There has been growing interest in the development of highly active catalysts for electroreduction of oxygen that could be effectively utilized in low-temperature fuel cells. The important practical issue is related to the need of lowering costs of catalysts by substituting the noble metals with inexpensive abundant elements. In this respect materials containing metallic moieties coordinated by nitrogen atoms embedded in the carbon matrix (M-N-C) are recognized as most suitable candidates to replace platinum catalysts. More recently, the approach of using such biomimetic centers has been considered for the carbon dioxide reduction, the reaction which permits generation of carbon-based chemicals, fuels or syngas. Since both reactions (O₂ and CO₂ reductions) are characterized by slow kinetics and may proceed through different pathways producing various products, their efficiency and selectivity still remain fundamental problems for practical applications.

It is well established that the best performing M-N-C catalysts (with high specific surface area and large fraction of micropores) are produced from nitrogen-containing polymeric precursors. In these study we present a new type of self-supporting M-N-C materials, namely nitrogen and sulfur co-doped iron containing highly porous carbon gels (obtained through pyrolysis of organic gels) as efficient non-precious metal catalysts for both the oxygen and carbon dioxide electroreductions. The precursors of the catalysts were prepared via the sol-gel polycondensation (induced with iron(III) cations) of resorcinol together with the mixture of two heterocyclic aldehydes containing nitrogen and sulfur. The role of S is to produce carbon gels with high specific surface areas (e.g. when compared to carbon gels containing solely N heteroatom).

It is commonly accepted that rotating ring(platinum)-disk(glassy carbon) electrode voltammetry can be effective diagnostic tool for elucidation of the performance and selectivity (towards water or hydrogen peroxide) of the oxygen electroreduction. We are going to demonstrate that a combination of the rotating ring-disk electrode methodology and stripping type voltammetry (at platinum ring) can be also used for the determination of the reaction mechanism, competitive formation (evolution) of hydrogen, and determination of CO-type adsorbates generated at the catalyst during the CO₂ electroreduction.