Contribution of Mg-templated porosity to activity and durability in Fe–N–C O₂ reduction catalysts

Atomically dispersed Fe in N-doped carbon (Fe–N–C) catalysts are leading platinum-group-metal-free candidates for the O₂ reduction reaction in proton exchange membrane fuel cells (PEMFCs). Zeolitic imidazolate framework (ZIF-8) derived Fe–N–C present the most promising performance; however, they possess a narrow distribution of small micropores, which limits active site accessibility. Here, to induce hierarchical porosity in Fe–N–C, we report a systematic study on MgCl₂·6H₂O-templated ZIF-8-derived Fe–N–C catalysts for the O₂ reduction reaction. MgCl₂·6H₂O addition induced complete Zn removal, collapse of the ZIF-8 framework, and formation of large micro- and mesopores, with graphene-like structures. N content was markedly reduced, with conversion from pyridinic to pyrrolic N species. Rotating disc electrode tests showed a progressive increase in O₂ reduction activity with MgCl₂·6H₂O, which is strongly correlated (R² = 0.98) to the formation of large micropores and small mesopores (1–4 nm). This introduces an indirect structure–activity design principle for Fe–N–Cs. The enhanced Fe–N–C porosity also leads to increased degradation rates under accelerated stress test conditions, which we attributed to the oxidation of disordered carbon domains and active Fe loss. This study highlights a key trade-off between porosity-driven O₂ reduction activity and durability in Fe–N–C catalysts.