Oscillatory instabilities during formic acid oxidation on Pt(100), Pt(110) and Pt(111) under potentiostatic control. I. Experimental

Abstract

The experimental characterization of the current/outer potential (I/U) behavior during the electrochemical CO oxidation on Pt(100), Pt(110) and Pt(111) is used as the first step towards a thorough investigation of the processes occurring during the electrochemical formic acid oxidation. The CO study is followed by new cyclovoltammetric results during the electrochemical formic acid oxidation on the corresponding Pt single crystals. At high concentrations of formic acid, the cyclovoltammograms revealed a splitting of the large current peak observed on the cathodic sweep into two peaks whose dependence on scan rate and reverse potential was investigated. It turned out that the presence of a sufficiently large ohmic resistance R was crucial for oscillatory instabilities. Given an appropriate resistance, all three Pt surfaces were found to exhibit current oscillations at both low and high formic acid concentrations. On Pt(100) stable mixed-mode oscillations were observed. In addition, the sensitivity of the oscillations to stirring was investigated. Whereas the period-1 oscillations were found to be independent of stirring, the mixed-mode oscillations transformed into simple oscillations with stirring. The mechanism giving rise to instability and oscillations is described.