Abstract
The formation and oxidation of the linear CO(a) from CH 3OH and HCOOH on a platinum electrode in 0.5 M H 2SO 4 has been studied by using in-situ polarization modulated infrared reflection-absorption spectroscopy as a function of the electrode potential. The formation from CH 3OH is greatly reduced in the hydrogen region, while from HCOOH it occurs more readily in the hydrogen region than at 0.4 V (vs. RHE). Linear CO(a) is oxidized off the Pt surface in a narrow potential range around 0.5 V, after which the rate of the electrooxidation of CH 3OH and HCOOH increases sharply. The poisoning effect of linear CO(a) was also confirmed by the rapid development of the infrared absorption intensity of the linear CO(a) band during continuous decrease of the electrocatalytic activity with time while the electrode was held at 0.4 and 0.2 V for methanol and formic acid, respectively. Reaction schemes to produce CO(a) from HCOOH and CH 3OH in both the hydrogen region and the double-layer region are proposed.
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