Worldwide energy demand has driven long-term efforts towards developing a clean, hydrogen-based energy economy. Polymer electrolyte membrane fuel cells (PEMFC) are low emissions and high efficiency devices that utilize the power of hydrogen and are a key enabling technology for the hydrogen economy. Carbon supported platinum-black is the state-of the art catalyst for oxygen reduction in a PEMFC because it can withstand the acidic environment. However, the high cost and low abundance of this precious metal has limited large-scale commercialization of PEMFCs. Current efforts focus on developing alternative inexpensive, non-noble metal-based catalysts for oxygen reduction with performance comparable to conventional platinum based electrocatalysts. In this work, inexpensive metal-nitrogen-carbon (MNC) catalysts have been synthesized by pyrolyzing transition metal and nitrogen precursors together with high surface area carbon materials in a closed, constant-volume quartz tube. High pressure generated due to nitrogen precursor evaporation lead to increased surface nitrogen content in the catalysts post-pyrolysis. Electrochemical oxygen reduction activity of MNC catalysts was analyzed using half-cell Rotating Ring Disc Electrode (RRDE) studies. The effect of nitrogen precursor morphology on the generation of active sites has been explored in detail. By increasing the Nitrogen/Carbon ratio of the nitrogen precursor, the accessible active site density increased by reducing carbon deposition in the pores of the carbon support during pyrolysis. The most active catalysts were obtained using melamine, having a N/C ratio of 2. Single PEMFC measurements employing MNC catalysts as cathodes indicated kinetic current density as high as 15 A cm-3 at 0.8 ViR-free and over 100 h of stable current at 0.5 V were observed. Effects of carbon free ammonia generating solid nitrogen precursors such as urea and ammonium carbamate were also studied. These precursors etched the carbon support and increased the porosity, particularly micro and mesopores of the catalysts that led to increased active site density and reduced oxygen transport hindrances respectively. Collaborative efforts with the University of New Mexico facilitated XPS characterization of MNC catalysts. XPS analyses indicated that pyridinic nitrogen sites, present in the edge plane of the catalysts and pyridinic nitrogen coordinated to transition metals correlated to oxygen reduction activity. Further insight into the role of transition metal and the structure of active site was gained through EXAFS measurements, carried out in collaboration with Northeastern University. Electrochemical studies performed in the presence of poisoning anions such as cyanide in alkaline environment indicated a 25% decrease in oxygen reduction activity, suggesting that the metal is part of the active sites and participates in oxygen reduction. In-situ EXAFS analysis of the catalysts indicated the active reaction site for oxygen reduction to be Fe metal coordinated to 4 nitrogen atoms. These low cost MNC catalysts find direct application in Proton Exchange Membrane Fuel cells for transportation applications, where there is a huge drive to improve the economy of the fuel cell by reducing the costs associated with state-of the art platinum-based catalysts.
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