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Advances in Physical Chemistry
Volume 2012 (2012), Article ID 491604, 17 pages
Review Article

Fundamental Mechanistic Understanding of Electrocatalysis of Oxygen Reduction on Pt and Non-Pt Surfaces: Acid versus Alkaline Media

Laboratory for Electrochemical Advanced Power, Department of Chemistry and Chemical Biology, Center of Renewable Energy Technology (NUCRET), Northeastern University, 360 Huntington Avenue, Boston, MA 02115, USA

Received 2 October 2011; Accepted 22 December 2011

Academic Editor: Milan M. Jaksic

Copyright © 2012 Nagappan Ramaswamy and Sanjeev Mukerjee. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.


Complex electrochemical reactions such as Oxygen Reduction Reaction (ORR) involving multi-electron transfer is an electrocatalytic inner-sphere electron transfer process that exhibit strong dependence on the nature of the electrode surface. This criterion (along with required stability in acidic electrolytes) has largely limited ORR catalysts to the platinum-based surfaces. New evidence in alkaline media, discussed here, throws light on the involvement of surface-independent outer-sphere electron transfer component in the overall electrocatalytic process. This surface non-specificity gives rise to the possibility of using a wide-range of non-noble metal surfaces as electrode materials for ORR in alkaline media. However, this outer-sphere process predominantly leads only to peroxide intermediate as the final product. The importance of promoting the electrocatalytic inner-sphere electron transfer by facilitation of direct adsorption of molecular oxygen on the active site is emphasized by using pyrolyzed metal porphyrins as electrocatalysts. A comparison of ORR reaction mechanisms between acidic and alkaline conditions is elucidated here. The primary advantage of performing ORR in alkaline media is found to be the enhanced activation of the peroxide intermediate on the active site that enables the complete four-electron transfer. ORR reaction schemes involving both outer- and inner-sphere electron transfer mechanisms are proposed.