Design principles for oxygen-reduction activity on perovskite oxide catalysts for fuel cells and metal-air batteries

• Published in: Nature chemistry Vol. 3; no. 7; pp. 546 - 550
• Main Authors: Suntivich, Jin, Gasteiger, Hubert A, Yabuuchi, Naoaki, Nakanishi, Haruyuki, Goodenough, John B, Shao-Horn, Yang
• Format: Journal Article
• Language: English
• Published: England Nature Publishing Group 12.06.2011
• Subjects: 30 DIRECT ENERGY CONVERSION; CATALYSTS; Chemistry; COMMERCIALIZATION; COST; COVALENCE; DESIGN; Electrodes; ELECTRONIC STRUCTURE; ENERGY STORAGE; FUEL CELLS; IONS; MATERIALS; Metal oxides; METAL-GAS BATTERIES; OXIDES; OXYGEN; PEROVSKITE; PLATINUM; REDUCTION; REGENERATION; SURFACES; United States > US; Massachusetts
• ISSN: 1755-4330; 1755-4349
• DOI: 10.1038/nchem.1069

The prohibitive cost and scarcity of the noble-metal catalysts needed for catalysing the oxygen reduction reaction (ORR) in fuel cells and metal-air batteries limit the commercialization of these clean-energy technologies. Identifying a catalyst design principle that links material properties to the catalytic activity can accelerate the search for highly active and abundant transition-metal-oxide catalysts to replace platinum. Here, we demonstrate that the ORR activity for oxide catalysts primarily correlates to σ-orbital (e(g)) occupation and the extent of B-site transition-metal-oxygen covalency, which serves as a secondary activity descriptor. Our findings reflect the critical influences of the σ orbital and metal-oxygen covalency on the competition between O(2)(2-)/OH(-) displacement and OH(-) regeneration on surface transition-metal ions as the rate-limiting steps of the ORR, and thus highlight the importance of electronic structure in controlling oxide catalytic activity.