Sulfur doped FeNC catalysts derived from Dual-Ligand zeolitic imidazolate framework for the oxygen reduction reaction.

Iron-nitrogen-carbon (FeNC) catalysts derived from zeolitic-imidazolate frameworks (ZIFs) are worldwide accepted to be the most promising candidates for the oxygen reduction reaction (ORR), but the insufficient stability, the low FeN exposure and poor density restrict their ORR activity. Here, we demonstrate a strategy to synthesize FeN sites embedded in a micro/mesoporous N, S co-doped graphitic carbon (FeNC/MUS) by tuning the ligand linkers via the addition of 2-undecylimidazole as a co-ligand in ZIF precursors, and optimizing the electronic structure of Fe center by an in-situ addition of thiourea molecules as sulfur (S) source. 2-undecylimidazole offered an open porous structure to incorporate more FeN, while the S-doping increased the density of FeN. Besides, 2-undeclyimidazole cooperatively with S-doping caused favorable changes into the catalyst structure, particularly improved the exposure and density of FeN sites and doubled the Brunauer-Emmetter-Teller surface area to 1132 m g contrasted to the pristine FeNC/M (544 m g). FeNC/MUS displayed an accelerated ORR activity with a higher half-wave potential of 0.86 V (vs. reversible hydrogen electrode (RHE)) than that of Pt/C (0.84 V) in addition of a longer durability with a 11 % of activity decay after 30000 s in alkaline media. This work offers a new insight to design optimal ZIFs precursor and a facile electron withdrawing S-doping strategy for efficient electrocatalysis.