The effect of electrochemical oxygen pumping on the steady-state and oscillatory behavior of CO oxidation on polycrystalline PtThe effect of electrochemical oxygen pumping on the steady-state and oscillatory behavior of CO oxidation on polycrystalline Pt Peer-Reviewed Journal Publication Δημοσίευση σε Περιοδικό με Κριτές 2015-10-291988enThe effect of electrochemically pumping O2− to or from a porous polycrystalline Pt catalyst film used for CO oxidation at atmospheric pressure and temperatures 250–600 °C was studied. The Pt film served both as a catalyst and as an electrode of the solid electrolyte cell CO, O2, Full-size image (<1 K) (Full-size image (<1 K). Under open-circuit conditions the Pt catalyst film operates as a regular CO oxidation catalyst. It was found that electrochemical O2− pumping has a dramatic non-Faradaic effect on the steady-state and oscillatory behavior of CO oxidation on Pt. The steady-state reaction rate typically increases or decreases by a factor of 2 but a 500% increase in reaction rate is observed under severely reducing conditions. The induced changes in reaction rate are typically two orders of magnitude higher than the rate of O2− transfer to or from the catalyst and are always accompanied by the appearance of activation overpotential at the catalyst electrode. Reaction rate oscillations can be induced or stopped at will by adjusting the rate of O2− transfer and consequently the potential of the catalyst-electrode. The frequency of electrochemically induced oscillations is linearly related to the applied O2− current. The observed phenomena are completely reversible and are due to electrochemically induced changes in the oxidation state and catalytic properties of the platinum surface. These changes appear to result from changes in the work function of the metal due to the interaction of O anions with the Pt surface. The very pronounced reaction rate increase upon O2− removal under reducing conditions appears to be caused by CO decomposition followed by fast carbon combustion by gaseous O2.http://creativecommons.org/licenses/by/4.0/Journal of Catalysis1111170-188 Gentekakis Ioannis Γεντεκακης Ιωαννης Vayenas, Costas G Elsevier CO oxidation Catalysis