Impedance spectroscopic investigation of a Rh/YSZ catalyst under polarization

Electrochemical impedance spectra at 450–600 °C and \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$${P_{{\rm{O}}_{\rm{2}} } = 0.5}$$\end{document} kPa of a rhodium catalyst interfaced with yttria-stabilized-zirconia (Rh/YSZ) were compared with a model based on the mechanism of electrochemical promotion. In the proposed equivalent electric circuit, existence of an “effective” double layer at the gas-exposed catalyst surface and its potential-controlled modification via diffusion of oxygen ions between the O2− conducting solid electrolyte support (YSZ) and the catalyst are represented by two additional elements: adsorption capacitance and Warburg impedance. Under positive polarization, the adsorption capacitance increases dramatically indicating reinforcement of the “effective” double layer at the catalyst/gas interface, in agreement with the observation known from electrochemical promotion practice that positive polarization of a rhodium electrode leads to rhodium oxide reduction, hence, to dramatic increase in catalytic reaction rate.