Journal of Applied Electrochemistry, Vol.38, No.8, 1075-1082, 2008
The phenomenon of "permanent" electrochemical promotion of catalysis (P-EPOC)
The phenomenon of electrochemical promotion of catalysis (EPOC) is most often fully reversible. Subsequent to long-lasting polarization, however, the new steady-state open-circuit catalytic activity after current interruption may remain significantly higher than that before polarization. This phenomenon, discovered in our laboratory in the late 1990s and called permanent electrochemical promotion of catalysis (P-EPOC), has been observed on both oxide (IrO2, RuO2) and metal (Rh) catalysts. P-EPOC is out of the state-of-the-art model of reversible EPOC, which considers the gas-exposed catalyst surface as the unique location of charge storage via backspillover of electrochemically generated promoter species accompanied by their consumption in the catalytic reaction ('sacrificial' promoter). Double step chronoamperometric and linear sweep voltammetric characterization of Pt catalyst deposited on YSZ solid electrolyte revealed the existence of a somewhat delayed oxygen storage occurring at the vicinity of the catalyst/electrolyte interface during prolonged anodic polarization. It is proposed that oxygen stored at this location, hidden for the reactant, and then released during relaxation was at the origin of P-EPOC on the Pt/YSZ catalyst observed in catalytic combustion of ethylene with oxygen. The effect of this 'hidden' promoter on the catalytic reaction rate was found to be highly non-Faradaic.