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CNTs were grown on iron-modified mesoporous graphitized carbon aerogel (GCA) at 700 °C, 800 °C and 900 °C using catalytic CVD method. Resultant CNT/GCA materials composition, morphology and structure were studied to understand their electrochemical stability and performance for oxygen reduction reaction (ORR) in acidic medium. CNT growth was increased from 700 °C to 800 °C, dominated by MWCNTs formation. In the temperature range from 800 °C to 900 °C, the growth was reduced by forming nanofiber/nanoribbon structures accompanied by MWCNTs. Mesoporosity of CNT/GCA composites declined at 700 °C and 800 °C due to MWCNT formation. However, CNT/GCA growth at 900 °C improved mesoporosity with substantial increase in pore volume (∼3 times of GCA) due to formation of nanofibers and nanoribbons. The structure of CNT/GCA materials revealed nitrogen doping and dispersion of FeN x phase. A synergistic contribution of CNT/GCA material structure and morphology to ORR activity was noticed. Among CNT/GCA materials, CNT-800 °C/GCA material showed ORR activity at lowest onset potential of 0.5 V. However, CNT-900 °C/GCA exhibits the highest ORR mass activity, with a half-wave onset potential difference of 120 mV with Pt (40 wt.%)/C. Moreover, CNT-900 °C/GCA demonstrates high selectivity (>3.97) to 4 electron ORR path, excellent methanol tolerance and electrochemical durability which makes it a potential DMFC cathode candidate. [ABSTRACT FROM AUTHOR]

Abstract: Graphitic carbon nanofibers (GCNFs) with diameters of approximately 300 nm were developed using bundles of aligned electrospun polyacrylonitrile (PAN) nanofibers containing phosphoric acid (PA) as the innovative precursors through thermal treatments of stabilization, carbonization, and graphitization. The morphological, structural, and mechanical properties of GCNFs were systematically characterized and/or evaluated. The GCNFs made from the electrospun PAN precursor nanofibers containing 1.5 wt.% of PA exhibited mechanical strength that was 62.3% higher than that of the GCNFs made from the precursor nanofibers without PA. The molecules of PA in the electrospun PAN precursor nanofibers initiated the cyclization and induced the aromatization during stabilization, as indicated by the FT-IR and TGA results. The stabilized PAN nanofibers possessed regularly oriented ladder structures, which facilitated the further formation of ordered graphitic structures in GCNFs during carbonization and graphitization, as indicated by the TEM, XRD, and Raman results. [Copyright &y& Elsevier]