Rationally-Designed Sandwiched Nanostructures Boosting Fe-N Based Catalysts toward Efficient Oxygen Reduction Electrocatalysis in an Acidic Medium
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Abstract: The development of acidic-available noble-metal-free oxygen reduction reaction (ORR) catalysts with high activity and good long-term durability is of significant importance for efficient proton exchange membrane fuel cells (PEMFC), but is still very challenging. Herein, we develop originally a facile wet-chemical-adsorption, pyrolysis and post-etching strategy to effectively intercalate Fe clusters among two nitrogen-doped carbon (NC) layers, forming unique hollow spherical nanostructures with sandwiched NC/Fe/NC shells as an active ORR catalyst. Thanks to the sandwiched nanostructure and the active Fe-N species, this as-prepared hollow sandwiched NC/Fe/NC catalyst could present superior ORR activity in an acidic medium, with a nice onset potential of 0.92 V and decent diffusion-limited current density of ~5.1 mA/cm2. The NC/Fe/NC catalyst manifests strong methanol tolerance and outstanding durability during a long-term acidic ORR operation, being a promising alternative to Pt-based catalysts toward efficient proton exchange membrane fuel cells. Synchrotron radiation characterizations and X-ray photoemission spectroscopy reveal at the atomic-level that the abundant robust Fe−N bonds presented in the sandwiched shells of hollow NC/Fe/NC spherical catalyst contribute substantially to high electrochemical activity and superior corrosion-resistance for efficient 4e− ORR in acidic electrolyte.
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Figure 1. Synthetic diagram, morphological and structural characteristics. (a) Illustration of the synthetic approach of NC/Fe/NC catalysts. (b−d) SEM, TEM, and TEM-EDS mapping images for NC/Fe/NC catalyst, where scan bar in the inset of (c) is 5, and that is 200 nm in (d). (e, f) SEM and TEM images for Fe/NC catalyst. (g) XRD patterns for NC/Fe/NC and Fe/NC catalysts.
Figure 2. Electrochemical performance results. (a) LSV curves recorded in O2-saturated 0.5 mol/L H2SO4 solution at 1600 r/min for NC/Fe/NC catalyst, Fe/NC catalyst, and commercial Pt/C catalyst. (b) CV curves collected in N2- or O2- saturated electrolyte at 0 r/min for the NC/Fe/NC catalyst. (c) LSV plots for NC/Fe/NC catalyst under various rotating speeds. (d) Chronoamperometric (I-t) tests for NC/Fe/NC and commercial Pt/C catalysts.
Figure 3. Structural and electrochemical examinations after ORR tests. (a) SEM image, (b) TEM image, and (c) LSV curves for the NC/Fe/NC catalysts after 1000 cycles ORR tests.
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