Effects of Composition and Annealing Conditions on Catalytic Activities of Dealloyed Pt-Cu Nanoparticle Electrocatalysts for PEMFC

Dealloyed Pt(25)Cu(75) bimetallic nanoparticle electrocatalysts exhibit up to six times higher oxygen reduction reaction activities than pure nanoparticle Pt catalysts at 0.9 V/ reversible hydrogen electrode (RHE). The active form of the catalyst is formed in situ from Pt-Cu precursor material using voltammetric dealloying. The effects of composition of precursors as well as effects of the annealing temperature and duration on the catalyst activity are studied. We vary the composition between Pt(25)Cu(75) and Pt(75)Cu(25) and change the annealing conditions from 600 to 950 degrees C and for 7 and 14 h. X-ray diffraction and electrochemical analyses are used to obtain insight on the structural details of the catalyst samples. Information regarding the extent of alloying, atomic ordering, the Pt and Cu compositions, and distributions on the nanoparticles and particle (crystallite) sizes is correlated with the trends observed from mass and specific activities of the catalysts. It was found that an annealing duration of 14 h offers little or no benefit to catalytic activities compared to 7 h. Dealloyed Pt(25)Cu(75) annealed for 7 h, at 800 degrees C yielded an optimal active material with respect to the extent of alloying and particle size growth and exhibited the highest Pt mass-based and favorable specific catalytic oxygen reduction reaction (ORR) activity. The occurrence and role of a noncubic Pt(50)Cu(50) Hongshiite phase is discussed. (C) 2008 The Electrochemical Society. [DOI: 10.1149/1.2988741] All rights reserved.