Pathways for the Non‐CO‐Involved Oxidation of Methanol on Pt(111)

The non‐CO‐involved oxidation of methanol (NCOIOM) on a Pt(111) surface is investigated by using density functional theory. Relative energy diagrams for the NCOIOM are established in which the reaction mechanisms for a catalytic cycle—including the associated barriers, the reactive energies, the intermediates, and the transient states—are shown. The results indicate that the reaction proceeds via the kinetically favored pathways: A) HCOH→HC(OH)₂→HCOOH→HCOO‐ ‐COOH]→CO₂ and B) CHO→HCOOH→HCOO‐ ‐COOH]→CO₂, with OH playing a key role in the entire process. The vibrational frequencies of the intermediate states derived from the calculations are in agreement with the experimental measurements.