman spectroscopy, UV-Vis spectroelectrochemistry, and cyclic voltammetry. The Nafion film onto the glassy carbon electrode shows a smooth disposition; when the tetraruthenated porphyrin is incorporated on the Nafion film, the complex is adsorbed in a homogeneous way. The modified electrode catalyzes HSO 3 − oxidation in water–ethanol solutions and shows an enhanced stability compared with the electrode modified with the dip coating method. Rotating disk electrode experiments showed a kinetic limitation to the electron transfer controlled by charge propagation in the film. I/E curves show a Tafel slope of 120 mV/decade corresponding to a first electron-transfer reaction, depending on the potential, as the determining step. Spectroelectrochemical experiments demonstrated that Ru(II) is the active site for the electrocatalysis.