Atomically Dispersed (AD)Fe-N-C Oxygen Reduction Catalysts for Polymer Electrolyte Membrane Fuel Cells

Sunday, 1 October 2017: 16:20
Maryland C (Gaylord National Resort and Convention Center)
H. T. Chung (Los Alamos National Laboratory), D. A. Cullen, B. Sneed, H. M. Meyer III (Oak Ridge National Laboratory), L. Lin, X. Yin (Los Alamos National Laboratory), K. L. More (Oak Ridge National Laboratory), and P. Zelenay (Los Alamos National Laboratory)
Atomically dispersed (AD)Fe-N-C catalysts are the ultimate goal towards achieving Fe catalyst size reduction. Such catalysts are expected to have unique properties that can be exploited for the purpose of developing highly active and durable oxygen reduction reaction (ORR) catalysts. The biggest challenge during the fabrication of atomically dispersed catalysts is to prevent clustering of atoms on the support during synthesis. In this work we address this challenge by employing metal organic frameworks (MOFs) as the structural precursor for (AD)Fe-N-C catalysts. Specifically, we (i) synthesize Fe-containing MOFs (Fe-MOFs) followed by (ii) heat treatment of the Fe-MOFs to produce (AD)Fe-N-C catalysts. The heat treatment converts Fe-MOFs to N-doped carbons, with the Fe atoms contained in the MOF being uniformly distributed on the N-doped carbons without observable agglomeration. In the approach used, maintaining the initial morphology of MOFs after the heat treatment step is key to taking advantage of the MOF structural features. In a preliminary experiment, we synthesized an Fe-containing nano platelet-shaped MOF support and heat-treated it at 1000 °C in an oxygen-free atmosphere to obtain atomically dispersed Fe atoms anchored on N-doped carbon nano-plates, (AD)Fe-N-Cnano-plates. Figure 1a (high angle annular dark field scanning transmission electron microscopy (STEM) images) demonstrates that the initial plate-like shape of the MOF, which is typically 30-50 nm wide and up to hundreds of nm long, is successfully maintained during the heat treatment at 1000 °C. Microporosity within the nano-plates is generated during the heat treatment, assuring high accessibility to the Fe atoms within the catalyst. The nitrogen content in the nano-plates measured by X-ray photoelectron spectroscopy is ca. 5 at.%. X-ray diffraction (XRD) confirms the absence of crystalline particles in (AD)Fe-N-Cnano-plates,, e.g., Fe-rich particles in particular. As shown in Figure 1b, aberration-corrected (AC)-STEM clearly indicates that all of the Fe is atomically dispersed over the N-doped carbon nano-plates (individual white dots in the image). No Fe-rich clusters or particles are observed, corroborating successful synthesis of atomically dispersed Fe-N-Cnano-plates catalysts. Electrochemical and fuel cell performance data will be presented attesting to high ORR activity of the (AD)Fe-N-Cnano-plates catalysts.