Stability of metallo-porphyrin networks under oxygen reduction and evolution conditions in alkaline media.

Autor: Hötger D; Max Planck Institute for Solid State Research, 70569 Stuttgart, Germany. r.gutzler@fkf.mpg.de., Etzkorn M, Morchutt C, Wurster B, Dreiser J, Stepanow S, Grumelli D, Gutzler R, Kern K
Jazyk: angličtina
Zdroj: Physical chemistry chemical physics : PCCP [Phys Chem Chem Phys] 2019 Jan 30; Vol. 21 (5), pp. 2587-2594.
DOI: 10.1039/c8cp07463a
Abstrakt: Transition metal atoms stabilised by organic ligands or as oxides exhibit promising catalytic activity for the electrocatalytic reduction and evolution of oxygen. Built-up from earth-abundant elements, they offer affordable alternatives to precious-metal based catalysts for application in fuel cells and electrolysers. For the understanding of a catalyst's activity, insight into its structure on the atomic scale is of highest importance, yet commonly challenging to experimentally access. Here, the structural integrity of a bimetallic iron tetrapyridylporphyrin with co-adsorbed cobalt electrocatalyst on Au(111) is investigated using scanning tunneling microscopy and X-ray absorption spectroscopy. Topographic and spectroscopic characterization reveals structural changes of the molecular coordination network after oxygen reduction, and its decomposition and transformation into catalytically active Co/Fe (oxyhydr)oxide during oxygen evolution. The data establishes a structure-property relationship for the catalyst as a function of electrochemical potential and, in addition, highlights how the reaction direction of electrochemical interconversion between molecular oxygen and hydroxyl anions can have very different effects on the catalyst's structure.
Databáze: MEDLINE