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Abstract This study investigates the importance of preconditioning in Pt‐alloy catalysts for oxygen–reduction reactions. Previous research indicated that slower scanning rates during preconditioning initially boost activity, but this is followed by a rapid decline. The study reveals the required number of cycles to achieve the first constant steady state activity in PtNiMo/C catalysts when using slower scanning rates during preconditioning. It also highlights the resulting activity differences. Remarkably, a catalyst preconditioned with 150 slow cycles showed an activity of approximately 1.25 mA cm−2 at 0.90 VRHE, significantly higher than one preconditioned at a fast rate (0.82 mA cm−2). Both ex–situ and in–situ analyses revealed that Pt, along with Ni, was leached during pretreatment. At slower scan rates of 20 mV s−1, the dissolved Pt redeposited as highly active, small‐sized clusters or single atoms. Fast scan rates of of 500 mV s−1, in contrast, resulted in fewer such clusters. Accelerated stress tests up to 1.10 VRHE confirmed the high stability of these clusters, demonstrating a substantial activity increase even after 24,000 cycles.

Abstract Pt‐based alloy catalysts supported on carbon are commonly characterized for oxygen reduction reaction (ORR) activity using the rotating disk electrode technique (RDE). Within this study, we show exemplarily for PtNiMo/C catalysts that the applied pretreatment influences strongly the determined activity. The classically employed descriptor of unchanged cyclic voltammetry response is insufficient to portrait completed surface restructuring, and gives an incorrect impression that stable activity can be determined. This might be one of the reasons for the strongly deviating activities reported in literature. Following the changes in activity during pretreatment also with in‐situ FTIR and online dissolution measurements gives insights to an up to now largely overseen high activity of the trimetallic catalysts. A maximum activity of 0.57 mA cmPt−2 at 0.95 VRHE is reached quickly during the first six cycles and decreases slowly subsequently. The maximum activity and change of activity over the cycle number is affected by the scan rate and electrolyte refreshing, while the gas atmosphere plays only a minor role. This exemplary study might be important for Pt alloy catalysts in general.