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Pt-Pd nanoelectrocatalyst of ultralow Pt content for the oxidation of formic acid: Towards tuning the reaction pathway

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Abstract

Synthesis of highly efficient functional electrocatalyst that favours the electrochemical oxidation of formic acid via CO-free dehydrogenation pathway is required for direct formic acid fuel cells. Traditional catalysts favour the dehydration pathway involving the generation of poisonous CO. Herein we demonstrate the superior electrocatalytic performance of Pt-Pd bimetallic nanoelectrocatalyst of ultralow Pt content and tuning the reaction pathway by controlling the Pt content. Bimetallic nanoparticles of Pt4Pd96, Pt7Pd93 and Pt47Pd53 compositions are synthesized by electrochemical co-deposition method in aqueous solution. The nanoparticles of ultralow Pt content, Pt4Pd96, favour the CO-free dehydrogenation pathway for formic acid oxidation with an onset potential of 0 V (SHE) whereas the Pt47Pd53 nanoparticles favour the dehydration pathway involving the formation of CO at high positive potential. The Pt content of the bimetallic nanoparticles actually controls the oxidation peak potential and catalytic activity. Significant negative shift (∼350 mV) in the oxidation peak potential and remarkable enhancement in the current density (2.6 times) are observed for Pt4Pd96 nanoparticles with respect to Pt47Pd53. The absence of three adjacent Pt and Pd atoms could be the reason for the suppression of CO pathway. The electrochemical impedance measurements indirectly support the CO-free pathway for the formic acid oxidation on Pt4Pd96 nanoparticles.

Electrochemical synthesis of Pt-Pd bimetallic nanoparticles of ultralow Pt content and tuning of reaction pathway for the electrochemical oxidation of formic acid are described.

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Acknowledgements

This work was financially supported by Department of Science and Technology, New Delhi.

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Authors and Affiliations

  1. Department of Chemistry, Indian Institute of Technology Kharagpur, Kharagpur, 721 302, India

    SOUROV GHOSH & C RETNA RAJ

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  1. SOUROV GHOSH
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  2. C RETNA RAJ
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Correspondence to C RETNA RAJ.

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Supplementary Information

Voltammetric response of the nanoparticle-based electrode, chronoamperometric response illustrating the stability of the electrode towards formic acid oxidation, Nyquist plot for the oxidation of formic acid on Pt7Pd93, Pt and Pd nanoparticle-based electrodes, tables summarizing the previous literature on formic acid oxidation and impedance parameters are presented in the supplementary information available at www.ias.ac.in/chemsci.

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GHOSH, S., RAJ, C.R. Pt-Pd nanoelectrocatalyst of ultralow Pt content for the oxidation of formic acid: Towards tuning the reaction pathway. J Chem Sci 127, 949–957 (2015). https://doi.org/10.1007/s12039-015-0854-6

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  • DOI: https://doi.org/10.1007/s12039-015-0854-6

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