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

Abstract

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 g_Pt^-1, respectively. Pt₃Fe/C exhibited excellent mass activity (0.454 A mg_Pt^-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.