Rational Development of Structurally Ordered Platinum Ternary Intermetallic Electrocatalysts for Oxygen Reduction Reaction

Abstract

Structurally ordered intermetallic structure is an efficient catalyst design strategy to significantly improve the catalytic performance of Pt alloy electrocatalysts for oxygen reduction reaction in fuel cells. However, a high structural ordering degree generally relies on high-temperature annealing, which results in detrimental catalyst particle sintering. Herein, we reveal that the incompatibility between high ordering degree and minimum particle sintering during thermal annealing can be resolved through rational development of structurally ordered Pt ternary alloys. Ordering transformation mediated by high-temperature annealing of three representative Pt ternary alloys (Pt–Fe–Co, Pt–Ni–Co and Pt–Fe–Ni) at a similar Pt composition was systematically studied. It was found that Fe can significantly promote the structural ordering due to a faster atomic diffusion, whereas Co can effectively inhibit the particle sintering. As a result of the synergy between Co and Fe, the ordered PtCoFe catalyst exhibited the highest ordering degree after thermal annealing at 600 °C with the minimum nanoparticle growth, leading to the highest catalytic activity (0.65 A/mgPt at 0.9 V, 4 times that of pure Pt catalyst) and best stability (16% drop after 10,000 potential cycles). This study provides important clues for the rational design of high-performance structurally ordered ternary Pt alloys.