Enhanced oxygen reduction reaction on caffeine-modified platinum single-crystal electrodes

Abstract Enhancing the activity of the oxygen reduction reaction (ORR) is crucial for fuel cell development, and hydrophobic species are known to increase the ORR activity. This paper reports that caffeine enhanced the specific ORR activity of Pt(111) 11-fold compared to that without caffeine in a 0.1 M HClO 4 aqueous solution. Moreover, caffeine increased the ORR activity of Pt(110) 2.5-fold; however, the activity of Pt(100) was unaffected. The infrared (IR) band of PtOH (blocking species of the ORR) decreased for all the surfaces. Caffeine was adsorbed with its molecular plane perpendicular to the Pt(111) and Pt(110) surfaces and tilted relative to the Pt(100) surface. Thus, the effects of caffeine on the ORR activity can be rationalized by a decrease in PtOH coverage and the difference in adsorption geometry of caffeine.