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Title: Electrochemical Dealloying of PdCu3 Nanoparticles to Achieve Pt-like Activity for the Hydrogen Evolution Reaction
Authors: Jana, Rajkumar
Bhim, Anupam
Bothra, Pallavi
Pati, Swapan Kumar
Peter, Sebastian C.
Keywords: Chemistry
electrochemical dealloying
hydrogen absorption
hydrogen evolution reaction
platinum-free catalyst
Oxygen Reduction Reaction
Enhanced Electrocatalytic Activity
Efficient Electrocatalyst
Nanowire Arrays
Issue Date: 2016
Publisher: Wiley-V C H Verlag Gmbh
Citation: Jana, R.; Subbarao, U.; Peter, S. C., Ultrafast synthesis of flower-like ordered Pd3Pb nanocrystals with superior electrocatalytic activities towards oxidation of formic acid and ethanol. Journal of Power Sources 2016, 301, 160-169
Abstract: Manipulating the d-band center of the metal surface and hence optimizing the free energy of hydrogen adsorption (G(H)) close to the optimal adsorption energy (G(H)=0) for hydrogen evolution reaction (HER), is an efficient strategy to enhance the activity for HER. Herein, we report a oleylamine-mediated (acting as the solvent, stabilizer, and reducing agent) strategy to synthesize intermetallic PdCu3 nanoparticles (NPs) without using any external reducing agent. Upon electrochemical cycling, PdCu3 transforms into Pd-rich PdCu (G(H)=0.05eV), exhibiting remarkably enhanced activity (with a current density of 25mAcm(-2) at approximate to 69mV overpotential) as an alternative to Pt for HER. The first-principle calculation suggests that formation of low coordination number Pd active sites alters the d-band center and hence optimal adsorption of hydrogen, leading to enhanced activity. This finding may provide guidelines towards the design and development of Pt-free highly active and robust electrocatalysts.
Description: Open Access (Accepted Manuscript)
ISSN: 1864-5631
Appears in Collections:Research Articles (Swapan Kumar Pati)
Research Papers (Sebastian C. Peter)

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