Beata Dembinska

Toward Pt-Free Anion-Exchange Membrane Fuel Cells: Fe–Sn Carbon Nitride–Graphene Core–Shell Electrocatalysts for the Oxygen Reduction Reaction

We report on the development of two new Pt-free electrocatalysts (ECs) for the oxygen reduction reaction (ORR) process based on graphene nanoplatelets (GNPs). We designed the ECs with a core–shell morphology, where a GNP core support is covered by a carbon nitride (CN) shell. The proposed ECs present ORR active sites that are not associated with nanoparticles of metal/alloy/oxide but are instead based on Fe and Sn subnanometric clusters bound in coordination nests formed by carbon and nitrogen ligands of the CN shell. The performance and reaction mechanism of the ECs in the ORR are evaluated in an alkaline medium by cyclic voltammetry with the thin-film rotating ring-disk approach and confirmed by measurements on gas-diffusion electrodes. The proposed GNP-supported ECs present an ORR overpotential of only ca. 70 mV higher with respect to a conventional Pt/C reference EC including a XC-72R carbon black support. These results make the reported ECs very promising for application in anion-exchange membrane fu...

Development of Bifunctional Carbon Nanotube-Supported Co-Porphyrin Electrocatalytic System for Oxygen Reduction

Combination of multiwalled carbon nanotubes, cobalt porphyrin and tungsten oxide produces a multifunctional electrocatalytic system capable of the effective reduction of oxygen in acid medium. The resulting inks have been utilized during sequential deposition of components. Co-existence of Co-porphyrin, tungsten oxide together with dispersed carbon nanotubes leads to synergistic effect that is evident from positive shift of the oxygen reduction potentials, significant increase of voltammetric currents (relative to those observed at a system not containing carbon nanotube-supported tungsten oxide) and decrease of hydrogen peroxide produced during oxygen reduction. It is reasonable to expect that the reduction of oxygen is initiated at metalloporphyrin redox centers, and the undesirable hydrogen peroxide intermediate is further reduced at partially reduced tungsten oxide. In addition to the methanol tolerance other important issue is the tolerance of the proposed system to ethanol that may appear due to crossover in the cathode compartments of ethanol fuel cells.

Graphene-Based Nanostructures in Electrocatalytic Oxygen Reduction

Application of graphene-type materials in electrocatalysis is a topic of growing scientific and technological interest. A tremendous amount of research has been carried out in the field of oxygen electroreduction, particularly with respect to potential applications in the fuel cell research also with use of graphene-type catalytic components. This work addresses fundamental aspects and potential applications of graphene structures in the oxygen reduction electrocatalysis. Special attention will be paid to creation of catalytically active sites by using nonmetallic heteroatoms as dopants, formation of hierarchical nanostructured electrocatalysts, their long-term stability, and application as supports for dispersed metals (activating interactions).

Reduced-Graphene-Oxide with Traces of Iridium or Gold as Active Support for Pt Catalyst at Low Loading during Oxygen Electroreduction

Chemically-reduced graphene-oxide-supported gold or iridium nanoparticles are considered here as active carriers for dispersed platinum with an ultimate goal of producing improved catalysts for electroreduction of oxygen in acid medium. Comparison is made to the analogous systems not utilizing reduced graphene oxide. High electrocatalytic activity of platinum (loading up to 30 {\mu}g cm-2) dispersed over the reduced-graphene oxide-supported Au (up to 30 {\mu}g cm-2) or Ir (up to 1.5 {\mu}g cm-2) nanoparticles toward reduction of oxygen has been demonstrated using cyclic and rotating ring-disk electrode (RRDE) voltammetric experiments. Among important issues are possible activating interactions between gold and the support, as well as presence of structural defects existing on poorly organized graphitic structure of reduced graphene oxide. The RRDE data are consistent with decreased formation of hydrogen peroxide.