Facile synthesis of palladium right bipyramids and their use as seeds for overgrowth and as catalysts for formic acid oxidation.

Controlling the shape and thus facets of metal nanocrystals is an effective way to enhance their performance in catalytic reactions. While Pd nanocrystals with a myriad of shapes have been successfully prepared with good uniformity and in high yield, Pd right bipyramids (RBPs) that have a singly twinned structure have been elusive. We report a facile route based on polyol reduction for the synthesis of Pd RBPs with purity >90% and sizes controlled in the range 5-15 nm. The success of our synthesis relies on the use of iodide ions to manipulate the strength of an oxidative etchant and selectively cap the Pd{100} facets. The as-prepared RBPs could serve as seeds to generate a set of Pd nanocrystals with novel shapes and structures. The RBPs also exhibited enhanced catalytic activity toward formic acid oxidation, with a current density 2.5 and 7.1 times higher than those of the single-crystal Pd nanocubes (which were also mainly covered by {100} facets) and commercial Pd black, respectively.