Identification of electrochemical reaction kinetics by dynamic methods

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Electrochemical energy conversion technologies are often seen as key components for the transition to an economy that is powered by renewable energy sources. Knowledge-based design and systematic improvement of electrochemical processes is only possible if the underlying reaction kinetics are well understood. This work is based on the hypothesis that a combination of dynamic electrochemical methods, in-operando techniques, and simulations is a feasible and advantageous way towards the determination of electrochemical reaction kinetics. To demonstrate advantages of such a combined approach, four model systems are studied. Differential electrochemical mass spectrometry (DEMS) data and electrochemical data is used to parameterise physical models of the CO and methanol electrooxidation. The second part covers bioelectrochemical reactions. The first DEMS results on acetate oxidation in electrochemically active biofilms are presented, and storage mechanisms for charge as well as substrate are quantified. Furthermore, conversion pathways and rate constants in bioelectrochemical glycerol oxidation are investigated. In conclusion, it is demonstrated that the identification of electrochemical macrokinetics benefits significantly from the application of dynamic techniques, concentration measurements, physical simulation models.