Influence of the catalyst layer thickness on the determination of the OER activity of Fe3O4@CoFe2O4 core-shell nanoparticles

Transition metal oxides-based catalytic layers often present a complex 3D porous architecture affecting the evaluation of their intrinsic electrocatalytic activity. In this work the oxygen evolution reaction activity of core-shell Fe3O4@CoFe2O4 nanoparticles combining a conductive magnetite core and a catalytically active cobalt ferrite shell was studied at different loading and thickness of the catalytic layer. It was observed that their apparent activity is decreasing and that the Tafel slopes are becoming convex when the loading increases. The activity decay could be attributed to the significant resistance to charge transport in the thick porous catalyst layer. This resistance could be estimated by fitting the electrochemical impedance spectra using the transmission line model. The influence of the layer thickness on the experimental current-potential curves and on their Tafel slopes could be simulated using a simple model based on the Telegrapher's equations. It is concluded that in order to measure accurately the activity and Tafel slopes of an electrocatalyst, thin layers must be used, notably for catalyst layers that are not highly conductive.