The electrochemical behaviors of dimethyl ether (CH(3)-O-CH(3), DME), which is a promising fuel for the fuel cell, on Pt(1 0 0) electrode in 0.5 M H(2)SO(4) solution have been investigated in detail by electrochemical and in situ infrared (IR) measurements. As the potential is swept from 0.05 V (vs. RHE) to positive direction at 50 mV s(-1), the dehydrogenation peak of DME is observed around 0.33 V to generate a reaction intermediate and is further converted to carbon monoxide (CO) in more positive potential region. The main peak for DME bulk oxidation locates around 0.80 and 0.72 V in the positive- and negative-going potential sweep, respectively. The positions of these peaks strongly depend on the scan rate. The in situ IR observations show that (CH(3)OCH(2)-)(ad) is an intermediate for the first dehydrogenation step of DME on Pt(1 0 0) surface and can serve as a precursor of the subsequent intermediate of adsorbed CO (CO(ad)). Cyclic voltammograms of Pt high index single crystal planes Pt(hkl) show that the direct oxidation of DME is suppressed by decreasing the (1 0 0) terrace width. Based on these results, a possible reaction mechanism for DME electro-oxidation on the platinum single crystal electrode surface is proposed. (C) 2010 Elsevier B.V. All rights reserved.