Synthesis of Chemically Ordered Pt3Fe/C Intermetallic Electrocatalysts for Oxygen Reduction Reaction with Enhanced Activity and Durability via a Removable Carbon Coating.

Recently, Pt3M (M = Fe, Ni, Co, Cu, etc.) intermetallic compounds have been highlighted as promising candidates for oxygen reduction reaction (ORR) catalysts. In general, to form those intermetallic compounds, alloy phase nanoparticles are synthesized and then heat-treated at a high temperature. However, nanoparticles easily agglomerate during the heat treatment, resulting in a decrease in electrochemical surface area (ECSA). In this study, we synthesized Pt-Fe alloy nanoparticles and employed carbon coating to protect the nanoparticles from agglomeration during heat treatment. As a result, Pt3Fe L12 structure was obtained without agglomeration of the nanoparticles; the ECSA of Pt-Fe alloy and intermetallic Pt3Fe/C was 37.6 and 33.3 m2 gPt-1, respectively. Pt3Fe/C exhibited excellent mass activity (0.454 A mgPt-1) and stability with superior resistances to nanoparticle agglomeration and iron leaching. Density functional theory (DFT) calculation revealed that, owing to the higher dissolution potential of Fe atoms on the Pt3Fe surface than those on the Pt-Fe alloy, Pt3Fe/C had better stability than Pt-Fe/C. A single cell fabricated with Pt3Fe/C showed higher initial performance and superior durability, compared to that with commercial Pt/C. We suggest that Pt3M chemically ordered electrocatalysts are excellent candidates that may become the most active and durable ORR catalysts available.