Nanoscience and Microsystems ETDs

Publication Date



Non-platinum catalysts are an attractive strategy for lowering the cost of fuel cells, but much more development is needed in order to replace platinum, especially at the cathode where oxygen is reduced. Research groups worldwide have donated material for a study in which precursor structure to catalyst activity correlations are made. The donated samples have been divided into three classes based on their precursor; macrocyclic chelates, small molecule, and polymeric precursors. The precursor is one activity-dictating factor among many, but it is one of the most influential. It was found that macrocyclic chelates on average produced the most active catalysts, having the highest limiting, diffusion-limited, kinetic, and exchange current densities, as well as the lowest overpotentials and H2O2 production. This suggests that the M-N4 atomic structure of the precursor remains largely static throughout heat treatment, as the M-Nx motif is the accepted active site conformation. The other classes were somewhat less active, but the breadth of precursor materials that range in structure and functionality, as well as low associated costs, make them attractive precursor materials. Careful precursor selection based on this analysis was applied to a new generation of catalyst derived from iron salt and 4-aminoantipyrine. An extensive investigation of the reduction of oxygen on the material performed in both acid and alkaline media, and it was found that reduction follows a two-step pathway. While the peroxide reducing step is also very fast, the first step is so rapid that, even at low active site density, the material is almost as active as platinum if all diffusion limitations are removed. In addition to bottom-up catalyst design, the catalyst:ionomer complex, by which catalyst is incorporated into the membrane electrode assembly, also affects reductive kinetics. A series of novel anionically conductive ionomers have been evaluated using a well-described cyanamide derived catalyst, and the ionomeric influence on activity was mechanistically evaluated. It was found that the water-uptake percentage of the ionomer and the ion exchange capacity has a major role in catalyzing the reaction. The ionomer content of the complex must balance ionic and electrical charge transfer, as well as manage a certain degree of hydration at the active site. In order for a catalyst to perform optimally in an operational fuel cell, design considerations must be addressed at the precursor, support, synthesis, morphological, and ionomer-complexing levels. If any level of design is neglected, catalytic performance will be sacrificed.


Oxygen Reduction Reaction, non-platinum, ionomer, mechanism, precursors, cathode catalyst

Document Type




Degree Name

Nanoscience and Microsystems

Level of Degree


Department Name

Nanoscience and Microsystems

First Advisor

Atanassov, Plamen

First Committee Member (Chair)

Kevin, Malloy

Second Committee Member

Halevi, Barr

Third Committee Member

Hibbs, Michael