Pt17 nanocluster electrocatalysts: preparation and origin of high oxygen reduction reaction activity.

We recently found that [Pt17(CO)12(PPh3)8]z (Pt = platinum; CO = carbon monoxide; PPh3 = triphenylphosphine; z = 1+ or 2+) is a Pt nanocluster (Pt NC) that can be synthesized with atomic precision in air. The present study demonstrates that it is possible to prepare a Pt17-supported carbon black (CB) catalyst (Pt17/CB) with 2.1 times higher oxygen reduction reaction (ORR) activity than commercial Pt nanoparticles/CB by the adsorption of [Pt17(CO)12(PPh3)8]z onto CB and subsequent calcination of the catalyst. Density functional theory calculation strongly suggests that the high ORR activity of Pt17/CB originates from the surface Pt atoms that have an electronic structure appropriate for the progress of ORR. These results are expected to provide design guidelines for the fabrication of highly active ORR catalysts using Pt NCs with a diameter of about 1 nm and thereby enabling the use of reduced amounts of Pt in polymer electrolyte fuel cells.

Simple and high-yield preparation of carbon-black-supported ∼1 nm platinum nanoclusters and their oxygen reduction reactivity.

The improvement of oxygen reduction reaction (ORR) catalysts is essential before polymer electrolyte fuel cells can be used widely. To this end, we established a simple method for the size-selective synthesis of a series of ligand-protected platinum nanoclusters with ∼1 nm particle size (Ptn NCs; n = ∼35, ∼51, and ∼66) and narrow size distribution (±âˆ¼4 Pt atoms) under atmospheric conditions. Using this method, each ligand-protected ∼1 nm Pt NC was obtained in a relatively high yield (nearly 80% for Pt∼66). We succeeded in adsorbing each ligand-protected ∼1 nm Pt NC on carbon black (CB) and then removing most of the ligands from the surface of the Pt NCs via calcination while maintaining the original size. The obtained Pt∼35/CB, Pt∼51/CB, and Pt∼66/CB exhibited ORR mass activities that were 1.6, 2.1, and 1.6 times higher, respectively, than that of commercial CB supported-Pt nanoparticles, and also display high durability.