Highly active Pt3Pb and core-shell Pt3Pb-Pt electrocatalysts for formic acid oxidation.

Formic acid is a promising chemical fuel for fuel cell applications. However, due to the dominance of the indirect reaction pathway and strong poisoning effects, the development of direct formic acid fuel cells has been impeded by the low activity of existing electrocatalysts at desirable operating voltage. We report the first synthesis of Pt(3)Pb nanocrystals through solution phase synthesis and show they are highly efficient formic acid oxidation electrocatalysts. The activity can be further improved by manipulating the Pt(3)Pb-Pt core-shell structure. Combined experimental and theoretical studies suggest that the high activity from Pt(3)Pb and the Pt-Pb core-shell nanocrystals results from the elimination of CO poisoning and decreased barriers for the dehydrogenation steps. Therefore, the Pt(3)Pb and Pt-Pb core-shell nanocrystals can improve the performance of direct formic acid fuel cells at desired operating voltage to enable their practical application.