Abstract
Modification with a protonic ionic liquid containing [7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (MTBD)][bis(pentafluoroethanesulfonyl)imide (beti)] enhanced the activities of the cathodic reactions of fuel cells (oxygen reduction reactions (ORR)) on Pt(111) and Pt(110), whereas it deactivated Pt(100). To elucidate the reaction mechanism, the ORR inhibiting species (PtOH) and the adsorption geometries of [MTBD][beti] on the low-index planes of Pt were studied using infrared reflection absorption spectroscopy (IRRAS). After modification with [MTBD][beti], the intensity of the bands representing PtOH decreased in the spectra of all the low-index planes. The adsorbed MTBD was tilted toward Pt(111) and vertically adsorbed onto Pt(110). On Pt(100), MTBD was adsorbed with its molecular plane parallel to the surface. Bands representing adsorbed beti were observed in the spectra of all surfaces. The increased ORR activities of the Pt(111) and Pt(110) surfaces were attributed to the decrease in PtOH formation after [MTBD][beti] modification and the low steric hindrance of the vertically adsorbed MTBD. Meanwhile, the deactivation of Pt(100) can be attributed to the increased steric hindrance of the parallel adsorption geometry of MTBD.
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