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Nanocrystalline intermetallics on mesoporous carbon for direct formic acid fuel cell anodes

Abstract

Shape- and size-controlled supported metal and intermetallic nanocrystallites are of increasing interest because of their catalytic and electrocatalytic properties. In particular, intermetallics PtX (X = Bi, Pb, Pd, Ru) are very attractive because of their high activity as fuel-cell anode catalysts for formic acid or methanol oxidation. These are normally synthesized using high-temperature techniques, but rigorous size control is very challenging. Even low-temperature techniques typically produce nanoparticles with dimensions much greater than the optimum <6 nm required for fuel cell catalysis. Here, we present a simple and robust, chemically controlled process for synthesizing size-controlled noble metal or bimetallic nanocrystallites embedded within the porous structure of ordered mesoporous carbon (OMC). By using surface-modified ordered mesoporous carbon to trap the metal precursors, nanocrystallites are formed with monodisperse sizes as low as 1.5 nm, which can be tuned up to 3.5 nm. To the best of our knowledge, 3-nm ordered mesoporous carbon-supported PtBi nanoparticles exhibit the highest mass activity for formic acid oxidation reported to date, and over double that of Pt–Au.

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Figure 1: Schematic illustrating the nucleated-growth synthesis of OMC-supported noble metal and intermetallic nanocrystallites.
Figure 2: TEM images demonstrating the formation of OMC-supported platinum nanocrystallites with dimensions of <2 nm.
Figure 3: XPS spectra of platinum and PtBi nanocrystallites supported on OMC.
Figure 4: TEM images and EDX maps of OMC-PtBi, revealing homogeneously dispersed 2–3 nm crystallites of the ordered intermetallic phase.
Figure 5: Cyclic voltammograms obtained for formic acid oxidation.
Figure 6: TEM and SEM images and an elemental map of nanocrystalline palladium (<3 nm) supported on OMC, prepared by the sulfur-functionalized OMC strategy.

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Acknowledgements

L.F.N. gratefully acknowledges the financial support of the National Science and Engineering Research Council (NSERC, Canada) through its Discovery Grant and Canada Research Chair programs. We thank R. Sodhi at Surface Interface Ontario, University of Toronto, for acquisition and processing of the XPS spectra and C. Mims for helpful discussions, N. Coombs at the Centre for Nanostructured Imaging, University of Toronto, for help with acquisition of the STEM imaging, and C. Andrei (McMaster University, Canadian Centre for Electron Microscopy) for help with the high-resolution imaging work. The experimental work on the FEI Titan 80–300 and FEI Titan 80–300 Cubed was carried out at the Canadian Centre for Electron Microscopy, a user facility supported by NSERC and McMaster University.

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X.J. and L.N. designed and conducted the research. Electrochemical experiments were performed by X.J., L.Z., and J.Z. K.L. and R.H. contributed analysis. TEM experiments were performed by G.B. and M.C. L.N. and X.J. wrote the paper.

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Correspondence to Linda F. Nazar.

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Ji, X., Lee, K., Holden, R. et al. Nanocrystalline intermetallics on mesoporous carbon for direct formic acid fuel cell anodes. Nature Chem 2, 286–293 (2010). https://doi.org/10.1038/nchem.553

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