On the role of Zn and Fe doping in nitrogen-carbon electrocatalysts for oxygen reduction

Zn is a frequently used and sometimes even an inevitably involved element (when zeolitic imidazolate framework-8 (ZIF-8) is adopted as the precursor) for preparing high-performance Fe-N-C oxygen reduction reaction (ORR) catalysts. However, how the Zn element affects the physicochemical architecture of the catalysts, how it enhances the catalytic activity and whether Zn atoms serve as the active centers remain unclear. Herein, we proposed a novel route that adopted pyrrole as the precursor and flexibly controlled the addition of exogenous Zn and Fe dopants before pyrrole polymerization. In this way, a series of nitrogen-carbon catalysts with or without Zn or Fe doping were synthesized. The detailed characterization revealed the role of Zn and Fe doping in the catalyst morphology, pore structure, active site configurations, ORR catalytic activity and fuel cell performance. Importantly, the findings revealed that Zn doping has little effect on the ORR mechanism and pathway. It enhances ORR activity primarily by increasing the number of active sites via introducing more micro- and meso-pores, rather than by creating new active sites. While Fe doping participated in forming both pores and active site centers. Moreover, the catalyst that co-doped with Zn and Fe atoms (Zn-FeNC), synthesized via this simple and template-free route we proposed, presented a unique hollow and hierarchical pore structure with highly boosted ORR activity. It exhibited a 40 mV higher E_1/2 value than Pt/C in alkaline media, along with a rapid current response in air-cathode of the direct formate fuel cell. These results are valuable in guiding the synthesis of high-performance Fe-N-C catalysts.