Showing papers by "Edson A. Ticianelli published in 2022"

Electrochemical Transformation of Fe-N-C catalysts into Iron Oxides in Alkaline Medium and Its Impact on the Oxygen Reduction Reaction Activity

Abstract: Precious metal-free Fe-N-C catalysts efficiently electrocatalyze the oxygen reduction reaction both in acid and alkaline electrolyte. Their stability is however limited in acidic medium, but generally accepted to be much higher in alkaline electrolyte. Herein, by combining advanced electron and X-ray based techniques, we provide comprehensive evidence of a Fe dissolution/reprecipitation mechanism, which partially transforms single Fe atoms into Fe oxide nanoparticles and Fe carbide nanoparticles into Fe carbide [email protected] oxide shell nanoparticles, and is independent on the gas atmosphere used during the accelerated stress tests. Our work shows that Fe-N-C materials based on zero-valent Fe nanoparticles should be designed so that all Fe nanoparticles are protected by a defect-free graphite shell, for improved durability. For single atom Fe-N-C catalysts, the present study raises the question of a possible synergy between minute amount of Fe oxide nanoparticles and Fe-NxCy single-atom sites, leading to the higher apparent durability of this catalyst.

Effects of Metal–Support Interaction in the Electrocatalysis of the Hydrogen Evolution Reaction of the Metal-Decorated Titanium Dioxide Supported Carbon

Abstract: It has been found that the electrocatalytic properties of metallic nanoparticles supported on transition metal oxides are affected by the existing strong metal–support interaction (SMSI). Herein, the effects of SMSI on the electrocatalysis of the hydrogen evolution reaction (HER) were investigated in acid electrolyte by using Pt and Ag nanoparticles supported on carbon and titanium oxide (TiO2). High-resolution transmission electron microscopy (HR–TEM) images showed that Pt and Ag nanoparticles present a spherical shape at the TiO2 support and an average size distribution of around 4.5 nm. The X-ray photoelectron spectroscopy (XPS) results for Pt/TiO2/C and Ag/TiO2/C evidenced higher amounts of surface oxides in the metallic particles, when compared to the materials supported on carbon. Consistently, electrode polarization and electrochemical impedance results revealed that both metal–TiO2 and metal–C-supported catalysts were more active in catalyzing the HER than the corresponding carbon-supported materials, with Pt presenting better results. These differences in the HER activities were related to the electronic effects of the TiO2/C substrate on the Pt and Ag metals, introduced by strong metal-support (SMSI) in the metal–TiO2/C catalysts.