Heterogeneous iron-containing carbon gels as catalysts for oxygen electroreduction: Multifunctional role of sulfur in the formation of efficient systems

(Co)polycondensation of resorcinol and heterocyclic aldehydes yields heteroaromatic porous polymers. Carbonization of such polymers results in N-doped, S-doped, N/S-co-doped or undoped carbon gels depending on the starting composition of reactants. If the (co)polycondensation is initiated with FeCl3, Fe-containing carbon gels are obtained. Depending on the nature of the heteroatom doping (solely N or S, both N and S or no heteroatom) the Fe-containing carbon gels exhibit distinct structural properties. While the presence of sulfur hinders Fe-driven graphitization, yielding carbons with high specific surface area (SSA), N-doping exhibits the contrary effect, resulting in highly graphitic structures with low SSAs. More importantly, increasing the Fe content in the N/S-co-doped carbons results in remarkable increases in microporosity, yielding materials with SSA of up to 1240 m2g-1. The Fe-containing carbon gels are considered non-precious metal catalysts for the oxygen reduction reaction. It is demonstrated that in the case of Fe/N/C/S type catalysts, the interaction between S, C and Fe (at the pyrolysis stage) results in the enhancement of microporosity, where S acts as a soft oxidant toward carbon, while Fe recaptures the sulfur- and carbon-containing pyrolytic gases. The incidental deposition of pyrolytic gases contributes significantly to the final structure of the catalysts.