The use of a ribbon-shaped Pt electrode gives rise to edge effects of the interfacial potential, as is predicted from the potential theory in the form of the corresponding reaction-migration equation. They are studied in the bistable region of formic acid oxidation. Essentially, the edges tend to be more passive than the bulk of the electrode, which also causes a passivation (activation) transition to originate from the edges (center) of the ribbon. The experimental results are in agreement with simulations of the reaction-migration system.
In the operation of a direct methanol fuel cell, the modification by chloride ions on the surface of a Pt cathode can facilitate the extraordinary increase of power performance and long-term stability. Analyzing the results of cyclic voltammograms and electrochemical impedance spectroscopy, the positive shift of Pt oxidation onset potential and the depression of oxidation current are observed, which results from the role of chloride as surface inhibitor. In addition, O(2) temperature-programmed desorption and X-ray photoelectron spectroscopy also reveal that the suppression of Pt surface oxide can be best understood in terms of lower binding of oxygen species by the alteration of electronic state of Pt atoms. Such a reduced surface oxide formation not only provides more efficient proton adsorption sites with high selectivity but also decreases the mixed potential by crossover methanol, resulting in higher performance and stability even under high voltage long-term operation.
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