Accurate Evaluation of Active-Site Density (SD) and Turnover Frequency (TOF) of PGM-Free Metal-Nitrogen-Doped Carbon (MNC) Electrocatalysts using CO Cryo Adsorption

The number of catalytically active sites (site density, SD) and the catalytic turnover frequency (TOF) are critical for meaningful comparisons between catalytic materials and their rational improvement. SD and TOF numbers have remained elusive for PGM-free, metal/nitrogen-doped porous carbon electrocatalysts (MNC), in particular, FeNC materials that are now intensively investigated and widely utilized to catalyze the oxygen reduction reaction (ORR) in fuel cell cathodes. Here, we apply CO cryo sorption and desorption to evaluate SD and TOF numbers of a state-of-art FeNC ORR electrocatalyst with atomically dispersed coordinative FeNx (x <= 4) sites in acid and alkaline conditions. More specifically, we study the impact of thermal pretreatment conditions prior to assessing the number of sorption-active FeNx sites. We show that the pretreatment temperature sensitively affects the CO sorption uptake through a progressive thermal removal of airborne adsorbates, which, in turn, controls the resulting catalytic SD numbers. We correlate CO uptake with CO desorption and analyze the observed temperature-programmed desorption characteristics. The CO uptakes increased from 45 nmol.mg(catalyst)(-1) at 300 degrees C cleaning to 65 nmol.mg(catalyst)(-1) at 600 degrees C cleaning, where it leveled off. These values were converted into apparent SD values of 2.7 x 10(19) to 3.8 x 10(19) surface sites per gram catalyst. Because of similar ORR activity of the pristine catalyst and of the sample after 600 degrees C cleaning step, we conclude that the nature and number of surface FeNx sites remained largely unaffected up to 600 degrees C and that cleaning to less than 600 degrees C was insufficient to free the sites from previously adsorbed species, completely or partially impeding CO adsorption. Cleaning beyond that temperature, however, led to undesired chemical modifications of the FeNx moieties, resulting in higher TOF. In all, this study identifies and recommends a practical and useful protocol for the accurate evaluation of catalytic SD and TOF parameters of PGM-free ORR electrocatalyst, which enables a more rational future catalyst development and improvement.