Electro-Oxidation of CO Saturated in 0.1 M HClO4 on Basal and Stepped Pt Single-Crystal Electrodes at Room Temperature Accompanied by Surface Reconstruction

Abstract

The electro-oxidation of CO on Pt surface is not only fundamentally important in electrochemistry, but also practically important in residential fuel cells for avoiding the poisoning of Pt catalysts by CO. We carried out cyclic voltammetry on Pt(111), (110), (100), (10 10 9), (10 9 8), (10 2 1), (432), and (431) single-crystal surfaces using a three compartment cell to understand the activity and durability towards the electro-oxidation of CO saturated in 0.1 M HClO4. During the potential cycles between 0.07 and 0.95 V vs. the reversible hydrogen electrode, the current for the electro-oxidation of CO at potentials lower than 0.5 V disappeared, accompanied by surface reconstruction. Among the electrodes, the Pt(100) electrode showed the lowest onset potential of 0.29 V, but the activity abruptly disappeared after one potential cycle; the active sites were extremely unstable. In order to investigate the processes of the deactivation, potential-step measurements were also conducted on Pt(111) in a CO-saturated solution. Repeated cycles of the formations of Pt oxides at a high potential and Pt carbonyl species at a low potential on the surface were proposed as the deactivation process.