Abstract
Active and inexpensive catalysts for oxygen reduction are crucially needed for the widespread development of polymer electrolyte fuelcells and metal−air batteries. While iron−nitrogen−carbon materials pyrolytically prepared from ZIF-8, a specific zeolitic imidazolate framework(ZIF) with sodalite topology, have shown enhanced activities toward oxygen reduction in acidic electrolyte, the rational design of sacrificialmetal−organic frameworks toward this application has hitherto remained elusive. Here, we report for the first time that the oxygen reduction activity of Fe−N−C catalysts positively correlates with the cavity size and mass specific pore volume in pristine ZIFs. The high activity of Fe−N−C materials prepared from ZIF-8 could be rationalized, and another ZIF structure leading to even higher activity was identified. In contrast, the ORR activity is mostly unaffected by the ligand chemistry in pristine ZIFs. These structure−property relationships will help identifying novel sacrificial ZIF or porous metal−organic frameworks leading to even more active Fe−N−C catalysts. The findings are of great interest for a broader application of the class of inexpensive metal−nitrogen−carbon catalysts that have shown promising activity also for the hydrogen evolution (Co−N−C) and carbon dioxide reduction (Fe−N−C and Mn−N−C).