Detailed surface vs. bulk composition studies of LaxCa1−xMnO3 oxides provide clear evidence that the ORR activity increases as the effective electron population at the Mn site increases.
General rightsThis document is made available in accordance with publisher policies. Please cite only the published version using the reference above. Abstract: The kinetics of the oxygen reduction reaction (ORR) at carbon supported transition metal oxides in alkaline solutions is systematically investigated as a function of the nature of the B-site. The study is focused on LaBO3 (B = Cr, Co, Fe, Mn and Ni) nanoparticles synthesized by an ionic liquid route, offering fine control over phase purity and composition. Activity towards the ORR was compared with commercial Pt/Etek catalyst. Detailed electrochemical analysis employing a rotating ring-disc electrode provides conclusive evidences that the carbon support plays an important contribution in the faradaic responses. Decoupling the contribution of the carbon support uncovers that the reactivity of LaMnO3 towards the 4e-ORR pathway is orders of magnitude higher than for the other lanthanides. We rationalise these observations in terms of changes in the redox state at the B-site close to the formal oxygen reduction potential.
Thermal decomposition of citric acid is one of the most common synthesis methods for fluorescent carbon dots; the reaction pathway is, however, quite complex and the details are still far from being understood. For instance, several intermediates form during the process and they also give rise to fluorescent species. In the present work, the formation of fluorescent C‐dots from citric acid has been studied as a function of reaction time by coupling infrared analysis, X‐ray photoelectron spectroscopy, liquid chromatography/mass spectroscopy (LC/MS) with the change of the optical properties, absorption and emission. The reaction intermediates, which have been identified at different stages, produce two main emissive species, in the green and blue, as also indicated by the decay time analysis. C‐dots formed from the intermediates have also been synthesised by thermal decomposition, which gave an emission maximum around 450 nm. The citric acid C‐dots in water show short temporal stability, but their functionalisation with 3‐aminopropyltriethoxysilane reduces the quenching. The understanding of the citric acid thermal decomposition reaction is expected to improve the control and reproducibility of C‐dots synthesis.
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