Non-PGM Electrocatalysts for PEM Fuel Cells: A DFT Study on the Effects of Fluorination of FeNx-Doped and N-Doped Carbon Catalysts

Fluorination is considered as a means of reducing the degradation of Fe/N/C, a highly active FeNx-doped disorganized carbon catalyst for the oxygen reduction reaction (ORR) in PEM fuel cells. Our recent experiments have, however, revealed that fluorination poisons the FeNx moiety of the Fe/N/C catalytic site, considerably reducing the activity of the resulting catalyst to that of carbon only doped with nitrogen. Using the density functional theory (DFT), we clarify in this work the mechanisms by which fluorine interacts with the catalyst. We studied 10 possible FeNx site configurations as well as 2 metal-free sites in the absence or presence of fluorine molecules and atoms. When the FeNx moiety is located on a single graphene layer accessible on both sides, we found that fluorine binds strongly to Fe but that two F atoms, one on each side of the FeNx plane, are necessary to completely inhibit the catalytic activity of the FeNx sites. When considering the more realistic model of a stack of graphene layers, only one F atom is needed to poison the FeNx moiety on the top layer since ORR hardly takes place between carbon layers. We also found that metal-free catalytic N-sites are immune to poisoning by fluorination, in accordance with our experiments. Finally, we explain how most of the catalytic activity can be recovered by heating to 900 °C after fluorination. This research helps to clarify the role of metallic sites compared to non-metallic ones upon the fluorination of FeNx-doped disorganized carbon catalysts.

Biodiesel Production from Waste Frying Oils by Potassium Methoxide Supported on Activated Carbon Catalysts from Lignocellulosic Biomass

Various carbon-rich solid catalysts are evaluated for the synthesis of biodiesel from waste frying oil. The study results showed that the use of activated carbon made of corn stalk could increase the biodiesel yield by 7%. The heterogeneous carbon-based catalysts made of lignocellulosic residues could successfully improve the quality of biodiesel properties. The results obtained revealed that the biodiesel properties, including relative density (852–900 kg·m−3) and kinematic viscosity (2.4–3.9 mm2·s−1), are in compliance with the standard limits of ASTM and the European Biodiesel Standard, suggesting that the biodiesel produced would be decent as a diesel fuel that potentially can minimize the serious damage of engine parts, and prolong the engine life.