RESUMO
Although they exhibit huge versatility, coordination complexes have been rarely investigated in the field of cathode materials for batteries. Despite their relatively high molecular mass, according to the nature of the metallic center and that of the ligand, the E° value and the electron transfer kinetics can be adjusted to develop a performant material compatible with the electrolyte. Here, we propose to investigate FeII poly-bipyridine complexes with a view to check the impact of the nature of the electrolyte as well as the influence of the distance between two redox centers when polymerized on the electrochemical response in battery conditions. To understand these changes, three lithium salts have been studied: LiClO4, LiPF6 and LiTFSI (TFSI = bis(trifluoromethane)sulfonimide). In order to mimic these impacts, monomer complexes (mono- and binuclear) have been electrochemically studied, whereas, thanks to ab initio calculations, their redox behavior has been correlated to the ligand environment of the metallic center. Finally, despite their expected low mass capacity, these polymeric coordination complexes have been involved in battery conditions.
RESUMO
Tuning the surface structure at the atomic level is of primary importance to simultaneously meet the electrocatalytic performance and stability criteria required for the development of low-temperature proton-exchange membrane fuel cells (PEMFCs). However, transposing the knowledge acquired on extended, model surfaces to practical nanomaterials remains highly challenging. Here, we propose 'surface distortion' as a novel structural descriptor, which is able to reconciliate and unify seemingly opposing notions and contradictory experimental observations in regards to the electrocatalytic oxygen reduction reaction (ORR) reactivity. Beyond its unifying character, we show that surface distortion is pivotal to rationalize the electrocatalytic properties of state-of-the-art of PtNi/C nanocatalysts with distinct atomic composition, size, shape and degree of surface defectiveness under a simulated PEMFC cathode environment. Our study brings fundamental and practical insights into the role of surface defects in electrocatalysis and highlights strategies to design more durable ORR nanocatalysts.