关键词: 氧化, 反应机理, 银, 甲醇, 从头计算法, 表面吸附, 原子簇

The equilibrium geometries and properties of stationary adsorbates which are produced in the process of oxidation of methanol over silver surface have been calculated by the cluster model with ab initio method, Our calculations show that methanol and formaldehyde have only weak physisorption on clean silver surface; if there is adsorbed oxygen atom O(a) on the surface, methanol can form two stable molecular chemisorption states; formaldehyde can coadsorb with OH(a) or H(a) on silver surface, and adsorbed formaldehyde is very easy to react with O(a) to form η^2-methylendioxy; the intermedidate methoxide can form stable adsorption on clean silver surface and it can easily react with the oxygen on the oxygen-rich silver surface to form formaldehyde. By comparing calculations with experiments, the reaction mechanism of oxidation of methanol over silver surface has been discussed.

Key words: OXIDATION, REACTION MECHANISM, SILVER, METHANOL, AB INITIO CALCULATION, SURFACES ADSORPTION