Surface electrochemistry of CO and methanol at 25-75 degrees C probed in situ by infrared spectroscopy

Effects of temperature and CO partial pressure on the adsorption of carbon monoxide at a polycrystalline platinum electrode in 0.1 M HClO4 were studie d with cyclic voltammetry and infrared spectroscopy. Appreciable CO coverag es were detected with infrared spectroscopy from ambient up to the high-tem perature limit of the experiments (75 degrees C). In CO saturated solution, voltammograms were dominated by the diffusion-controlled current arising f rom the oxidation of bulk CO. However, under these conditions the adsorbed CO layer was readily detected with infrared spectroscopy. At 75 degrees C, a strong atop CO band (2075-2080 cm(-1)) was observed at double layer and h ydrogen adsorption potentials. Loss of the adlayer due to oxidation cm occu rred at potentials positive of 0.3 V (vs KCI saturated Ag/AgCl). In GO-free electrolyte solution, atop CO band intensities measured at 75 degrees C we re lower than those recorded in CO saturated solution by about 50%, and the adlayer was more easily oxidized. CO formed from solutions of 0.3 M methan ol in 0.1 M HClO4 was detected at 25 and 50 degrees C. Temperature did not have a strong effect on the equilibrium methanolic CO coverages under these conditions.