| Renewable hydrogen-fuelled proton exchange membrane (PEMFC) fuel cells have consistently demonstrated great promise as a future source of energy due to their high conversion efficiency, lower temperature of operation and lack of greenhouse emissions. One of the major impediments in the commercialization of polymer electrolyte membrane fuel cells is the insufficient catalytic reactivity and higher cost of Pt electrocatalysts which are utilized for the electroreduction of oxygen from air.;This dissertation focuses primarily on a family of Pt alloy fuel cell electrocatalysts referred to as de-alloyed core-shell electrocatalysts. These materials are bimetallic or multimetallic nanoparticles, mostly supported on conductive supports which were first described in a dissertation by Dr. S. Koh earlier in 2009.1 De-alloyed Pt nanoparticle electrocatalysts are formed from base metal rich binary Pt-M and ternary Pt-M1-M 2 (M, M1, M2 = Cu, Co, Ni, Fe and Cr) alloy nanoparticle precursors. The precursors are transformed and activated by electrochemical selective dissolution of the less noble metal component of the precursors (de-alloying). They have shown exceptional activity for oxygen reduction reaction (ORR) in idealized electrochemical half cell measurements, in particular rotating disk electrode experiments. However, these materials were never tested or implemented in realistic Membrane Electrode Assemblies (MEA) and single PEM fuel cells. The objective of this work was to implement de-alloyed Pt particle catalysts in realistic fuel cell electrode layers as well as a detailed characterization of their behavior and stability. The major challenges of MEA implementation consists of the behavior of the new nanostructured electrocatalysts inside the complex three-phase interface of polymer membrane ionomer, liquid water, metal catalyst, support, and reactant gas.;Activity measurements were followed by medium and long-term durability analysis by potential cycling of the membrane electrode assemblies to high potentials. These de-alloyed catalysts show improved resistance to electro-chemical surface area degradation as compared to state of the art available commercial Pt/C catalysts. TEM imaging with combination of electrochemical characterization helps in determining the mechanisms for particle growth and failures. Anomalous small angle x-ray scattering (ASAXS) and x-ray diffraction (XRD) techniques were also used in the characterization of these materials. |
