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Electrochemical Dealloying of PdCu 3 Nanoparticles to Achieve Pt‐like Activity for the Hydrogen Evolution Reaction
Author(s) -
Jana Rajkumar,
Bhim Anupam,
Bothra Pallavi,
Pati Swapan K.,
Peter Sebastian C.
Publication year - 2016
Publication title -
chemsuschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 2.412
H-Index - 157
eISSN - 1864-564X
pISSN - 1864-5631
DOI - 10.1002/cssc.201601081
Subject(s) - overpotential , oleylamine , electrochemistry , adsorption , materials science , nanoparticle , catalysis , hydrogen , chemical engineering , intermetallic , water splitting , nanotechnology , chemistry , combinatorial chemistry , electrode , organic chemistry , metallurgy , alloy , engineering , photocatalysis
Manipulating the d‐band center of the metal surface and hence optimizing the free energy of hydrogen adsorption (Δ G H ) close to the optimal adsorption energy (Δ 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 PdCu 3 nanoparticles (NPs) without using any external reducing agent. Upon electrochemical cycling, PdCu 3 transforms into Pd‐rich PdCu (Δ G H =0.05 eV), exhibiting remarkably enhanced activity (with a current density of 25 mA cm −2 at ∼69 mV 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.