Role of Electronic Perturbation in Stability and Activity of Pt-based Alloy Nanocatalysts for Oxygen Reduction Reaction

Role of Electronic Perturbation in Stability and Activity of Pt-based Alloy Nanocatalysts for Oxygen Reduction Reaction
Issue Date
2013 MRS Spring Meeting
As the interest for hydrogen economy grows, the research about the hydrogen storage, the hydrogen production, and the fuel cells is expanding.1 Especially, polymer electrolyte membrane fuel cells (PEMFCs) are promising alternative devices for reducing our reliance on unfriendly fossil fuels; however, several problems should be overcome before they become more economically attractive.1 One of the most pivotal issues is the large overpotential associated with the slow reaction rate of the oxygen reduction reaction (ORR) at the cathode.2 This has been the focus of attention of the need for better catalysts with decreased Pt content. Considerable efforts have been devoted previously to understand the kinetics and mechanisms of the ORR in order to search for inexpensive and catalytically active electrocatalysts such as bi- and multimetallic alloys.2-5 Furthermore, in recent times, studies have been conducted on the correlation between the electronic structure and catalytic activity of metallic alloys for the ORR.6 The adsorption energy of oxygen is proportional to the oxygen&#8211;metal bond strength and the relative position of the d-band center to the Fermi level. Another tremendous challenge is the stability of electrochemical reactions such as metal dissolution and surface oxide formation, which occur intensively in acid mediums (<pH 1) at high potentials (>0.8 V).4-7 Recently, Nørskov et al., Chorkendorff et al., and Yoo et al. reported stable cathode catalysts by alloying Pt with early transition metals such as Hf, La, Sc or Y.7b-7e Markovic et al. and Adzic et al. demonstrated a stable cathode catalyst by alloying Pt with a 3-d transition metal (especially, Pt-skin surface alloys) and by modifying Pt with a Au cluster, respectively; in this manner, they emphasized the significance of stability considerations.6a,8 However, despite the significant technological interest in finding active and stable catalys
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