Elucidation of Electrochemical Oxidation Mechanism of DME on Platinum Single Crystalline Electrodes

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The kinetics and mechanisms for electro-oxidation of dimethyl ether (DME) on platinum single crystal and polycrystalline electrodes have been investigated. In addition to the conventional electrochemical technique, in situ infrared spectroscopy and EC-STM measurements have been employed to characterize the reaction intermediates/products on the electrode surface. It was found the oxidation activities are significantly dependent on the surface structures of Pt electrodes. Pt(100) showed the highest activity in DME oxidation in the high overpotential region where DME was oxidized through methoxy to CO_2. On the other hand, DME was also sequentially decomposed to (CH_3OCH_2)_<ad> and (CO)_<ad> in the lower overpotential region. Based on the time-resoled IR measurement, we are able to quantitatively analyze the oxidation kinetics behaviors and propose a reaction mechanism for the oxidation process for DME.