Synthesis and characterization of nanostructured palladium-based alloy electrocatalysts
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Low temperature fuel cells like proton exchange membrane fuel cells (PEMFC) are expected to play a crucial role in the future hydrogen economy, especially for transportation applications. These electrochemical devices offer significantly higher efficiency compared to conventional heat engines. However, use of exotic and expensive platinum as the electrocatalyst poses serious problems for commercial viability. In this regard, there is an urgent need to develop low-platinum or non-platinum electrocatalysts with electrocatalytic activity for the oxygen reduction reaction (ORR) superior or comparable to that of platinum. This dissertation first investigates non-platinum, palladium-based alloy electrocatalysts for ORR. Particularly, Pd-M (M = Mo and W) alloys are synthesized by a novel thermal decomposition of organo-metallic precursors. The carbon-supported Pd-M (M = Mo, W) electrocatalyts are then heat treated up to 900 oC in H2 atmosphere and investigated for their phase behavior. Cyclic voltammetry (CV) and rotating disk electrode (RDE) measurements reveal that the alloying of Pd with Mo or W significantly enhances the catalytic activity for ORR as well as the stability (durability) of the electrocatalysts. Additionally, both the alloy systems exhibit high tolerance to methanol, which is particularly advantageous for direct methanol fuel cells (DMFC). The dissertation then focuses on one-pot synthesis of carbon-supported multi-metallic Pt-Pd-Co nanoalloys by a rapid microwave-assisted solvothermal (MW-ST) method. The multi-metallic alloy compositions synthesized by the MW-ST method show much higher catalytic activity for ORR compared to their counterparts synthesized by the conventional borohydride reduction method. Additionally, a series of Pt encapsulated Pd-Co nanoparticle electrocatalysts are synthesized by the MW-ST method and characterized to understand their phase behavior, surface composition, and electrocatalytic activity for ORR. Finally, the dissertation focuses on carbon-supported binary Pt@Cu and ternary PtxPd1-x@Cu “core-shell” nanoparticles synthesized by a novel galvanic displacement of Cu by Pt4+ and Pd2+ at ambient conditions. Structural characterizations suggest that the Pt@Cu nanoparticles have a Pt-Cu alloy layer sandwiched between a copper core and a Pt shell. The electrochemical data clearly point to an enhancement in the activity for ORR for the Pt@Cu “core-shell” nanoparticle electrocatalysts compared to the commercial Pt electrocatalyst, both on per unit mass of Pt and per unit active surface area basis. The increase in activity for ORR is ascribed to electronic modification of the outer Pt shell by the Pt-Cu alloy core. However, incorporation of Pd to obtain PtxPd1-x@Cu deteriorates the activity for ORR.